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This application is a continuation of application Ser. No. 08/372,871 filed on Jan. 13, 1995, which is a continuation of application Ser. No. 07/970,829 filed on Nov. 3, 1992, now abandoned. BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to an image processing apparatus which is preferably embodied in an image forming apparatus or the like to which a plurality of data output apparatuses such as computers or the like can be connected. 2. Related Background Art Hitherto, in a construction in which a plurality of computers are connected to one image forming apparatus, in the case where image forming commands are generated from the plurality of computers, the computer which generated the image forming command for the first time preferentially executes the image formation and after completion of all of the image forming operations of such a computer, the image forming operation of the computer which secondly generated the image formation request is performed. As mentioned above, when the image formation requests are supplied from a plurality of computers to the image forming apparatus, one computer monopolizes the image forming apparatus. Therefore, for instance, there is a problem such that just after the image formation request was generated to print a large amount of data, in the case where the image formation request is generated from another computer in order to print one paper, the computer which generated the image formation request later can start the print only after waiting for the completion of the print of such a large amount of data by the first image information request even if the number of papers to be printed by such a second computer is equal to one. SUMMARY OF THE INVENTION It is an object of the invention to solve the above problem. Another object of the invention is to improve an image processing apparatus which can be connected to a plurality of data generating sources. Still another object of the invention is to provide an image forming apparatus which can prevent that the waiting time vainly becomes long. According to the invention, by providing a control mechanism of a microcomputer or the like to each function unit and by transmitting and receiving control signals between such a control mechanism and a control mechanism for controlling an image input/output unit, even in the case where image formation requests are generated from a plurality of computers, image storage means is used and the waiting times which are required until the print-out in response to the image formation requests by a plurality of computers can be uniformed. The above and other objects and features of the present invention will become apparent from the following detailed description and the appended claims with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram of a construction of the first embodiment of the invention; FIG. 2 is a diagram of a whole image forming apparatus of the first embodiment; FIG. 3 is a block diagram of each function unit and an image input/output mechanism unit in the first embodiment; FIG. 4 is an operation flowchart of the first embodiment; FIG. 5 is a block diagram showing a characteristic construction in the first and second embodiments; FIG. 6 is an operation flowchart of the second embodiment; FIG. 7 is an operation flowchart of the third embodiment; and FIG. 8 is a block diagram showing a characteristic construction in the third embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the invention will be described hereinbelow with reference to the drawings. (Embodiment 1) In FIG. 1, reference numeral 100 denotes a scanner section as an image input apparatus for converting an original image into image data; 101 a printer section which has cassettes of a plurality of kinds of recording papers and is used to print out the image data onto a paper by a print-out command in each function (hereinafter, a construction including the scanner section 100 and the printer section 101 is called an image forming apparatus (copying machine) 1000); 102 a display unit to electrically display the image data; and 103 an image output control apparatus for switching an image output signal from each function to the printer section 101 or display unit 102. Reference numeral 104 denotes a filing unit for recording the image data read by the scanner section 100 onto a storage medium 105 and for sending the image data stored in the storage medium 105 to the image output control apparatus 103. Reference numeral 106 denotes a facsimile unit for compressing the image data obtained from the scanner section 100 to the data based on the standard (MH, MR, MMR) of the facsimile and transmitting the compressed data by using a telephone circuit 107 and for expanding the facsimile data transmitted through the telephone circuit 107 and converting into the image data. Reference numeral 108 denotes a printer controller unit for converting a printer control command such as a page description language or the like sent from a computer 109 or the like into image data. Reference numeral 110 denotes storage means having functions such that the image data derived from the scanner section 100, filing unit 104, facsimile unit 106, and printer controller unit 108 can be stored and the image data can be generated to the image output control apparatus 103. The filing unit 104, facsimile unit 106, printer controller unit 108, storage means 110, and the like are enclosed in a casing of an external apparatus 23 (FIG. 2) or the like. In FIG. 2, the fundamental operations of the scanner section 100 and printer section 101 serving as an image input/output unit will now be described. Originals put on a document feeder 1 are sequentially conveyed one by one onto a glass surface of an original supporting plate 2. When the original is conveyed, a lamp of a scanner portion 3 is lit on and a scanner unit 4 is moved and illuminates the original. The reflected light from the original is reflected by mirrors 5, 6, and 7 and passes through a lens 8. After that, the light enters an image sensor unit 9. The image signal supplied to the image sensor unit 9 is processed by the image output control apparatus 103 (FIG. 1) including a CPU or the like. The processed signal is sent to the printer section 101. The signal supplied to the printer section 101 is converted into the photo signal by an exposure control unit 10 and a photo sensitive material 11 is illuminated in accordance with the image signal. A latent image formed on the photo sensitive material 11 by the illumination light is developed by a development unit 13. A copy transfer paper is picked up and conveyed from a transfer paper stacking unit 14 or 15 in accordance with the timing of the latent image. The paper is positioned to a copy transfer unit 16 by registration rollers 21. After that, the developed image is copy transferred. The transferred image is fixed onto a copy paper by a fixing unit 17. After that, the copy paper is discharged to the outside of the apparatus by a discharging unit 18. Reference numeral 20 denotes an intermediate tray which is used in the both-sided printing mode and 19 indicates a change-over flapper to switch a mode to discharge the copy paper and a mode to convey the copy paper to the intermediate tray 20. FIG. 3 is a block diagram showing an example of a construction of the external apparatus 23. In FIG. 3, a file circuit unit 1005, a facsimile circuit unit 1006, an LBP circuit unit 1007, and storage means 1019 in FIG. 3 correspond to the filing unit 104, facsimile unit 106, printer controller unit 108, and storage means 110 in FIG. 1, respectively. The operation in case of filing an original will be first explained with reference to FIG. 3. In this case, a desired original is put on the original supporting plate and various setting operations about the filing are executed. After that, by depressing a copy start key, the various set data is sent from the image forming apparatus (copying machine) 1000 to a CPU 1010 through a selector 1002 by a communication line 1013. The set data is likewise sent from the CPU 1010 to the file circuit unit 1005 by the communication line 1013. On the basis of the set data, the file circuit unit 1005 performs the setting operations according to those data and transmits a signal indicative of the completion of the preparation to the CPU 1010. When the CPU 1010 receives such a signal, the CPU controls the selector 1002 so as to allow the image data to flow in the direction from the image forming apparatus 1000 to a rotation processing circuit 1003. Further, the CPU 1010 controls a selector 1004 and an input selector 1008 so that the image data flows from the rotation processing circuit 1003 to the file circuit unit 1005 via the selector 1004 and the input selector 1008. In this manner, a series of routes of the image data are determined. The CPU 1010 subsequently transmits a signal indicative of the completion of the image fetching preparation to the image forming apparatus 1000. When the image forming apparatus 1000 receives such a signal, the apparatus 1000 starts the fundamental operation of the image forming apparatus such that the lamp of the scanner portion 3 (FIG. 2) is lit on and the scanner unit 4 (FIG. 2) is moved and illuminates the original. An input signal from the scanner section 100 is processed by a CPU of the image forming apparatus 1000. The processed signal passes through an image data line 1014 and is supplied to the selector 1002. The signal is supplied to the file circuit unit 1005 by the flow of the image data as mentioned above. In this instance, when it is necessary to rotate the whole image data, the image data is subjected to the rotating process by the rotation processing circuit 1003. When there is no need to rotate the image data, the image signal is not processed by the rotation processing circuit 1003 and is generated as it is. The file circuit unit 1005 converts the image data into the data of a structure according to the format of a disc and records. After completion of the reading operation, a signal indicative of the end of the reading operation is transmitted from the file circuit unit 1005 to the CPU 1010. When the CPU 1010 receives such a reading end signal, the CPU controls the selector 1002 so as to disconnect the image forming apparatus 1000 from the image data line. The CPU 1010 subsequently transmits a signal indicative of the end of the reading operation to the image forming apparatus 1000, so that the image forming apparatus is returned to the inherent state. Even in case of facsimile transmitting on original, the operations are substantially the same as those in the above filing case except that the image data is merely supplied to the facsimile circuit unit 1006 in place of the file circuit unit 1005. The case of printing the filed original will now be described. By depressing the copy start key after various data for printing was set, the various set data is sent from the image forming apparatus 1000 to the CPU 1010 through the selector 1002 by the communication line 1013. The set data is likewise sent from the CPU 1010 to the file circuit unit 1005 by the communication line 1013. On the basis of the set data, the file circuit unit 1005 perform the setting operations according to them and transmits a signal indicative of the completion of the preparation to the CPU 1010. When the CPU 1010 receives such a signal, the CPU controls an output selector 1009 so as to allow the image data to flow in the direction from the file circuit unit 1005 to the rotation processing circuit 1003. Further, the CPU shuts off the selector 1004 and controls the selector 1002 so as to allow the image data to flow from the rotation processing circuit 1003 to the image forming apparatus 1000 through the selector 1002. In this way, a series of routes of the image data are determined as mentioned above. Subsequently, the CPU 1010 transmits a signal indicative of the completion of the preparation of the image output to the image forming apparatus 1000. When the image forming apparatus 1000 receives such a signal, the apparatus 1000 starts the printing operation. The image data is supplied to the image output control apparatus 103 in FIG. 1. The signal supplied to the printer section 101 is printed by the foregoing operation. In this instance, when it is necessary to rotate the whole image data, the image data is rotated by the rotation processing circuit 1003. When there is no need to rotate the image data, the image signal is generated as it is without being processed in the rotation processing circuit 1003. After completion of the print, a signal indicative of the end of the print is transmitted from the image forming apparatus 1000 to the CPU 1010. When the CPU 1010 receives the print end signal, the CPU controls the selector 1002 so as to disconnect the image forming apparatus 1000 from the image data line. Subsequently, the CPU 1010 transmits the print end signal to the file circuit unit 1005, so that the file circuit unit 1005 is returned to the inherent state. Further, the operation when the data which is transmitted from the computer is generated will now be described. When the foregoing printer control command is transmitted from the computer, it is sent to the LBP circuit unit 1007 through an external interface 1011 and the CPU 1010. When the LBP circuit unit 1007 receives the printer control command, the LBP circuit unit develops the image data into a memory (not shown) in the LBP circuit unit 1007 or into the storage means 1019 in accordance with the printer control command system. After completion of the development, a CPU (not shown) in the LBP circuit unit generates an image data output request to the CPU 1010. A flow of the subsequent processes is similar to that in case of printing out the filed original. Even in case of printing the image data which has been facsimile transmitted, the image data is merely generated to the facsimile circuit unit 1006 in place of the file circuit unit 1005 and the other operations are substantially the same as those in case of generating the image data from the file circuit unit 1005. The case of facsimile transmitting the filed original will now be described. After the setting operations for various files and facsimile were performed, by depressing the copy start key, the above various set data is sent from the image forming apparatus 1000 to the CPU 1010 through the selector 1002 by the communication line 1013. The set data is similarly sent from the CPU 1010 to the file circuit unit 1005 and the facsimile circuit unit 1006 by the communication line 1013. On the basis of the set data, the file circuit unit 1005 and the facsimile circuit unit 1006 perform the setting operations according to the set data and transmit the preparation completion signals to the CPU 1010. When the CPU 1010 receives such signals, the CPU controls the output selector 1009 so as to allow the image data to flow in the direction from the file circuit unit 1005 to the rotation processing circuit 1003. Further, the CPU 1010 controls the selector 1004 and the input selector 1008 so as to allow the image data to flow from the rotation processing circuit 1003 to the facsimile circuit unit 1006 through the selector 1004. The series of routes of the image data are determined in this manner. The CPU 1010 transmits the image output preparation completion signal to the file circuit unit 1005. When the CPU 1010 receives such a signal, the CPU starts the image data transmitting operation. In this instance, when it is necessary to rotate the whole image data, the image data is rotated by the rotation processing circuit 1003. When there is no need to rotate the image data, the image data is generated as it is without being processed in the rotation processing circuit 1003. After completion of the transmission, a transmission end signal is transmitted from the file circuit unit 1005 to the CPU 1010. When the CPU 1010 receives such a transmission end signal, the CPU controls the output selector 1009 so as to disconnect the image forming apparatus from the image data line. Subsequently, the CPU 1010 transmits a transmission end signal to the facsimile circuit unit 1006, so that the facsimile circuit unit 1006 is returned to the inherent state. Even in the case where the image data which has been facsimile transmitted is filed, where the data sent from a computer is filed, or where the data transmitted from a computer is facsimile transmitted, operations similar to those in the foregoing are executed except that a flow of the image data is merely changed. The characteristic operations in the embodiment will now be described. FIG. 4 shows a flowchart showing a whole processing procedure in the case where a plurality of computers are connected to the apparatus of the invention and while one of the computers is printing out, a print request is generated from another computer. FIG. 5 shows a block diagram in such a case. First, in FIG. 5, the CPU 1010 detects the number n of computers 109 which can be connected to the external I/F 1011 (n=the number of connectable computers). The inside of the storage means 110 of a large capacity is divided (into n) by only the number of computers 109 every memory space unit in which at least one image can be developed. When a print-out request is generated from one of a plurality of computers 109 connected, from which computer the print-out request was generated are detected. With respect to the computer m (m=1, 2, . . . , n) which generated the print-out request, the development of the printer control commands into the image data is started in the divided memory space m (m=1, 2, . . . , n) in the storage means 110. After completion of the development of every page, the image data is sent from the memory spaces to the image output control apparatus 103 and is printed out by an image output apparatus. When a timer value reaches a certain set value during the development of the image, the development to the image data of the computer m is temporarily stopped, the timer is reset to 0 and started, and the development into the image data of the next computer (m+1) is started. By time-sharingly (at intervals of the set value of the timer) processing the print requests from a plurality of computers as mentioned above, while a certain one computer is printing out a large amount of data, even if another computer generates the print-out requests, such another computer can print out without waiting for completion of the whole printing-out operation of the computer which is at present printing out. Further, by controlling the sorter attached to the paper discharging unit of the printer unit, each computer is allocated to each discharge tray, so that it is possible to know that the output original relates to the output result from which one of the computers. (Embodiment 2) As a second embodiment, FIG. 6 shows a flowchart of the embodiment. Since a construction of the second embodiment is similar to that of FIG. 5, its description is omitted here. In the first embodiment, one LBP function is time-divided at predetermined time intervals and the print-out commands from a plurality of computers are received and the processes are executed. In the second embodiment, however, by switching the output requests from the computers every data amount of predetermined printer control commands sent from the computers, while a certain one computer is printing out a large amount of data, even when another computer generates the print-out request, such another computer can print out without waiting for the completion of the whole printing-out operation of the computer which is at present printing out. Further, by controlling the sorter attached to the paper discharging unit of the printer unit, each computer is allocated to each discharge tray, so that it is possible to know that the output original relates to the output result from which one of the computers. (Embodiment 3) As a third embodiment, FIG. 7 shows a flowchart of the embodiment. FIG. 8 shows a block diagram. The same component elements as those in the first embodiment are designated by the same reference numerals and their descriptions are omitted here. In the first embodiment, one LBP function is time-divided at predetermined time intervals, the print-out commands from a plurality of computers 109 are received, the inside of the storage means 110 of a large capacity is divided, and the processes are executed. In the third embodiment, however, when the print requests are simultaneously generated from a plurality of computers 109, after completion of the development of one page in one computer, the use right of the LBP function of the printer controller unit 108 is transferred to another computer which generated the print request without executing the development of the next page, and such one computer is set into a temporary standby mode. After the computer to which the use right of the LBP function has been given finished the development of one page, the use right is also transferred to the next computer. In this manner, by transferring the use right of one LBP function, each time the development of one page was finished, it is sufficient that the storage means 110 has only the areas in which the data of one page can be developed. An effect similar to that in the first embodiment is obtained. As described above, in the image forming apparatus to which a plurality of computers are connected, when the print requests are simultaneously generated from a plurality of computers, the operator who generated the print-out request later can print out without waiting for the completion of the printing-out operations of all of the computers which had generated the print-out requests before his request. In case of a conventional system in which a plurality of computers are connected to one image forming apparatus, while one computer is printing out a large amount of data, even when another computer generates the print-out request, such another computer can print out only after completion of the previous printing-out operation of all of a large amount of data. According to the invention, however, such a drawback is eliminated and by equivalently giving the use right of the image forming apparatus to all of the computers, the whole waiting time can be reduced.
An image processing apparatus comprises an input unit to supply code data from a plurality of data output devices, a converter to convert the code data supplied by the input unit into the image data every dot, and a generating unit to generate the image data obtained by the converter to a recording device. When print requests from a plurality of data output devices are simultaneously received, the image based on the data from each of the data output devices is switched every predetermined unit and generated.
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CROSS-REFERENCE TO RELATED APPLICATION [0001] This application is a continuation of copending International Application No. PCT/EP01/14194, filed Dec. 4, 2001, which designated the United States and was not published in English. BACKGROUND OF THE INVENTION Field of the Invention [0002] The present invention relates to a washing container for a dishwashing machine, which container includes several parts connected to one another. [0003] German Utility Model DE 75 20 122 U discloses a container for a dishwashing machine. This known container has a cover part that is U-shaped in plan view to which are joined a base and lid part. The base and lid parts are attached to the cover part by way of folded joints. Such a structure of a container hardly permits variation options for the structure of a washing container of dishwashing machines adapted to special, specific applications. SUMMARY OF THE INVENTION [0004] It is accordingly an object of the invention to provide a washing container for a dishwashing machine that overcomes the hereinafore-mentioned disadvantages of the heretofore-known devices of this general type and that is easily adapted to varying predefined requirements according to the configuration of the dishwasher. [0005] With the foregoing and other objects in view, there is provided, in accordance with the invention, a washing container for a dishwashing machine, including a plurality of parts connected to one another, the parts including a frame and at least one part selected from the group consisting of a wall, a base and a lid attached to the frame. [0006] According to the present invention, the washing container has a frame with wall, base, and/or lid parts attached thereto. Wall, base, and/or lid parts specially configured to perform specific functions to be carried out can be attached to the frame. The invention has succeeded in configuring a washing container of the type initially described such that it can easily be adapted to varying predefined requirements according to the configuration of the dishwasher. [0007] In accordance with another feature of the invention, the frame has receptacles for the wall, base, and/or lid parts attached thereto, enabling simple fastening, made even more secure according to another feature of the invention by the receptacles fully peripherally enclosing the wall, base, and/or lid parts attached to the frame. [0008] The frame can additionally be fitted directly with further functional elements. For such a purpose, in accordance with a further feature of the invention, the other functional parts disposed directly on the frame are disposed in the corner regions of the frame, for which at least one corner stay of the frame appropriately has at least one receptacle for the other functional parts disposed directly on the frame. These other functional parts can, in particular, be receptacles for adding washing and/or cleaning agent. A device for water softening can easily also be built onto the frame. Such outfitting with additional elements is, then, also possible without much complexity, if the outfitting entails a washing container that can be withdrawn from the housing of the dishwashing machine. Then, the corresponding parts can be assembled without any hindrance outside the housing of the dishwashing machine. [0009] Because the wall, base, and/or lid parts are manufactured as separate parts, they can each have a corresponding special structure for satisfying diverse functions. Thus, at least one wall part can be a heat exchanger and the base part can be a filter. Separate assembly of those elements customary in dishwashing machines can, therefore, be dispensed with. [0010] In accordance with an added feature of the invention, the modular structure of the washing container also permits the wall, base, and/or lid parts to be of various materials. [0011] In accordance with an additional feature of the invention, a simple fastening option is provided by adhesion of the wall, base, and/or lid parts to the frame. In a particularly advantageous fashion, manufacturing of the frame and also fastening of the wall, base, and/or lid parts is realized by the frame being monobloc. Adhesion is an especially good option when the frame and the parts to be connected thereto are of a plastic material. Should the frame and the parts be made of metal, then fastening by welding is appropriate. However, still other types of fastening are also feasible. For example, the frame and the parts to be attached to it need not be of the same material. This means that metal and plastic parts can be combined with one another. [0012] With the objects of the invention in view, there is also provided a washing container for a dishwashing machine, including at least one part selected from the group consisting of a removable wall, a removable heat exchanger wall, a removable base, a base filter, and a removable lid, a monobloc frame having receptacles receiving the at least one part and at least one corner stay having at least one receptacle, and at least one functional part removably disposed in the at least one receptacle of the at least one corner stay. [0013] Other features that are considered as characteristic for the invention are set forth in the appended claims. [0014] Although the invention is illustrated and described herein as embodied in a washing container for a dishwashing machine, it is, nevertheless, not intended to be limited to the details shown because various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims. [0015] The construction and method of operation of the invention, however, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWING [0016] The FIGURE is an exploded perspective view of a washing container according to the invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0017] Referring now to the figures of the drawings in detail and first, particularly to FIG. 1 thereof, there is shown a frame 1 that has a base part 2 that is, at the same time, a filter and corner stays 3 connected thereto. On a side opposite the base part 2 , the corner stays 3 are connected to a frame part 4 . The corner stays 3 can be made as separate parts and, then, attached to the base part 2 and connected to the frame part 4 . But, as shown in the embodiment, it is also possible to have the base part 2 , the corner stays 3 , and the frame part 4 be a monobloc configuration. In the corner regions of the frame 1 —in the illustrated embodiment in two corner stays 3 of the frame part 4 —receptacles 5 and 6 are formed. For example, a non-illustrated container that can be filled with a washing and/or cleaning agent can be incorporated into one receptacle 5 and a device for water softening 7 can be built into the other receptacle 6 . [0018] The frame 1 has wall openings 8 , which are configured as receptacles and which can, in turn, be sealed by separate wall parts 9 and 10 . The receptacles 8 fully peripherally enclose the wall parts 9 and 10 and, optionally, also the base 2 and/or lid parts attached to the frame 1 . The wall parts 9 and 10 , of the illustrated embodiment are connected suitably to the frame 1 , e.g., by adhesion, welding or the like. [0019] Of wall parts 9 and 10 , in the illustrated embodiment, one wall part 9 is configured as a simple wall part having only a closing function. In comparison, the other wall part 10 is configured as a heat exchanger. It is usual in dishwashing machines to utilize heat exchangers for economizing on power, through which preheating of the washing liquid utilized in rinse cycles following an introductory rinse cycle takes place, or that are filled in a drying cycle with cold water, to create large condensation surfaces. Through integration of heat exchangers in one or several wall parts 10 of the washing container, there is practically no additional space requirement and a higher heat recovery and/or improved drying can be achieved from configuring several wall parts 10 as heat exchangers. [0020] If the washing container is a washing container that can be withdrawn from the housing of a dishwashing machine, then slide grooves 11 can also be provided on the frame 1 , with which the washing container can, then, be slid on slide rails available on the housing of the dishwashing machine. [0021] If appropriate, the modular structure of the washing container also allows the use of wall, base, and/or lid parts 2 , 9 , 10 being of various materials, for example, plastic or metal. [0022] If the base part 2 , the corner stays 3 , the frame part 4 and, optionally, a non-illustrated lid part that can be set onto the frame part 4 are configured as separate parts, then washing containers can be manufactured easily with different dimensions. Because the individual parts exhibit relatively simple forms, namely, rod or plane form, they are also easy and cost-effective to manufacture. [0023] The invention has succeeded, therefore, in configuring a washing container that can easily be adapted to varying predefined requirements according to the configuration of the dishwasher.
A washing container for a dishwasher having several parts joined together, including a frame with walls, a base, and/or a cover attached thereto. The container can easily be adapted to varying predefined requirements according to the design of the dishwasher.
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CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of the previously filed Korean Patent Application No. 10-2007-0011801 that has a filing date of Feb. 5, 2007. FIELD OF THE INVENTION [0002] The present invention relates to a connector. BACKGROUND [0003] Generally, an electrical connector functions to electrically connect separate parts of a circuit. Electrical connectors often comprise a cap and a plug as a pair. Electrical connectors are widely used to supply electric power to various machines and electronic appliances. Electrical connectors are also used to intermittently connect various electric operation signals with one another. [0004] However, when connecting the cap to the plug of a conventional connector, an operator has to grip the cap and the plug using both hands and apply a great force to the cap and the plug in opposite directions. Therefore, connection of the cap and the plug is sometimes very laborious, especially when doing so within the confines of a small space. [0005] To solve such problems, a lever connector has been introduced that forcibly connects a cap and a plug of the lever connector with each other by pivoting a lever that is mounted to the connector. In such a conventional lever connector, however, since the lever is pivotable in one direction, and enough space for the pivoting of the lever is required, a length of the lever is necessarily increased. SUMMARY [0006] The present invention relates to, in one embodiment among others, a connector having a first connector portion and a lever movably connected to an outside of the first connector portion. The lever is rotatable with respect to the first connection portion and the lever is translatable with respect to the first connection portion. A guide projection is connected to the lever and the connector further has a second connector portion. The second connector portion has a guide channel having an open upper part, at least a portion of the guide channel having a sloped portion being sloped with respect to a direction in which the first connector portion is connectable to the second connector portion, the guide channel configured to receive the guide projection through the open upper part of the guide channel. BRIEF DESCRIPTION OF THE DRAWINGS [0007] The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which: [0008] FIG. 1 is an oblique view of a connector according to an embodiment of the present invention; [0009] FIG. 2 is an orthogonal view of the connector of FIG. 1 before assembly; [0010] FIG. 3 is an orthogonal view of the connector of FIG. 1 during assembly; and [0011] FIG. 4 is an orthogonal view of the connector of FIG. 1 after assembly. DETAILED DESCRIPTION OF THE EMBODIMENTS [0012] Hereinafter, an exemplary embodiment of the present invention will be described in detail with reference to the accompanying drawings. [0013] Referring to FIG. 1 , a connector 1 according to an embodiment of the present invention comprises a first connector portion 10 and a second connector portion 20 that are connected to each other, thereby supplying power or connecting electric signals. The connector 1 further comprises a lever 30 for pivoting that is mounted to an outside of the second connector portion 20 . The connector 1 can be easily assembled with minimal force using the principle of leverage, more specifically, by forcibly connecting the first connector portion 10 with the second connector portion 20 by pivoting operation of the lever 30 . [0014] The first connector portion 10 comprises a first terminal 11 formed at one end thereof for connection with a circuit board or a cable, and a guide channel 12 formed on an outer surface thereof to be engaged with the lever 30 so that the first connector portion 10 is introduced into the second connector portion 20 by pivoting the lever 30 . [0015] The second connector portion 20 supplies power or connects electric signals through connection with the first connector portion 10 . The first connector portion 10 is inserted in and engaged with the second connector portion 20 . The second connector portion 20 comprises a second terminal 21 at one end for connection with the circuit board or the cable to be supplied with the power or the electric signals, and first shafts 22 formed at opposite positions on an outer surface of the second connector portion 20 for the lever 30 to be hinged upon. [0016] The lever 30 is hinged on the outside of the second connector portion 20 to pivot vertically with respect to the second connector portion 20 , thereby forcing the first connector portion 10 into the second connector portion 20 . For this operation, the lever 30 comprises first apertures 32 engaged with the first shafts 22 , and a guide projection 31 formed to be projecting inwardly at a lower part of the first aperture 32 to be engaged with the guide channel 12 of the first connector portion 10 . [0017] The guide channel 12 is recessed from the outer surface of the first connector portion 10 and open at the upper part thereof in a state where the lever 30 is maximally lifted, such that the guide projection 31 can be conveniently engaged with the guide channel 12 . In addition, the guide channel 12 is sloped downward in a direction opposite to the lever 30 . Therefore, the guide projection 31 is slid into the guide channel 12 by leverage with respect to the first shafts 22 . [0018] The lever 30 further comprises second apertures 33 formed on lateral sides of the lever 30 in a longitudinal direction corresponding to a pivoting motion of the lever 30 . In addition, a second shaft 23 is formed on the outer surface of the second connector portion 20 and inserted in a second aperture 33 . The first aperture 32 is in the form of slot allowing the lever 30 to move horizontally with respect to the second connector portion 20 . [0019] According to this structure, when the lever 30 pivots vertically relative to the second connector portion 20 , the lever 30 is also able to move horizontally depending on positions thereof. Therefore, a moving distance of the guide projection 31 can be maximized in proportion to a pivoting angle of the lever 30 . Consequently, a length of the lever 30 can minimized, thereby reducing the overall size of the connector 1 . [0020] The second connector portion 20 further includes upper and lower lock projections 24 formed on the outer surface at positions corresponding to a highest position and a lowest position of the lever 30 , respectively. The lever 30 includes a third aperture 34 for receiving the lock projections 24 therein so as to secure the lever 30 at the highest position and the lowest position, thereby preventing disassembling of the connector 1 by an external impact applied to the lever 30 . Preferably, movement of the lever 30 is prevented to avoid deviation between the guide channel 12 and the guide projection 31 , during assembling of the connector 1 . [0021] FIGS. 2-4 show the operation of the connector 1 according to the embodiment of the present invention. When connecting the first connector portion 10 and the second connector portion 20 , which are separated, to each other, the lever 30 is lifted to the highest position as shown in FIG. 2 , thereby engaging the upper lock projection 24 with the third aperture 34 . In this state, the lever 30 is prevented from pivoting downward by gravity. [0022] In this state, since the lever 30 is moved outward relative to the second connector portion 20 by pivoting, the guide projection 31 is maintained at a position corresponding to the open part of the guide channel 12 . When the first connector portion 10 and the second connector portion 20 are pushed toward each other, the guide projection 31 is inserted in the guide channel 12 , hence completing a primary step of assembling connector 1 . [0023] Next, when the lever 30 is pivoted as shown in FIG. 3 , the lever 30 moves down, maintaining engagement between the second shaft 23 and the second aperture 33 , thereby moving toward the second connector portion 20 . Simultaneously, as the guide projection 31 moves along the guide channel 12 , the first connector portion 10 is pulled into the second connector portion 20 . [0024] When being pivoted down to the lowest position, the lever 30 is fully moved toward the second connector portion 20 . Simultaneously, the guide projection 31 is inserted up to an inner end of the guide channel 12 , thereby completely connecting the first connector portion 10 and the second connector portion 20 to each other so that the power supply connection or the signal connection is accomplished. [0025] After the lever 30 is pivoted down to the lowest position, the third aperture 34 of the lever 30 is fixed by engagement with the lower lock projection 24 of the second connector portion 20 so that the lever 30 is not affected by an external impact or the like. Accordingly, undesired separation of the first connector portion 10 from the second connector portion 20 is prevented. [0026] As apparent from the above description, the present invention provides a connector 1 capable of forcibly connecting a first connector portion 10 and a second connector portion 20 with each other through a pivoting operation of a lever 30 mounted to the first connector portion 10 . According to the present invention, assembly of the connector 1 can be achieved even with minimal force since the first connector portion 10 and the second connector portion 20 are easily connected by the principle of leverage of the lever 30 even though the connector 1 includes a plurality of first and second terminals 11 and 21 . Furthermore, since a length of the lever 30 can be reduced, the overall size of the connector 1 can be minimized, while maximizing a moving distance of the connector 1 . [0027] The connector 1 according to the present invention enables both vertical and horizontal movements of the lever 30 relative to the first connector portion 10 , by comprising first apertures 32 and second apertures 33 formed on the lever 30 . As a result, the structure of the connector 1 is simplified, further simplifying the manufacture of the connector 1 . Further, assembly and disassembly of the connector 1 can be performed more precisely. [0028] Moreover, since the lever 30 is fixed at highest and lowest positions thereof by third apertures 34 and lock projections 24 , undesired movement of the lever 30 is prevented before assembly of the connector 1 . Consequently, more precise assembly is achieved while preventing failure in connection due to movement of the lever 30 after assembly. [0029] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
A connector having a first connector portion and a lever movably connected to an outside of the first connector portion is disclosed. The lever is rotatable with respect to the first connection portion and the lever is translatable with respect to the first connection portion. A guide projection is connected to the lever and the connector further has a second connector portion. The second connector portion has a guide channel having an open upper part, at least a portion of the guide channel having a sloped portion being sloped with respect to a direction in which the first connector portion is connectable to the second connector portion, the guide channel configured to receive the guide projection through the open upper part of the guide channel.
11,838
This application is a continuation of application Ser. No. 07/489241, filed Mar. 5, 1990, now abandoned. FIELD OF THE INVENTION This invention is directed toward outdoor gas lanterns and more specifically toward means for releasably attaching a gas lantern mantle to the burner tube. DESCRIPTION OF THE PRIOR ART Dating back at least to 1909, as exemplified by U.S. Pat. No. 919,645 by Rybar, gas lanterns or lamps utilize a bag-like gas permeable mantle over the opening at one end of a gas tube and the lantern is turned on by allowing the gas mixture to flow into the burner tube and igniting the gas in the mantle which then provides the glow or light. Typically and conventionally, the mantle is a relatively open mesh bag made of suitably treated interwoven fibers or threads and has an opening or mouth which fits over and totally encloses the burner tube opening. Also typically and conventionally, the mantle may be reused a number of times but eventually deteriorates and has to be replaced. The aforementioned Rybar patent shows a ring and collar combination for removably attaching the mantle to the burner tube. This requires a collar permanently attached to the burner tube around or closely adjacent the gas outlet opening and a ring, suitably attached around the mouth of the mantle, with hooks to engage the collar. As explained in the Rybar patent, to remove the mantle the ring is lifted upwardly until the hooks are elevated above lugs on the collar and then the ring is turned until the hooks are free from engagement with the collar. The Rybar arrangement therefore requires that the ring be an integral part of the mantle and that the burner tube be modified to make the collar an integral part of the burner tube. It also requires some dexterity on the part of the user to remove and replace the mantle. Typically and conventionally, in general the contemporary manner of attaching the mantle to the burner tube is by use of a drawstring interwoven in the mantle at or near the mouth or opening of the mantle. After the user slips the mantle opening over the open end of the burner tube, the two ends of the drawstring are pulled tight and knotted together. Any extending ends are then snipped off. This makes it quite cumbersome for a camper or outdoorsman to replace the mantle. Not only is it awkward because of the confined area that the camper's fingers have to work in, but if the weather is cold, the fingers do not have the necessary dexterity. The use of the drawstring for attaching the mantle appears to be illustrated, but not described, in U.S. Pat. Nos. 4,599,683 by Beckham, et al. SUMMARY OF THE INVENTION For a conventional gas lantern which has a burner tube and a mantle enclosing the gas outlet end of the burner tube, a resilient clip made of resilient wire is provided having a circular or bight portion for surrounding the mouth or opening of the mantle for holding it securely in place around the open end of the burner tube and ends which can be pushed or squeezed together to expand the bight portion to release the mantle from the burner tube. In one embodiment the clip encircles the outside of the mantle opening to hold it releasably secured to the burner tube. In another embodiment the bight portion of the clip is threaded through the mantle at or near the opening or mouth of the mantle to encircle the mouth. Preferably the clip ends have short angled arms which can be easily grasped between the fingers of the user and squeezed together to expand the bight portion of the clip to slip the clip over the end of the tube for attaching and removing the mantle. Neither embodiment requires any modification of the lantern burner tube. For the embodiment in which the mantle is threaded onto the clip, it is quite easy to thread the clip in and around the mouth of the mantle. This may be done at the time the mantle is made so that the user doesn't have to do it. The instant invention thereby avoids and eliminates the cumbersome act of having to tighten and knot a drawstring and clipping off the ends of the drawstring. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an elevational view of a typical and conventional gas lantern or lamp with which the instant invention is used; FIG. 2 is a closeup view illustrating the manner in which the instant invention is utilized in a conventional gas lantern; FIG. 3 is a somewhat perspective view illustrating an embodiment of the invention with the clip threaded onto the mantle; FIG. 4 is a view illustrating how the clip is moved to expand the bight or circular opening; and FIG. 5 illustrates another embodiment in which the clip is placed around the outside of the mouth of the mantle. DESCRIPTION OF THE PREFERRED EMBODIMENT Typically and conventionally a portable gas lantern 10 suitable for and often used outdoors for camping has a fuel tank 11 as its base supporting a vertical collar 12 and a supporting plate 13 at the top of collar 12 on which rests a cylindrical transparent globe 14, a top, generally designated by reference number 15, over the top end of globe 14 which is held in place by an integrally threaded knurled or wing nut screwed onto a threaded stud, not shown. In the interior of globe 14 extending downward from and in gas communication with a gas manifold, now shown, are a pair of burner tubes 17 which are open at their bottom ends 18. Surrounding and enclosing each of the open ends 18 of burner tubes 17 are mantles 19 (only one shown for clarity). Mantles 19 are conventional and are commercially available. Mantle 19 is an air or gas porous or permeable bag made out of suitably treated interwoven threads or fibers and having a mouth or opening 20 which is placed over the open end 18 of burner tube 17. Near its open end 18 burner tube 17 has an outer annular recess 21. Mouth 20 of mantle 19 is placed over the open end 18 of burner tube 17 to extend partly over the annular recess 21. In the past, conventionally, a drawstring which was threaded into the mantle around the mantle mouth would then be pulled tightly and snugged down in the annular recess 21 and then the ends tied or knotted together to hold the mantle in place on the burner tube. As mentioned earlier, any extending ends of the drawstring would then be snipped off. Instead of a drawstring, the present invention provides a clip, generally identified by reference numeral 25, which is made of some suitable resilient metal wire and shaped to have a circular or bight section 25A and a pair of distal ends 25B and C. Clip 25 is formed so that the diameter of the circular or bight section 25A, when at rest, is somewhat smaller than the outer diameter of the annular recess 21. Ends 25B and C can be squeezed together to enlarge the opening of the bight section 25A so that it is greater than the outer diameter of burner tube 17. In use, using the embodiment illustrated in FIG. 5, the mouth or opening 20 of mantle 19 is slipped through the opening of bight 25A and over the outside of the open end 18 of burner tube 17 until it is slightly past recess 21. The ends 25B and C of clip 25 are squeezed together by the fingers, as illustrated in FIG. 2, so that the bight portion 25A is expanded to slip over the outside of the mantle and then released to come to rest in the annular recess 21 to hold the mantle snugly onto the burner tube 17. Alternatively, as illustrated in FIG. 3, mantle 19 can be threaded onto the bight portion 25A generally surrounding mouth 20 and the mantle with the attached clip can then be attached to burner tube 17 by squeezing together the ends of clip 25 until the bight and mantle mouth openings enlarge enough to slip over the ends 18 of burner tube 17 and the ends are then released to allow the clip to rest in the recess 21. To release the mantle for replacement, the ends 25B and C are again squeezed together until the bight portion 25A expands or enlarges beyond the outside of burner tube 17 and the mantle and clip are then slipped off the burner tube. Preferably, attached to and extending outward from ends 25B and C are arm members 26 which provide some extra leverage and make it more convenient to squeeze the ends together. Also, upstanding fingers 27 may be provided at the distal ends of arms 26 as a further convenience. Some experimentation has shown that, at worse, the metal clip only gets warm to the touch even after the lamp has been lit for some time. However, preferably, clip 25 should be made of a material which has the desired resiliency and also be able to withstand any significant deterioration at elevated temperature. Naturally, since a lantern of this nature might be used in very cold climates, the clip material should not lose any significant resiliency at the low temperatures which might be encountered.
A resilient wire clip goes around the mouth of a gas latern mantle to hold the mantle securely in place around the opening of the tube and can be manually expanded to release the mantle when it has to be replaced.
8,926
TECHNICAL FIELD [0001] This invention is directed to antimicrobial oxazolidinone compounds which are active against Gram-positive and some Gram-negative bacteria, showing specifically a potent activity against linezolid-resistant (LNZ-R) strains of Gram-positive bacteria and more specifically against Gram-positive pathogenic respiratory bacteria. BACKGROUND ART [0002] Oxazolidinones are Gram-positive antimicrobial agents. Oxazolidinones bind to the 50S subunit of the prokaryotic ribosome, preventing formation of the initiation complex for protein synthesis. This is a novel mode of action. Other protein synthesis inhibitors either block polypeptide extension or cause misreading of mRNA. Linezolid (N-[[(5S)-3-[3-fluoro-4-(4-morpholinyl)phenyl]-2-oxo-5-oxazolidinyl]methyl]acetamide), U.S. Pat. No. 5,688,792, is the first approved antimicrobial oxazolidinone for clinical use in the United States and elsewhere. The structural formula of linezolid is: [0000] [0003] Linezolid minimal inhibitory concentrations (MICS) vary slightly with the test mode, laboratory, and significance attributed to thin hazes of bacterial survival, but all workers find that the susceptibility distributions are narrow and unimodal with MIC values between 0.5 and 4 μg/mL for streptococci, enterococci and staphylococci. Full activity is retained against Gram-positive cocci resistant to other antibiotics, including methicillin-resistant staphylococci and vancomycin-resistant enterococci. MICS are 2-8 μg/mL for Moraxella, Pasteurella and Bacteroides spp. but other Gram-negative bacteria are resistant as a result of endogenous of activity as well as the intake presented by Gram-negative bacteria outer membrane cell. Linezolid is indicated for the treatment of adult patients with the following infections: vancomycin-resistant Enterococcus faecium infections, including concurrent bacteremia; nosocomial pneumonia; complicated skin and skin structure infections; community-acquired pneumonia, including concurrent bacteremia; diabetic foot infections; and uncomplicated skin and skin structure infections. [0004] Unfortunately, some Gram-positive bacteria such as Staphylococcus aureus (LNZ-R 432), Haemophylus influenzae (ATCC 49247), Bacteroides fragilis (ATCC 25285), Moraxella catarrhalis (HCl-78), and Enterococcus faecium (LNZ-R) show an important resistance to linezolid, thus suggesting the need of new oxazolidinone compounds active in these strains. Some of them are the origin of severe and sometimes fatal infections such as sepsis and septic shock. Further, there is an increasing need for improved agents against Gram-positive pathogenic respiratory bacteria, like Streptococcus pneumoniae, Haemophylus influenzae , and Moraxella catarrhalis. SUMMARY OF THE INVENTION [0005] Surprisingly the compounds of the present application are potent active antimicrobial agents showing a relevant activity against LNZ-R Gram-positive bacteria and more specifically against Gram-positive pathogenic respiratory bacteria. Differential characteristic properties of the compounds of the present invention versus linezolid indicate the potential use thereof in severe infections that cannot be properly treated with linezolid. [0006] In a first aspect the present invention refers to a compound of formula (I), [0000] [0000] in free or pharmaceutically acceptable salt, solvate, hydrate, or enantiomeric form, wherein: R is a N-linked 5-membered fully or partially unsaturated heterocyclic ring, containing 0 to 3 further nitrogen heteroatoms, which ring is optionally substituted on any available carbon atom with a substituent selected from linear or branched (1-6C)alkyl, (3-6C)cycloalkyl, halogen, OR 4 , S(O) m R 5 , COOH, COOR 6 , COR 7 , CONH 2 , CONHR 8 , CONR 9 R 10 , SO 2 NH 2 , SO 2 NHR 11 , SO 2 NR 12 R 13 , NH 2 , NHR 14 , NR 15 R 16 , NHCOR 17 , N(R 18 )COR 19 , NHSO 2 R 20 , N(R 21 )SO 2 R 22 , CN, CF 3 , NO 2 , phenyl optionally substituted with up to three substituents independently selected from linear or branched (1-6C)alkyl, (3-6C)cycloalkyl, halogen, OR 23 , S(O) n R 24 , NH 2 , NHR 25 , NR 26 R 27 , NHCOR 28 , N(R 29 )COR 30 , NHSO 2 R 31 , N(R 32 )SO 2 R 33 , CN, CF 3 , NO 2 , and 5-6 membered heteroaryl group containing one to three heteroatoms selected from nitrogen, oxygen and sulfur, optionally substituted with up to three substituents independently selected from linear or branched (1-6C)alkyl, (3-6C)cycloalkyl, halogen, OR 34 , S(O) p R 35 , NH 2 , NHR 36 , NR 37 R 38 , NHCOR 39 , N(R 40 )COR 41 , NHSO 2 R 42 , N(R 43 )SO 2 R 44 , CN, CF 3 , and NO 2 , said ring being optionally fused with a phenyl or 5-6 membered fully or partially unsaturated heterocycle containing one to three heteroatoms selected from nitrogen, oxygen and sulfur to form a benzo-fused or hetero-fused system, wherein the benzo- or hetero-moiety is optionally substituted with up to three substituents independently selected from linear or branched (1-6C)alkyl, (3-6C)cycloalkyl, halogen, OR 45 , S(O) q R 46 , NH 2 , NHR 47 , NR 48 R 49 , NHCOR 50 , N(R 51 )COR 52 , NHSO 2 R 53 , N(R 54 )SO 2 R 55 , CN, CF 3 , and NO 2 ; R 1 and R 2 are radicals identical or different and are independently selected from hydrogen, and fluorine; R 3 is a linear or branched (1-6C)alkyl group optionally substituted by a group selected from fluorine, hydroxy, and OR 56 ; R 4 to R 56 are identical or different linear or branched (1-6C)alkyl groups; or R 9 +R 10 , R 12 +R 13 , R 15 +R 16 , R 26 +R 27 , R 37 +R 38 , and R 48 +R 49 together with the nitrogen atom carrying them, form a monocyclic 5-, 6- or 7-membered saturated heterocycle optionally containing in the cyclic system a second hetero atom selected from oxygen and nitrogen; and m, n, p and q are identical or different integers independently selected from 0, 1, and 2. [0014] In a second aspect the present invention refers to a process for preparing a compound of formula (I) in free or pharmaceutically acceptable salt, solvate, hydrate, or enantiomeric form that comprises: (i) a) reacting an intermediate of formula (II), [0000] wherein R 1 , R 2 and R 3 are as defined above, and R 57 is selected from methyl, phenyl, p-tolyl, p-bromophenyl, p-nitrophenyl, trifluoromethyl, and 2,2,2-trifluoroethyl, with an intermediate of formula RH (III), wherein R is as defined above; or b) reacting an intermediate of formula (IV), [0000] wherein R, R 1 and R 2 are as defined above and R 58 is selected from linear or branched (1-6C)alkyl, and benzyl optionally substituted in the phenyl ring by up to three linear or branched (1-6C)alkyl groups, with an intermediate of formula (V), [0000] wherein R 3 is as defined above, R 59 is a linear or branched (1-6C)alkyl group, and X is a halogen atom; and (ii) recovering the resultant compound of formula (I) in free or pharmaceutically acceptable salt, solvate, hydrate, or enantiomeric form. [0021] In a third aspect the present invention refers to a pharmaceutical composition comprising a therapeutically effective amount of the compound of general formula (I) according to the first aspect of the invention, together with the appropriate amounts of pharmaceutical excipients or carriers. [0022] In a fourth aspect the present invention refers to a compound of formula (I) according to the first aspect of the invention, for use as a medicament. [0023] In an fifth aspect the present invention refers to the use of a compound of formula (I) according to the first aspect of the invention for the manufacture of a medicament for the treatment of bacterial infections in an animal or human. This aspect may also be formulated as a compound of formula (I) according to the first aspect of the invention for use in the treatment of bacterial infections. [0024] Another object of this invention is to provide novel methods to treat a mammal, including a human, suffering from a bacterial infection by administering a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable salt, solvate, hydrate, or enantiomeric form thereof. DETAILED DESCRIPTION OF THE INVENTION [0025] The term “pharmaceutically acceptable salts” used herein encompasses any salt formed from organic and inorganic acids, such as hydrobromic, hydrochloric, phosphoric, nitric, sulfuric, acetic, adipic, aspartic, benzenesulfonic, benzoic, citric, ethanesulfonic, formic, fumaric, glutamic, lactic, maleic, malic, malonic, mandelic, methanesulfonic, 1,5-naphthalendisulfonic, oxalic, pivalic, propionic, p-toluenesulfonic, succinic, tartaric acids, and the like, and any salt formed from organic and inorganic bases, such as the alkali metal and alkaline earth metal salts, especially the sodium and potassium salts, ammonium salts and salts of amines, including lower alkylated amines, such as methylamine, ethylamine, trimethylamine and the like, hydroxyloweralkylamines, such as ethanolamine and diethanolamine, and heterocyclic amines, such as morpholine and piperazine. [0026] In a preferred embodiment, the present invention refers to a compound according to the first aspect of the invention wherein R is selected from benzotriazolyl, 1-imidazolyl, 4-acetylpyrazol-1-yl, 4-bromopyrazol-1-yl, 4-nitropyrazolyl, 3-trifluoromethyl-pyrazol-1-yl, 3-phenylpyrazol-1-yl, 3-(2-fluorophenyl)-pyrazol-1-yl, 3-(4-trifluoromethyl-phenyl)-pyrazol-1-yl, 4-(4-fluorophenyl)-pyrazol-1-yl, 4-(2-methoxyphenyl)-pyrazol-1-yl, 4-(4-nitrophenyl)-pyrazol-1-yl, 4-(2-trifluoromethyl-phenyl)-pyrazol-1-yl, 4-pyrazin-2-yl-pyrazol-1-yl, 4-pyridin-4-yl-pyrazol-1-yl, 4-pyrimidin-4-yl-pyrazol-1-yl, 1-tetrazolyl, 2-tetrazolyl, 5-methyltetrazol-2-yl, 5-methylsulfanylltetrazol-2-yl, 5-phenyltetrazol-2-yl, 5-p-tolyltetrazol-2-yl, 5-thiophen-2-yl-tetrazol-2-yl, 1-triazolyl, 2-triazolyl, [1,2,3]triazol-1-yl, [1,2,3]triazol-2-yl, (3-cyanophenyl)-[1,2,3]triazol-2-yl], 4-pyridin-2-yl-[1,2,3]triazol-2-yl, and [1,2,4]triazol-1-yl is R 1 is fluorine, R 2 is selected from fluorine and hydrogen, and R 3 is methyl. [0027] Preferably, the compound according to the first aspect of the invention is selected from the group consisting of: N-((5S)-3-{3-fluoro-4-[3-(2-triazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(1-triazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-[3-fluoro-4-[3-(1-imidazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(2-tetrazolyl)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(1-tetrazolyl)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-{(5S)-3-[3-fluoro-4-(3-[1,2,4]triazol-1-yl-pyrrolidin-1-yl)-phenyl]-2-oxo-5-oxazolidinylmethyl}acetamide; N-((5S)-3-{3-fluoro-4-[3-(benzotriazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(4-nitropyrazolyl)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(5-p-tolyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(4-pyrimidin-4-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(4-pyrazin-2-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(5-phenyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(5-methylsulfanylltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(5-thiophen-2-yl-tetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(5-methyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(4-bromopyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(4-pyridin-4-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3-[4-(4-nitrophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-[(5S)-3-(3-fluoro-4-{3-[4-(2-trifluoromethyl-phenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-[(5S)-3-(3-fluoro-4-{3-[4-(2-methoxyphenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-((5S)-3-{3-fluoro-4-[3-(4-acetylpyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3-(3-phenylpyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3-[4-(4-fluorophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-[(5S)-3-(3-fluoro-4-{3-[3-(2-fluorophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-((5S)-3-{3-fluoro-4-[3-(3-trifluoromethyl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3-[3-(4-trifluoromethyl-phenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-((5S)-3-{3-fluoro-4-[3-(4-pyridin-2-yl-[1,2,3]triazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3-[4-(3-cyanophenyl)-[1,2,3]triazol-2-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-{(5S)-3-[3,5-difluoro-4-[3-([1,2,3]triazol-2-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide; N-{(5S)-3-[3,5-difluoro-4-[3-([1,2,3]triazol-1-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide; N-{(5S)-3-[3,5-difluoro-4-[3-(tetrazol-2-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide; N-{(5S)-3-[3,5-difluoro-4-[3-(tetrazol-1-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(2-triazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(1-triazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-[3-fluoro-4-[3(R)-(1-imidazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(2-tetrazolyl)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(1-tetrazolyl)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-{(5S)-3-[3-fluoro-4-(3(R)-[1, 2, 4]triazol-1-yl-pyrrolidin-1-yl)-phenyl]-2-oxo-5-oxazolidinylmethyl}acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(benzotriazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(4-nitropyrazolyl)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(5-p-tolyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(4-pyrimidin-4-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(4-pyrazin-2-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(5-phenyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(5-methylsulfanylltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(5-thiophen-2-yl-tetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(5-methyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(4-bromopyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(4-pyridin-4-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3(R)-[4-(4-nitrophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-[(5S)-3-(3-fluoro-4-{3(R)-[4-(2-trifluoromethyl-phenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-[(5S)-3-(3-fluoro-4-{3(R)-[4-(2-methoxyphenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(4-acetylpyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(3-phenylpyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3(R)-[4-(4-fluorophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-[(5S)-3-(3-fluoro-4-{3(R)-[3-(2-fluorophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(3-trifluoromethyl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3(R)-[3-(4-trifluoromethyl-phenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-((5S)-3-{3-fluoro-4-[3(R)-(4-pyridin-2-yl-[1,2,3]triazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3(R)-[4-(3-cyanophenyl)-[1,2,3]triazol-2-yl]pyrrolidin-1-yl}phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-{(5S)-3-[3,5-difluoro-4-[3(R)-([1,2,3]triazol-2-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide; N-{(5S)-3-[3,5-difluoro-4-[3(R)-([1,2,3]triazol-1-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide; N-{(5S)-3-[3,5-difluoro-4-[3(R)-(tetrazol-2-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide; N-{(5S)-3-[3,5-difluoro-4-[3(R)-(tetrazol-1-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(2-triazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(1-triazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-[3-fluoro-4-[3(S)-(1-imidazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(2-tetrazolyl)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(1-tetrazolyl)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-{(5S)-3-[3-fluoro-4-(3(S)-[1,2,4]triazol-1-yl-pyrrolidin-1-yl)-phenyl]-2-oxo-5-oxazolidinylmethyl}acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(benzotriazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(4-nitropyrazolyl)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(5-p-tolyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(4-pyrimidin-4-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(4-pyrazin-2-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(5-phenyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(5-methylsulfanylltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(5-thiophen-2-yl-tetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(5-methyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(4-bromopyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(4-pyridin-4-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3(S)-[4-(4-nitrophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-[(5S)-3-(3-fluoro-4-{3(S)-[4-(2-trifluoromethyl-phenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-[(5S)-3-(3-fluoro-4-{3(S)-[4-(2-methoxyphenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(4-acetylpyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(3-phenylpyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3(S)-[4-(4-fluorophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-[(5S)-3-(3-fluoro-4-{3(S)-[3-(2-fluorophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(3-trifluoromethyl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3(S)-[3-(4-trifluoromethyl-phenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-((5S)-3-{3-fluoro-4-[3(S)-(4-pyridin-2-yl-[1,2,3]triazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide; N-[(5S)-3-(3-fluoro-4-{3(S)-[4-(3-cyanophenyl)-[1,2,3]triazol-2-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide; N-{(5S)-3-[3,5-difluoro-4-[3(S)-([1,2,3]triazol-2-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide; N-{(5S)-3-[3,5-difluoro-4-[3(S)-([1,2,3]triazol-1-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide; N-{(5S)-3-[3,5-difluoro-4-[3(S)-(tetrazol-2-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide; and N-{(5S)-3-[3,5-difluoro-4-[3(S)-(tetrazol-1-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide. [0124] The compounds of general formula (I) may be prepared by (i) a) reacting an intermediate of formula (II), [0000] wherein R 1 , R 2 and R 3 are as defined above, and R 57 is selected from methyl, phenyl, p-tolyl, p-bromophenyl, p-nitrophenyl, trifluoromethyl, and 2,2,2-trifluoroethyl, with an intermediate of formula RH (III), wherein R is as defined above, in an inert solvent and in the presence of a base; or b) reacting an intermediate of formula (IV), [0000] wherein R, R 1 and R 2 are as defined above and R 58 is selected from linear or branched (1-6C)alkyl, and benzyl optionally substituted in the phenyl ring by up to three linear or branched (1-6C)alkyl groups, with an intermediate of formula (V), [0000] wherein R 3 is as defined above, R 59 is a linear or branched (1-6C)alkyl group, and X is a halogen atom, in an inert solvent and in the presence of a strong basic catalyst; and (ii) recovering the resultant compound of formula (I) in free or pharmaceutically acceptable salt, solvate, hydrate, or enantiomeric form. [0131] Preferably R 57 is methyl, R 58 is benzyl, R 59 is methyl, and X is bromine. [0132] Inert solvents in step (ia) are preferably aprotic solvents. Suitable aprotic solvents are polar ethers such as, for example, tetrahydrofuran, methyltetrahydrofuran, dioxane, tert-butylmethylether, or dimethoxyethylether, or amides such as, for example, dimethylformamide, or lactams such as, for example, N-methylpyrrolidone, and mixtures thereof. Examples of bases include carbonates such as lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, and the like, and mixtures thereof. [0133] Inert solvents in step (ib) are preferably aprotic solvents. Suitable aprotic solvents are polar ethers such as, for example, tetrahydrofuran, methyltetrahydrofuran, dioxane, tert-butylmethylether, or dimethoxyethylether, or amides such as, for example, dimethylformamide, or lactams such as, for example, N-methylpyrrolidone, and mixtures thereof. Suitable solvents are also mixtures of such aprotic solvents and alcohols such as, for example, methanol or ethanol. Examples of strong basic catalysts include hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, alkoxides, such as lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide, alkyllithiums such as tert-butyllithium, n-butyllithium, and methyllithium, dialkylamides such as lithium diisopropylamide, disilylamides such as lithium hexamethyldisilazide, potassium hexamethyldisilazide, and sodium hexamethyldisilazide, and hydrides such as lithium hydride, sodium hydride, and potassium hydride. [0134] Useful processes for recovering the resultant compounds in step (ii) include conventional methods known to the person skilled in the art such as crystallization and chromatographic processes, resolution of racemic forms by chromatographic separation using a chiral stationary phase, and also processes involving fractional crystallization. This can, in particular, involve the separation of individual enantiomers, for example, diastereoisomeric salts formed with chiral acids, for example (+)-tartaric acid, (−)-tartaric acid, or (+)-10-camphorsulfonic acid. [0135] The compounds are useful antimicrobial agents, effective against a number of human and veterinary microorganisms. Some non limitative examples of these microorganisms are Staphylococcus aureus, Streptococcus pneumoniae, Haemophylus influenzae, Bacteroides fragilis, Moraxella catarrhalis , and Enterococcus faecium. [0136] The compounds of the present invention can be normally formulated in accordance with standard pharmaceutical practice as a pharmaceutical composition. [0137] The pharmaceutical compositions of this invention may be administered in standard manner for the disease condition that it is desired to treat, for example by oral, parenteral, inhalatory, rectal, transdermal or topical administration. For these purposes the compounds of this invention may be formulated by means known in the art in the form of, for example, tablets, capsules, syrups, aqueous or oily solutions or suspensions, emulsions, dispersible powders, inhalatory solutions, suppositories, ointments, creams, drops and sterile aqueous or oily solutions or suspensions for injection and the like. The pharmaceutical compositions may contain flavoring agents, sweeteners, etc. in suitable solid or liquid carriers or diluents, or in a suitable sterile media to form suspensions or solutions suitable for intravenous, subcutaneous or intramuscular injection. Such compositions typically contain from 1 to 40%, preferably 1 to 10% by weight of active compound, the remainder of the composition being pharmaceutically acceptable carriers, diluents, solvents and the like. [0138] The compounds of formula (I) are administered in an amount of 0.1 to 100 mg/kg of body weight/day, preferably 1 to 50 mg/kg of body weight/day. The compounds and compositions of the present invention are useful in the treatment of conditions such as nosocomial pneumoniae, community acquired pneumoniae, caused by methicillin-resistant Staphylococcus aureus (MRSA), including concurrent bacteremia, penicillin resistance and sensitive Streptococcus pneumoniae , diabetic foot infections and skin and skin structure infections, and all other infections caused by bacteria sensitive to the compounds described in the invention. The compounds of the present invention are effective against a number of human or animal pathogens, clinical isolates, including vancomycin-resistant organisms, methicillin-resistant organisms, and LNZ-R organisms. [0139] Throughout the description and claims the word “comprise” and variations of the word, such as “comprising”, are not intended to exclude other technical features, additives, components, or steps. Additional objects, advantages and features of the invention will become apparent to those skilled in the art upon examination of the description or may be learned by practice of the invention. The following Examples are provided by way of illustration, and are not intended to be limiting of the present invention. EXAMPLES Example 1 N-{(5S)-3-[3-fluoro-4-(3-methylsulfonyloxy pyrrolidin-1-yl)-phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide [0140] [0141] The N-{(5S)-3-[3-fluoro-4-(3-hydroxypyrrolidin-1-yl)-phenyl]-2-oxo-5-oxazolidinylmethyl}acetamide (2.8 g), prepared as described in WO 96/13502, and triethylamine (2.3 mL, 2 eq) were dissolved in dichloromethane (DCM) at room temperature and purged under argon. Methanesulfonyl chloride (0.9 mL, 1.5 eq) was added at 0° C. and overnight at room temperature. Triethylamine and methanesulfonyl chloride were added to convert remaining alcohol. The reaction mixture was washed with water, brine and the organic layers dried over MgSO 4 . The concentrated residue was purified by column chromatography (silica gel, DCM/MeOH increasing polarity) to afford 1.97 g of title compound. [0142] HPLC (t, %): 6.53 min, 90%. [0143] MS (ESI) m/z=416(M+1) [0144] 1 H NMR (400 MHz, δ, ppm, DMSO): 2.21 (2H, m), 3.24 (3H, m), 3.35 (5H, m), 3.67 (2H, m), 4.05 (1H, t, J=8 Hz), 4.67 (1H, m), 5.35 (1H, m), 6.80 (1H, t, J=9.6 Hz), 7.11 (1H, dd, J=2.4, 8.4 Hz), 7.43 ((1H, dd, J=2.8, 16 Hz), 8.24 (1H, NH) Example 2 N-((5S)-3-{3-fluoro-4-[3-(2-triazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide [0145] [0146] K 2 CO 3 (0.6 mmol) and N-{(5S)-3-[3-fluoro-4-(3-methylsulfonyloxy pyrrolidin-1-yl)-phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide (200 mg) were weighted and purged under argon in a 25 mL-round bottom flask. Dimethylformamide (DMF) and 1,2,3-triazole were added and the mixture refluxed at 70° C. overnight. Cold water and DCM were added and the separated organic layer dried over MgSO 4 and concentrated under reduced pressure. The mixture of regioisomers was purified by column chromatography (silica gel, DCM/MeOH 95:5) to give 46 mg of the title compound as a major regioisomer (Yield=25%). [0147] HPLC (t, %): 6.8 min, 88%. [0148] MS(ESI) m/z=389 (M+1) [0149] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 1.98 (3H, s), 2.55 (1H, m), 2.65 (1H, m), 3.62 (5H, m), 3.87 (1H, m), 3.97 (1H, m), 4.71 (1H, m), 5.31 (1H, m), 6.72 (1H, m), 6.98 (1H, m), 7.35 (1H, m), 7.59 (2H, s) Example 3 N-((5S)-3-{3-fluoro-4-[3-(1-triazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide [0150] [0151] It was obtained concomitantly with compound of Example 2, which after column chromatography afforded 36 mg of title compound (Yield=32%). [0152] HPLC (t, %): 6.1 min, 99%. [0153] MS(ESI) m/z=389 (M+1) [0154] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.82 (3H, s), 2.45 (1H, m), 2.55 (1H, m), 3.37 (3H, m), 3.55 (1H, M), 3.65 (2H, m), 3.85 (1H, m), 4.05 (1H, t, J=8.8 Hz), 4.71 (1H, m), 5.38 (1H, m), 5.75 (1H, s), 6.83 (1H, st, J=10 Hz), 7.11 (1H, dd, J=2.4, 9 Hz), 7.41 (1H, dd, J=3, 16 Hz), 7.75 (1H, s), 8.21 (1H, s), 8.22 (1H, NH) Example 4 N-((5S)-3-[3-fluoro-4-[3-(1-imidazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide [0155] [0156] It was prepared following the same procedure as in Example 2, obtaining 28 mg of title compound purified by preparative HPLC. [0157] HPLC (t, %): 6.18 min, 90%. [0158] MS(ESI) m/z=388 (M+1) [0159] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 1.98 (3H, s), 2.20 (1H, m), 2.50 (1H, m), 3.37 (1H, m), 3.61 (6H, m), 3.98 (1H, t, J=8.8 Hz), 4.71 (1H, m), 4.82 (1H, m), 6.66 (1H, st, J=9.2 Hz), 7.01 (3H, m), 7.35 (1H, dd, J=2.8, 15 Hz), 7.62 (1H, s), 8.05 (1H, NH) Example 5 N-((5S)-3-{3-fluoro-4-[3-(2-tetrazolyl)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide [0160] [0161] It was prepared following the same procedure as in Example 2, obtaining 45 mg of title compound purified by preparative HPLC. [0162] HPLC (t, %): 6.53 min, 92%. [0163] MS(ESI) m/z=390 (M+1) [0164] 1 H NMR (400 MHz, δ, ppm, DMSO): 2.00 (3H, s), 2.66 (2H, m), 3.71 (7H, m), 4.73 (1H, m), 5.55 (1H, m), 5.96 (1H, m), 6.69 (1H, t, J=10 Hz), 7.02 (1H, m), 7.36 (1H, m), 8.50 (1H, s) Example 6 N-((5S)-3-{3-fluoro-4-[3-(1-tetrazolyl)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide [0165] [0166] It was obtained concomitantly with compound of Example 5, which after HPLC purification afforded 11 mg of title compound. [0167] HPLC (t, %): 6.10 min, 94%. [0168] MS(ESI) m/z=390 (M+1) [0169] 1 H NMR (400 MHz, δ, ppm, DMSO): 2.00 (3H, s), 2.39 (1H, m), 2.64 (1H, m), 3.55 (7H, m), 3.98 (1H, t, J=8.8 Hz), 4.70 (1H, m), 5.39 (1H, m), 6.70 (1H, t, J=9.6 Hz), 7.01 (1H, m), 7.36 (1H, dd, J=15, 2.4 Hz), 8.77 (1H, s) Example 7 N-{(5S)-3-[3-fluoro-4-(3-[1, 2, 4]triazol-1-yl-pyrrolidin-1-yl)-phenyl]-2-oxo-5-oxazolidinylmethyl}acetamide [0170] [0171] It was prepared following the same procedure as in Example 2, obtaining 27 mg of title compound. [0172] HPLC (t, %): 5.99 min, 90%. [0173] MS(ESI) m/z=389 (M+1) [0174] 1 H NMR (400 MHz, δ, ppm, DMSO): 2.00 (3H, s), 2.49 (2H, m), 3.65 (7H, m), 3.98 (1H, t, J=8.8 Hz), 4.74 (1H, m), 5.07 (1H, m), 6.36 (1H, NH), 6.67 (1H, t, J=9.2 Hz), 7.05 (1H, m), 7.35 (1H, dd, J=15, 2.8 Hz), 7.93 (1H, s), 8.18 (1H, s) Example 8 N-((5S)-3-{3-fluoro-4-[3-(benzotriazolyl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide [0175] [0176] It was prepared following the same procedure as in Example 2, obtaining 71.5 mg of title compound as a mixture of the two possible regioisomers. [0177] HPLC (t, %): 4.68 min, 37.7%; 5.08, 57.8%. [0178] MS(ESI) m/z=439 (M+1) Example 9 N-((5S)-3-{3-fluoro-4-[3-(4-nitropyrazol)pyrrolidinyl]-phenyl}-2-oxo-5-oxazolidinyl methyl)acetamide [0179] [0180] It was prepared following the same procedure as in Example 2, obtaining 49.1 mg of title compound. [0181] HPLC (t, %): 4.68 min, 97%. [0182] MS(ESI) m/z=433 (M+1) [0183] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.84 (3H, s), 2.45 (2H, m), 3.39 (3H, m), 3.58 (1H, m), 3.68 (2H, m), 3.79 (1H, m), 4.06 (1H, m), 4.69 (1H, m), 5.18 (1H, m), 6.84 (1H, t, J=8 Hz), 7.12 (1H, d, J=6.2 Hz), 7.42 (1H, d, J=13 Hz), 8.23 (1H, NH), 8.32 (1H, s), 8.99 (1H, s) Example 10 N-((5S)-3-{3-fluoro-4-[3-(5-p-tolyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0184] [0185] It was prepared following the same procedure as in Example 2, obtaining 41.1 mg of title compound. [0186] HPLC (t, %): 5.45 min, 95%. [0187] MS(ESI) m/z=480 (M+1) [0188] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.84 (3H, s), 2.38 (3H, s), 2.65 (2H, m), 3.40 (2H, m), 3.48 (1H, m), 3.67 (2H, m), 3.90 (1H, m), 3.97 (1H, m), 4.07 (1H, m), 4.69 (1H, m), 5.74 (1H, m), 6.88 (1H, t, J=7.5 Hz), 7.13 (1H, d, J=6.7 Hz), 7.37 (2H, d, J=6.2 Hz), 7.42 (1H, d, J=13 Hz), 7.95 (2H, d, J=6.2 Hz), 8.24 (1H, NH) Example 11 N-((5S)-3-{3-fluoro-4-[3-(4-pyrimidin-4-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0189] [0190] It was prepared following the same procedure as in Example 2, obtaining 61.7 mg of title compound. [0191] HPLC (t, %): 4.08 min, 96%. [0192] MS(ESI) m/z=466 (M+1) [0193] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.84 (3H, s), 2.45 (2H, m), 3.39 (3H, m), 3.59 (1H, m), 3.68 (1H, m), 3.81 (2H, m), 4.06 (1H, m), 4.69 (1H, m), 5.18 (1H, m), 6.85 (1H, t, J=7.5 Hz), 7.12 (1H, d, J=6.7 Hz), 7.43 (1H, d, J=12.5 Hz), 7.76 (1H, d, J=4 Hz), 8.23 (2H, m), 8.64 (1H, s), 8.69 (1H, d, J=4 Hz), 9.05 (1H, s) Example 12 N-((5S)-3-{3-fluoro-4-[3-(4-pyrazin-2-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0194] [0195] It was prepared following the same procedure as in Example 2, obtaining 62.1 mg of title compound. [0196] HPLC (t, %): 4.20 min, 98%. [0197] MS(ESI) m/z=466 (M+1) [0198] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.84 (3H, s), 2.45 (2H, m), 3.39 (3H, m), 3.59 (1H, m), 3.68 (1H, m), 3.81 (2H, m), 4.06 (1H, m), 4.69 (1H, m), 5.18 (1H, m), 6.85 (1H, t, J=7.5 Hz), 7.12 (1H, d, J=6.7 Hz), 7.43 (1H, d, J=12.5 Hz), 8.17 (1H, s), 8.24 (1H, m), 8.42 (1H, s), 8.55 (1H, s), 8.58 (1H, s), 9.01 (1H, s) Example 13 N4(5S)-3-{3-fluoro-4-[3-(5-phenyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0199] [0200] It was prepared following the same procedure as in Example 2, obtaining 61.6 mg of title compound. [0201] HPLC (t, %): 5.22 min, 96%. [0202] MS(ESI) m/z=466 (M+1) [0203] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.84 (3H, s), 2.65 (2H, m), 3.40 (2H, m), 3.48 (1H, m), 3.67 (2H, m), 3.90 (1H, m), 3.97 (1H, m), 4.07 (1H, m), 4.69 (1H, m), 5.76 (1H, m), 6.88 (1H, t, J=7.5 Hz), 7.13 (1H, d, J=6.7 Hz), 7.44 (1H, d, J=13 Hz), 7.56 (3H, m), 8.06 (2H, m), 8.24 (1H, NH) Example 14 N-((5S)-3-{3-fluoro-4-[3-(5-methylsulfanylltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0204] [0205] It was prepared following the same procedure as in Example 2, obtaining 55 mg of title compound. [0206] HPLC (t, %): 4.72 min, 98%. [0207] MS(ESI) m/z=436 (M+1) [0208] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 2.02 (3H, s), 2.65 (2H, m), 2.66 (3H, s), 3.59 (2H, m), 3.70 (3H, m), 3.90 (1H, m), 4.02 (2H, m), 4.75 (1H, m), 5.45 (1H, m), 6.68 (1H, t, J=7.4 Hz), 7.03 (1H, m), 7.36 (1H, d, J=12 Hz) Example 15 N-((5S)-3-{3-fluoro-4-[3-(5-thiophen-2-yl-tetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0209] [0210] It was prepared following the same procedure as in Example 2, obtaining 50 mg of title compound. [0211] HPLC (t, %): 5.07 min, 97%. [0212] MS(ESI) m/z=472 (M+1) [0213] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 2.02 (3H, s), 2.65 (1H, m), 2.80 (1H, m), 3.60 (2H, m), 3.72 (3H, m), 3.97 (2H, m), 4.08 (1H, m), 4.74 (1H, m), 5.53 (1H, m), 5.96 (1H, m), 6.71 (1H, t, J=7.5 Hz), 7.04 (1H, m), 7.15 (1H, m), 7.37 (1H, d, J=12 Hz), 7.45 (1H, m), 7.79 (1H, s) Example 16 N-((5S)-3-{3-fluoro-4-[3-(5-methyltetrazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0214] [0215] It was prepared following the same procedure as in Example 2, obtaining 36.6 mg of title compound. [0216] HPLC (t, %): 4.25 min, 95%. [0217] MS(ESI) m/z=404 (M+1) [0218] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 2.02 (3H, s), 2.53 (3H, s), 2.61 (2H, m), 3.58 (2H, m), 3.70 (3H, m), 3.90 (1H, m), 4.02 (2H, m), 4.75 (1H, m), 5.46 (1H, m), 5.96 (1H, m), 6.68 (1H, t, J=7.4 Hz), 7.03 (1H, d, J=8 Hz), 7.36 (1H, d, J=11 Hz) Example 17 N-((5S)-3-{3-fluoro-4-[3-(4-bromopyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0219] [0220] It was prepared following the same procedure as in Example 2, obtaining 51.7 mg of title compound. [0221] HPLC (t, %): 4.92 min, 97%. [0222] MS(ESI) m/z=466-468 (M+1) [0223] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.84 (3H, s), 2.45 (2H, m), 3.39 (3H, m), 3.54 (1H, m), 3.60 (1H, m), 3.68 (1H, m), 3.75 (1H, m), 4.06 (1H, m), 4.69 (1H, m), 5.08 (1H, m), 6.84 (1H, t, J=8 Hz), 7.12 (1H, d, J=6.2 Hz), 7.42 (1H, d, J=13 Hz), 7.59 (1H, s), 8.11 (1H, s), 8.23 (1H, NH) Example 18 N-((5S)-3-{3-fluoro-4-[3-(4-pyridin-4-yl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0224] [0225] It was prepared following the same procedure as in Example 2, obtaining 61.6 mg of title compound. [0226] HPLC (t, %): 3.50 min, 96%. [0227] MS(ESI) m/z=465 (M+1) [0228] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.84 (3H, s), 2.45 (2H, m), 3.42 (3H, m), 3.59 (1H, m), 3.69 (1H, m), 3.81 (2H, m), 4.06 (1H, m), 4.69 (1H, m), 5.12 (1H, m), 6.85 (1H, t, J=7.5 Hz), 7.12 (1H, d, J=6.7 Hz), 7.42 (1H, d, J=12.5 Hz), 7.59 (2H, m), 8.12 (1H, s), 8.24 (1H, NH), 8.49 (1H, m), 8.56 (1H, s) Example 19 N-[(5S)-3-(3-fluoro-4-{3-[4-(4-nitrophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide [0229] [0230] It was prepared following the same procedure as in Example 2, obtaining 52.2 mg of title compound. [0231] HPLC (t, %): 5.20 min, 99%. [0232] MS(ESI) m/z=509 (M+1) [0233] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.84 (3H, s), 2.45 (2H, m), 3.39 (5H, m), 3.59 (1H, m), 3.69 (1H, m), 3.81 (2H, m), 4.06 (1H, m), 4.69 (1H, m), 5.13 (1H, m), 6.85 (1H, t, J=7.5 Hz), 7.12 (1H, d, J=6.7 Hz), 7.42 (1H, d, J=12.5 Hz), 7.89 (2H, m), 8.15 (1H, s), 8.24 (3H, m), 8.59 (1H, s) Example 20 N-[(5S)-3-(3-fluoro-4-{3-[4-(2-trifluoromethyl-phenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide [0234] [0235] It was prepared following the same procedure as in Example 2, obtaining 55 mg of title compound. [0236] HPLC (t, %): 5.62 min, 99%. [0237] MS(ESI) m/z=532 (M+1) [0238] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 2.02 (3H, s), 2.53 (2H, m), 2.50 (1H, m), 3.55 (2H, m), 3.70 (5H, m), 3.82 (1H, m), 3.89 (1H, m), 4.01 (1H, m), 4.75 (1H, m), 5.08 (1H, m), 6.03 (1H, NH), 6.47 (1H, s), 6.71 (1H, m), 7.03 (1H, d, J=7 Hz), 7.37 (1H, m), 7.45 (1H, m), 7.54 (1H, m), 7.66 (1H, m), 7.73 (1H, m) Example 21 N-[(5S)-3-(3-fluoro-4-{3-[4-(2-methoxyphenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide [0239] [0240] It was prepared following the same procedure as in Example 2, obtaining 21.6 mg of title compound. [0241] HPLC (t, %): 5.28 min, 96%. [0242] MS(ESI) m/z=494 (M+1) [0243] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 2.02 (3H, s), 2.52 (2H, m), 3.55 (2H, m), 3.70 (4H, m), 3.87 (1H, m), 3.88 (3H, s), 3.99 (1H, m), 4.01 (1H, m), 4.75 (1H, m), 5.08 (1H, m), 5.98 (1H, NH), 6.70 (1H, m), 6.78 (1H, s), 7.00 (3H, m), 7.37 (1H, m), 7.52 (1H, s), 7.91 (1H, d, J=6.4 Hz) Example 22 N-((5S)-3-{3-fluoro-4-[3-(4-acetylpyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0244] [0245] It was prepared following the same procedure as in Example 2, obtaining 34.6 mg of title compound. [0246] HPLC (t, %): 8.38 min, 96%. [0247] MS(ESI) m/z=430 (M+1) [0248] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 2.02 (3H, s), 2.47 (1H, m), 2.56 (4H, s), 3.48 (1H, m), 3.60 (1H, m), 3.70 (3H, m), 3.85 (2H, m), 4.01 (1H, m), 4.75 (1H, m), 5.08 (1H, m), 5.99 (1H, m), 6.71 (1H, t, J=7.6 Hz), 6.79 (1H, s), 7.05 (1H, d, J=6.8), 7.38 (1H, d, J=12 Hz), 7.52 (1H, s) Example 23 N-((5S)-3-{3-fluoro-4-[3-(3-phenylpyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0249] [0250] It was prepared following the same procedure as in Example 2, obtaining 43.7 mg of title compound. [0251] HPLC (t, %): 5.35 min, 96%. [0252] MS(ESI) m/z=464 (M+1) [0253] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 2.02 (3H, s), 2.52 (2H, m), 3.55 (2H, m), 3.73 (3H, m), 3.85 (2H, m), 4.01 (1H, m), 4.75 (1H, m), 5.08 (1H, m), 5.99 (1H, m), 6.56 (1H, s), 6.71 (1H, t, J=7.3 Hz), 7.04 (1H, d, J=6 Hz), 7.26 (1H, m), 7.38 (3H, m), 7.52 (1H, s), 7.79 (1H, d, J=6 Hz) Example 24 N-[(5S)-3-(3-fluoro-4-{3-[4-(4-fluorophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide [0254] [0255] It was prepared following the same procedure as in Example 2, obtaining 48.7 mg of title compound. [0256] HPLC (t, %): 5.42 min, 99%. [0257] MS(ESI) m/z=482 (M+1) [0258] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 2.02 (3H, s), 2.50 (2H, m), 3.55 (2H, m), 3.71 (3H, m), 3.83 (2H, m), 4.01 (1H, t, J=7 Hz), 4.75 (1H, m), 5.06 (1H, m), 5.96 (1H, m), 6.51 (1H, s), 6.71 (1H, t, J=7.6 Hz), 7.05 (3H, m), 7.37 (1H, d, J=13 Hz), 7.51 (1H, s), 7.76 (1H, m) Example 25 N-[(5S)-3-(3-fluoro-4-{3-[3-(2-fluorophenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide [0259] [0260] It was prepared following the same procedure as in Example 2, obtaining 26 mg of title compound. [0261] HPLC (t, %): 5.42 min, 99%. [0262] MS(ESI) m/z=482 (M+1) [0263] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 2.02 (3H, s), 2.50 (2H, m), 3.55 (2H, m), 3.71 (3H, m), 3.83 (2H, m), 4.01 (1H, t, J=7 Hz), 4.75 (1H, m), 5.06 (1H, m), 5.96 (1H, m), 6.71 (2H, m), 7.10 (3H, m), 7.37 (1H, d, J=13 Hz), 7.51 (1H, s), 7.98 (1H, m) Example 26 N-((5S)-3-{3-fluoro-4-[3-(3-trifluoromethyl-pyrazol-1-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0264] [0265] It was prepared following the same procedure as in Example 2, obtaining 62.2 mg of title compound. [0266] HPLC (t, %): 5.18 min, 99%. [0267] MS(ESI) m/z=456 (M+1) [0268] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 2.02 (3H, s), 2.50 (2H, m), 3.47 (1H, m), 3.59 (1H, m), 3.70 (4H, m), 4.02 (1H, t, J=7 Hz), 4.75 (1H, m), 5.09 (1H, m), 5.96 (1H, m), 6.53 (1H, s), 6.70 (1H, t, J=7.4 Hz), 7.04 (1H, d, J=6 Hz), 7.39 (1H, d, J=12 Hz), 7.57 (1H, s) Example 27 N-[(5S)-3-(3-fluoro-4-{3-[3-(4-trifluoromethyl-phenyl)-pyrazol-1-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide [0269] [0270] It was prepared following the same procedure as in Example 2, obtaining 37.2 mg of title compound. [0271] HPLC (t, %): 5.83 min, 98%. [0272] MS (ESI) m/z=532 (M+1) [0273] 1 H NMR (400 MHz, δ, ppm, CDCl 3 ): 2.02 (3H, s), 2.52 (2H, m), 3.55 (2H, m), 3.70 (4H, m), 3.87 (1H, m), 3.88 (3H, s), 3.99 (1H, m), 4.01 (1H, m), 4.75 (1H, m), 5.08 (1H, m), 5.98 (1H, NH), 6.60 (1H, s), 6.72 (1H, t, J=7.5 Hz), 7.05 (1H, d, J=7 Hz), 7.38 (1H, d, J=12 Hz), 7.55 (1H, s), 7.63 (2H, d, J=7 Hz), 7.89 (2H, d, J=6 Hz) Example 28 N-((5S)-3-{3-fluoro-4-[3-(4-pyridin-2-yl-[1,2,3]triazol-2-yl)pyrrolidin-1-yl]-phenyl}-2-oxo-5-oxazolidinylmethyl)acetamide [0274] [0275] It was prepared following the same procedure as in Example 2, obtaining 76.6 mg of title compound as a mixture of the two possible regioisomers (only major shown). [0276] HPLC (t, %): 4.15 min, 16%; 4.57 min, 82%. [0277] MS(ESI) m/z=466 (M+1) Example 29 N-[(5S)-3-(3-fluoro-4-{3-[4-(3-cyanophenyl)-[1,2,3]triazol-2-yl]pyrrolidin-1-yl}-phenyl)-2-oxo-5-oxazolidinylmethyl]acetamide [0278] [0279] It was prepared following the same procedure as in Example 2, obtaining 64.7 mg of title compound as a mixture of the two possible regioisomers (only major shown). [0280] HPLC (t, %): 4.85 min, 19%; 5.27 min, 77%. [0281] MS(ESI) m/z=490 (M+1) Example 30 3,5-difluoro-4-(3-hydroxy pyrrolidin-1-yl)-4-nitrobenzene [0282] [0283] 3-pyrrolidinol (2 mL, 24.7 mmol) and potassium carbonate (4.8 g) were dissolved in DMF (5 mL), and 3,4,5-trifluoronitrobenzene (2.6 mL) was slowly added and stirred under argon at room temperature overnight. The mixture was treated with cold water and the product was separated as a solid. This solid was filtered, washed with water and dried at 60° C. under vacuum to give 5.4 g (Yield=89%) of title compound. [0284] HPLC (t, %): 7.71 min, 100%. [0285] MS(ESI) m/z=245 (M+1) [0286] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.87 (2H, m), 3.45 (1H, m), 3.69 (1H, m), 3.85 (2H, m), 4.33 (1H, m), 5.05 (1H, m), 7.86 (2H, dd, J=2.8, 9.6 Hz) Example 31 3,5-difluoro-4-(3-methylsulfonyloxy pyrrolidin-1-yl)nitrobenzene [0287] [0288] 3,5-difluoro-4-(3-hydroxy pyrrolidinyl)-nitrobenzene (5.4 g) and triethylamine (6.1 mL) were dissolved in DCM (125 mL) at room temperature and purged under argon. Methanesulfonyl chloride (2.6 mL) was added at 0° C. and over night at room temperature. The reaction mixture was washed with water, brine and the organic layers dried over MgSO 4 . The concentrated residue was transferred to a mortar and dried under vacuum at 55° C. for 3 hours to afford 6.4 g of title compound. [0289] HPLC (t, %): 8.32 min, 100%. [0290] MS(ESI) m/z=323 (M+1) [0291] 1 H NMR (400 MHz, δ, ppm, DMSO): 2.2 (2H, m), 3.26 (3H, s), 3.83 (3H, m), 4.09 (1H, m), 5.38 (1H, s), 7.90 (2H, dd, J=2.8, 9.2 Hz) Example 32 3,5-difluoro-4-[3-([1,2,3]-triazol-2-yl)pyrrolidinyl]-nitrobenzene [0292] [0293] K 2 CO 3 (322 mg) and 3,5-difluoro-4-(3-methylsulfonyloxy pyrrolidinyl)-nitrobenzene (500 mg) were weighted and purged under argon in a 25 mL-round bottom flask. DMF (10 mL) and triazol (0.135 mL) were added and the mixture refluxed at 70° C. overnight. Cold water and DCM were added and the separated organic layer dried over MgSO 4 and concentrated under reduced pressure. The mixture of regioisomers was purified by column chromatography (silica gel, DCM/MeOH 95:5) to give 274 mg of the title compound as a major regioisomer (Yield=60%). [0294] HPLC (t, %): 8.79 min, 100%. [0295] MS(ESI) m/z=296 (M+1) [0296] 1 H NMR (400 MHz, δ, ppm, DMSO): 2.49 (2H, m), 3.88 (2H, m), 4.11 (1H, m), 4.27 (1H, m), 5.37 (1H, m), 7.83 (2H, s), 7.90 (2H, dd, J=2, 9.2 Hz) Example 33 3,5-difluoro-4-[3-([1,2,3]-triazol-1-yl)pyrrolidinyl]-nitrobenzene [0297] [0298] It was obtained concomitantly with compound of Example 32, which after column chromatography afforded 72 mg of title compound (Yield=15%). [0299] HPLC (t, %): 7.72 min, 80%. [0300] MS(ESI) m/z=296 (M+1) [0301] 1 H NMR (400 MHz, δ, ppm, DMSO): 2.49 (2H, m), 3.88 (2H, m), 4.08 (1H, m), 4.27 (1H, m), 5.36 (1H, m), 7.76 (1H, s), 7.92 (2H, dd, J=2.4, 9.2 Hz), 8.28 (1H, s) Example 34 3,5-difluoro-4-[3-(tetrazol-2-yl)pyrrolidin-1-yl]-nitrobenzene [0302] [0303] K 2 CO 3 (322 mg) and 3,5-difluoro-4-(3-methylsulfonyloxy pyrrolidinyl)-nitrobenzene (500 mg) were weighted and purged under argon in a 100 mL-round bottom flask. DMF (10 mL) and tetrazole solution (3% wt. in acetonitrile, 13.76 mL) were added and the mixture refluxed at 100° C. overnight when complete reaction was observed by HPLC-MS. The reaction mixture was poured into crushed ice and the separated solid was washed with cold water to give 278 mg of a mixture of regioisomers. The aqueous organic layers were extracted with DCM and the separated organic layer dried over MgSO 4 and concentrated under reduced pressure recovering 100 mg of the mixture of regioisomers. The crude compounds as a mixture of regioisomers were purified by column chromatography (silica gel, DCM/EtOAc increasing polarity) to give 180 mg of the title compound as a major regioisomer (Yield=40%). [0304] HPLC (t, %): 8.34 min, 100%. [0305] MS(ESI) m/z=297 (M+1) [0306] 1 H NMR (400 MHz, δ, ppm, DMSO): 2.56 (2H, m), 3.91 (2H, m), 4.15 (1H, m), 4.36 (1H, m), 5.73 (1H, m), 7.92 (2H, dd, J=2.4, 9.2 Hz), 9.01 (1H, s) Example 35 3,5-difluoro-4-[3-(tetrazol-1-yl)pyrrolidin-1-yl]-nitrobenzene [0307] [0308] It was obtained concomitantly with compound of Example 34, which after column chromatography afforded 30 mg of title compound (Yield=15%). [0309] HPLC (t, %): 7.72 min, 96%. [0310] MS(ESI) m/z=297 (M+1) [0311] 1 H NMR (400 MHz, δ, ppm, DMSO): 2.56 (2H, m), 3.88 (2H, m), 4.10 (1H, m), 4.31 (1H, m), 5.45 (1H, m), 7.92 (2H, dd, J=2.4, 9.2 Hz), 9.55 (1H, s) Example 36 N-{(5S)-3-[3,5-difluoro-4-[3-(tetrazol-2-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide [0312] 3,5-difluoro-4-[3-(tetrazol-2-yl pyrrolidin-1-yl)]-phenylamine [0313] [0314] 3,5-difluoro-4-[3-(tetrazol-2-ylpyrrolidin-1-yl)]-nitrobenzene (4 g) was dissolved in methanol (300 mL) and minimum quantity of DCM. The mixture was hydrogenated in a continuous-flow hydrogenation reactor using hydrogen generated in-situ from the electrolysis of water. First, the substrate is combined at room temperature with hydrogen at atmospheric pressure. And then, the mixture was passed through a packed Pd on Carbon (10%) cartridge where the reaction takes place. The product eluted out of the cartridge and into a collection vial to give after concentration 3.6 g of compound of 99% purity (100% Yield). [0315] HPLC (t, %): 7.41 min, 98%. [0316] MS(ESI) m/z=267 (M+1). [0317] 1 H NMR (400 MHz, ppm, DMSO): 2.54 (2H, m), 3.26 (1H, m), 3.42 (1H, m), 3.54 (1H, m), 3.75 (1H, m), 5.59 (1H, m), 6.18 (2H, d, J=12 Hz), 8.97 (1H, s). 3,5-difluoro-4-[3-(tetrazol-2-yl pyrrolidin-1-yl)]-phenyl carbamic acid benzyl ester [0318] [0319] 3,5-difluoro-4-[3-(tetrazol-2-ylpyrrolidin-1-yl)]-phenylamine (3.6 g) was dissolved in acetone (100 mL) and cooled to 0° C. Sodium hydrogencarbonate (4.6 g, 4 eq) in water (50 mL) was added, followed by benzyl chloroformate (3.9 mL, 2 eq) over 30 minutes. The mixture was stirred and the temperature allowed rise to ambient over 12 hours. DCM was added and the organic layer separated, and washed with water and brine. The combined organic layers were dried over magnesium sulfate and concentrated. The residue was purified by column chromatography over silica eluting with DCM and DCM/AcOEt from 0 to 10% to give 6.29 g of title product (94% Yield). [0320] HPLC (t, %): 9.71 min, 94%. [0321] MS(ESI) m/z=401 (M+1). [0322] 1 H NMR (400 MHz, ppm, DMSO): 2.54 (2H, m), 3.4 (2H, m), 3.61 (1H, m), 3.73 (1H, m), 3.94 (1H, m), 5.13 (2H, s), 5.64 (1H, m), 7.09 (2H, d, J=12 Hz), 7.38 (5H, m), 8.99 (1H, s). N-{(5S)-3-[3,5-difluoro-4-[3-(tetrazol-2-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide [0323] [0324] To a solution of 3.5 g of 3,5-difluoro-4-[3-(tetrazol-2-yl pyrrolidin-1-yl)]-phenyl carbamic acid benzyl ester in 5 mL of DMF was added 22 mL of a solution of 1M of lithium tert-butoxide in THF and stirred at room temperature for 30 minutes. 0.6 mL of methanol and a solution of 3.5 g of (S)—N-(3-bromo-2-acetoxypropyl)acetamide in 5 mL of DMF were added and allowed to stand at room temperature for two days at which point HPLC showed nearly complete conversion. DCM and saturated aqueous ammonium chloride were added to the reaction solution and the separated organic layer was washed with water, brine and dried over anhydrous magnesium sulfate. The solvent was evaporated and the residue was purified by silica gel column chromatography (DCM/AcOEt from 0 to 10% and DCM/Methanol at 10%) to afford 2.6 g of the title compound (86% Yield). [0325] HPLC (t, %): 6.95, 100. [0326] MS(ESI) m/z=407 (M+1) [0327] 1 H NMR (400 MHz, ppm, DMSO): 1.82 (3H, s), 2.55 (2H, m), 3.39 (2H, m), 3.51 (1H, m), 3.67 (2H, m), 3.81 (1H, m), 4.02 (2H, m), 4.71 (1H, m), 5.66 (1H, m), 7.22 (2H, d, J=12 Hz), 8.24 (1H, NH), 8.99 (1H, s). Example 37 N-{(5S)-3-[3,5-difluoro-4-[3-([1,2,3]triazol-2-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide [0328] [0329] It was obtained from compound of Example 32 following procedure described in Example 36 to give after column chromatography 2.6 g of title compound. [0330] HPLC (t, %): 7.22 min, 99%. [0331] MS(ESI) m/z=407 (M+1) [0332] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.82 (3H, s), 2.49 (2H, m), 3.50 (1H, m), 3.65 (2H, m), 3.76 (1H, m), 3.92 (1H, m), 4.04 (1H, t, J=8.8 Hz), 4.69 (1H, m), 5.31 (1H, q, J=4.4 Hz), 7.20 (2H, d, J=12 Hz), 7.81 (2H, s), 8.22 (1H, NH) Example 38 N-{(5S)-3-[3,5-difluoro-4-[3-([1,2,3]triazol-1-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide [0333] [0334] It was obtained from compound of Example 33 following procedure described in Example 36 to give after column chromatography 1.29 g of title compound. [0335] HPLC (t, %): 6.52 min, 97%. [0336] MS(ESI) m/z=407 (M+1) [0337] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.82 (3H, s), 2.35 (1H, m), 2.55 (1H, m), 3.83 (2H, m), 3.65 (2H, m), 3.88 (1H, m), 4.05 (1H, t, J=8 Hz), 4.70 (1H, m), 5.33 (1H, m), 7.22 (2H, d, J=12 Hz), 7.75 (2H, d, J=0.8 Hz), 8.19 (1H, d, J=1.2 Hz), 8.22 (1H, NH) Example 39 N-{(5S)-3-[3,5-difluoro-4-[3-(tetrazol-1-yl pyrrolidin-1-yl)phenyl]-2-oxo-5-oxazolidinyl methyl}acetamide [0338] [0339] It was obtained from compound of Example 35 following procedure described in Example 36 to give after column chromatography 0.5 g of title compound. [0340] HPLC (t, %): 6.48 min, 98%. [0341] MS(ESI) m/z=408 (M+1) [0342] 1 H NMR (400 MHz, δ, ppm, DMSO): 1.82 (3H, s), 2.41 (1H, m), 2.56 (1H, m), 3.34 (2H, m), 3.62 (4H, m), 3.87 (1H, m), 4.00 (1H, t, J=9.2 Hz), 4.71 (1H, m), 5.40 (1H, m), 7.23 (2H, d, J=12 Hz), 8.23 (1H, NH), 9.48 (1H, s) Example 40 Antibacterial Activity [0343] MICS were determined by using a standard micro dilution method according to The National Committee for Clinical Laboratory Standards (NCCLS), 5 th Approved standard M7-A5, 2001, Wayne, Pa., USA. All compounds were tested against Gram-positive and Gram-negative bacteria showing relevant different susceptibility and resistance specifications. The used microorganisms were selected from laboratory reference bacteria and from clinical isolates. The tested concentrations were double dilutions from 0.06 μg/mL to 128 μg/mL in 96-well micro titter plates. [0344] MICs were determined in the Brucella Blood medium supplemented for the anaerobic strains, and in the Mueller-Hinton culture medium (cation-adjusted) for the aerobic bacteria. [0345] The tested compounds were dissolved in DMSO, and were diluted as far as 2560 μg/mL with the different media according to the specific requirements for each group of strains. The 96-well sealed micro titter plates containing bacteria were incubated in different laboratory conditions depending on the nature of the microorganism. Thus, the aerobic bacteria were incubated during 16-24 h at 35° C. and the so-called fastidious bacteria, such as M. catarrhalis and S. pneumoniae , during 20-24 h at 35° C. in a microaerobiotic atmosphere containing 5% CO 2 (Anaerocult C, MERCK). The results of these tests are given in Table 1. [0000] TABLE 1 Com- Microorganism pound (1) (2) (3) (4) (5) (6) (7) (8) (9) Ex. 3 1 1 0.5 16 4 4 1 1 8 Ex. 9 1 0.25 1 8 1 2 0.5 1 4 Ex. 11 0.5 0.125 0.25 2    NT (*) 4 0.5 0.5 8 Ex. 15 0.5 0.125 0.25 4 NT 8 0.5 2 8 Ex. 17 1 0.25 0.5 8 1 1 0.5 2 1 Ex. 18 0.5 0.06 0.25 2 NT 4 0.25 0.5 8 Ex. 19 0.5 0.125 0.25 2 NT 4 1 1 64 Ex. 26 2 0.5 1 16 1 1 1 2 2 Line- 1.00 1.00 0.50 16-32 128  16 2 2 64 zolid (1) S. aureus ATCC25923 MS (2) S. pneumoniae ATCC49619 PR (3) E. faecium ATCC51559 MDR (4) S. aureus LNZ-R 432 (5) S. haemolyticus (6) H. influenzae ATCC49247 (7) B. fragilis sp. fragilis ATCC25285 (8) M. catarrhalis HCI-78 (9) E. faecium LNZ-R LR-4 (*) NT: Not Tested Example 41 Pharmaceutical Compositions [0346] The following illustrate representative pharmaceutical compositions containing a compound of formula (I) or a pharmaceutically acceptable salt thereof for antimicrobial use in humans or animals: [0000] Tablet 1 mg/tablet Active ingredient 100 Lactose 179 Croscarmellose sodium 12 Polyvinylpyrrolidone 6 Magnesium stearate 3 [0000] Tablet 2 mg/tablet Active ingredient 50 Lactose 229 Croscarmellose sodium 12 Polyvinylpyrrolidone 6 Magnesium stearate 3 [0000] Tablet 3 mg/tablet Active ingredient 1 Lactose 92 Croscarmellose sodium 4 Polyvinylpyrrolidone 2 Magnesium stearate 1 [0000] Capsule mg/capsule Active ingredient 10 Lactose 389 Croscarmellose sodium 100 Magnesium stearate 1 [0000] Injection 50 mg/mL Active ingredient 5.0% w/v Isotonic aqueous solution to 100% [0347] Buffers, pharmaceutically acceptable co-solvents such as polyethylene glycol, polypropylene glycol, glycerol or ethanol or complexing agents, may be used to aid formulation. [0348] The above formulations may be prepared by well-known conventional procedures in the pharmaceutical art. The tablets 1-3 may be enteric coated by conventional means, for example to provide a coating of cellulose acetate phthalate.
The invention provides new oxazolidinone compounds of formula (I) wherein R, R 1 , R 2 and R 3 have different meanings. Preparative processes, pharmaceutical compositions, and uses thereof in the treatment of bacterial infections are also provided.
74,972
RELATED APPLICATION The present application claims priority from and the benefit of U.S. Provisional Patent Application No. 62/192,311, filed Jul. 14, 2015, the disclosure of which is hereby incorporated herein by reference in its entirety. FIELD OF THE INVENTION The present invention relates generally to protection of electronic equipment, and more particularly to protection of the transition area from cable to a remote radio unit (RRU), antenna or the like. BACKGROUND Cables are typically attached to electronic equipment such as RRUs and antennas via mating connectors, one of which terminates the cable, and the other of which is mounted on the electronic equipment. The interface between the connectors can be vulnerable to precipitation and other environmental conditions. As such, in many instances a protective cover or boot may enclose the interface to protect it. Exemplary boots are discussed in U.S. Patent Publication No. 2015/0136439, filed Apr. 4, 2014, the disclosure of which is hereby incorporated herein in its entirety. In the design of a cable assembly it is often required that the separated cables be protected from certain birds, in particular cockatoos, that tend to damage the cables through unwanted pecking. To “bird-proof” the cables, a protective conduit is typically used. The protective conduit is generally greater than 19 mm in diameter to prevent the birds from pecking at and damaging the cables. However, the covers or boots may still be susceptible to damage from birds. SUMMARY As a first aspect, embodiments of the invention are directed to an assembly, comprising: a cable; a first connector attached to the cable; a second connector that mates with the first connector to form an interface; a sealing boot that encloses the interface, the sealing boot including a cable section that fits conformably over the cable; a conduit that circumferentially overlies a portion of the cable adjacent the first connector, the conduit including a plurality of first corrugations; and a protective cover that overlies the corrugations of the conduit and the sealing boot, the cover including at least one second corrugation on an inner surface thereof that interdigitates with one of the first corrugations. As a second aspect, embodiments of the invention are directed to a protective cover for a sealing boot of a coaxial connector interface, comprising two mating halves, each of the halves including a coupler section at one end, an intermediate section that merges with and is smaller in diameter than the coupler section, and a conduit section that merges and is smaller in diameter than the intermediate section, wherein the conduit section has an inner surface with a corrugated profile. As a third aspect, embodiments of the invention are directed to an assembly, comprising: a cable; a first connector attached to the cable; a second connector that mates with the first connector to form an interface; a protective barrier that encloses the interface, the protective barrier including a cable section that fits conformably over the cable; a conduit that circumferentially overlies a portion of the cable adjacent the first connector, the conduit including a plurality of first corrugations; and a protective cover that overlies the corrugations of the conduit and the protective barrier, the cover including at least one second corrugation on an inner surface thereof that interdigitates with the first corrugations. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a side section view of an interface between a remote radio head and a coaxial cable protected by a sealing boot, with a conduit in place over the coaxial cable. FIG. 2 is an end view of a protective cover for the interface and sealing boot of FIG. 1 , with the cover in an unassembled condition. FIG. 3 is a side view of the unassembled protective cover of FIG. 2 . FIG. 4 is a side section view of the interface and sealing boot of FIG. 1 protected within the cover of FIG. 2 . DETAILED DESCRIPTION The present invention is described with reference to the accompanying drawings, in which certain embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments that are pictured and described herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. It will also be appreciated that the embodiments disclosed herein can be combined in any way and/or combination to provide many additional embodiments. Unless otherwise defined, all technical and scientific terms that are used in this disclosure have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the above description is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this disclosure, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will also be understood that when an element (e.g., a device, circuit, etc.) is referred to as being “connected” or “coupled” to another element, it can be directly connected or coupled to the other element or intervening elements may be present. In contrast, when an element is referred to as being “directly connected” or “directly coupled” to another element, there are no intervening elements present. Referring now to the figures, a cable-equipment interface, designated broadly at 10 , is shown in FIG. 1 . The interface 10 includes a cable 12 terminated with a connector 14 . A piece of electronic equipment 16 , such as an RRU or antenna, includes a connector 18 mounted thereon that mates with the connector 14 of the cable 12 . In the illustrated embodiment, the connectors 14 , 18 are secured with a coupling nut 20 . The interface between the cable 12 and the equipment 16 is protected by a sealing boot 22 . As can be seen in FIG. 1 , the sealing boot 22 includes a generally cylindrical interconnection section 32 . A flange 34 is mounted to the interconnection section 32 via a short trunk 36 . A generally cylindrical main section 38 merges with the interconnection section 32 opposite the trunk 36 . The main section 38 is smaller in diameter than the interconnection section 32 . A tapered transition section 40 merges with the main section 38 ; in turn, a generally cylindrical cable section 42 merges with the transition section 40 . Thus, the hollow, generally coaxial sections of the boot 22 define a continuous bore 46 . The boot 22 may be formed of any number of materials, but is typically formed of an elastomeric material, such as rubber, that can recover to its original shape after significant deformation. The boot 22 is typically formed as a unitary member, and in particular may be formed via transfer, compression or injection molding. Those skilled in this art will recognize that other boot configurations may be suitable. Still referring to FIG. 1 , a conduit 26 is positioned over the cable 12 . The conduit includes circumferential corrugations 28 . The conduit 26 is formed of a material such as nylon that is sufficiently hardy to resist damage from birds. The conduit 26 in the illustrated embodiment is 19 mm in diameter, but may be sized differently (e.g., larger than 19 mm) as desired or needed. As can be seen in FIG. 1 , the conduit 26 does not protect the boot 22 from exposure to birds. As such, the boot 22 may be vulnerable to damage from birds. Referring now to FIGS. 2 and 3 , a hollow protective cover for the boot 22 , designated broadly at 100 , is illustrated therein. The cover 100 includes two halves 102 , 104 that are connected with three hinge strips 106 . Each of the halves 102 , 104 has a coupler section 108 at one end, an intermediate section 110 that merges with the coupler section 108 , and a conduit section 112 that merges with the intermediate section 110 . As can be seen in FIG. 3 , the conduit section 112 has corrugations 122 on its inner surface. The cover 100 may be formed of a number of different materials. The cover 100 may be formed of a polymeric material with sufficient flexibility to enable the hinge strips 106 to serve as “living hinges”. Exemplary materials for the cover 100 are nylon and high density polyurethane. The halves 102 , 104 can be mated to form the cover 100 . The hinge strips 106 are sufficiently flexible that the edges of the halves 102 , 104 can be brought together to mate in facing relationship. Alignment pins 114 are present on the edges of the half 102 ; corresponding holes 116 are present in the edges of the half 104 . When the halves 102 , 104 are brought together, the pins 114 are inserted into the holes 116 to secure the halves 102 , 104 into a hollow enclosure. Those skilled in this art will appreciate that other securing features (e.g., latches, clips and the like) may be employed to secure the halves 102 , 104 together. To protect the boot 22 , the cover 100 can be mated as described above over the boot 22 and conduit 26 (see FIG. 4 ). The cover 100 is positioned so that the corrugations 122 of the conduit section 112 are interdigitated with the corrugations 28 of the conduit 26 . This interdigitation helps to secure the cover 100 in place over the conduit 26 . The intermediate section 110 of the cover 100 overlies the main section 34 of the boot 22 . The coupler section 108 overlies the interconnection section 32 of the boot 22 . Thus, the cover 100 generally surrounds the boot 22 and protects it from damage due to avian activity. Those skilled in this art will appreciate that other forms of protective barriers of the cable-equipment interface, such as vinyl and/or butyl mastic tape, may be suitable for use with covers of the present invention. In addition, those skilled in this art will appreciate that cover 100 may take other forms. For example, the halves 102 , 104 may be separate components, rather than being connected via the hinge strips 106 , or may be connected to each other by some other means (for example, a wire or string). Also, the halves 102 , 104 may be secured to each other via other means, such as adhesive, hook-and-loop strips, screws, or the like. Moreover, the corrugations 122 may be circumferentially discontinuous about the inner diameter of the cover 100 , and/or a single corrugation (rather than a plurality) may be present. Other variations will be apparent to those of skill in this art. The foregoing is illustrative of the present invention and is not to be construed as limiting thereof. Although exemplary embodiments of this invention have been described, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the claims. The invention is defined by the following claims, with equivalents of the claims to be included therein.
An assembly includes: a cable; a first connector attached to the cable; a second connector that mates with the first connector to form an interface; a sealing boot that encloses the interface, the sealing boot including a cable section that fits conformably over the cable; a conduit that circumferentially overlies a portion of the cable adjacent the first connector, the conduit including a plurality of first corrugations; and a protective cover that overlies the corrugations of the conduit and the sealing boot, the cover including at least one second corrugation on an inner surface thereof that interdigitates with one of the first corrugations.
11,666
FIELD OF THE INVENTION [0001] The present invention relates to a method for education, teaching of concepts and values, sales and persuasion, sales and teacher training, and apparatuses therefor. BACKGROUND [0002] Teachers, salespeople, counselors and hostage negotiators often use questions to lead participants (e.g., students, visitors, prospects, customers, patients, etc.) to reason for themselves and reach a logical conclusion desired by the interrogator through use of the Socratic Method. The advent of computers and the world wide computer network commonly referred to as the “Internet” has caused a rapid increase in contacts where a self-directed participant initiates contact with and explores a website. (Applicant at times refers to a “website” as a “site” herein.) However, the use of questions or prompts based on prior responses in a series leading to a particular desired conclusion has not been automated to utilize these innovations. [0003] Currently a site or software at a site may be designed for a “target participant” and be capable of handling common questions, objections, concerns, or misconceptions in a broadcast manner, with at most, an offer of “more information.” A “target participant” is a person exhibiting a predetermined set of characteristics i.e., characteristics preferred by the operator or owner of the site. A site may be constructed without the site's designer knowing whether common parameters apply to a particular visitor. Unlike an inter-personal contact between, for example, a student and a teacher, which is interactive, customized and variable, sites have not been designed to attempt to lead any particular individual participant regardless of who they are to a desired conclusion by using a participant's own responses to a series of prompts. [0004] Presently many designers of software programs for sites obtain data through surveys to determine what presentations are preferable for “target participants,” and what are the potential objections, attitudes, preferences and values of participants. Present day designers of sites use this information to create materials to display at websites. The viewing of such displays at sites by individuals is similar to a TV commercial broadcast, that is, the material presented is created with the aid of market research to be appealing to the expected general viewer. TV commercial broadcast and present day websites do not customize the message for each individual TV viewer or web site page visitor in a persistent interactive way. [0005] Some present day websites or software programs permit the website visitor to provide additional information so that a determination may be made as to what other material or information to display to the site visitor. For example, a site that is directed to movies and theater may have the capacity to receive Zip Code information from the viewer. The viewer may then enter a Zip Code and the display will change to list the theaters within the Zip Code area along with the movies being shown at each theater and the show times. However, present day websites suffer from the limitation that they do not reason with the individual site visitor and they do not utilize the knowledge, prejudices and personal characteristics of a particular site visitor in order to change the mind of the visitor. Some present day websites may display questions and request responses to test the understanding of the participant before the participant is taken to the next step, or next web page, (i.e. next display). However, such websites though they may provide test results (i.e., visitor response data to the operator of the website) and may even require a certain response before displaying the next web page, they do not attempt to persuade, reason or lead the visitor to a conclusion in a persistent “interactive” fashion. Such websites merely elicit present opinion, knowledge or other types of information from the site visitor, or offer opinion, knowledge or other types of information to the site visitor. Sites that are more than a survey (i.e., more than mere data gathering sites) still do not attempt in a step-by-step logical manner, to lead the visitor to change his mind, make a decision or learn by repeated questioning to determine whether the participant reads, understands or is satisfied with the information already presented, providing additional persuasive material, and testing whether he has been led to reevaluate his position or change his mind on a particular topic or issue. (As used herein, masculine pronouns include the feminine and vice versa.) [0006] There is thus a need for interactive websites and the like which are capable of using logic and reason to guide a visitor from an initial position or opinion to a position or opinion desired by the site designer in a logical and rational manner and, potentially, to elicit some action by the visitor which is desired by the site designer or operator. Additionally, there is a need for interactive websites and the like which are capable of using logic and reason to reinforce a position or opinion of a visitor that concurs with the position or opinion desired by the website designer or operator through a logical, rational process, and potentially to elicit some desired action by the visitor. SUMMARY OF THE INVENTION [0007] The invention may be utilized in but is not limited to areas of sales, general education, politics, mental health, marital and family counseling, conflict resolution, religion, morality, and any other activity where the participant's reasoning can be logically guided by the designer's questions toward alignment with the designer's preferred conclusion. [0008] The invention may be implemented on an array of electronic devices, including, but not limited to the Internet, a local area network, an individual computer, cell phone, interactive television or any other device where questions and answers can be programmed in advance, communicated to a participant and a response by the participant can call up the next related question. Every reference to “question,” “questions” and “question(s)” herein is intended to include prompts of any kind, and every reference to “answer,” “answers” and “answers(s)” means a response or potential response to the prompt or question. [0009] As will be appreciated, the invention may be practiced in various modes. By way of example, and not by way of limitation, the designer of a website (or the like) may start by determining the goal. For example, a goal may be changing an individual's opinion from “in favor of a higher minimum wage” to “against a higher minimum wage,” or changing a person's opinion of a product, service or other matter from negative to positive, or guiding a student to figure out how to do math in binary, or any other goal that may be arrived at in a logical manner. The designer then determines what steps are necessary or advisable to lead participants to align with the predetermined goal. [0010] The designer prepares “key” questions, one or more answers to which indicates progress toward the goal. The “key” questions are similar to major intersections on a logic diagram, or map. The intersections on the logic diagram or map represent primary nodes in the logical structure of the diagram or map which also includes the alternate paths that may be taken when a participant does not choose the direct route to the designer's goal or does not choose the answer most in alignment with the designer's goal. Although it may assist in accomplishing the design process, it is not required that the logic diagram or structure actually be drawn or written, especially as the logic diagram is not limited to two-dimensions. The logic structure may be N-dimensional, where N=2, 3, 4 . . . The logic structure remains invisible to the participant who experiences each question and multiple-choice answer subset as if taking a survey. In reality, each question actually puts him at a crossroads with a choice of directions to take. If he could see the map, he would realize that all the answers represent steps on the way to the same destination, but that there are alternate routes which are only sometimes overlapping and of various lengths. [0011] Between any two primary nodes in the logic structure there may be one or more secondary nodes. The secondary nodes are thus transition positions between the primary nodes and are representative of logical steps between the primary nodes. Between any two secondary nodes in the logic structure, there may be one or more tertiary or third level nodes, which are transition positions or logical steps between the secondary nodes. This logic structure may be repeated at lower logic levels, e.g., between fourth, fifth, . . . , etc. level nodes. As will be appreciated, the logic structure may be highly complex. [0012] A participant answers a series of questions from a predetermined universe of question and answer subsets, as if taking a survey. The participant is presented with one question at a time along with a subset of answers. The participant selects an answer to the question, with which he agrees, from the list of predetermined answer choices. Each answer he selects causes him to be presented with another predetermined question and answer subset from the universe of question and answer subsets. Unlike a survey, the participant may feel as if an interested listener is interviewing him, because the question presented to him tends to follow or be related to his previous answer. [0013] The universe of question and answer subsets optimally comprises qualifying question and answer subsets, leading question and answer subsets and closing question and answer subsets. The universe of question and answer subsets is described in detail herein. [0014] Participants may participate either electronically, or person-to-person. In a preferred embodiment, a computer system is utilized with the question and answer subsets being capable of being projected on a display. Each answer chosen by the participant may be linked to a predetermined question and related answers i.e., the question and answers displayed are responsive to the answer chosen by the participant to the previous question, and follows logically toward the predetermined goal of the designer. The designer's goal may be a particular answer(s) to a particular question or series of questions (hereinafter the “Target Answer”). BRIEF DESCRIPTION OF THE DRAWINGS [0015] The following drawings are for illustrative purposes and are schematic in nature. [0016] FIG. 1 is a diagram showing the interrelationship of various question and answer subsets of a preferred embodiment of the invention; [0017] FIG. 2 is a diagram of an apparatus implementing a preferred embodiment of the invention; [0018] FIG. 3 is a diagram illustrating the relationship of a question and its associated multiple choice answers in a preferred embodiment of the invention; [0019] FIG. 4 is a diagram of two questions and their associated answers in a preferred embodiment of the invention. DESCRIPTION OF PREFERRED EMBODIMENT [0020] The present invention will now be described more fully hereinafter with reference to the accompanying drawings in which preferred embodiments of the invention are shown. The invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the scope of the invention to those skilled in the art. The applicant incorporates by reference herein the Summary of the Invention set forth above. [0021] Initially referring to FIG. 1 , there is depicted therein, a diagram illustrating the interrelationship of three question and answer subsets. The universe of question and answer subsets comprises qualifying question and answer subsets 100 , leading question and answer subsets 110 and closing question and answer subsets 120 . The term universe of question and answer sets does not refer to all possible questions and answer sets that are theoretically possible but to the questions and answer sets determined by the designer. [0022] If a participant agrees to participate, the procedure begins 50 . A set 100 of qualifying questions is presented with a plurality of answers for each question. In a preferred embodiment of the invention, described in detail herein, a display such as a video display terminal, is utilized. It will be understood that the invention is not limited to the visual display of question and/or answers but includes the audio communication thereof Accordingly, while the description below is directed to visual displays of information, the invention is not so limited but includes the audio communication of information to and from the participant. [0023] Only one question at a time appears on the video display terminal along with the question's respective multiple choice answers, i.e., a single question appears on the display with a list of multiple choice answers from which the participant may choose a response. (As described below a question may also request a reply comprising specific information.) The participant chooses an answer from the list of multiple choice answers and signifies his choice. The participant signifies his choice through the equipment used to communicate with the computer, such as a keyboard, touch screen, mouse controlled pointer or other type of computer control communication device. For example, the first question may be “What language do you prefer?” This question may appear with a list of languages as alternative languages. The answer chosen by the participant determines the language of the remainder of the questions and answers. Any questions, the answers to which are not subject to change and which the designer desires to accommodate by customizing the remainder of the process are preferably asked first. As will be appreciated, the participant may signify his choice verbally and the verbal response may be interpreted by the use of verbal recognition equipment well known to those skilled in the art, or by another individual acting as an intermediary. [0024] As those having ordinary skill in the art will appreciate, the participant may give the answers to questions by choosing the answer from a provided list of possible answers or by the participant entering certain specific information in one or more designated areas of the display. For example, a participant may be asked, “What is your age?” and be provided with a list of numbers representing age and the participant may choose his age from the list. Alternatively, the question “What is your age?” may be followed by an area on the display in which the participant may enter using a device such as a keyboard, a number signifying his age in a conventional manner. [0025] These initial qualifying questions, if any, are preferably followed by the question needed to determine participant's current state in relation to the Target Answer(s), the answer(s) desired by the designer. This question may be exactly the same question as the Target Question or a variation thereof. [0026] As may be appreciated, some participants may already agree with the designer's Target Answer(s) or already have competence in the concept being taught, while others do not, as indicated by their answer(s). [0027] The designer's primary purpose is to organize and design questions in such a way that it seems to the participant as if the process desires to find out, using qualifying questions, who the participant is and where he is starting in relation to the designer's goal, and to instill confidence in the participant by referring to answers or further expounding on answers the participant provided and agreed with, using sales and teaching techniques well known to those having ordinary skill in the art. [0028] Although, for purposes of illustration, qualifying questions are asked first followed by leading questions, qualifying questions may be asked whenever thought useful (in sales, this is known as or called “re-qualifying”). Sometimes it may be of benefit to delay some qualifying questions until a later relevant point in the process. [0029] The initially asked qualifying question(s) should be ordered to lead to the Target Question(s) which identifies the participant's current state in relation to the designer's desired state. [0030] Preferably, further qualifying question or questions follow, designed to elicit the reasons for the participant's current opinion or the level of the participant's current understanding, as appropriate, or, if the answer given is the desired answer to the Target Question, a question(s) evaluating the strength of that opinion or further testing of the participant's competence regarding a subject may be presented. [0031] Those participants whose answers indicate continued agreement or competence may then be asked the Target Question again (or a variation thereof) and/or be asked closing questions 120 . The process ends 130 at a point that is determined based upon the participant's response(s) to various question(s) in the universe of question and answer subsets as determined by the designor. [0032] The qualifying questions preferably end with a “Key” qualifying question designed to separate various participants' responses along the most divergent lines applicable by offering diverging answers. For example, the question “Why?” may be followed by a choice of answers comprising a plurality of likely responses. [0033] In a preferred embodiment, the participant may be questioned regarding his position on an issue. For example, if the issue is the minimum wage, the target qualifying question, “Do you think the minimum wage should be raised?” may be asked with the following presented answers: “Yes,” “No,” or “I don't know.” Each of these responses may be followed by the key qualifying question “Why?” In this example, for the participant who initially answered “Yes,” the answer choices for the next question (“Why?”) might include “My party recommends it,” “I have many friends who work for minimum wage and need the money,” or “It will help the less fortunate.” (Note that the second answer may also serve to make the participant realize that he does not know anyone who works for minimum wage.) [0034] The participant that answered “No” may be given a choice of answers for why he does not think the minimum wage should be raised. When “No” is the Target Answer, this also serves the purpose of reminding him of additional reasons to reinforce his response of “No.” [0035] After the participant responds to the qualifying subset of questions and answers, the participant is provided questions and answers from the leading question and answer subsets 110 . [0036] Leading questions and corresponding answers may become increasingly specific (whereas qualifying questions may tend to diverge). For example, the participant that answered, “yes” to the target qualifying question may be presented with a leading question requesting the participant to select a reason for the participant's position from a predetermined list of reasons. One or more primary and/or secondary issue questions may be asked concerning the participant's current opinions, conclusions, values, goals, or any issue chosen by the designer. As will be explained in further detail below, the participant's response may aid in determining a preferred approach to reasoning with the participant. [0037] Each participant in choosing answers to a series of leading questions follows a path determined by his chosen answers to the presented questions. (It should be understood that the term “leading question” as used herein does not necessarily mean a question which suggests a particular answer. In the invention, a question may or may not suggest an answer. Instead, a “leading question” is one in a series of questions or prompts leading the participant to follow a line of reasoning toward the Target Answer(s). Depending on his prior answer(s), questions (and their respective answers) preferably begin to either reinforce or challenge his beliefs and conclusions. [0038] The participant who aligns with the designer's goal may advance quickly, even directly to the closing question and answer subset 120 . A participant who does not align with the designer's goal is led to examine his logic, facts and/or strength of his conviction through the question(s) and answers presented to him For example, if a participant suggests a solution to a problem which is not a step toward the desired solution or goal and/or which could potentially cause an ancillary problem or undesirable consequence(s), the participant may be asked if he considered a certain potential problem(s) or consequence(s) in choosing a solution. He may then be questioned on this opinion concerning the magnitude of the potential problem(s) and/or the probability of the potential problem(s) occurring and/or the cost of correcting the potential problem(s) or consequence(s). Multiple-choice answers offered to the participant may also cause the participant to consider such answers and the potential consequence(s) of a prior choice(s). A subsequent question(s) and its respective list of answers may ask whether potential or an actual problem(s) caused by his preferred solution (i.e. answer) is worse than the original problem. Thus, the participant is questioned concerning the unintended consequence(s) of his previous choice or answer and is helped to abandon short-sighted positions or to build upon knowledge he already has by following a line of reasoning to its logical conclusion. [0039] The designer's objective is to get the participant to adopt the designer's preferred position and abandon the participant's initial position if it is in conflict. Similarly, the sales technique of asking questions about the prospect's needs, asking whether particular features of a product meet those needs, and ultimately to obtain a purchase commitment (e.g., “Will that be cash or charge?”) can be automated by linking questions to answers given by the prospect, in a way that is special to the prospect. [0040] At a point during the participant's responses to the leading questions, when a particular chosen answer by the participant indicates that the participant has shifted his perception, opinion or understanding toward a particular key question or toward the Target Answer(s), the participant may be exposed to the closing question and answer subset 120 . Closing questions and answers may be displayed on the display in response to the answer signifying the participant's shift. The closing question and answer subset 120 tests whether the participant has abandoned his original conclusion, belief or opinion or learned a new concept, or whether the participant still has other reasons for objecting to or disagreeing with the designer's goal. Depending on the participant's answer(s) to question(s) in the closing question and answer subset, the participant may be routed to a previous key question where the participant may then choose a different answer from the list of multiple choice answers, and start on a “side-trip” or alternative series of question(s) and answers regarding the issue or concept, as described in additional detail below. [0041] After displaying one or more key closing questions and receiving an answer choice from the participant that is as close to the designer's objective as is acceptable to the designer, in a preferred embodiment, the display will present indicia thanking the participant for participating and may also include offers to join, purchase, be contacted, or whatever option the designer deems appropriate. These offers may vary, again, depending on the prior answer(s). The procedure is then completed 130 . [0042] The invention is sufficiently flexible that the participant's responses to the qualifying question and answer subsets 100 may fall within a predetermined response pattern indicating that the participant's opinion or position is such that the participant will be transferred to the closing question and answer subsets 120 (bypassing the leading question and answer subsets 110 ) or the process may be ended 130 . For example, the participant may be directed to the closing question and answer subsets when the participant's responses to the qualifying question and answer subsets indicates that the participant is already in agreement with the designer's Target Answer. [0043] Similarly, a participant's responses to the leading question and answer subsets may fall within a predetermined response pattern indicating that the participant's opinion or position is variable and the participant may be redirected to the qualifying question and answer subsets 100 or the process may be ended 130 . For example, the participant may be redirected to the qualifying question and answer subsets when the participant's responses to the leading question and answer subsets indicates that the participant has an inconsistent opinion, i.e., the participant responds to the leading question and answer subsets in a manner indicating that the participant's opinion concerning a topic or issue is changing or unsettled. [0044] Also, the designer's sequence(s) to certain of the question and answer subsets may be such that the designer has predetermined that at a certain point the participant should be routed to the closing question and answer subsets 120 or to the leading question and answer subsets 110 . For example, this may occur when the participant chooses the designer's preferred response to one or more “key” questions on a particular issue(s) and the participant is routed to the closing questions and answer subsets. Also if the participant provides an answer to one or more of the questions in the closing question and answer subsets which indicates he is not in agreement with the designer's goal, the participant may be routed back to the qualifying question and answer subsets or the leading question and answer subsets. [0045] It will be appreciated that all references to “questions” and “answers” herein could just as well be described as “prompts” and “responses” and to the extent that questions and answers are used, the participant may believe he is participating in a survey. However, though it is possible to keep the participants' answers as data, it is rather the process of being led to consider data and learn new concepts through the use of questions and answers that is the purpose for asking specific questions in a sequence order determined by both designer and participant interactively. [0046] In general, an attempt should be made to present all of the participants with an answer to each question in the displayed multiple-choice format with which the participant can agree. Preferably, questions are phased in a neutral manner. It may, however, be useful at times to display non-neutral questions, but offer in the list of possible answers an answer that states that the participant believes the question is manipulative, biased and/or not relevant. Sufficiently often to prevent frustration, the participant may be offered an answer which allows him to abandon the line of reasoning and be offered the next “key” question or alternate line of reasoning which is not dependent on having obtained his agreement with or understanding of the prior “key” question, issue or concept. A determinedly disagreeable participant may get through the questions as quickly as an agreeable one. Participants who are open to examining an issue or concept without a preconceived opinion or position, may take a circuitous route, answering most questions inconsistently and/or frequently changing their minds. [0047] In another preferred embodiment, an answer to one or more of the questions may be to contact the designer to suggest another answer. This allows the designer to consider these answers for addition along with any counter-arguments (in the form of additional question and answer subsets which may be created) and helps prevent frustrating the participant. When such an option is chosen, the participant may also be invited to return and choose a second answer or be asked another question returning to the leading question and answer subsets 110 (or one of the other question and answer subsets) at an appropriate point. In another preferred embodiment, the ability to “go back,” or “undo” a previous answer(s) may be included, as at times participants may desire to reconsider an answer (e.g., when more than one is agreeable or when the participant simply changes his mind, etc.) Though it may appear to the participant that he is changing his answer to a survey, the purpose of allowing a changed answer is to present a different follow-up question(s) to the participant. [0048] In still another embodiment of the invention two or more answers to a question may elicit the same next question. This would occur when the designer decides that more than one answer leads logically to the same next question, or because the real purpose of the question is to get the participant to consider the alternate answers or the data contained in them. For example, if, after having determined that a participant has an unyielding opinion regarding the proper political solution to a problem, the designer wishes to demonstrate to the participant that as strongly as he might prefer that solution, he does not have a strong enough majority to prevail, the alternate solutions he rejects serve to make the point that there is little or no consensus. [0049] The next question may ask about the likelihood of reaching consensus to test whether the point has been understood and, if it has, the next question may offer a compromise solution. [0050] There may be other instances where, regardless of which answer is chosen, the same next question may be presented. In this way, new ideas may be suggested in the answers presented and, regardless of which answer is chosen, one question may be presented as the follow-up to two or more of the multiple choice answers presented. Similarly, ideas, facts or information may be contained in the displayed answers to a question instead of set forth in the question. In this way, the participant may reject the information if he chooses (e.g., if he thinks it is biased) and choose an answer with which he agrees. A different participant may choose differently. Each participant would then follow a different course in the structured question and answer subsets. [0051] Generally, it is preferable to not attempt to force agreement. The participant, if he feels he is being compelled or forced to accept a particular opinion or position, may react negatively and he may perceive his prior opinion or position strengthened. Additionally, the participant may cease participating thus eliminating the opportunity of potentially changing the participant's opinion or position. [0052] Questions may also be implied, as when a sentence is started, and the multiple choice “answers” consist of phrases completing the sentence. Alternatively, the question may not directly set forth an answer, but the multiple choice responses may comprise one or more comments or responses, which do not directly answer the question. [0053] Also, questions and answers are not limited to text. Pictures, video clips or animation may be used. For example, a participant who has stated that handguns should be banned for the safety of the population might be asked the question “Which one of these people would probably win if they fought?” followed by a picture of a large threatening man and another picture of a little old lady. The participant may then pick one. Regardless of which one he picks, the next leading question presented is “Which one of these people would probably win if they fought?” Following the question may be a picture of a little old lady, and another picture of a little old lady holding a baseball bat. The participant then picks one. [0054] Regardless of which one he picks, the next leading question, for example, presented is: “Which of these two people would probably win if they fought?” Two pictures may, for example, then presented: One of a large threatening man holding a bat, and one of a little old lady pointing a handgun, plus a third answer may be presented in text form such as: “Stop trying to manipulate me; I still don't believe little old ladies should have guns.” Such a sequence illustrates a question and answer subset directed toward the designer's target goal of increasing support for relaxing handgun restrictions for self-defense using pictures. [0055] Pictures used in either questions or answers may be animated or moving pictures such as video clips, with or without audio. A “virtual” person representing a sales person, teacher, counselor or guide could be created to present each question using such a technique. [0056] As explained above, questions and answers may be presented to the participant audibly through the use of technologies such as speech recognition technologies and the like and a participant's answers may be recognized either by traditional response technologies such as a keyboard, computer, mouse, etc. or the participant verbally responds and the response may be may be accepted and utilized in the invention by means of voice recognition technology known by those having ordinary skill in the art. Likewise, an individual may act as intermediary such that a participant may respond to questions by telephone, where the questions are read to him by another individual who also inputs his responses into a computer, calling up the next question to be read. [0057] Referring now to FIG. 2 , there is shown therein a memory media 210 on which is stored a master question and answer set 220 . The memory media 210 and the master question and answer set 220 are able to communicate with the computer 230 by means of communications channel 240 . The communications channel 240 is of the type well known to those having ordinary skill in the art and may be cables, fiber optics, or any other type of communications channel, which is capable of transmitting digital or analog signals. [0058] A computer 230 is operably connected to one end of a communications link 250 . The communications link 250 may be a type of communications channel including but not limited to cables, local area network, the Internet, or any other apparatus or hardware, either individually or combined, which is capable of transferring digital or analog signals. Another end of the communications link 250 is operably connected to a display device 260 and an answering device 270 . The display device 260 could be any type of display including but not limited to a computer monitor, liquid crystal display (“LCD”), touch screen monitor, plasma screen, etc. The answering device may be any type of hardware which is capable of taking input from a user and converting it to digital signals to be sent to a computer or other type of digital processor. Such answering devices include but are not limited to computer keyboards, touch screens, computer mouse, cellular telephone or other type of telecommunications device and the like. Technologies such as speech recognition apparatus may also be utilized as answering devices. [0059] The communications link is such that information may be sent from the computer 230 to the display device 260 and, similarly, signals from the answering device 270 may be sent to the computer 230 . [0060] Located within the computer or the memory media is an operating program which coordinates the presentation of questions and related answers on the display device as described herein. [0061] Any software or hardware may be used which allows questions to be stored and presented in response to responses by the user. Question and answer subsets may be stored in a database as individual records or placed, for example, on web pages together with other data. One preferred embodiment of the invention is to use HTML and make every question an “anchor” (i.e. unique location), and each answer in its subset of answers a “hyperlink” to (bring up on the display in response to a chosen answer) the next question and its respective subset of answers thereto. Any data collected for use in generating subsequent questions or answers can be stored in the form of “cookies” or otherwise, in a manner well known to those having ordinary skill in the art. [0062] It is not necessary to collect or save data given by the participant in response to questions, as in a survey. However, data may be collected and used to further customize the presentation of subsequent questions or answers by, for example, referring to the participant by name, referencing what type of pet they have in a later hypothetical question, or by the use of if/then logic in the program determining what questions to present. Further, programming could be used to generate custom questions or answers based on the data collected. [0063] Next, referring to FIG. 3 , there is shown therein a random leading question N 310 . The leading question N 310 has associated with it answer 1 N 315 ; answer 2 N 317 , answer 3 N 319 , answer 4 N 321 , and answer 5 N 323 . It will be appreciated by those having ordinary skill in the art that the leading question N 310 may have associated with it more or less than 5 possible answers in the invention. Five potential answers are displayed in FIG. 3 for illustrative purposes only. As described in detail herein, leading question N 310 is presented to the participant along with answer 1 N 315 , answer 2 N 315 , answer 3 N, 319 , answer 4 N 321 and answer 5 N 323 . The participant then chooses which of answers 1 N through 5 N, inclusive, that he prefers. [0064] Each of answers 1 N through 5 N has associated with it a leading question. In this illustration, answer 1 N has associated with it leading question P 325 . Similarly, answer 2 N ( 317 ) has associated with it leading question Q ( 327 ). Answers 3 N, 4 N and 5 N ( 319 , 321 and 323 ) have associated with them leading questions R, S and T ( 329 , 331 , and 333 respectively). [0065] Additionally, each of the leading questions P, Q, R, S and T ( 325 , 327 , 329 , 331 , and 333 ) has associated with it an answer subset. In the illustration, leading question P has associated with it answer P 1 , answer P 2 , answer P 3 , answer P 4 and answer P 5 ( 335 , 337 , 339 , 341 and 343 , respectively). In the invention, if answer 1 N ( 315 ) is chosen by the participant then the next question presented to the participant is leading question P ( 325 ) along with its answer subset P 1 through P 5 ( 335 , 337 , 339 , 341 and 343 , respectively). Similarly, leading question Q ( 327 ) has associated with it a predetermined set of answers: answer Q 1 ( 345 ), answer Q 2 ( 347 ) answer Q 3 ( 349 ), answer Q 4 ( 351 ) and answer Q 5 ( 353 ). If the participant chooses answer 2 N ( 317 ) then the next question presented to the participant is leading question Q ( 327 ) along with the set of answers associated with leading question Q, that is, answers Q 1 through Q 5 ( 345 , 347 , 349 , 351 and 353 ), respectively. [0066] Each of the other answers 3 N, 4 N and 5 N ( 319 , 321 and 323 ) has associated with it leading questions R, S and T ( 329 , 331 and 333 ), respectively. Each of the leading questions R, S and T has with it a particular answer subset as described herein. The aforesaid question and answer subsets reside in memory such as media 210 . It will be appreciated that any type of memory such as a computer hard drive, read only memory (ROM) or any other type of machine readable memory may be utilized. [0067] Next, referring to FIG. 4 , there is illustrated therein in schematic form two question and answer subsets with a plurality of answers leading to the same subsequent question. Q J is a question having associated answers A J,1 , A J,2 , through A J,e , ( 415 , 420 and 425 , respectively.) It is important to realize that the number of answers presented to Q J ( 410 ) need not be any specific number in the invention. For illustrative purposes only, the number of answers associated with the question Q J is e in the illustration. A J,e ( 425 ) may be the answer desired by the designer. Similarly, question Q K ( 430 ) has associated with it answers A K,1 , A K,2 through A K,f ( 435 , 440 and 445 , respectively). In the illustration, question Q K ( 430 ) has associated with it f multiple choice answers. In the illustration, A K,f ( 445 ) has been predetermined to be the desired answer. [0068] In the illustration, A J,1 and A J,2 415 , 420 if chosen by the participant, indicate that there is no concurrence and the invention provides that the participant will be asked another leading question at step 450 . In the illustration, the next leading question based upon the answer chosen by the participant is question Q L 455 , which also has a predetermined set of answers associated with it, A L,1 , A L,2 , . . . , A L,g , Similarly, if the participant chooses answer A K,1 or A K,2 to question Q K , such answers indicate that there is no concurrence by participant and at step 450 the determination is made to ask the participant another leading question. The next question is Q L 455 . [0069] If the participant chooses answer k J,e to Q J or answer A K,f to question Q K the answer indicates concurrence. The invention recognizes this and begins to present to the participant closing questions and answer subsets at step 460 . [0070] By way of example and not by way of limitation, applicant sets forth below an example. The example, regarding a local government issue, demonstrates how a participant may respond to questions and the choosing of subsequent questions by use of the invention. In the example below, the answers chosen by the participant to each of the questions is indicated by underlining. For brevity, qualifying questions and answers have been omitted. However, those having ordinary skill in the art will appreciate that such qualifying question and answer subsets may be utilized. [0071] The objective in the example is to get the participant to agree that an existing utility tax is too high, is not fair, is not well spent, or actually hurts some people or themselves. Agreement with the “key questions,” are steps toward having the participant agree to vote to lower the tax, the Target Answer. (Studies indicate that a strong agreement with any one of these key questions is sufficient to get support.) An additional objective is to have the participant feel negatively toward the opponents of a utility tax decrease. Another goal is to have the participant's values validated when it concurs with the designer's objectives. Ancillary to getting the Target Answer (a “yes” vote) is obtaining other types of support for the ballot measure. [0072] The exemplary questions and answers follow: [0073] 1. Voters in the City are about to decide whether to set utility taxes at the average rate collected by nearby cities of similar size. This will save money for users of gas, electricity, water, telephone and video services, because the City now has the highest rate of tax of any city in California. What do you think? I will probably vote “yes.” I will probably vote “no.” I probably won't vote. I need more information. [0078] 2. Which statement is true? City Council members, City employees, their unions and others predicting disaster if this passes: Are telling the truth. Are genuinely worried about the consequences and may be exaggerating to influence voters, but they may also be partly right. Would say anything to make sure they can keep collecting as much money from me as they can. [0082] 3. Suppose we vote “yes” for an average tax. The City budget will go back to 1995 levels. What's the worst that could happen? City officials could actually cut the most basic and popular services such as emergency response and street repair. City officials could actually cut things no one will miss or that can easily be provided voluntarily by others. City officials could resign in protest. In 1995 the City was a fine place to live. I'd be happy with the budget we had then. Revenues will soon creep up again. [0088] 4. When your utility rates go up, you have to pay more tax. The City gets to spend it, even though they weren't expecting it and it wasn't in the budget. Is this fair? No, but it's not a big deal to me. No. They should reduce the tax when prices spike up. It's not about “fair.” Taxes aren't earned anyway; they're taken for a good cause. [0092] Note: Because fairness is a key consideration, even if the participant answers that this tax is not fair, the issue is further explored, and all answers lead to the next question, i.e., all responses to question number 4 are followed by question number 5: 5. If you needed to, how could you compensate for higher utility costs? Vote “yes” to lower the tax. Eat out more often. Take my clothes to a Laundromat. Change the thermostat. Skip the Christmas lights. Buy more energy-efficient appliances. Move to almost any other city in California where the tax is lower or non-existing. [0101] Note: Either of the two answers underlined above produce the same next question, i.e., question number 6: [0102] 6. Unless they leave the City, everyone in it will be affected by reducing the utility tax to average. Which group(s) below are you most concerned will be hurt by the loss of revenue for the City? Families with children Condominium/Apartment owners/renters People with medical needs People with low incomes Seniors Landowners/homeowners Employees of the City [0110] Note: Each of the above answers leads to questions based upon concrete examples. For example, choosing the answer “Families with children” or “People with low incomes” may lead to the next question (question number 7). [0111] 7. Jane Jones is a single mom with a low income. She is forced to pay for low-cost lunches for seniors, even though seniors are the wealthiest segment of the population. Is that fair? Life isn't fair. Taxes aren't fair, but we have to have them. I support a City utility tax of 11%. Sometimes people need help and who will do it if the government doesn't? Maybe generous donors will help those less fortunate, but there are still other groups I worry will be hurt by cuts to city revenue. Okay. Maybe the tax is too high to be fair to everyone. [0116] 8. Who do you think is most successful at getting what they need from City officials? Fire/police Downtown Business Association/Chamber of Commerce members Individual non-union employees Major employers Service clubs/organizations such as Friends of the Dog Park Federal or State government Average individual citizen [0124] Note: In this example, all of the answers above lead to the next question (question number 9). [0125] 9. If you had a pet project you were passionate about, and you had lots of well-organized supporters, what would you prefer to do? Go to the City and submit to their requirements and approval process in order to get some of our money back for the project Skip the City approval process by raising the money among my well-organized supporters from their utility tax savings or other sources. [0128] 10. Which of the following would you be willing to do in order to save on your utility tax? Vote to lower it. Nothing. I don't want to save. Send the kids to grandma's or call Mom collect. Install a wind-turbine or get an antenna for my televisions. Bathe less often Wait for the City Council to lower it. [0135] 11. Suppose this tax reduction goes too far and cuts programs and services too much. What can we do? Raise it, again. Wait for revenues to catch up. Raise it, but I'm worried we can't do it fast enough. Note: Each of the two underlined answers leads to question number 12, which is the Target Question: [0139] 12. If the vote to set the City utility tax at the average of nearby similar-size cities was held today, how would you vote? Yes. No. I still don't know. I can't vote in the City, but if I could it would be “yes.” I can't vote in City, but if I could it would be “no.” [0145] Note: “Yes” is the Target Answer. The Target Answer leads to question number 13. [0146] 13. Thank you for exploring the City Utility Tax website. Please remember to vote “yes” on Apr. 13, 2004. [0147] The remainder of the “map” is filled in with alternate routes that can be taken when a participant does not choose the direct route (i.e., the answer most in alignment with the designer's Target Answer(s)). The “map” is usually not two-dimensional but multi-dimensional. The map remains invisible to the participant who experiences each question and multiple-choice answer subset as if at a crossroads with a choice of directions to take, not knowing where any of them lead, or that many answers may take different routes to the same destination (i.e. the goal). [0148] The following is an example of a side-trip or exploration which leads from one “key” question to the next “key” question: [0149] 1. Voters in the City are about to decide whether to set utility taxes at the average rate collected by nearby cities of similar size. This will save money for users of gas, electricity, water, telephone, and video services because the City now has the highest rate of tax of any city in California. What do you think? I will probably vote “yes.” I will probably vote “no.” I probably won't vote. I need more information. [0154] The above underlined choice leads to the following question and answer subset: [0155] 2. Why won't you vote? I'm not eligible to vote. I'm not registered to vote. I don't care what happens. I don't think my vote counts. I hate politics. Voting only encourages politicians. [0161] Note: Each of the above underlined choices leads to the following question and answer subset: [0162] 3. Suppose you could wave a magic wand and implement the measure to make the utility tax in the City average. Would you? Yes, I would make the utility tax average. No, I would keep it at 11% [0165] The following is another example of a side trip or exploration. [0166] 1. If you needed to, how could you compensate for higher utility costs? Vote “yes” to lower the tax. Eat out more often. Take my clothes to a Laundromat. Change the thermostat. Skip the Christmas lights. Buy more energy-efficient appliances. Move to almost any other city in California where the tax is lower or non-existing. [0174] 2. If you eat at a restaurant in the City, whose money pays for the restaurant's utility tax? Mine, and that's fair Mine, and that's not fair My boyfriend's. [0178] Any time a participant chooses a potential solution to a problem which causes a problem(s) of its own, the participant may be asked what the problem(s) might be, and then if it is worse than the original problem, and further, how likely that his potential solution will ever be applied. Similarly, if a participant seeks a certain benefit, he can be asked if certain features (e.g., of a product, service, membership, etc.) would help provide that benefit, and then whether those features remove his objection. [0179] Another potential concern arises when questions with potentially many preferred answers. These can keep looping back until the participant decides to continue. The following is an example of this looping technique: [0180] 1. What is your main concern? I'm afraid if it passes, my favorite programs and services will be hurt. I just don't feel that taking money from the City (and their employees) is very nice. They need the money. I'm afraid they'll find out I (we) voted for it and be angry with me. What if they raise other taxes and fees? [0185] 2. Select a favorite program or service: Schools Independence Day Fireworks Public Library Emergency response (Fire/Police) I'd like to go back and pick different reason for voting against an average tax. What you say here about my favorite programs and services has not convinced me to vote “yes” to make our utility taxes average. But I keep hearing bad things will happen. Are they lying? [0193] 3. Good News! Utility taxes don't pay for schools; they have separate funding. Better News! Reducing the utility tax to average will save City private schools, homeschoolers, teachers and employees who live in the City money. Okay, I might vote “yes” or just stay out of it. I'd like to pick a different program or service that concerns me. No matter what you say about my favorite programs or services, I think they may be hurt, and I'm still against making our utility taxes average. What about the claims of people who are against it? Are they lying? I'm not interested in most of these programs or services. [0199] 4. Select a favorite program or service: Schools Independence Day Fireworks Public Library Emergency response (Fire/Police) I'd like to go back and pick different reason for voting against an average tax. What you say here about my favorite programs and services has not convinced me to vote “yes” to make our utility taxes average. [0206] 5. Good News! The public library is run by Los Angeles County from an entirely different budget. By reducing the utility tax to average, library patrons will save money, too. Okay. I might vote “yes” or just stay out of it. I'd like to pick a different program or service that concerns me. No matter what you say about my favorite programs or services, I think they may be hurt, and I′m still against making our utility taxes average. What about the people who are against it. Are they lying? I'm not interested in most of these programs or services. [0212] 6. Select a favorite program or service: Schools Independence Day Fireworks Public Library Emergency response (Fire/Police I'd like to go back and pick different reason for voting against an average tax. What you say here about my favorite programs and services has not convinced me to vote “yes” to make our utility taxes average. But I keep hearing bad things will happen. Are they lying? [0220] 7. What is your main concern? I'm afraid if it passes, my favorite programs and services will be hurt. I just don't feel that taking money from the City (and their employees) is very nice. They need the money. I'm afraid they'll find out I (we) voted for it and be angry with me. What if they raise other taxes and fees? [0225] 8. A “yes” vote on this measure will not take one single penny from the City. [0226] Instead, it reduces the amount of money the City takes every month from you. You know what I mean: they're counting on being able to get that money from us to pay for programs and services. I'm a City employee or contractor. I need the money. I know a City employee or contractor. They need the money. It's my duty. [0231] Note: Each of the above-indicated underlined choices leads to the same question (in this example the following question): [0232] 9. Why would the City Council place the employee's or contractor's job in jeopardy? Their work is not necessary. They aren't worth what they're paid They do a great job and their services are necessary, but if the City loses tax revenue, they'll be cut, anyway. [0236] All of the choices above, lead to the following question: [0237] 10. Which statement is true? City Council members, City employees, their unions and others predicting disaster if this passes: Are telling the truth. Are genuinely worried about the consequences and may be exaggerating to influence voters, but they may also be partly right Would say anything to make sure they can keep collecting as much money from me as they can. Examples of Closing Questions [0241] At any point during the preceding examples that the designer has predetermined that a particular answer indicates that the participant has shifted his opinion or understanding toward a particular “key” question or toward the Target Answer(s), closing questions may be asked. The closing questions test whether the participant has abandoned his original opinion or understanding (or learned a new concept), or whether the participant still has other reasons for resisting the Target Answer(s). Depending on his answers, the “map” may send him back to a previous “key” question where the participant may choose a different answer from his previous answer, or start him on a “side-trip” or series of questions regarding the issue or concept. [0242] The ultimate sequence of the closing questions in a preferred embodiment includes a “Thank you” message and may be followed by offers to join, purchase, be contacted, or sent a certificate, or whatever the designer deems appropriate. Note that these offers may vary, again, depending on the prior answer(s). Set forth below is an example of closing questions. [0243] 1. Will you vote “yes” on Measure U? Yes No I don't know I can't vote [0248] 2. Thank you for exploring the City Utility Tax website. Please remember to vote “yes” on Apr. 13, 2004. Would you be willing to: Donate funds toward a mailing encouraging a “Yes” vote? Donate funds toward printing signs supporting the tax reduction? Put a sign in your front yard? None of the above, but I will vote “Yes.” [0253] The participant may then be presented with the appropriate contact information on the display in response to his answer to question number 2. [0254] In an alternative embodiment, one answer for a plurality of the questions may be to contact the designer and suggest an answer other than the multiple choice answers provided. This allows the designer to consider these answers for addition along with any counter-arguments (in the form of questions and answers) and helps prevent frustrating the participant. When such an option is chosen, the participant may be invited, also, to return and choose another answer or be asked another question returning to the “map” at another appropriate point. [0255] The ability to “go back” is utilized in another preferred embodiment. This allows the participant to reconsider an answer. It is also possible that more than one answer may be agreeable and a different follow-up question may be presented to the participant. [0256] As discussed and illustrated above, it is also possible that all answers (or less than all answers) to a question may elicit the same next question since sometimes the point the designer wishes to make is taught by the juxtaposition of the answers. Often, regardless of the answer chosen, the next question may be relevant. Also, ideas, facts and information may be contained in the answers presented instead of trying to put the information into the question. A participant may reject the information if he desires (e.g., if he thinks it is biased). Agreement should not be forced upon the participant. [0257] Questions may also be implied, as when a sentence is started, and the “answers” consists of choosing one of the presented alternatives to finish it. Also, answers may be responses to the question which do not answer the question (e.g., a comment or question). [0258] Software or hardware may be used which allows questions to be stored and presented in response to input by the participant. Question and answer subsets may be stored in a database as individual records or placed on web pages together with other subsets. Question or answers may also be generated by software combining generic questions or answers with data provided earlier by the participant, or by using the data provided to determine how questions or answers are selected. One preferred embodiment to implement the invention on the Internet (or a computer network) is to use Hyper Text Markup Language code (“HTML”) and make every question an “anchor” (unique location) and every answer a “hyperlink” to (bringing up on the screen) the next question and answer subset. [0259] While the invention has been described by way of example and in terms of the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. To the contrary, it is intended to cover various modifications and similar arrangements (as would be apparent to those skilled in the art). Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.
A method and apparatus for influencing a person to develop, accept and/or understand a concept, position or idea using questioning, including a technique sometimes known as the Socratic Method. A universe of question and answer subsets comprising questions and respective multiple choice answers to each question designed in advance, arranged and inter-connected on a stand-alone computer, a computer on a local area network or computer network, or any computer network and displayed in such a way as to allow the participant to follow the individual's own path by selecting answers he accepts, which tend to logically lead the individual toward agreement and or understanding on the subject.
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BACKGROUND In a medical setting, sensor devices physically attached to a patient are used to monitor the vital signs of a patient. Vital signs that are commonly monitored include blood pressure, temperature, heart rate, oxygen saturation, etc. Medical information obtained from these sensor devices is typically transferred to a patient monitor device, where the information can be processed and displayed. Medical information transferred between devices typically contains large, high-integrity, highly-defined packets that require a certain level of processing. The packets are typically sent and received through several layers of buffers, each building around the previous. Some medical devices, for example handheld and wireless medical devices, have small processors and typically do not have the processing power required to do extensive packet processing. SUMMARY Embodiments of the disclosure are directed to systems and methods for processing medical information transferred to and from medical devices physically attached to a patient. In one aspect, a method of communicating information from a host computer to a sensor device includes: receiving a data stream from the host computer, the data stream including a plurality of bytes, one or more bytes of the plurality of bytes being associated with obtaining medical related information, one or more of the one or more bytes associated with obtaining medical related information including one or more named fields; parsing one or more bytes in the data stream at the sensor device; as a result of parsing the one or more bytes, identifying a type of medical related information; obtaining the medical related information from the sensor device, the medical related information being obtained using the one or more named fields, the one or more named fields determining a format of the medical related information; and sending the medical related information to the host computer; wherein the parsing of the one or more bytes in the data stream is performed using a single pass through the data stream, one or more data validity checks being performed during the single pass, the medical related information being obtained after the data stream is parsed in the single pass through the data stream. In another aspect, a first computing device comprises a processing unit and system memory, the memory of the first computing device including instructions that, when executed by the processing unit cause the first computing device to receive a data stream that includes a plurality of bytes, one or more bytes of the plurality of bytes being associated with obtaining medical related information, one or more of the one or more bytes associated with obtaining medical related information including one or more named fields, parse each byte of the data stream serially, identify metadata relating to actionable data in the data stream, use the metadata to determine where to store the actionable data on the first computing device, after each byte of actionable data is parsed, store the parsed byte of actionable data in a buffer memory on the first computing device, the parsed byte of actionable data being stored in the location of buffer memory indicated by the metadata, use the actionable data in the buffer memory to obtain medical device information at the first computing device, the medical device information being obtained via a sensor included on the first computing device, the medical device information being obtained using the one or more named fields, the one or more named fields determining a format of the medical related information. The actionable data is obtained as a result of a single pass through the data stream received at the first computing device. In yet another aspect, a computer-readable storage medium comprises instructions that, when executed by a computing device, cause the computing device to: receive a data stream that includes a request for medical device information; use actionable data in the data stream, obtain the requested medical device information at the computing device; serialize the obtained medical device information; and send the serialized medical device information to a host computer. The details of one or more techniques are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of these techniques will be apparent from the description, drawings, and claims. DESCRIPTION OF THE DRAWINGS FIG. 1 shows an example system that includes a small footprint medical sensor device and a patient monitor. FIG. 2 shows example modules of an example small footprint medical sensor device of FIG. 1 . FIG. 3 shows an example architecture of a small footprint medical sensor device that includes the modules of FIG. 2 . FIG. 4 shows an example structure of a data packet used in transmitting medical information. FIG. 5 shows example data formats for the envelope, message and object shown in FIG. 4 . FIGS. 6 , 7 and 8 show a flow chart of a method for processing a data packet that includes medical device information. FIGS. 9 , 10 and 11 show an example method for deserializing metadata in an object. FIGS. 12 , 13 and 14 show an example method for serializing metadata obtained from a medical sensor device. DETAILED DESCRIPTION The present disclosure is directed to systems and methods for processing medical information transferred to and from medical devices physically attached to a patient. In some examples, the medical information is processed on a byte-by-byte basis without extensive buffer processing and without the use of an operating system. The systems and methods provide a streamlined, small-footprint approach to processing medical device information. The systems and methods implement a small-footprint communication protocol, also known as a communications stack. Each medical device includes a processor that implements a state-based software program used to process the medical information. The medical information is included in packets of data received by and sent from each medical device. For each packet of data, the software program categorizes the data into structure, integrity and actionable data. The software program parses each byte of data to determine the structure of the data and to organize storage for the actionable data. Actionable data is data that the software program can use to obtain the medical information. Actionable data includes commands and parameters associated with commands. An example command is TEMP. An example parameter is degrees Fahrenheit (° F.). Bytes that involve actionable data are stored until the complete packet is parsed and the integrity of all bytes in the packet are verified. The actionable data typically includes a command issued from a host computer. For example, the host computer may request a temperature reading from a patient. Application software included on the medical device processes the actionable data, obtains the requested information, for example the temperature of the patient, from the medical device and sends a response with the requested information back to the host computer. The software program processes the packet data using a single pass over the packet data in which each byte of packet data is processed serially. Using a single pass provides speed advantages over software protocol parsers that copy the entire packet into a buffer and make several passes over the buffer in order to process elements in the packet data. The use of a single pass reduces processing latency. It is also possible for the medical device to receive a second data packet at the same time as a first data packet is being processed. FIG. 1 shows an example system 100 that implements a small-footprint method of processing medical device information. FIG. 1 shows a plurality of example medical sensor devices 102 , 104 , 106 , 108 physically attached to a patient 101 . In example system 100 , device 102 is an ECG sensor used to measure heart function as part of during an electrocardiogram, device 104 is a blood pressure sensor, device 106 is an SPO 2 sensor that measures oxygen saturation and device 108 is a thermometer that measures the temperature of the patient. Alternatively, device 108 may be a temperature sensor that is attached to the patient, for example to an ear. For the purposes of this disclosure, device 108 is considered to be a temperature sensor. Other medical devices are possible. Also shown in FIG. 1 is an example patient monitor 110 that receives medical information from devices 102 , 104 , 106 , 108 processes the medical information and displays the medical information. The example patient monitor 110 also sends request for medical information to devices 102 , 104 , 106 , 108 . The patient monitor 110 is a computing device. For the purposes of this disclosure, the patient monitor 110 is considered to be a host computer. In this disclosure patient monitor 110 and host computer 110 are used interchangeably. The medical sensor devices 102 , 104 , 106 , 108 may be physically attached to patient monitor 110 , typically via a USB connection to patient monitor 110 or the medical sensor devices may be attached to patient monitor 110 via a wireless connection. An example wireless connection is one that uses Bluetooth wireless technology. In example system 100 , blood patient monitor 104 is physically attached to patient monitor 110 and ECG sensor 102 , SPO 2 sensor 106 and temperature sensor 108 are connected to patient monitor 110 using Bluetooth. FIG. 2 shows example modules included in blood pressure monitor device 104 . These same example modules are also included in example ECG sensor device 102 , SPO 2 sensor device 106 and temperature sensor 108 . The example device 104 includes a processor 202 , system memory 204 , metadata storage ROM 206 , physical interface module 208 , stream processing module 210 and application module 212 . The processor 202 is a computing device that includes instructions for processing data received from and sent to host computer 110 and instructions for processing medical device information on device 104 . The system memory 204 may be volatile (such as RAM), non-volatile (such as ROM, flash memory, etc.) or some combination of the two. However, because data is processed on device 104 in a simplified manner, one-byte at a time, because actionable is moved directly from an incoming data stream to a single static buffer and because actionable data is organized as it arrives so that dynamic memory allocation is not needed, an operating system is not required and system memory 204 does not typically require an operating system. The system memory also includes one or more software applications for processing requests for medical device information and may include program data. The processor 202 and system memory 204 are typically part of a microcontroller included in device 104 , wherein the system memory 204 is internal memory on the microcontroller. A typical medical sensor device 102 , 104 , 106 , 108 ranges from 0.014 to 0.06 square inches in size. The example system memory 204 includes a read only memory (ROM) 206 that stores metadata. The metadata stored in metadata storage ROM 206 is used to process data received from and sent to host computer 110 . The metadata is generated once by an application program, typically run on a personal computer, based on a hardware abstraction of the sensor device being used, for example sensor device 102 , 104 , 106 , 108 , etc. The metadata generated by the application program is stored in metadata storage ROM 206 on the sensor device being used, for example sensor device 104 . Data is received from host computer 110 in a serial data stream. The metadata stored in metadata storage ROM 206 facilitates the deserialization of incoming data in the data stream and the serialization of outgoing data. The metadata is typically stored in a C programming language structure that includes version and type information, information about static and dynamic variables in the data stream and information about any objects in the data stream. The metadata describes how to move data from the stream to the C structure and back. The objects include fields that identify the type and structure of medical information to be obtained from sensor device 104 . Example objects include structure for medical information to be obtained, such as temperature, blood pressure, etc. A separate object is used for each type of medical information. Other example objects include patient identification, clinician identification and time and date information. The example physical interface module 208 provides a physical interface that receives messages from host computer 110 and that sends responses to host computer 110 . The messages are in the form of packets that include an envelope, a message and optionally one or more objects with medical device information. The example stream processing module 210 processes the incoming and outgoing packets, deserializing information in the incoming packets and serializing information in the outgoing packets. Using metadata provided by metadata storage ROM 206 , the stream processing module 210 writes actionable data included in the incoming packet into buffer memory area on sensor device 104 . The example application module 212 processes actionable data included in the incoming packet and obtains medical information from a sensor device. For example, for sensor device 104 , the application module 212 initiates a blood pressure cuff inflation process and obtains blood pressure readings from sensor device 104 . For sensor device 108 , the application module 212 obtains temperature readings from sensor device 108 . FIG. 3 shows modules used in an example architecture for blood pressure monitor sensor device 104 . These same example modules are also included in example ECG sensor device 102 , SPO 2 sensor device 106 and temperature sensor 108 . The example sensor device 104 includes a physical interface module 208 , input parser module 302 , metadata deserialization module 304 , application module 208 , metadata serialization module 306 and output function module 308 . The example input parser module 302 , metadata serialization module 304 , metadata serialization module 306 and output function module 308 are part of the example stream processing module 210 . The example physical interface module 208 includes circuitry to send and receive packet data. Packet data is typically received from patient monitor 110 when patient monitor 110 requests an update of sensor data, for example when patient monitor 110 requests a blood pressure reading. Packet data is sent from sensor device 104 when sensor device 104 obtains a blood pressure reading on patient 101 and sends the obtained blood pressure reading to patient monitor 110 . Once a request for a blood pressure reading is received by sensor device 104 , sensor device 104 may send a plurality of blood pressure readings to patient monitor 110 so that the progress of the blood pressure reading is displayed. The physical interface module 208 implements I/O commands such as data stream reads, data stream writes, and data stream flushing. A data stream comprises a string of bytes read from or written to the packet data. A data stream flush is accomplished at the end of every complete message. The example input parser module 302 parses the input stream of packet data sent from example patient monitor 110 . One byte is parsed at a time. The packet data conforms to a medical device communication protocol that defines the format of data within the packet. The packet includes header fields that specify the meaning of bytes that follow in the packet, that specify the size and structure of actionable data bytes in the packet and that specify the point at which the actionable data bytes start in the packet. The packet also includes the actionable data bytes. In the input stream of packet data, the actionable data bytes represent a command sent from the example patient monitor 110 for patient information. For example, the actionable data bytes may includes a string of bytes requesting the blood pressure of patient 101 from sensor device 104 . As another example, the actionable data bytes may include a string of bytes requesting the temperature of the patient in degrees Fahrenheit. Temperature sensor 108 provides the temperature of the patient. The specific details of how the input parser module parses data in the input stream is discussed later on in this specification. The example metadata deserialization module 304 receives each byte of actionable data, stores each byte in a data buffer and performs a data integrity check, typically a CRC (cyclic redundancy check) calculation on the data. The metadata deserialization module 304 uses data type flags obtained from metadata stored by metadata storage ROM 206 to determine the structure of the actionable data. The specific details of how this is accomplished are discussed later on in this specification. The example application module 212 implements the action specified by the actionable data stored. For example, if the action specified is to obtain a blood pressure reading from patient 101 , the application module 212 initiates a blood pressure read operation and monitors the example blood pressure sensor device 104 for blood pressure readings. A blood pressure read operation includes pressuring and then depressurizing a blood pressure cuff on the arm of the patient. As the cuff inflates, the application module 212 obtains blood pressure readings from sensor device 104 . At a predetermined sampling time, the application module 212 sends each obtained blood pressure reading to the example metadata serialization module 306 so that the blood pressure reading can be sent to patient monitor 110 and displayed. When the blood pressure operation is completed, the application module 212 calculates the systolic and the diastolic blood pressure for the patient and sends bytes corresponding to the systolic and diastolic blood pressure to the metadata serialization module 306 . The example metadata serialization module 306 receives one or bytes of data from the application module and serializes this data so that it can be returned to example patient monitor 110 . For example, during a blood pressure measurement operation, bytes corresponding to each sample of blood pressure readings are serialized. Similarly, at the completion of the blood pressure measurement operation, bytes corresponding to the systolic and diastolic blood pressure of the patient are serialized. The specific details of how serialization is accomplished are discussed later on in this disclosure. The example output function module 308 receives data bytes from the application module 212 corresponding to operation performed, for example the results of a blood pressure reading and incorporates the received data bytes into an output packet. The output function module 308 provides an envelope for the received data and includes the required format expected by the patient monitor 110 . When the output packet is completed, the output function module 308 sends the output packet to the physical interface module 208 . The physical interface module 208 sends the output packet to patient monitor 110 . FIG. 4 shows the structure of an example packet 400 of input data that is consistent with the medical device communication protocol discussed in this disclosure. FIG. 4 shows that each packet includes three sections, an envelope section 402 , a message section 404 and an object section 406 . In addition, a CRC 408 is included at the end of object section 406 , a CRC 410 is included at the end of message section 404 and a CRC 412 is included at the end of envelope section 402 . Each CRC 408 , 410 , 412 is a 2-byte field that stores a cyclic redundancy check (CRC) used to verify the data integrity of the corresponding packet section—envelope, message and object. As explained later in this document, separate CRC calculations are performed for the envelope section 402 , the message section 404 and the object section 406 . For each CRC calculation, the CRC is stored in a separate 2-byte area of memory, typically 2-bytes in an array. FIG. 5 shows the sections of the example packet 400 in more detail. The example envelope section 402 includes a preamble section 502 , packet length bytes 504 , and message section 404 , followed by CRC 412 . In the example shown in FIG. 5 , the preamble section 502 includes a 3-byte preamble. However, more or fewer bytes may be included in the preamble. Each of the preamble bytes determines an internal state of operation. Thus, the first preamble byte corresponds to state 1 , the second preamble byte corresponds to state 2 and the third preamble byte corresponds to state 3 . The preamble bytes are preprogrammed so they can be recognized by input parser module 302 . In one example, the first preamble byte is CNTL W, the second preamble byte is CNTL A and the third preamble byte is CTNL L. Other examples are possible. Following the preamble bytes is a four-byte field 504 that represents the size of the envelope section 402 . Reaching field 504 corresponds to state 4 . Following the field 504 is the start of message 404 . The details of message 404 are shown in the center section of FIG. 5 . The example message section 404 includes a message class ID 508 and payload 406 , followed by CRC 410 . The example message class ID 508 is a 4-byte field corresponding to a specific message class. The CRC 410 represents a calculated CRC for the sum of the bytes in message section 404 . The example message class ID 508 includes a family, a genus and a species. The family represents the purpose of the data, the genus represents an action (for example a request, response, command, etc.) and the species represents a specific type of operation (for example, get the name of a clinician or start a non-invasive blood pressure (NIBP) operation or obtain a blood pressure reading from a patient. The species represents a named field corresponding to the type of information requested, for example, the name of the clinician or a blood pressure reading. The named field permits application module 212 to determine a format for the requested information, permitting application module 212 to obtain the requested information without any additional data conversion or processing. For example, a species of GET-CLINICIAN indicates that the name of the clinician is to be returned as one or more characters. As another example, a species of GET_BP indicates that the blood pressure is to be returned as one or more numbers. In some examples payload 406 corresponds to object 406 in FIG. 4 . This is for the case where there is only one object included in example packet 400 . However, in other examples, packet 400 may have one or more additional objects embedded in payload 406 . Typically, there is not more than one object embedded within an object. Object 406 is a medical device object that includes specific medical information. In examples, object 406 may include a patient's name, identification number, a clinician's name and identification number, and a time stamp. Object 406 may also include an identifier representing the type of information requested, such as temperature, systolic blood pressure, diastolic blood pressure, mean arterial pressure, heart rate, oxygen saturation, etc. Other types of information are possible. The details of object 406 are shown in the bottom section of FIG. 5 . The example object 406 includes object class ID 516 , object size 518 , object version 520 , bit mask 522 and data payload 524 , followed by CRC 408 . The example object class ID 516 is a 4-byte field corresponding to a specific object class. Two example object classes are CNIBPDStd and CDeviceDStd. The example CNIBPDStd class belongs to the family for non-invasive blood pressure (FmNIBP), and includes members for systolic blood pressure, diastolic blood pressure, and mean arterial pressure, heart rate, status flags and a time stamp. The example CDeviceDStd class belongs to the family for device (FmDEVICE) and includes information about the device, including the model name, serial number, etc. The object size 518 is the size of object field 406 , the object version 520 is a version identifier for object 406 and bit mask field 520 is a one-byte bit mask associated with object 406 . The data payload represents a static or dynamic payload. The CRC 408 represents a calculated CRC for the sum of the bytes in object section 406 . FIGS. 6 , 7 and 8 show an example method 600 for processing a data packet that includes medical device information. The example data packet is sent from a host computer, for example a host computer included in patient monitor 110 and the data packet is processed on a medical device, for example on blood pressure monitoring device 104 . The example blood pressure monitoring device 104 contains electronic components, including a processor and memory, which are used to process the data packet. The processing is done in streamlined fashion, without the use of an operating system and by performing a single pass over the packet data. At operation 602 , the processor reads a byte in the packet data stream. At operation 604 , a determination is made as to whether the byte read at operation 602 is part of the envelope 402 . As shown in FIG. 4 , the envelope 402 includes the message 404 , the object 406 , object CRC 408 and message CRC 410 . However, the envelope 402 does not include the envelope CRC 412 . When a determination is made at operation 604 that the byte read at operation 602 is not part of the envelope, at operation 606 a determination is made as to whether the byte read at operation 602 is part of the envelope CRC 412 . When it is determined at operation 606 that the byte read at operation 602 is part of the envelope CRC 412 , control passes to operation 636 , as discussed later in this disclosure. When it is determined at operation 606 that the byte read at operation 602 is not part of envelope CRC 412 , meaning that the byte read at operation 602 is an unexpected byte, the byte is discarded and control passes to operation 602 where another byte is read in the packet data stream. When it is determined at operation 604 that the byte read at operation 602 is part of the envelope 402 , at operation 608 a first CRC is updated. The first CRC is a 16-bit number stored in a first area of memory, typically two bytes in an array, dedicated to perform an integrity check on the envelope 402 portion of the packet data. For the example method 600 , the envelope portion 402 of the packet data includes the preamble 502 , the envelope size 504 and the message 404 . When the first CRC is updated, the first CRC is recalculated to include the byte read at operation 602 . At operation 610 , a determination is made whether the byte read at operation 602 is part of message 404 . A byte that is part of message 404 includes any byte within the message class ID 508 or message payload 406 , but does not include message CRC 410 . When it is determined that the byte read at operation 602 is not part of message 404 , at operation 612 a determination is made as to whether the byte read at operation 602 is part of the message CRC 410 . When it is determined at operation 606 that the byte read at operation 602 is part of the message CRC 410 , control passes to operation 630 , as discussed later in this disclosure. When it is determined at operation 612 that the byte read at operation 602 is not a part of the message CRC 410 , control passes to operation 602 and another byte is read from the data stream. When it is determined at operation 610 that the byte read at operation 602 is part of the message 404 , at operation 614 , a second CRC is updated. The second CRC is a 16-bit number stored in a second area of memory, typically two bytes in an array, dedicated to perform an integrity check on the message 404 portion of the packet data. For the example method 600 , the message 404 portion of the packet data includes the message class ID 508 and the payload 406 . The second area of memory is different than the first area of memory, typically a separate row in the array. When the second CRC is updated, the second CRC is recalculated to include the byte read at operation 602 . At operation 616 , a determination is made as to whether the byte read at operation 602 is part of object 406 . A byte that is part of object 406 includes any byte within the object 406 , but does not include object CRC 408 . When it is determined that the byte read at operation 602 is not part of object 406 , at operation 618 a determination is made as to whether the byte read at operation 602 is part of the object CRC 408 . When it is determined at operation 618 that the byte read at operation 602 is part of the object CRC 408 , at operation 619 , the object CRC 408 is read from the packet data stream. Control then passes to operation 626 , as discussed later in this disclosure. When it is determined at operation 618 that the byte read at operation 602 is not a part of the object CRC 408 , control passes to operation 602 and another byte is read from the data stream. When it is determined at operation 616 that the byte read at operation 602 is part of the object 406 , at operation 620 , a third CRC is updated. The third CRC is a 16-bit number stored in a third area of memory, typically two bytes in an array, dedicated to perform an integrity check on the object 406 portion of the packet data. For the example method 600 , the object 406 portion of the packet data includes the object class ID 516 , the object size 518 , the object version 520 , the bit mask 522 and the data payload 524 . The third area of memory is different than the first and second areas of memory, typically a separate row in the array. When the third CRC is updated, the third CRC is recalculated to include the byte read at operation 602 . At operation 622 , a determination is made as to whether the byte read at operation 602 includes actionable data. Most bytes of object 406 include actionable data, with the exception of certain status bytes and similar non-actionable bytes. When it determined at operation 622 that the byte read at operation 602 includes actionable data, at operation 624 the byte read at operation 602 is stored in buffer memory. Buffer memory is typically a static memory area of device 102 , 104 , 106 , 108 that stores the actionable bytes in object 406 . Control then passes to operation 602 and another byte is read from the packet data stream. When it is determined at operation 622 that the byte read at operation 602 does not include actionable data, the byte read at operation 602 is not stored in buffer memory. Instead, control passes to operation 602 and another byte is read from the packet data stream. At operation 626 , a determination is made as to whether the object CRC 408 read from the packet data stream matches the third CRC. When the object CRC 408 matches the third CRC, validating the integrity of data within object 406 , control passes to operation 602 and another byte is read from the packet data stream. When the object CRC 408 does not match the third CRC, at operation 628 an error response is generated and the data packet processing operation ends. At operation 612 when a determination is made that the byte read at operation 602 is part of the message CRC 410 , at operation 630 the message CRC 410 is read from the packet data stream. At operation 632 , a determination is made whether the message CRC 410 read from the packet data stream matches the second CRC. When the message CRC 410 matches the second CRC, validating the integrity of data within message 404 , control passes to operation 602 and another byte is read from the packet data stream. When the message CRC 410 does not match the second CRC, at operation 634 an error response is generated and the data packet processing operation ends. At operation 606 when a determination is made that the byte read at operation 602 is part of the envelope CRC 412 , at operation 636 the envelope CRC 412 is read from the packet data stream. At operation 638 , a determination is made whether the envelope CRC 412 read from the packet data stream matches the first CRC. When the message CRC 410 matches the first CRC, validating the integrity of data within envelope 402 , at operation 642 message class ID 508 and the data object stored in buffer memory are sent to application module 212 for processing. When the envelope CRC 412 does not match the first CRC, at operation 640 an error response is generated and the data packet processing operation ends. The example method 600 illustrated in FIGS. 6 , 7 and 8 describes a process in which CRC checks are performed for three sections of the incoming data packet—the envelope 402 , the message 404 and the object 406 . However, in examples there may be one or more additional objects embedded in object 406 , depending on the type of medical device information being requested. For the examples where there are objects embedded within objects, an additional CRC check is performed for each embedded object. The CRC for each additional CRC check is stored in a separate area of memory, typically a separate row in the array that stores the CRCs for the envelope 402 , message 404 and object 406 . Typically, because of space and processing considerations, not more than one object is embedded in object 406 . FIGS. 9 , 10 and 11 show an example method 1000 for deserializing data in an object, for example object 406 . Method 900 starts when a byte read from the received packet data is identified as being part of object 406 . At operation 902 , a layer of CRC processing is added and a CRC count is incremented for object 406 . The CRC count represents the number of CRC calculations performed during packet processing, so one additional a count is being added at operation 902 for object 406 . At operation 904 , a byte of object 406 is parsed. The first bytes of object 406 comprise header information and typically indicate the type of object, for example via object class ID 516 , the size of the object, for example by object size 518 , a version of the object, for example via object version 520 and information about the object, for example via information included in object class ID 516 . The header information in object 406 is not stored in memory because it is not needed by the application. As each byte of data in the object 406 is parsed, at operation 906 pointers are adjusted to point to the start of a buffer memory and to point to a location in the buffer memory corresponding to an end of data. The buffer memory is the area of memory in which the data payload of object 406 , for example data payload 524 , is to be stored. The buffer memory for storing the data payload is variable in size because different objects have different memory requirements. The start of the buffer memory is the first location of buffer memory that stores data payload 524 . The pointer corresponding to the end of data is the start of the buffer memory plus the size of a static structure obtained from metadata stored in metadata storage ROM 206 . The static structure represents static variables that are included in the object. An example of a static variable is a patient's name or identification number. The pointer to end of data points to the buffer memory following the end of the static variables included in the object. This provides a pointer for storing any additional data that may be included in the packet following the end of the static variables. At operation 908 , a determination is made as to whether the end of data in the data stream for the object 406 has been reached. When it is determined that the end of data has not been reached, at operation 914 , data type flags are obtained from the metadata. For example, the data type flags may specify that the data type is an integer, 4-bytes in length. At operation 916 , a write-target is set equal to the start of data plus a field offset obtained from the metadata. The write target provides an indication to the application where specific fields in the packet data are located. For example, for a first data field in the packet data, the offset is zero, so that that first field, for example a static variable, is written to buffer memory at the start of data. However, for a second data field, for example, a second static variable, if the data type is an integer, the write-target is offset four-bytes from the start of data, since an integer, in this example, is 4-bytes long. At operation 918 , a determination is made as to whether the object includes dynamic data. When the object includes dynamic data a dynamic flag is set in the metadata. For dynamic data, the amount of the dynamic data is determined by a host computer, for example the host computer at patient monitor 110 . The host specifies how many numbers or letters or objects are included in the data. For example, if the data is a wave, the data may include a variable number of samples, for example 10 samples or 100 samples. For static data, the amount of static data is determined from the metadata. When it is determined that a dynamic flag is set, at operation 920 , the location of a count field is obtained from the metadata. The count field specifies the number of samples of a dynamic type of medical information that are included in the data packet. For example, the count field may specify the number of samples of temperature data or the number of samples of a wave function. At operation 922 the count field is read from the packet data stream and at operation 924 , the count field is stored in memory. Typically, the count field is included in the packet data stream immediately preceding the dynamic medical information, for example before the samples of temperature data, etc. At operation 926 , a write-target pointer is set to the end of data and stored in memory. The end of data is the current end of data as determined in operation 906 . To take into account the dynamic data, at operation 928 , the end of data is increased by the value of the count field multiplied by the data type size. For example, if the count indicates that there are 5 bytes of dynamic data, each byte being an integer 4-bytes in length, the end of data is increased by 20 bytes and the write target is set to this new end of data. When it is determined at operation 918 that the metadata does not include a dynamic field, at operation 948 , a determination is made as to whether the metadata includes an array field. For example, if the object includes the name of a patient, the name may be stored in an array of characters. When an object includes an array field an array flag is set in the metadata. When it is determined that the object 406 includes an array flag, at operation 950 the count of array elements is read from the metadata. For example, the metadata may specify the number of characters in the array. When it is determined at operation 950 that the array flag is not set, at operation the count of array elements is set to 1. At operation 954 , a determination is made as to whether an object flag is set. The object flag indicates whether one object is embedded in a second object. An example of one object being imbedded in a second object is a temperature object, representing the temperature of a patient, embedded in an object including a scanned bar code for the patient. In examples, the bar code object may be embedded in the temperature object. The object flag is set in the metadata for an object. When a determination is made that the object flag is set, for example by evaluating the metadata, at operation 926 , a write-target is set to the end of data and at operation 928 , the end of data is increased by a count representing the number of objects multiplied by a data type size representing the size of each object. The write-target is a pointer that keeps track of the next free memory location. When actionable data, such as a number, is read from the data stream, the actionable data is written to the memory location pointed to by the write-target. At operation 930 , a determination is made whether the current field is an object. If the current field is not an object, at operation 942 , a primitive type is read from the packet data stream. A primitive type can be either a character or a number. At operation 944 , the primitive type is stored in memory at the location pointed to by the write target. At operation 946 , the write target is advanced by the size of the data type, for example by 4-bytes for an integer and by one-byte for a character. At operation 938 , the count set earlier is decremented by one. Then, at operation 942 , a determination is made as to whether the count is equal to zero. If a determination is made that the count is equal to zero, control proceeds to operation 908 , and if the end of data is not reached, another byte of packet data is processed. However, if a determination is made at operation 942 that the count is not zero, control proceeds to operation 930 and a determination is made whether the current field is an object. The count is not zero if there are more bytes of an array, more dynamic bytes or more embedded objects to process, as determined by the count read at operations 950 and 922 for arrays and dynamic elements, respectively. Typically, only one object is embedded. At operation, 930 , when a determination is made that the field is an object, a pointer is set to point to the write-target that points to the end of data, resulting in a double pointer. At operation 934 , the write target is advanced by the size of the pointer. At operation 936 , deserialization is entered recursively. Entering deserialization recursively writes a new structure starting at end of data. The size and format of the new structure is determined when the embedded object is received from the host computer 110 and parsed. At operation 908 , when it is determined that the end of data has been reached, the CRC of the object, for example CRC 408 is read. At operation 910 , CRC 408 is compared with the CRC calculated during the processing of the object, as discussed in relation to operation 632 . In addition, a layer of CRC processing is removed, indicating that the CRC of the object has been processed. FIGS. 12 , 13 and 14 show an example flow chart of a method 1200 for serializing data for an object, for example object 406 . The intent of serializing the data is to insert data obtained from an application in a medical device, for example the temperature of the patient or blood pressure readings from the patient, into an object that can be interpreted by a host computer, for example by host computer 110 . The data is stored in a buffer memory and serialized into a data stream to be sent to host computer 110 . At operation 1200 , metadata is located on the medical device based on an object class ID. The metadata is generated once by an application program, typically run on a personal computer, and stored in metadata storage ROM 206 in a C programming language structure. The object class ID corresponds to an object, for example object 406 , for which medical information is obtained on the medical device. The obtained medical information is stored in memory on the medical device. For example, if a request was made to obtain the temperature of a patient using medical device 110 , a software application on medical device 110 obtains the temperature and stores the temperature data according to example class ID 516 . In this example, class ID 516 specifies temperature and also specifies data to be returned with the temperature. For example, temperature may be associated with object 406 , wherein the temperature may be included as one or more static variables. As another example, the data stream in operation 1200 may represent blood pressure data from example medical device 104 . This data stream typically includes dynamic data and may be associated with object 406 , wherein the blood pressure readings may be included as one or more dynamic variables. At operation 1204 , a layer of CRC processing is added for the data in the stream. This layer of CRC processing calculates a CRC for the data in the stream. The CRC is calculated for each byte in the stream as it is received. When completed the CRC is inserted at the end of the object, for example as CRC 408 . At operation 1206 , object headers are written for the data stream. The object headers reflect the structure of the data as determined by the object class ID. For example, the data stream may include static variables, dynamic variables or a combination of static and dynamic variables. At operation 1208 , a size measurement algorithm is run based on the object headers, the size of the dynamic data is determined and the dynamic data size is stored in memory, for example as dynamic size variable 630 . At operation 1210 , a determination is made as to whether the end of the data stream has been reached. When it is determined that the end of the data stream has not been reached, at operation 1214 , data type flags are obtained from the metadata. For example, the data type flags may specify that the data type is an integer, 4-bytes in length. At operation 1216 , the read location is obtained from the metadata. The read location corresponds to the location in buffer memory from which a byte of obtained medical device information is to be read. At operation 1218 , a determination is made as to whether a dynamic flag is set in the metadata. When a determination is made that a dynamic flag is set, indicating that the obtained medical device information in buffer memory includes dynamic information, at operation 1220 the location of the count field is obtained from the buffer memory. The count field specifies the number of elements of dynamic information included in the buffer memory, for example the number of samples of a wave. At operation 1222 , the count field is read and at operation 1224 , the count field is written to the data stream. The count field is written to the data stream immediately before the dynamic data, for example before the wave samples. At operation 1224 , pointers are adjusted to a new read location. For example, the size of the dynamic data area is calculated based on the count and data type flags and read pointers are adjusted to point just past the end of the dynamic data area so that additional data can be obtained. When it is determined at operation 1218 that a dynamic flag is not set, at operation 1228 a determination is made as to whether an array flag is set in the metadata. When it is determined that an array flag is set, at operation 1230 , the read count is obtained from the metadata. When the array flag is set, the read count specifies the number of elements in an array, for example an array that stores a patient's name. When it is determined that an array flag is not set, at operation 1232 , the count is set equal to 1. At operation 1234 , a determination is made as to whether an object flag is set. When it is determined that an object flag is set, at operation 1226 , a read pointer is adjusted to a new read location. The read pointer is adjusted to point just past the object so that additional data can be read from the buffer memory. At operation 1236 , a determination is made whether the current field is an object. If the current field is not an object, at operation 1238 , a primitive type is read from the current read location. A primitive type can be either a character or a number. At operation 1240 , the primitive type is written to data stream. At operation 1242 , the read location is advanced by the size of the data type, for example by 4-bytes for an integer and by one-byte for a character. At operation 1244 , the count set earlier is decremented by one. Then, at operation 1246 , a determination is made as to whether the count is equal to zero. When a determination is made that the count is equal to zero, control proceeds to operation 1210 , and if the end of data is not reached, another byte of packet data is processed. However, if a determination is made at operation 1246 that the count is not zero, control proceeds to operation 1236 and a determination is made whether the current field is an object. The count is not zero if there are more bytes of an array, more dynamic bytes or more embedded objects to process, as determined by the count read at operations 1230 and 1222 for arrays and dynamic elements, respectively. Typically, only one object is embedded. At operation, 1236 , when a determination is made that the field is an object, this is an indication of an object embedded inside another object. At operation 1248 , serialization is entered recursively, starting at the target pointed to by the current read location. At operation 1250 , the read location is advanced by the size of a pointer corresponding to an embedded object. At operation 1244 , the count is decremented by one and at operation 1246 a determination is made whether the count is equal to zero. Control then passes to either operation 1210 or operation 1236 as discussed above. At operation 1210 , when it is determined that the end of data has been reached, the CRC of the object, for example CRC 408 is read. At operation 1210 , CRC 408 is compared with the CRC calculated during the processing of the metadata stream, as discussed in relation to operation 632 . In addition, a layer of CRC processing is removed, indicating that the CRC of the object has been processed. The various embodiments described above are provided by way of illustration only and should not be construed to limiting. Various modifications and changes that may be made to the embodiments described above without departing from the true spirit and scope of the disclosure.
A method of communicating information includes receiving a data stream from the host computer, the data stream including a plurality of bytes, one or more bytes of the plurality of bytes being associated with obtaining medical related information, and parsing one or more bytes in the data stream at the sensor device. As a result of parsing the one or more bytes, the method includes identifying a type of medical related information, obtaining the medical related information from the sensor device, and sending the medical related information to the host computer. The parsing of the one or more bytes in the data stream is performed using a single pass through the data stream, one or more data validity checks being performed during the single pass, the medical related information being obtained after the data stream is parsed in the single pass through the data stream.
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CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This patent application is based on the provisional patent application No. 60/209,351 filed on 06/05/2000 by Michael P. Farrell of Sugar Grove, Ill. [0002] REFERENCES [0003] U.S. PATENT DOCUMENTS [0004] 4,786,600 November 1998 Kramer et al [0005] 4,988,617 January 1991 Landegren et al [0006] 5,112,734 May 1992 Kramer et al [0007] 5,399,491 March 1995 Kacian et al [0008] 5,407,798 April 1995 Martinelli et al [0009] 5,616,478 April 1997 Chetvarin et al [0010] 5,837,466 November 1998 Lane et al [0011] 5,763,171 June 1998 Stefano J. E. [0012] Other Publications [0013] Tyagi S, Landegren U, Tazi M, Lizardi P M, Kramer F R. Extremely sensitive, background-free gene detection using binary probes and beta replicase. Proc Natl Acad Sci USA May 28, 1996;93(11):5395-400 [0014] Lomeli H, Tyagi S, Pritchard C G, Lizardi P M, Kramer F R. Quantitative assays based on the use of replicatable hybridization probes. 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Quantitative assays based on the use of replicatable hybridization probes. Clin Chem September 1989 35(9):1826-31 [0021] Brown D, Gold L. Biochemistry November 1995 14;34(45):14775-82 Selection and characterization of RNAs replicated by Q beta replicase. [0022] Rohde N, Daum H, Biebricher C K. The mutant distribution of an RNA species replicated by Q beta replicase. J Mol Biol 1995 Jun 16;249(4):754-62 [0023] Moody M D, Burg J L, DiFrancesco R, Lovem D, Stanick W, Lin-Goerke J, Mahdavi K, Wu Y, Farrell M P. Evolution of host cell RNA into efficient template RNA by Q beta replicase: the origin of RNA in untemplated reactions Biochemistry 1994 Nov 22;33(46):13836-47 [0024] Tuerk C, Gold L. Science Agust 1990 3;249(4968):505-10 Systematic evolution of ligands by exponential enrichment: RNA ligands to bacteriophage T4 DNA polymerase. [0025] Brown D, Gold L. Template recognition by an RNA-dependent RNA polymerase: identification and characterization of two RNA binding sites on Q beta replicase. Biochemistry November 1995 14;34(45):14765-74 [0026] Blok HJ, Kramer F R. Amplifiable hybridization probes containing a molecular switch. Mol Cell Probes Jun 1997; 1l(3):187-194 [0027] Thompson J D, Decker S, Haines D, Collins RS, Feild M, Gillespie D. Enzymatic amplification of RNA purified from crude cell lysate by reversible target capture. Clin Chem September 1989 35(9):1878-81 [0028] Chen H, Brown D, Gold L. Novel methods of generating specific oligonucleotide inhibitors of viral polymerases. Methods Enzymol 1996;275:503-20 [0029] Biebricher C K. Replication and evolution of short-chained RNA species replicated by Q beta replicase. Cold Spring Harb Symp Quant Biol 1987;52:299-306 [0030] Miele E A, Mills D R, Kramer F R. Autocatalytic replication of a recombinant RNA. J Mol Biol December 1983 15;171(3):281-95 [0031] Hanes J. and Pluckthun A. In vitro selection and evolution of functional proteins by using ribosome display. Proc. Nat. Acad. Sci. USA 1997 Vol 94 pp. 4937-4942 [0032] Roberts R. W. and Szostak J. RNA-peptide fusions for the in vitro selection of peptides and proteins. Proc. Nat. Acad. Sci. USA 1997 Vol 94 pp. 12297-12302 [0033] Gold L. Polisky B., Uhlenbeck 0. & Yarus M. (1995) Ann. Rev. biochem. Vol 64 pp 763-797. BACKGROUND OF THE INVENTION [0034] The single stranded RNA genomes of positive strand RNA bacteriophages such as Q-beta are replicated by means of an RNA replicase. The enzyme is produced in infected cells when a subunit encoded by the bacteriophage combines with subunits encoded by the bacterial cell to generate a multi-subunit replicase. This enzyme can use the positive strand from the infecting bacteriophage as a template for production of a complementary strand, the minus strand. Both the plus and minus strands can function as templates for the next round of replication. This leads to an exponential amplification of the bacteriophage genome. Although the enzymes exhibit a great deal of specificity for Bacteriophage RNA as templates for exponential amplification they can also catalyze the exponential replication of certain small RNA molecules. The prototype of such molecules is Midi-variant, usually referred to as MDV. This 221 nucleotide RNA molecule can function as a template for synthesis of it's complementary RNA strand by Q-beta replicase in the presence of ribo-nucleotides and magnesium in an appropriate pH and temperature range. Because the daughter strand so made can also function as an efficient template for synthesis of it's complement (the parent strand) the result is an exponential increase in the number of molecules of each strand in the mixture. One molecule of this template can give rise to a few micrograms of RNA in as little as 15 minutes under favorable reaction conditions. [0035] In addition to MDV, other molecules are known which can function as templates for exponential amplification by q-beta replicase. These include, for example, MNV11, WS1, RQ120, RQ135 and others. Each of these molecules is a member of a family of closely related sequences. Several such families are known and others may remain to be discovered. Many mutated relatives of each replicator can function efficiently in amplification reactions. Under fixed conditions, one variant or another may have a greater ability to replicate. For example, a mutant MDV was selected which was better able to replicate in the presence of ethidium bromide than the parental molecule. Each of these molecules is referred to as a ‘replicator’. [0036] This amplification phenomenon has been used in assays. In the simplest case replicator molecules containing hybridization probe sequences, inserted at a location which interferes minimally with replication, are used as probes in hybridization assays to detect complementary nucleic acid targets. Non-hybridized probe molecules are washed away and the remaining molecules are amplified to the point where they can be detected by conventional methods (eg by fluorescence in the presence of dyes) and interpreted as an indication of the presence of target molecules. Because of their high efficiency as templates every non-hybridized probe molecule must be washed away to eliminate background signal in assays of this type. This has led to elaborate washing schemes including repeated cycles of capture on and release from surfaces such as magnetic particles. [0037] To avoid this washing requirement several schemes were devised such that the replicator probes would have reduced replicatability unless exposed to the correct target nucleic acid. One such scheme involved the attachment of inhibitory RNA sequences to the 3′ end of a replicatable molecule and their removal in a target dependent fashion by means of a ribozyme whose structure was completed by the presence of the target molecule. Another scheme was to use pieces of replicatable RNA, none of which were able to replicate without the others, and to ligate them together in a target dependent manner to produce the fully replicatable RNA molecule. Yet another scheme was to use fragments of DNA which are not independently replicatable and to ligate them together in a target dependent manner to produce a contiguous sequence which can be used as a template for production of fully replicatable RNA molecules. [0038] There are limitations with all of these schemes, however. The inhibition of replication by adding 3′RNA extensions to the replicator is not very effective in practice so that in hybridization assays a very substantial washing requirement remains. The binary probe schemes involving ligation have two common problems: [0039] 1. The introduction of probe sequence into the replicator sequence both slows replication and increases the number of molecules required to get a response (ie sensitivity is reduced). [0040] Because two probe fragments must hybridize with discrimination the probe sequence is typically longer than that required by the original unitary probe method. Long inserts in a replicator result in longer amplification times. The sensitivity reduction can be avoided to some extent by bounding the probe sequence with empirically chosen spacer sequences, which separate the probe from the replicator. Such spacer elements are identified empirically by a screening process. This is a laborious and time-consuming activity, which does not always result in structures with single molecule sensitivity. In addition, the spacers further increase the size of the insert and this also prolongs the amplification time. [0041] 2. The template activity of the replicator is greatly reduced by splitting it into two pieces, as done in the binary probe methods that have been described. However, the ability of the replicase, with very low efficiency, to use the 3′ fragment of a replicator as a template for replication can result in false positives in amplification assays. Typically if an amplification reaction contains more than about 10 5 molecules of the 3′ fragment an amplification response will result. This places great demands on the washing technology. These demands have limited the application of the amplification technology. [0042] A further problem can occur with some binary probe schemes. If the two pieces (the 5′ piece and the 3′ piece) of a binary probe replicator are mixed together at high concentration, a small fraction of the pieces can come together to form complexes capable of functioning as templates for the replicase. The formation of these “HOP complexes” does not require the presence of a hybridization target. Their formation can be inhibited by the addition of oligonucleotides complementary to short segments of one of the binary probe fragments (HOP blockers). This further complicates the assay and is not entirely successful since inhibition of HOP complex formation is not complete. [0043] Strategically, these schemes start with an excellent replicator and try to reduce it's replicatability such that it can be restored in a target dependent manner. However, the attempts to implement this strategy are affected by three significant limitations: [0044] 1. Inactivation of replicator is incomplete as described above this results in assay background which imposes washing requirements and increases assay complexity. [0045] 2. When the assay requires that replicatability be restored in response to target the restoration of replicatability is incomplete (because of hybridization inefficiencies, washing effects and ligation limitations). [0046] 3. Furthermore, ligation restores, not the original efficient replicator, but the molecule with reduced replicatability that contains probe and spacer inserts. BRIEF SUMMARY OF THE INVENTION [0047] This document describes a novel strategy for using Q-beta replicase in assays. This strategy provides certain advantages not found in other methods: [0048] 1. The probe is a chimera of RNA and DNA that does not include the complete sequence of a replicator. The 3′ termini needed for efficient initiation of replication are not present. The absence of the 3′ terminal sequences reduces assay background. [0049] 2. The nucleotide sequence of the probe molecule is such that the nucleic acid sequences that encode the replicator are permuted and inverted to eliminate replicatability. It is only by means of Reverse Transcriptase activity that the order of sequence elements and consequently the sequence of the replicator can be restored. [0050] 3. Although the probe molecule can contain a hybridization probe sequence for any target, the assay generates a complete replicator lacking inserts and which has the full replication ability of the original replicator. [0051] Generally, there are three kinds of assays to which this strategy can contribute. [0052] 1. Reverse Transcriptase Assays [0053] A method is described which makes the generation of efficient replicators completely dependent on the enzyme reverse transcriptase. This is an ultra-sensitive assay for reverse transcriptase activity. This is also the basis of the nucleic acid hybridization assays and the ligand-target assays described below. [0054] 2. Nucleic Acid Hybridization Assays [0055] Methods are described which link the reverse transcriptase assay to nucleic acid hybridization assays, allowing Q-beta replicase to be used for ultra-sensitive detection of nucleic acid targets without the background signal exhibited by the other methods. Methods are described which make the Reverse Transcriptase facilitated generation of replicatable RNA dependent on the presence of hybridization targets. These are referred to as ‘smart probe’ methods. [0056] 3. Ligand Target Assays [0057] A further elaboration of this method allows it to be used for detection of targets independent of nucleic acid hybridization. This involves the use of nucleic acid sequences, aptomers, which bind to target molecules without forming the double stranded structures typical of nucleic acid hybridization. For example RNA aptomers which bind a protein can be used for ultra-sensitive detection of that protein by Q-beta replicase. Ligands moieties may be chemically coupled to the chimeric molecules, preferably at the d-e insert. ‘Smart probe’ ligand-target assay methods are described. [0058] The Reverse Transcriptase Assay [0059] Reverse transcriptase (RT) is an enzyme which catalyses the condensation of deoxy-ribonucleotides to generate DNA with a deoxy-nucleotide sequence complementary to a template RNA molecule. The reaction requires an RNA template and a primer, which can be DNA or RNA. The product of reverse transcription is a DNA molecule which remains on it's RNA template in the form of a double stranded DNA-RNA hybrid. In the life-cycle of retroviruses the RNA strand is removed by RNAase H, an enzyme which hydrolyses the RNA strand of RNA-DNA hybrids. [0060] The assay described here makes use of a chimeric molecule that includes an RNA segment preceded by a DNA segment and bounded on the other side by another DNA segment partially complementary to the RNA sequence and capable of functioning as a primer for reverse transcription. The template for reverse transcription is within the RNA segment that forms part of the tripartite chimeric molecule. After the reverse transcription reaction the template RNA segment is removed by digestion with RNAaseH. The RNAaseH activity results in the generation of two DNA molecules, the shorter of which primes the synthesis of DNA complementary to the longer molecule. The product of this reaction is a double stranded DNA molecule encoding the replicator nucleotide sequence downstream of a promoter for T7 RNA polymerase. Transcription by T7 RNA polymerase results in production of the non-interrupted replicator RNA that can be exponentially amplified by Q-beta replicase. [0061] The general scheme, referred to as ‘ the basic method ’ is illustrated in the FIG. 1. FIG. 1 illustrates the basic scheme which can be used for assaying reverse transcriptase. The other two assay classes to which the invention applies involve inserting additional nucleic acid sequences ( called d/e inserts) between d and e in the chimeric molecule illustrated in FIG. 1. For nucleic acid hybridization assays the inserted sequence (the d/e insert) is complementary to a target sequence which is to be assayed. For ligand-target assays the inserted sequence contains a sequence which binds to the target being assayed. In this case the target might be a protein molecule and the d/e insert an RNA aptomer specific for that protein. In both of these assay classes modifications are described which reduce background signal from chimeric probe molecules which may be present but not bound to target. The d-e insert may not itself bind to a target analyte but may be chemically coupled to a moiety which can bind a target of interest-e.g. an antigen, biotin, antibody, streptavidin etc. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS [0062] [0062]FIG. 1 a [0063] Part I shows a chimeric probe molecule composed of a piece of RNA bounded at both ends by DNA segments. The thick line, from a to b represents the first DNA segment starting at the 5′ end. The RNA segment extending from c to d, is represented by the thin line. The RNA segment ends at d where it joins the second DNA segment which extends from e to it's 3′ end at g. Part of the second DNA segment, from f to g, is composed of a deoxy-nucleotide sequence complementary to part of the RNA segment to which it can hybridize so as to prime synthesis by reverse transcriptase. [0064] Part II shows the same molecule as in part I but after reverse transcriptase has made a DNA copy of the RNA strand, starting at g where priming takes place and extending to the end of the template at h. The lower dotted line from g to h represents the DNA product of the reverse transcription reaction. [0065] Part III illustrates the same molecule as Part II but after RNAaseH activity has digested the RNA strand of the double stranded region produced by copying the RNA strand as DNA. The top dashed line represents the degraded RNA. [0066] Part IV shows the same molecule as part III but after the RNA strand has been completely digested. Note that this is a partially double stranded DNA molecule. The short segment corresponding to the first DNA segment, from a to b in part I above, is annealed to the 3′ end of the DNA strand generated by reverse transcription. [0067] Part V illustrates the same thing as part IV. [0068] [0068]FIG. 1 b [0069] Part VI shows the same thing as FIG. 1 a part V but in a simpler drawing. This shows the primer-template combination resulting from the enzymatic activities described above. This is the structure on which DNA polymerase activity generates a double stranded DNA molecule. [0070] Part VII shows the resulting double stranded DNA molecule. The top dashed line represents the newly made DNA. The DNA segment corresponding to the first DNA segment, a to b, in FIG. 1 a part I is here identified as including a sequence which can function as a promoter for T7 RNA polymerase. [0071] Part VIII illustrates the RNA made by transcribing the molecule shown in part VII with T7 RNA polymerase. This RNA begins with the 5′ GGG and ends with the CCC3′ OH sequence typical of the replicators described in the text. Such replicators are efficient amplification templates for Q-beta replicase. One molecule can rapidly be amplified to produce micrograms of RNA in a short time under appropriate reaction conditions. [0072] [0072]FIG. 2 [0073] The nucleotide sequence of double stranded DNA encoding the replicator, WS 1. The top strand represents the plus strand of WS 1 as DNA. [0074] [0074]FIG. 3 [0075] The RNA sequence of WS 1 plus strand; a computer generated folded structure of the RNA is shown. [0076] [0076]FIG. 4 [0077] This shows three strands of nucleic acid. All three are shown with the 5′ end at the left and the 3′ OH end at the right, as indicated in the figure. The top strand shows the DNA representing the plus strand of the WS 1 replicator. This is the same as the top strand shown in FIG. 2. The bottom strand shows, as DNA, the minus strand of the WS 1 replicator. This is the same as the bottom strand shown in FIG. two but here the 5′ end is on the left. The middle section shows a chimeric molecule made up from part of the plus strand and part of the minus strand of WS 1 nucleotide sequence together with DNA corresponding to the top strand of a promoter for T7 RNA polymerase. The part of the WS 1 plus strand that is in the chimera is made of RNA. The part of the WS1 minus strand present in the replicator is made of DNA. The T7 RNA polymerase promoter segment is made of DNA. The result is a chimera consisting of and RNA segment bounded at each end by a DNA segment. The chimera is labeled with lower case letters, a through g, corresponding to the labelling in FIG. 1 a and 1 b . The first DNA segment, the T7 promoter, extends from a to b (bold letters). From c to d (underlined letters) is an RNA segment composed of the first 47 nucleotide residues of the plus strand of WS 1. From e to g (upper case italics) is a DNA segment corresponding to the first 54 nucleotides of the minus strand of WS 1. [0078] [0078]FIG. 5 [0079] This shows the chimeric molecule from FIG. 4 and how it can form a structure capable of priming the reverse transcriptase reaction. The nucleotide residues are numbered from the 5′ end. (The use of lower case letters for part of the molecule is an illustration device required by the graphics program and has no other significance.) [0080] [0080]FIG. 6 [0081] This shows the double stranded DNA resulting from the application of the enzymatic treatments described in the basic method to the tripartite chimeric molecule shown in FIGS. 4 and 5 above. The first 22 nucleotides comprise a T7 promotor for transcription beginning at nucleotide 23 and continuing to the end of the molecule. The transcript is a single stranded WS 1 plus strand RNA. This is an amplification template for Q-beta replicase. [0082] [0082]FIG. 7 [0083] This is the same as FIG. 1 a part I. DETAILED DESCRIPTION OF THE INVENTION [0084] A replicator called WS 1, has been chosen for demonstrating this invention. In addition to being an excellent replicator, WS1 is only 90 nucleotides long and it's small size facilitates the synthesis of the chimeric probe molecules which are the subject of this invention. The nucleotide sequence of double stranded DNA encoding the WS 1 RNA is shown in FIG. 2. The top strand is referred to as the plus strand of WS 1. A computer generated folded structure of the 90 nucleotide WS 1 plus strand RNA is shown in FIG. 3. An example chimeric molecule, showing how parts of the WS 1 nucleotide sequence are incorporated into a tripartite chimera and identifying the boundaries of the RNA and DNA segments is shown in FIG. 4 and FIG. 5. [0085] In the 125 nucleotide chimeric probe molecule shown in FIG. 4 and FIG. 5, there are three segments. [0086] 1. Residues 1 to 22 are deoxy-ribonucleotides, the sequence of which, correspond to one strand of a promoter for T7 RNA polymerase. [0087] 2. Residues 23 to 70 are ribonucleotides in the sequence of residues 1 to 47 of the plus strand of WS 1. [0088] 3. Residues 71 to 125 are deoxyribonucleotides corresponding to the sequence of nucleotides 1 to 54 of the minus strand of WS 1. Neither residues 48 to 90 of the plus strand nor residues 55 to 90 of the minus strand are present in the chimera. This chimera contains self-complementary sequences, which form stem-loops and duplex regions, some of which are shown in the computer generated structure in FIG. 5. Note the duplex formed by the annealing of residues 59 through 71 to the complementary sequence extending from residue 1 11 to residue 125. [0089] This duplex will be referred to as the priming segment. [0090] The proximal part of the primer segment (residues 59 through 71) will be called the primer binding sequence (PBS). [0091] The distal part (residues 111 to 125) will be called the primer. [0092] The segment preceding the PBS, residues 1 to 22 (DNA) through residues 23 to 70 (RNA) is called the RT template. [0093] The PBS is composed of ribonucleotides (RNA). The Primer is composed of deoxyribonucleotides (DNA). [0094] The RT template is composed of both RNA and DNA as indicated in FIG. 3 and FIG. 4. [0095] Reverse transcription of this template, initiated on the primer, produces DNA complementary to residues from 58 back to residue 1. The chimera is elongated from the primer by the addition of deoxy-ribonucleotides starting with residue 125 and continuing to residue 184. This activity generates, as DNA, both the 3′ end of the minus strand of WS 1 and the bottom strand of the T7 promoter, all as parts of the resulting 184 nucleotide long chimeric molecule. [0096] RNAaseH treatment of the resulting molecule digests the RNA segment, residues 23 to 70, allowing residues 1 to 22 (DNA) to function as a primer for DNA synthesis. Synthesis primed from this site uses the DNA made by reverse transcription as the initial part of the template and the contiguous residues 153 to 76 as the distal portion of the template. [0097] The result is a double stranded DNA molecule from which T7 RNA polymerase can transcribe the complete WS 1 replicator. This is shown in FIG. 6. The addition of Q-beta replicase and ribonucleotide triphosphates under appropriate buffer and temperature conditions causes RNA amplification, resulting in accumulation of RNA to a point where it can be detected by routine methods. [0098] Further Development of the Invention [0099] Consider the general chimeric probe molecule illustrated in FIG. 1 a , part I, and shown below. This is composed of three segments. From a to b is a DNA segment which encodes the top strand of a T7 RNA polymerase promoter and, perhaps, the 5′ end of the replicator. From b to e is composed of RNA and encodes part of the plus strand of a replicator. This b to e segment would include the 5′ end of the replicator if this is not encoded in the a to b segment. The entire segment from b through c to d is in the contiguous sequence of the replicator (partly as DNA and partly as RNA) from it's 5′ end to an internal position chosen on the basis of considerations outlined below. The third segment extending from e to g is composed of DNA and encodes part of the minus strand of a replicator, including the 5′ end which begins at e. [0100] Certain points about these segments are highlighted here [0101] 1. The T7 promoter segment encodes only one strand of the promoter and is not, without it's complement, a functional promoter. Furthermnore there is no template strand from which it might promote transcription. [0102] 2. The RNA segment, c to d, encodes, as RNA, part of the plus strand of the replicator. This may include the 5′ end or it may in some cases be preferable to encode the 5′ end as DNA to reduce replicatability. The choice of how much of the plus strand of the replicator sequence is present in the c to d segment is based on these considerations: [0103] a. Since it is RNA and therefore inherently a better potential Q-beta replicase template than the DNA segments, it should be as short as possible. It must nevertheless be long enough to anneal to the priming segment. [0104] b. Also, since it is RNA, it should lack high affinity binding sites for Q-beta replicase. Such high affinity binding sites typically occur in good replicators. A good strategy is to chose strands and breakpoints which permit the nucleotide sequences that (as RNA) comprise the high affinity binding sites for Q-beta replicase to be located in DNA segments. [0105] 3. The RNA segment, c to d , must be long enough so that when it is in the form of an RNA/DNA hybrid, as after reverse transcription, it is a good substrate for RNAaseH. It should be at least 8 nucleotides long but can be much longer. [0106] 4. The segment e to g 0 is DNA comprising part of the nucleotide sequence of the minus strand of the replicator. It must contain the primer segment, f to g and end with a 3′ hydroxyl, capable of priming reverse transcription. The segment e to g includes, as DNA beginning at e, the 5′ end of the minus strand of the replicator nucleotide sequence. [0107] 5. The segment f to g must be complementary to the 3′ end of the RNA segment c to d as shown in the figure. This segment must be long enough to form a stable priming duplex with it's complementary sequence in the c to d segment as shown. The priming DNA segment, f to g, must be long enough so that it's stability forces a priming configuration on the chimeric molecule. It must be chosen and tested to ensure that this occurs. [0108] Variations on the Theme [0109] 1. In the general scheme described above the RNAaseH reaction results in a long DNA molecule with a shorter molecule annealed to it. This structure can prime DNA synthesis catalyzed by a DNA polymerase to generate the double stranded DNA molecule from which the RNA replicator can be transcribed by T7 RNA polymerase. However, the DNA polymerase activity is not necessary for the assay because T7 RNA polymerase can use the RNAaseH product as a template for efficient transcription of the replicator. This is possible because reverse transcriptase activity has already generated the complete T7 promoter and the transcription template. Although it's promoter is double stranded DNA,T7 RNA polymerase does not require that the template strand be part of a double stranded structure. This can eliminate a step in the assay. Only three enzymatic reactions are then required to produce the molecules which can be amplified by Q-beta replicase with single molecule sensitivity. Reverse transcriptasae, RNAaseH, and T7 RNA polymerase. In some cases, however, extensive secondary structure in the template strand could interfere with transcription of a single stranded template by T7 RMA polymerase. Converting the RNAaseH product to the double stranded DNA structure shown in the general scheme can help to overcome such interference and double stranded DNA is the preferred template of T7 RNA polymerase (REFS). [0110] 2. The DNA segment a to b, encoding the T7 promoter, can be omitted from the chimeric probe molecule. This permits a bipartite chimeric molecule to be used in place of the tripartite chimera shown in the general scheme. This bipartite chimera includes the RNA segment c to d (which would include the 5′ end of the replicator) and the DNA segment e to g. Using such a bipartite chimeric probe the result of reverse transcription and RNAase H activity is a single stranded DNA molecule comprising, as DNA, the complete minus strand of the replicator. Such DNA molecules can function as templates for generation of RNA by Q-beta replicase. Typically, for a replicator that gives a response from one molecule of RNA a response from the corresponding DNA requires about 100 DNA molecules. This can provide adequate sensitivity in some applications and would permit the use of a bipartite chimera rather than a tripartite chimeric molecule. From a manufacturing point of view this would have value. This variation requires only two enzyme reactions prior to Q-beta replicase amplification, reverse transcription and the RNAaseH reaction. The sensitivity of such an assay can be further increased, by using the promoter-independent ability of T7 RNA polymerase to generate RNA from single stranded DNA templates. A small fraction of the transcripts initiated on single stranded DNA proceed to the point where the enzyme takes on it's elongating conformation and continues transcribing to the end of the template. Each transcript molecule generated in this way is a template for Q-beta replicase. [0111] d/e Inserts [0112] d/e inserts are the basis of both nucleic acid hybridization assays and ligand-target assays using the chimeric molecules described here. [0113] In FIG. 7, taken from FIG. 2, which illustrates the basic method, position d represents the last ribonucleotide before the second DNA segment begins. In the basic method this is a part of the replicator sequence selected as described above. Position e is the first deoxynucleotide residue after the RNA segment and is, as DNA, the first nucleotide of the minus strand of the replicator-usually the first of several deoxy-guanosine residues. As shown in the general scheme, ribonucleotide residues preceding this do not occur in the template generated by the RNAaseH activity that occurs after reverse transcription. (Additional nucleotides in the initial Q-beta replicase template molecule can have a small affect on initiation of the first round of amplification by Q-beta replicase but they do not occur in the product of that round or interfere with subsequent amplification. Nevertheless it is preferable to exclude them.) [0114] It is possible to insert additional nucleotide residues between d and e without disrupting the structure of the replicator eventually produced by the assay because such additional residues are external to the replicator coding sequence to which they become appended at the 3′ end. These will be referred to as d/e inserts. [0115] Nucleic Acid Probes [0116] One use for d/e inserts lies in their application as hybridization probes. A ribonucleotide sequence complementary to a target sequence can be inserted between d and e. The resulting chimeric molecule can be used as a hybridization probe. In the simplest case the chimera can be hybridized to target nucleic acid, the non hybridized molecules washed away and the residual molecules subjected to reverse transcription, RNAaseH treatment, optional DNA polymerase treatment, transcription by T7 RNA polymerase and amplification by Q-beta replicase. However this assay would require a very effective washing method because every probe molecule has the potential to become a replicator when subjected to the enzyme treatments described in the ‘basic method’. [0117] ‘Smart Probe’ Methods for the Reduction of Assay Background are Described Here [0118] 1. Background Reduction by Chain Termination [0119] Generally, the hybridization of d/e inserts to target nucleic acid would inhibit the priming DNA sequence, f to g, from annealing to it's complement, the primer binding sequence located in the RNA segment, c to d. Target sequences can be chosen such that their complements maximize this inhibition. Longer probe sequences are more effective than shorter sequences. Shorter primer sequences are more subject to inhibition than their longer counterparts. By bounding the probe sequence with additional spacer elements, empirically chosen, it is possible to further maximize the inhibition of priming in a probe-target complex. [0120] After hybridization of such a chimeric probe to target nucleic acid the result is typically a mixture of hybridized and non-hybridized probe molecules. The non-hybridized molecules are capable of priming reverse transcriptase activity. The hybridized probes are in a conformation that prevents this priming. The addition of chain terminating nucleotides (e.g. dideoxy nucleotide tri-phosphates, ddNTP's) and reverse transcriptase at this point results in the incorporation of the ddNTP into any molecules that can function in the priming reaction, thereby terminating their priming ability. The hybridized probe molecules are unaffected by this reaction. The subsequent addition of an excess of dNTP's and release of the probe from it's target allow the molecules which had been hybridized to recover their priming ability. This is most easily envisioned by considering an assay format usually referred to as a ‘sandwich assay’ in which the probe-target complex is captured (e.g. by a biotinylated oligonucleotide) on a surface (e.g. a magnetic particle coated with streptavidin). The initial Reverse Transcriptase activity in the presence of chain terminating nucleotides can be done while the probe is on the surface. Washing to remove the chain terminating nucleotides is followed by release of the hybridized probes from the target followed by reverse transcription in the presence of dNTP's and continuing the assay as described above. [0121] In some cases a homogeneous assay may be preferred. This could be done by performing the terminating reaction with a low concentration of chain terminating nucleotides (e.g. a ddNTP) and then using a vastly greater amount of dNTP for the second RT reaction which takes place after release of probes from target. Since this application is not an assay for RT, the nature of the particular RT being used can be chosen to facilitate the assay. For example the termination step could be done using an RT that efficiently incorporates chain terminating nucleotides while the second step could be done, possibly after inactivating the first RT, using an RT that preferentially incorporates dNTP's even in the presence of chain terminating nucleotides. Such enzymes may occur naturally or be generated by mutational methods. [0122] 2. Background Reduction by RNAase H [0123] A unitary ‘smart probe’ method is also possible using RNAaseH. A background reduction step would be a post-hybridization treatment with RNAaseH. Non-hybridized unitary probes form priming competent complexes. These are substrates for RNAaseH activity which can destroy the primer binding segment (complementary to f-g). Subsequent inactivation or removal of RNAaseH followed by release of hybridized probe molecules from target is followed by the basic method as described above (FIG. 2). Such background reduction steps reduce washing requirements and facilitate simple assay protocols and assay automation [0124] 3. Background Reduction by Using a Binary Chimera [0125] A second way to make the generation of replicator molecules dependent on hybridization to target molecules involves making the chimeric probe in two pieces, each containing part of the hybridization probe segment. In this case a chimeric probe is designed by placing a probe sequence as a d/e insert. A breakpoint is chosen within the d/e hybridizing segment. The chimeric probe molecule is then produced as two separate bipartite chimeric pieces which, when ligated together, generate the tripartite chimera. When the two segments are hybridized to a target molecule the ends are juxtaposed so as to permit priming without ligation or ligation to generate the molecules which can form a priming structure. In the latter case hybridization to target is followed by ligation to generate the chimeric molecules from which replicator template can be generated by reverse transcription, RNAaseH, DNA polymerase, and T7 RNA polymerase activities as described above. In this case ligation is done either enzymatically using T4 DNA ligase or by chemical methods. Non-hybridized probe molecules are not brought together and consequently not ligated. Neither of the two individual chimeric probe segments can be RT templates because each lacks either the priming segment or the primer binding segment. Furthermore, if aberrant priming of RT does occur within one of the binary probe fragments, this does not result in the generation of a replicator. For some probe designs, hybridized, ligated molecules, although they cannot prime RT activity because of conformational constraints, contain all the required sequences. Neither of the free pieces encode a complete replicator sequence and both of them lack the 3′ ends needed for initiation of replication. [0126] 4. d/e Insert as RNA [0127] The d/e insert comprising the hybridization probe can be either RNA or DNA. If it is RNA then no further assay modifications are required. If it is DNA then a further consideration becomes relevant. According to the basic method shown in FIG. 2 the nucleotide sequence comprising the d/e insert becomes an extra-replicator segment contiguous with the 5′ end of the minus strand of the replicator which is generated as DNA by the combined activities of RT and RNAaseH. If the hybridization probe sequence is made as RNA then this extra segment is also composed of RNA. In the standard scheme this segment becomes part of the template for synthesis of the plus strand DNA by the second round of RT activity which results in it being part of the resulting double stranded molecule. This makes it subject to the activity of RNAaseH which removes it. The resulting template strand contains only non-interrupted replicator sequence without additions. [0128] 5. d/e Insert as DNA [0129] However, if the d/e insert is composed of DNA then the extra-replicator sequence becomes part of the double stranded transcription template as described above but, being DNA, cannot be removed by RNAaseH. In this case the sequence of the d/e insert at the junction with the 5′ end of the minus strand should be chosen such that a restriction endonuclease can remove the extra sequence from the resulting double stranded DNA molecule. A good choice of sequence is CCCGGG which is cleaved by SmaI between the middle C and G. In this case the first G in the sequence is the 5′ G of the minus strand of the replicator which typically begins with GGG. The d/e insert must end with CCC which will be juxtaposed to the GGG at e to generate the SmaI site. Removal of the extra-replicator sequence is advantageous because of a small effect on sensitivity in Q-beta replicase amplification caused by such additions. [0130] 6. Background Reduction by Combining Binary and Chain Termination Methods [0131] Some assay background could occur due to the two probe fragments inefficiently coming together without target. This could produce a priming-competent configuration. Therefore a further background reduction step may be advantageous. A further elaboration of the method is to use the binary method described above followed by the chain terminator method, described in 1 . above, for additional background reduction if needed. [0132] 7. Background Reduction by Blocking Oligonucleotides [0133] An alternative additional background reduction step is the addition to the assay of short oligonucleotides which interfere with target independent annealing of the two binary probe fragments to inhibit formation of priming-competent complexes. The length, nucleotide sequence and composition of these molecules can be chosen based on empirical studies depending on the replicator being used. The parameters have to be chosen such that annealing of the binary probe fragments to target is not unduly inhibited. These primer-blocking oligonucleotides would lack the 3′ hydroxyl group needed for RT priming activity. This step could be combined with the RNAaseH based background reduction steps decribed below. Nucleic acid analogs could be used for this blocking function e.g PNA. [0134] 8. Background Reduction by RNAaseH in Binary Method [0135] Another alternative background reduction step would be a post-hybridization treatment with RNAaseH. Any non-hybridized binary probe fragments which come together to form priming-competent complexes will become substrates for RNAaseH activity. This will destroy the primer binding segment (complementary to f-g) eliminating the possibility of subsequent RT activity on these molecules and removing a vital part of the replicator sequence. Inactivation or removal of RNAaseH followed by release of hybridized probe molecules from target is followed by the basic method as described above (FIG. 2). Such background reduction steps reduce washing requirements and facilitate simple assay protocols and assay automation. Since this approach does not result in probe sequence within a replicator the amplification step does not place constraints on the choice of probe sequence or length. The hybridization requirements can therefore be given greater weight in the choice of probe sequence and length. [0136] Ligand-Target Assays [0137] Above I have described the use of chimeric DNA-RNA-DNA molecules for Reverse Transcriptase assays and similar molecules containing d/e inserts, composed of either RNA or DNA, for use in hybridization probe assays. A further application of d/e inserts is described here. Since d/e inserts are absent from the replicator generated by the assay they do not interfere with it's replication. This provides a wide latitude for the choice of such inserts. [0138] The work of Szostack, and that of Gold and others (refs) has shown that selection procedures combined with combinatorial methods can be used to identify nucleic acid sequences which bind with high affinity to other substances. Such nucleic acids, here referred to as aptomers, can be composed of either RNA or DNA. [0139] Here I describe a method for using such sequences, as part of chimeric molecules, for the ultra-sensitive detection of their cognate ligands. In essence the ligand-binding nucleic acid sequence is inserted into the basic assay chimera as a d/e insert. A binary version of the method makes use of two ligand binding segments chosen such that they can be ligated together when bound to target. Ligation, either chemically or enzymatically using for example T4 RNA ligase or T4 DNA ligase, generates a chimera from which a replicator can be produced by application of the basic method described above. [0140] An RNA sequence that binds a certain ligand can be identified by the SELEX procedure, for example. In the simplest case this RNA sequence is used directly as a d/e insert, producing a chimeric probe molecule containing all the elements described in the basic assay in addition to the ligand-binding RNA segment. In a simple assay the chimeric probe is exposed under appropriate binding conditions to the ligand-containing sample, possibly fixed to a surface. After the binding reaction, non-bound probe molecules are washed away and the remaining molecules are used as templates for RT and the other basic reaction components to generate Replicator molecules which are then amplified by Q-beta replicase. [0141] Further Elaborations of the Invention [0142] 1. Ligand-Target Assay Using Unitary Probe and Background Reduction by Chain Terminating Method or RNAaseH Method [0143] Usually, the ligand-binding RNA sequence (aptomer) is originally identified in a nucleic acid sequence context different from that of the chimeric molecules described here. In some cases incorporation into these chimeras may interfere with ligand-binding activity of the aptomer. This inhibition can be prevented by separating the aptomer from the basic chimera by bounding it on one or both sides with spacer elements. The spacer elements may reconstitute the original sequence context in which the aptomer was identified or they may be chosen in the context of this assay based on empirical studies. They must not interfere with RT primer activity of non-bound molecules. If the aptomer-spacer combination results in inhibition of primer binding (and therefore reverse transcriptase activity) on ligand-bound probe molecules but not on free probe molecules then one or more of the background reduction techniques described above for hybridization assays can be used. Such aptomer-spacer sets can be found by a combination of design and empirical studies. After the ligand binding step the free molecules are reacted with chain terminating agents or RNAaseH or both. After removal of RNAaseH and chain terminators the bound chimeras are released and subjected to the steps of the basic method and amplified. This is a unitary probe method. [0144] 2. Binary Probe Methods Using Aptomers [0145] In this case two aptomers are used, each being part of a separate piece of a chimeric binary probe. Conceptually, two aptomers are joined together and used as a d/e insert. For assays, the chimeric molecule is produced in two pieces, each containing one of the two aptomers. The chimera is split between the two aptomers. In this case the spacer considerations described above for a unitary aptomer-containing probe apply. There are additional spacer considerations here, however: [0146] The assay requires that when the two aptomer-containing probe fragments are bound to the ligand they can either form a priming competent structure or be ligated together to produce the chimera which becomes the RT template from which the basic assay can produce replicator RNA for amplification by Q-beta replicase. This means that both aptomers, when part of separate molecules, must be able to bind simultaneously to the same ligand molecule and, when so bound, have ends in a conformation that allows them to form a priming competent structure or to be ligated together. Such aptomer combinations, and the sequences that separate them in which ligation occurs, can be chosen based on selection experiments and on empirical studies for each target species. Ligation can be done by T4 RNA ligase which ligates single stranded nucleic acids. T4 DNA ligase can be used if the aptomer separator element permits annealing to a short oligonucleotide which would produce a double stranded structure across the ligation point on ligand bound but not on free probe fragments. Chemical ligation is possible in either case. If RNA ligase is to be used then aptomer-spacer combinations can be designed such that the juxtaposition of the two probe fragments when bound to ligand would result in formation of an optimal structure for RNA ligation by this enzyme (ref Orgel). Additional background reduction using RNAaseH and/or chain termination methods may be added as described above for unitary ligand-target and for nucleic acid hybridization assays. [0147] 3. The use of aptomers with the chimeric molecules described here has another application in reverse transcriptase assays. For the reverse transcriptase assay it may be useful in some applications to use as a d/e insert an RNA sequence that functions as a high affinity ligand for a particular reverse transcriptase. This could allow the assay to preferentially detect that reverse transcriptase rather than others which could be present in the sample. For example RNA sequences that bind with high affinity to the HIV reverse transcriptase have been described. Such a sequence could be inserted between d and e. To avoid interference with the binding activity of this RNA to HIV reverse transcriptase empirically chosen spacer elements bounding the binding segment on one or both sides may be needed as described above. [0148] 4. Above, RT aptomers are used to increase the affinity of a chimeric probe for RT, thereby giving the assay increased specificity for that RT rather than others. The converse is also possible. Probes containing aptomers that inhibit one RT but not another can be used to assay other RT's in the presence of the one being inhibited. RNA aptomers which inhibit the HIV reverse transcriptase have been described (ref Brown and Gold.). Aptomers specific for other RT's are also described in the literature.(Gold.)
Certain small RNA molecules can serve as templates for exponential replication by Q-beta replicase. A single molecule can give rise to easily detectable replication products. This permits their detection at the single molecule level. In this patent application tripartite chimeric molecules composed of an RNA segment bounded on each side by a DNA segment are described. Although these chimeras are not templates for exponential amplification by Q-beta replicase they can give rise to such templates by enzymatic reactions which depend on the activity of reverse transcriptase. They can therefore be used as the basis for ultra-sensitive assays for reverse transcriptase. Modifications of the templates and the assays permit application of these chimeras and Q-beta replicase to ultra-sensitive nucleic acid hybridization assays and to assays for non-nucleic acid targets.
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BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the treatment of benign pigmented moles (naevi) of the skin and mucous membranes; in particular nevus cell nevi, of lentigos and pigmented nevi of the mucous membranes with locally applied, but in particular with topical formulations. Furthermore, it relates to topical formulations which are suitable for this purpose. 2. Discussion of Background Information The term nevus cell nevi means different benign skin changes, pigmented moles (birthmark, liver spot) that are composed in cellular terms of so-called nevus cells. Nevus cells are a defective development of the normal pigment-forming cells, the melanocytes. Melanocytic nevi occur in different number, size and color intensity in virtually all human beings. The outward appearance of nevi can be very different. They can be pigmented moles lying at the skin level or raised above the skin level (rounded, pediculate or flat) punctiform but also large-scale, wart-like, uneven or smooth, and the color ranges from skin-colored to brown to black. The number of melanocytic nevi acquired increases over the course of life. Nevus cell nevi with conspicuous structure have an increased risk of degeneration and are called dysplastic or atypical nevus cell nevi. A malignant melanoma, that is black skin cancer, may possibly develop from a nevus cell nevus. In over 60 percent of all cases it develops from a nevus cell nevus. In recent decades a clear increase in the incidence of melanoma has been registered. While in the U.S. in 1960 a lifetime risk of approx. 1:600 was assumed, today one of 1:100 is observed. Thus, according to Dr. Matthias Volkenandt (Clinic for Dermatology and Allergiology of Ludwig-Maximilian University, Munich, Frauenlobstrasse 9, 80337 Munich), for example, melanoma has an incidence in the region of Bavaria of approx. 14 (i.e., 14 new cases) per 100,000 inhabitants a year. This corresponds to a lifetime risk of approx. 1% (every 100 th person will be diagnosed with a melanoma in the course of his/her life). Given this figure, melanoma is not the most frequent tumor in humans, but the rise in the incidence according to Volkenandt is greater than with any other tumor. According to the current level of knowledge, there is no preventative treatment or therapy that combats the degeneration of nevus cell nevi. Nevi with an increased risk of degeneration are chiefly surgically removed. Laser treatment plays more of a role in cosmetic aspects. Both methods are invasive, associated with certain risks (scarring, skin discoloration, etc.) and high costs. The development of an acquired nevus is always preceded by a small, sometimes microscopically small, red spot (a bleeding or hemangioma). From this nevus precursor a larger red, somewhat raised mole frequently develops. From the nevus precursors then the brown nevus cell nevi develop, of different size, brown color and structure. Artemisinine (also called qinghaosu) is a sesquiterpene lactone with a peroxide group, which has hitherto been examined and used mainly as a systematically active antimalarial drug. Artemisinine is very hard to dissolve in water; however, water-soluble derivatives of artemisinine have been developed. The systemic or topical use of artemisinine and derivatives thereof for the treatment of psoriasis, diseases of viral origin (warts, molluscum contagiosum and ovinia), ultraviolet radiation-induced diseases (polymorphous light dermatosis, “collagen vascular disease”, premalignant keratosis, Bowen syndrome, lentigo maligna, basal-cell carcinoma, squamous cell carcinoma and malignant melanoma), vesicular skin diseases and hemorrhoids is described in EP-A-O 428 773. SUMMARY OF THE INVENTION The object of the present invention is to provide locally acting, but preferably topical formulations that are effective against benign pigmented moles, in particular against melanocytic nevi and thus can also be used in the prevention of skin cancer. The object is attained according to the invention in that active ingredients from a class of compounds with the formula (I): in which formula (I) X represents CO, CHOZ or CHNRZ, where Z is chosen from: hydrogen; straight-chain and branched (C 1 -C 6 ) alkyl; straight-chain or branched (C 2 -C 6 ) alkenyl; straight-chain or branched (C 2 -C 6 ) alkynyl; (C 3 -C 8 ) cycloalkyl; (C 6 -C 24 ) aryl; (C 7 -C 24 ) aralkyl; m- and p-CH 2 (C 6 H 4 )COOM; COR 3 ; CSR 3 ; C(NR 6 )R 3 ; SOR 4 ; SO 2 OM; SO 2 NR 7 R 8 ; SO 2 O-artemisinyl; SO 2 NH-artemisinyl; POR 4 R 5 and PSR 4 R 5 ; wherein R 3 is straight-chain or branched (C 1 -C 6 ) alkyl; straight-chain or branched (C 1 -C 6 ) alkoxy; straight-chain or branched (C 2 -C 6 ) alkenyl; straight-chain or branched (C 2 -C 6 ) alkynyl; (C 3 -C 8 ) cycloalkyl; (C 6 -C 24 ) aryl; (C 6 -C 10 ) aryloxy; (C 7 -C 24 ) aralkyl; —(CH 2 ) n —COOM, with n as an integer from 1 through 6; or 10α-di-hydroartemisinyl; R 4 and R 5 are selected independently of one another from straight-chain or branched (C 1 -C 6 ) alkyl; straight-chain or branched (C 2 -C 6 ) alkenyl; straight-chain or branched (C 2 -C 6 ) alkynyl; (C 3 -C 8 ) cycloalkyl; (C 6 -C 24 ) aryl; (C 7 -C 24 ) aralkyl; OM; straight-chain or branched (C 1 -C 6 ) alkoxy; (C 6 -C 10 ) aryloxy and NR 7 R 8 ; R 6 is selected from straight-chain or branched (C 1 -C 6 ) alkyl; straight-chain or branched (C 2 -C 6 ) alkenyl; straight-chain or branched (C 2 -C 6 ) alkynyl; (C 3 -C 8 ) cycloalkyl; (C 6 -C 24 ) aryl and (C 7 -C 24 ) aralkyl; M is hydrogen or a pharmaceutically acceptable cation; and R 7 and R 8 independently of one another are hydrogen or straight-chain or branched (C 1 -C 6 ) alkyl, or R 7 and R 8 together form a (C 4 -C 6 ) alkylene bridge; and R is selected from hydrogen and the groups listed for R 6 ; are used to produce the locally applied, in particular topical formulation against benign pigmented moles. DETAILED DESCRIPTION OF THE INVENTION Surprisingly, it was found that pigmented moles of the skin, in particular those of melanocytic origin, can be successfully treated locally very early with the above-referenced active agents, in particular with topical (e.g., cutaneous) preparations. It was also found that the prevention of skin cancer (in particular basal cell carcinoma or melanoma) is possible through the treatment of nevus cell nevi with compounds of formula (I). Furthermore, it was found that these active agents are also effective with local application in the prevention of benign pigmented moles, in particular of acquired nevus cell nevi. Within the scope of the present application, “benign pigmented moles” are understood to be in particular: nevi, in particular nevus cell nevus (banal or dysplastic; the nevus cell nevus is also often called melanocytic nevus); including its three subtypes that can be differentiated by place of origin, junction nevus cell nevus (boundary zone epidermis/dermis), compound nevus cell nevus (connective tissue of the dermis) and dermal nevus cell nevus (deep layers of the dermis), and its subtypes that can be differentiated according to time of occurrence, congenital nevus cell nevus (=birthmark) and acquired nevus cell nevus. A subgroup of acquired nevus cell nevi are recurrent nevi, which develop after the surgical removal of another benign birthmark. One example of a congenital junction nevus cell nevus is the Naevus Spilus, an example of an acquired junction nevus cell nevus or compound nevus cell nevus is the halo nevus (Naevus Sutton); and examples of acquired melanocytic junction nevus cell nevi, compound nevus cell nevi or dermal nevus cell nevi are the Naevus Spitz and the Naevus Reed. An example of a congenital dermal nevus cell nevus is the Mongolian spot (=Naevus Bleu) and an example of a congenital compound nevus cell nevus or dermal nevus cell nevus is the congenital giant pigment nevus (Naevus gigantus); lentigos (such as liver spots—lentigo simplex, freckles=lentigo solaris, age spots —lentigo senilis, PUVA lentigos); disorders of the melanin pigmentations (such as freckles=ephelides); and pigmented moles of the mucous membranes (such as connective tissue nevus in the eye, nevus on the lips and oral mucosa and on reproductive organs). The compounds of formula (I) are effective in the treatment of all above-mentioned benign pigmented moles, in particular the acquired or congenital nevus cell nevi. Among the above-mentioned nevi, the dysplastic (atypical) nevus cell nevi have a higher probability of degenerating to skin cancer and are therefore nevi that are preferably treated with compounds of formula (I) to prevent skin cancer. For the (C 1 -C 6 ) alkyl, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl,t-butyl, n-pentyl, sec-pentyl, neo-pentyl, n-hexyl, sec-hexyl and neo-hexyl are preferred. More preferably is a straight-chain (C 1 -C 3 ) alkyl, and particularly preferred is methyl or ethyl. For the straight-chain or branched (C 2 -C 6 ) alkenyl, (C 2 -C 4 ) alkenyls, such as vinyl, allyl, 1-methylvinyl, 2-methylvinyl, but-1-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, but-1-en-2-yl, but-2-en-2-yl, but-3-en-2-yl, 2,2-dimethylvinyl and 1,2-dimethylvinyl are preferred. For the straight-chain or branched (C 2 -C 6 ) alkynyl, e.g., ethynyl, propargyl, prop-1-yn-1-yl, but-1-yn-1-yl, but-2-yn-1-yl, but-3-yn-1-yl, but-3-yn-2-yl, 3-methylbut-1-yn-1-yl, 3,3-dimethylbut-1-yn-1-yl, 1,1-dimethylbut-2-yn-1-yl and 1,1-dimethylprop-2-yn-1-yl are preferred. For the (C 3 -C 8 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl are preferred. For the (C 6 -C 24 ) aryl, (C 6 -C 10 ) aryls, such as phenyl, naphth-1-yl and naphth-2-yl, are preferred. For the (C 7 -C 24 ) aralkyl, (C 7 -C 12 ) aralkyls, such as benzyl, phenethyl, (naphth-1-yl)methyl and (naphth-2-yl)methyl, are preferred. For the alkyl in (C 1 -C 6 ) alkoxy, the same radicals are preferred as exemplified above for (C 1 -C 6 ) alkyl. Preferably it is a (C 1 -C 3 ) alkoxy, and more preferably it is methoxy, ethoxy or n-propoxy. For the aryl in (C 6 -C 10 ) aryloxy the same radicals are preferred as exemplified above for the (C 6 -C 24 ) aryl. More preferably it is phenoxy or α- or β-naphthoxy. Within the scope of the present application, the term “artemisinyl” denotes a group of formula (I) where X=CH—, so that this group can be bound to the oxygen or the nitrogen via the free valence of the carbon. Within the scope of the present application, the term “10-α-dihydroartemisinyl” denotes —O-artemisinyl, where artemisinyl has the above meaning. In formula (I), for Z hydrogen; straight-chain or branched (C 1 -C 6 ) alkyl, m- and p-CH 2 (C 6 H 4 )COOM; COR 3 ; SOR 4 ; SO 2 OM; SO 2 NR 7 R 8 ; SO 2 NH-artemisinyl and POR 4 R 5 are preferred. For the pharmaceutically acceptable cation as M, for example, cations of alkali metals, e.g., of lithium, sodium or potassium, or alkaline earth metals, e.g., of magnesium and calcium, ammonium, and H + N(R X R Y R Z ) can be mentioned by way of example, wherein R X , R Y , R Z independently of one another can be methyl or ethyl. For Z as COR 3 it is preferred if R 3 is a straight-chain or branched (C 1 -C 6 ) alkyl; straight-chain or branched (C 1 -C 6 ) alkoxy; —(CH 2 ) n —COOM or artemisinyl. In particular, for M here hydrogen, sodium, potassium or ammonium is preferred. For Z as SO 2 OM it is preferred if M is an alkali metal, an alkaline earth metal or ammonium. For Z as POR 4 R 5 it is preferred if R 4 and R 5 are selected from OM and straight-chain or branched (C 1 -C 6 ) alkoxy. More preferably one of R 4 and R 5 is OM, wherein the M is in particular sodium, potassium or ammonium, and the other one straight-chain or branched (C 1 -C 6 ) alkoxy or OH. The compounds of formula (I) are known or can be produced analogously to known compounds of formula (I). The compound where X=CO is the artemisinine, and the compound in which X=CHOH is the dihydroartemisinine. The compounds in which X=CHOZ, with Z different from hydrogen, or wherein X=CHNRZ, are referred to below as “derivatives of dihydroartemisinine.” The compounds of formula (I) can be obtained as follows: Artemisinine (X=CO) can, as is known, be isolated from the plant Artemisia Annua. Dihydroartemisinine (X=CHOH) is known and can be produced, for example, through the reduction of artemisinine with sodium borohydride in methanol at approx. 0° C. The derivatives of dihydroartemisinine, where X=CHOZ, wherein Z is a straight-chain or branched (C 1 -C 6 ) alkyl, straight-chain or branched (C 2 -C 6 ) alkenyl, straight-chain or branched (C 2 -C 6 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 6 -C 24 ) aryl or (C 7 -C 24 ) aralkyl; can be produced from dihydroartemisinine, in that it is first converted with trimethylsilyl chloride into its trimethylsilyl ether, the trimethylsilyloxy group is exchanged with trimethylsilyl bromide for bromine (according to Example 1 of US-A-2005/0119232), and then the bromine atom is in turn substituted in the presence of a base with an HOZ which if desired is used in an excess, wherein Z has the indicated meaning. Among these derivatives artemether (Z=Me) and arteether (Z=Et) are known compounds. The derivatives of dihydroartemisinine, where X=CHNRZ, wherein R has the meaning indicated for formula (I) and Z=hydrogen, straight-chain or branched (C 1 -C 6 ) alkyl, straight-chain or branched (C 2 -C 6 ) alkenyl, straight-chain or branched (C 2 -C 6 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 6 -C 24 ) aryl or (C 7 -C 24 ) aralkyl; can be produced from dihydroartemisinine, in that this is first converted with trimethylsilyl chloride into its trimethylsilyl ether, the trimethylsilyloxy group is exchanged for bromine with trimethylsilyl bromide (according to Example 1 of US-A-2005/0119232) and then the bromine atom, in turn, is substituted in the presence of a base with an amine HNRZ which if desired is employed in an excess, wherein R and Z have the indicated meaning. The derivatives of dihydroartemisinine, where X=CHOZ or CHNRZ, wherein R has the meaning indicated with formula (I) and Z=m- or p-CH 2 (C 6 H 4 )COOM (definition of M as given for formula (I)), are available from dihydroartemisinine or the derivative of dihydroartemisine where X=CHNRH, in that they are alkylated with m- or p-bromomethyl benzoic acid methyl ester in the presence of a base, followed by hydrolysis of the methyl ester and suitable salt formation, if M is not to be hydrogen. Among these derivatives, the derivative where X=CHOZ and Z=p-CH 2 (C 6 H 4 )COOH is known as “artelinic acid”. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, R having the meaning indicated with formula (I), Z=COR 3 or means CSR 3 and R 3 is straight-chain or branched (C 2 -C 6 ) alkoxy or (C 6 -C 10 ) aryloxy, can be produced by reacting dihydroartemisinine or the derivative of dihydroartemisinine where X=CHNRH with the suitable chlorocarbonic acid-(C 1 -C 6 ) alkyl ester or chorocarbonic acid-(C 6 -C 10 ) aryl ester or chlorthiocarbonic acid-(C 1 -C 6 ) alkyl ester or chlorthiocarbonic acid-(C 6 -C 10 ) aryl ester and a base. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, wherein R has the meaning indicated with formula (I), Z=COR 3 and R 3 is a straight-chain or branched (C 1 -C 6 ) alkyl, straight-chain or branched (C 2 -C 6 ) alkenyl, straight-chain or branched (C 2 -C 6 ) alkynyl; (C 3 -C 8 ) cycloalkyl, (C 6 -C 24 ) aryl or (C 7 -C 24 ) aralkyl; can be produced by reacting dihydroartemisinine or the derivative of dihydroartemisinine where X=CHNRH with an acyl chloride and a base, wherein the acyl chloride is substituted with the suitable R 3 . The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, R having the meaning indicated with formula (I), Z=CSR 3 and R 3 is a straight-chain or branched (C 1 -C 6 ) alkyl, straight-chain or branched (C 2 -C 6 ) alkenyl, straight-chain or branched (C 2 -C 6 ) alkynyl; (C 3 -C 8 ) cycloalkyl, (C 6 -C 24 ) aryl or (C 7 -C 24 ) aralkyl; can be obtained by reacting the corresponding derivative described above where Z=COR 3 with Lawesson's reagent. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, R having the meaning indicated with formula (I), Z=COR 3 and R 3 is —(CH 2 ) n —COOM (M having the meaning indicated with formula (I)), can be prepared by reacting dihydroartemisinine or the derivative of dihydroartemisinine where X=CHNRH with a cyclic acid anhydride (if n=2 or is 3) or with MeOOC—(CH 2 ) n —COOMe. In the latter case in the case where X=CHOZ a basic catalyst such as NEt 3 can also be used, and the methyl alcohol released during the transesterification can be withdrawn from the equilibrium, such as by evaporation under reduced pressure. If M is not hydrogen, a corresponding salt formation can follow, in that the remaining methyl ester group is split, e.g., with M-cyanide. Among these derivatives, the one where X=CHOZ, n=2 and M=hydrogen is known as “artesunate”. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, R having the meaning indicated with formula (I), Z=CSR 3 and R 3 is —(CH 2 ) n —COOM (M having the meaning indicated with formula (I)), can be produced in that in MeOOC—(CH 2 ) n —COOMe one of the two carbonyl oxygens is replaced by sulfur with Lawesson's reagent and this hemithio-diester is reacted with dihydroartemisinine or the derivative of dihydroartemisinine where X=CHNRH, followed by hydrolysis of the still free —COOMe group to COOH and corresponding salt formation, if M is not hydrogen. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, R having the meaning indicated with formula (I), Z=C(NR 6 )R 3 (R 6 having the meaning indicated with formula (I)) and R 3 is a straight-chain or branched (C 1 -C 6 ) alkoxy or (C 6 -C 10 ) aryloxy, can be obtained, in that an isocyanate R 6 —NCO, in which R 6 has the indicated meaning, is reacted with a corresponding (C 1 -C 6 ) alcohol or (C 6 -C 10 ) aryl alcohol, and the urethane thus obtained is reacted with POCl 3 and then with dihydroartemisinine or the derivative of dihydroartemisinine where X=CHNRH in the presence of a base. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, R having the meaning indicated in formula (I), Z=C(NR 6 )R 3 (R 6 having the meaning indicated with formula (I)) and R 3 is straight-chain or branched (C 1 -C 6 ) alkyl, straight-chain or branched (C 2 -C 6 ) alkenyl, straight-chain or branched (C 2 -C 6 ) alkynyl; (C 3 -C 8 ) cycloalkyl, (C 6 -C 24 ) aryl or (C 7 -C 24 ) aralkyl, can be obtained in that an isocyanate R 6 —NCO, where R 6 has the indicated meaning, is reacted with a corresponding Grignard reagent R 3 MgBr, where R 3 has the indicated meaning, and the amide thus obtained is reacted with POCl 3 and then with dihydroartemisinine or the derivative of dihydroartemisinine where X=CHNRH in the presence of a base. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, R having the meaning indicated with formula (I), Z=C(NR 6 ) and R 3 is —(CH 2 ) n —COOM (M and R 6 having the meaning indicated with formula (I)) can be obtained in that a compound MeOOC—(CH 2 ) n —CONHR 6 , wherein n and R 6 have the indicated meaning, are reacted with POCl 3 and then with dihydroartemisinine or the derivative of dihydroartemisinine where X=CHNRH in the presence of a base, and the methyl ester is hydrolyzed, and, if M is not hydrogen, a suitable salt formation is carried out. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ R having the meaning indicated with formula (I)), where Z=SOR 4 and R 4 ═OMe, can be obtained by reacting dihydroaratemisinine with excess dimethyl sulfite (DRP 487253), optionally in the presence of a basic catalyst, and distillation of the released methanol and finally the excess dimethyl sulfite under reduced pressure. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, R having the meaning indicated with formula (I), and Z=SOR 4 (R 4 being a straight-chain or branched (C 1 -C 6 ) alkoxy or (C 6 -C 10 ) aryloxy), can be obtained through reaction of the corresponding derivative where X=CHOH or CHNRH with excess thionyl chloride and a suitable base, such as pyridine, removal of the excess thionyl chloride and subsequent reaction of the obtained sulfurous acid derivative with the corresponding straight-chain or branched (C 1 -C 6 ) alcohol or (C 6 -C 10 ) aryl alcohol in the presence of a suitable base, such as pyridine. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, R having the meaning indicated with formula (I) and Z=SOR 4 (R 4 being (C 1 -C 6 ) alkyl, straight-chain or branched (C 2 -C 6 ) alkenyl, straight-chain or branched (C 2 -C 6 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 6 -C 24 ) aryl or (C 7 -C 24 ) aralkyl), can be obtained by reacting a Grignard reagent R 4 MgBr, wherein R 4 has the indicated meaning, with excess thionyl chloride, removal of the excess thionyl chloride and subsequent reaction of the R 4 —SOCl obtained with the corresponding dihydroartemisinine derivative where X=CHOH or CHNRH in the presence of a suitable base, such as pyridine. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, R having the meaning indicated with formula (I) and Z=SOR 4 (R 4 being NR 7 R 8 , and R 7 and R 8 having the meaning indicated with formula (I)) can be obtained by reacting an amine HNR 7 R 8 with excess thionyl chloride, removal of the excess thionyl chloride, and subsequent reaction of the RR 7 R 8 NSOCl obtained with the corresponding dihydroartemisinine derivative where X=CHOH or CHNRH in the presence of a suitable base, such as pyridine. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, with Z=SO 2 OM (M having the meaning indicated with formula (I)) can be obtained by reacting the corresponding derivative where X=CHOH or CHNRH with pyridine-sulfur trioxide complex and exchange of the pyridinium counterion of the sulfonate obtained for M. The derivatives of dihydroartemisinine, where X=CHOZ or is CHNRZ, where Z=SO 2 NR 7 R 8 and R, R 7 and R 8 have the meaning indicated with formula (I), can be obtained by reacting the dihydroartemisinine derivative where X=CHOZ or CHNRH with 1 eq. of sulfuryl chloride in the presence of a base, such as, e.g., pyridine and subsequent reaction with 1 eq. of an amine HNR 7 R 8 , where R 7 and R 8 have the indicated meaning, in the presence of base such as pyridine. The derivative of dihydroartemisinine, where X=CHOZ, where Z=SO 2 O-artemisinyl, can be obtained by reaction of 2 eq. of dihydroartemisinine with 1 eq. of sulfuryl chloride in the presence of base such as pyridine. The derivative of dihydroartemisinine, where X=CHOZ, where Z=SO 2 NH-artemisinyl, can be obtained by reacting dihydroartemisinine with 1 eq. of sulfuryl chloride in the presence of base such as pyridine and subsequent reaction with 1 eq. of the artemisinine derivative where X=CHNH 2 in the presence of base such as pyridine. The derivative thus obtained is identical to the derivative where X=CHNHZ and Z=SO 2 O-artemisinyl. From the derivative thus obtained, subsequently the derivatives of dihydroartemisinine where X=CHNRZ, R having the meaning indicated with formula (I) except for hydrogen, can be obtained by deprotonation on the sulfamido nitrogen and alkylation with an alkylbromide RBr, where R has the indicated meaning. The derivative of dihydroartemisinine, where X=CHNHZ, where Z=SO 2 NH-artemisinyl, can be produced according to Example 2 of US-A-2005/0119232. From this in turn the derivatives of dihydroartemisinine can be produced, where X=CHNRZ, R having the meaning indicated with formula (I) except for hydrogen, by deprotonation on one of the two sulfamido nitrogens and alkylation with an alkylbromide RBr, where R has the given meaning. The derivatives of dihydroartemisinine, where X=CHOZ or CHNHZ, where Z=POR 4 R 5 or PSR 4 R 5 , and R, R 4 and R 5 have the meaning indicated with formula (I), can be obtained in that first dihydroartemisinine or the dihydroartemisinine derivative where X=CHNRH is reacted with excess POCl 3 (or PSCl 3 ) and the excess POCl 3 (or PSCl 3 ) is removed by distillation. To the raw product obtained, where X=CHOPOCl 2 (or CHOPSCl 2 ) or CHNRPOCl 2 (or CHNRPSCl 2 ), depending on the type of radicals R 4 and R 5 to be introduced, these are introduced as Grignard reagent R 4 MgBr/R 5 MgBr (if R 4 and/or R 5 are to be (C 1 -C 6 ) alkyl, straight-chain or branched (C 2 -C 6 ) alkenyl, straight-chain or branched (C 2 -C 6 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 6 -C 24 ) aryl or (C 7 -C 24 ) aralkyl)) in the form of an alcoholate R 4 O − /R 5 O − (if R 4 and/or R 5 are to be straight-chain or branched (C 2 -C 6 ) alkoxy or (C 6 -C 10 ) aryloxy)) or in the form of amines HNR 7 R 8 or in the form of water or hydroxide; with the provisos that these reagents are preferably added in the order of their increasing nucleophilicity and, if at least one is to be R 4 and/or R 5 OM, the MOH necessary for this purpose is added as the last reagent. With the compounds where X=CHOZ or CHNRZ, the configuration on this C atom (i.e., the C 10 atom of the sesquiterpene backbone) can be (R) or (S). The compound of formula (I) can also be used in the form of a C 10 -epimer mixture, wherein the ratio of the two epimers can be caused by the preceding reduction of artemisinine and/or by the exchange of the C 10 -hydroxyl group for a different hydroxyl derived from water or for one of the nucleophiles used in the syntheses. Those active agents of the above formula (I) which are selected from artemisinine, dihydroartemisinine, the derivatives containing carboxyl groups (in particular artesunate), arthemeter, arteether, propylcarbonate of dihydroartemisinine and artelinic acid are preferred. Artemisinine, dihydroartemisinine and artesunate are particularly preferred. The compounds of formula (I) can be used individually or as a combination of two or more of these compounds. The compounds of formula (I), in particular artesunate, are also effective in the prevention of acquired nevus cell nevi. For the prevention of nevus cell nevi, the compounds of formula (I), in particular artesunate, are applied extensively over the entire skin, to skin zones with increased probability of the formation of nevi, or to already visible nevus precursors. Skin zones with increased probability of the formation of nevi are on the one hand skin areas that are more frequently exposed to UV radiation. On the other hand, such skin zones are often present in the vicinity of a nevus cell nevus already formed (e.g., in a radius of typically up to 5 cm around the nevus already present). The compounds of formula (I), in particular artesunate, thereby have the further advantageous property that they render visible already existing nevus precursors that are so weak that they are hardly visible to the naked eye. Under the action of the compounds of formula (I), the still invisible nevus precursors first form small red dots, which become dark to black after a few days and in part look like dark crystals sitting in pores. In favorable cases, a reflected light microscope examination of the skin regions at issue is therefore no longer necessary. For application, the active agents of formula (I) can be formulated in a suitable formulation for local application, in particular for topical (cutaneous) application. The concentration of the active agents in the formulations (preparations) produced is not particularly critical. Formulations with a concentration of approx. 0.1 to approx. 40% by weight, based on the formulation, can be produced. For the treatment of nevus cell nevi (congenital=birthmarks or acquired) the formulations preferably contain approx. 5 to approx. 20% by weight of the active agent, and particularly preferably they contain approx. 10% by weight, based on the formulation. For the prevention of the acquired nevus cell nevi, the formulations preferably contain up to approx. 5% by weight of the compound of formula (I), based on the formulation; more preferably they contain approx. 1 to approx. 5% by weight. The precise therapeutically required quantity of active agent depends on the active agent itself, the base used, the prepared galenic form (such as ointment, suspension, pastes, plaster, cream, gel, solution) and on the additives used and can be determined by one skilled in the art by simple effectiveness tests. The duration of treatment of existing nevus cell nevi (congenital=birthmarks or acquired) depends on the type, size, structure, pigmentation and the age of the nevus. Preferably the treatments are carried out cyclically with high concentrations of the compound of formula (I). Initial reactions are often visible after the first few days of treatment. It can take up to several months before there is a clear improvement or change, which is shown by a fading or a disappearance of the nevus cell nevus. This period can be longer in the case of older patients, since the renewal of the epidermis takes much longer with increasing age. For the prevention of acquired nevus cell nevi an application twice or three times is sufficient. Larger nevus precursors are preferably treated longer until the fading or disappearance of the nevus precursors. The active agent of formula (I) should penetrate into the skin to different depths depending on the therapeutic approach: For the treatment of nevus cell nevi (congenital=birthmarks or acquired), the active agent preferably penetrates up to the upper dermis, depending on the type and age of the nevus. For the prevention of acquired nevus cell nevi, the active agent preferably penetrates through the epidermis up to the junction zone, the border between epidermis and dermis. As formulation base for the active agents of formula (I) all bases which are usual for local formulations and are inert toward these agents are suitable. In particular such bases for topical formulations can be petrolatum, fats, waxes, fatty acid esters paraffins, oils, silicones and polymers thereof. Preferably the active agents are formulated with approx. 60 to approx. 99.9% by weight, more preferably with approx. 80 to approx. 95% by weight of formulation base, based on the finished formulation. If hydrophilic/aqueous topical formulation bases are used, such as, e.g., hydrogels, creams, the active ingredients can be protected from degradation by nano-encapsulation, enclosure in liposomes or complexing with, e.g., cyclodextrins. Regarding the complexing of artemisinine and derivatives thereof with cyclodextrins, reference is made by way of example to US-A-2005/187189. Topical formulations with an anhydrous, single-phase base, e.g., a pure fat phase that is anhydrous, are referred to as ointments according to the German Pharmacopeia. Ointments in which the active agents of formula (I) are used according to the invention, thus consist of an ointment base of this type, which can contain the finely distributed active agent(s) for application to the skin. If the topical formulation is to be an ointment, the formulation base can preferably consist of lipophilic constituents with an N-octanol/water partition coefficient at room temperature of approx. 1 to approx. 10 5 , more preferably approx. 10 to approx. 10 5 and particularly preferably approx. 50 to approx. 10 4 . Examples of the formulation base are here, for instance, petrolatum, fats, waxes, fatty acid esters, paraffins, oils, silicones and polymers thereof (e.g., polydialkylsiloxanes, silicone elastomers, silicone waxes, silicone emulsifiers). In the application of an ointment the active agent of formula (I) leaves the topical base surrounding it and penetrates into the skin. The lipophilic base adheres very well to the skin and forms a water-repellent layer to the outside. This layer likewise prevents water leaving the skin to the outside (occlusion effect). Through this effect the skin is kept moist and it heats up because less water can evaporate. Through the increased moisture, the skin also becomes more elastic, which promotes the absorption of active agent. In contrast to the ointment, two-phase systems (aqueous and fat phase) are called creams. The compounds of formula (I) can also be formulated as a cream. The same substances are possible for the fat phase as are exemplified above for the ointment base. In addition to water, the aqueous phase can also optionally contain buffering agents that cause a pH of the aqueous phase well tolerated by the skin, or it can also contain known gel forming polymers, such as, e.g., hydroxypropylmethylcellulose, carboxymethylcellulose, polyvinyl alcohol with crosslinkers (such as borax or multivalent metal cations such as Mg 2+ or Ca 2+ ) and the like. For emulsification, conventional surface-active substances well tolerated by the skin such as, e.g., fatty acid mono and diglycerides, PEG-40 hydrogenated castor oil (Cremophor®) or lecithin can be used. As auxiliary agents for topical formulations, conventional penetration accelerators (such as dimethylacetamide, dimethylformamide, propylene glycol, fatty alcohols, triethanolamine, dimethylsulfoxide, azones and the like) keratolytics to improve effectiveness (such as salicylic acid, urea, retinoids) and preservatives are possible. Additives generally serve to improve the effectiveness, stability, durability and consistency of a galenic form of administration. The compounds of formula (I) are preferably formulated in topical formulations essentially free of penetration-enhancing substances. The compounds of formula (I) are also preferably formulated essentially free of (C 5 -C 19 ) moncarboxylic acids, esters thereof and amides thereof. Within the scope of the present application, “essentially free” means that the topical formulation has less than 1% by weight, preferably less than 0.1% by weight of penetration-enhancing substances, based on the formulation. All the derivatives with a carboxyl group, in particular artesunate, are preferred as compounds of formula (I) for pastes, ointments, creams, solutions, gels, spray or suspensions. The carboxyl group can thereby optionally be present in the form of the alkali metal, alkaline earth metal or ammonium salt. The active agents of formula (I) for application onto or into the skin are preferably applied to a plaster in the form of a topical formulation, in particular in the form of a paste, ointment, suspension, solution, gel, spray or cream, particularly preferably in the form of an ointment. This plaster can optionally have a material which takes up or absorbs the topical formulation. However, the active agent can also be directly suspended or dissolved in an inert adhesive of the plaster; analogous to known plasters, such as for scopolamine (e.g., “Scopoderm TTS”) or for estradiol (e.g., “Estraderm TTS”). In this manner active agents can be in contact with the location to be treated directly and over a longer period. In addition, an occlusion effect occurs, which improves the active agent penetration. Further forms of application of the active agents of formula (I) would be pastes, solutions, suspensions, gels and creams and sprays. The semisolid or liquid formulations of the cited active agents can also be present in the form of a stick (e.g., like a felt tip for precise dosage) or a roller (with active agent in suitable base, solution, suspension, ointment, cream). Further examples of local application forms that can be used according to the invention for the compounds of formula (I) are applicators that effect the penetration of the compounds of formula (I) into the skin or mucous membrane by means of ultrasound, by means of electric fields or by means of microneedles. Known applicators that use ultrasound and can be used according to the invention are disclosed, e.g., in U.S. Pat. No. 6,908,448, which is hereby incorporated by reference. Applicators that use electric fields for the application of the active agents (which therefore use the principle of iontophoresis) have been known for a long time. They are suitable according to the invention for those active agents of formula (I) that are saline, i.e., those where X is CHOZ or CHNRZ, Z being selected from m- and p-CH 2 (C 6 H 4 )COOM, SO 2 OM and POR 4 R 5 , where one of R 4 and R 5 is OM and the other one is a straight-chain or branched (C 1 -C 6 ) alkoxy or OH, and M represents a pharmaceutically acceptable cation. For known applicators with microneedles for the local application according to the invention of active agents to the skin, reference can be made by way of example to US-A-2005/065463, which is likewise incorporated by reference herein. Another example of a local form of application that can be used according to the invention is a technique in which the skin is lifted by means of a suction cup at the location to be treated and on the raised portion of the skin a part of the layer thickness of the dermis is removed mechanically, such as with a blade. This portion of the skin with partially removed dermis is more permeable for compounds of formula (I) and permits the local treatment of deeper layers of the dermis at this location. The equipment necessary for this is described in WO-A-95/15783, incorporated by reference herein. A low-risk, non-invasive preventative or therapeutic treatment of acquired nevus cell nevi or of acquired or congenital nevus cell nevi (=birthmarks) with artemisinine and derivatives thereof (dihydroartemisinine, arteether, arthemeter, artesunate semisynthetic derivatives thereof and synthetically analogous compounds) represents enormous progress in the treatment of nevus cell nevi and could drastically reduce the risk of skin cancer. The invention is thus of great significance not only medically but also socioeconomically. No allergic skin reactions to the compounds were observed with the described topical treatments with the compounds of formula (I), in particular artesunate. It is also remarkable that healthy tissue is not damaged and the treatment is painless and simple. In view of the results obtained so far, it can be assumed that the local, in particular topical therapy with artemisinine and derivatives thereof is very effective and, considered in the long term, as prevention and treatment of nevi is more cost-effective and low-risk than traditional and invasive treatment methods. The invention is now further illustrated by the following examples. EXAMPLE 1 Topical Formulation 3 g of artesunate were stirred homogenously with 27 g of Exipial® fat ointment. EXAMPLES 2a-8h Topical Formulations Different quantities of artesunate (see Table 1) were incorporated into the various bases. In part surface-active substances were also added to the formulations. TABLE 1 Example Artesunate No. (in g) Additives Base q.s. ad 100 g 2a-2h 2a: 0.1 — White Petrolatum 2b: 0.5 2c: 1.0 2d: 5.0 2e: 10.0 2f: 15.0 2g: 30 2h: 40 3a-3h 3a: 0.1 Polysorbate 0.5 g; White Petrolatum 3b: 0.5 Macrogol 2000- 3c: 1.0 Stearate 0.5 g 3d: 5.0 PEG-40-Sorbitan 3e: 10.0 Peroleate 0.5 g 3f: 15.0 3g: 30 3h: 40 4a-4h 4a: 0.1 Beeswax 4b: 0.5 4c: 1.0 4d: 5.0 4e: 10.0 4f: 15.0 4g: 30 4h: 40 5a-5h 5a: 0.1 soya lecithin 2 g Paraffin 5b: 0.5 5c: 1.0 5d: 5.0 5e: 10.0 5f: 15.0 5g: 30 5h: 40 6a-6h 6a: 0.1 Macrogol 2000- Rapeseed oil 6b: 0.5 Stearate 2 g 6c: 1.0 6d: 5.0 6e: 10.0 6f: 15.0 6g: 30 6h: 40 7a-7h 7a: 0.1 Isopropyl myristate 1 g Decamethyl cyclo- 7b: 0.5 pentasiloxane (19 g) 7c: 1.0 Silicone elastomer 7d: 5.0 gel (ad 100 g) 7e: 10.0 7f: 15.0 8a-8h 8a: 0.1 Decamethyl cyclo- 8b: 0.5 pentasiloxane (25 g) 8c: 1.0 Mineral oil ad 100 g 8d: 5.0 8e: 10.0 8f: 15.0 EXAMPLES 9a-9i Topical (Cutaneous) Applications in the Treatment or Prevention of Pigmented Moles a) A 13-year old boy with a raised dark-brown birthmark (dysplastic nevus cell nevus) on the chest, with uneven structure approx 1.2 cm in diameter was treated 2-3 times per week with the 10% artesunate petrolatum ointment from Example 2a. After 2 weeks the birthmark was light brown with a few dark small punctiform spots which looked like “crystallized” coloring matter. The birthmark is dry and flaking and looks as though it is receding from the “inside”. b) A woman with 3 black birthmarks raised over the surface of the skin (junction nevi on the trunk) with a diameter of 0.5 to 1.0 cm applied the 10% artesunate petrolatum ointment from Example 2a 3 times per week under occlusion (as a plaster) overnight. After one week a dark spot was discernible in each birthmark. After 3 weeks the skin flaked off together with this dark crystal-like formations. Three pale birthmarks remained, with pigment-free places, which are no longer raised above the surface of the skin. A continuation of the treatment leads to a further fading and flaking of the skin at the treated locations. c) Treatment of 2 nevus cell nevus precursors, that is extravasated raised areas of the skin with a diameter of 0.3-0.4 cm: A three time application of the plaster with the 10% artesunate ointment from Example 2a overnight after two weeks led to a change in color, light red formation with dark spots. The raised, changed area of the skin could be detached. Two small wounds remained, due to detachment too early, which healed. d) A female test subject with a nevus of approx. 3-4 cm in diameter (basiloma) applied the 10% artesunate ointment from Example 1 over 3 months (cyclically, in the evening, every other week). Initially the nevus exhibited a redness (similar to inflammation process). After 3 months a recession (in terms of color and structure) could be seen of approx. 90%. After approx. 5 months the nevus was no longer visible. e) A female test subject with a nevus on her arm (unction nevus) likewise applied the 10% artesunate ointment from Example 1. Since the test subject was not monitored, no precise data can be given here on the frequency of application; however, the application of the ointment extended over several weeks. The nevus is hardly visible today. f) A 13-year old male test subject with a congenital nevus in the root of the nose/eye area applied the 10% artesunate ointment from Example 1 twice to three times a week under occlusion (plaster) for two months. At first the nevus exhibited many small dark spots. It reacts more slowly. However, initial successes are already indicated. Overall it has become much paler and exhibits several skin-colored areas. g) A 13-year old female patient with a dermal nevus applied the 10% artesunate ointment from Example 1 for 3 days. An immediate concentration with the formation of 3 dark spots in the nevus occurred and the remaining area is virtually colorless. h) A female test subject applied the 10% artesunate ointment from Example 1 twice (once each on 2 consecutive days) over a large area on the abdomen, where she already had numerous nevus cell nevi (unction nevi). In addition to the existing nevi, red, in part nevus precursors of the type described at the outset already became visible on the 2 nd day of treatment in the form of tiny dots that were unevenly distributed over the treated areas. These nevus precursors were already in existence, but were made visible only by the treatment with the ointment. After 2-3 days they became dark to black. In part they looked like dark crystals sitting in pores. They flaked off within 2-3 weeks with the upper stratum corneum layer or detached if scratched a little with a fingernail. i) A female test subject treated the backs of her hands, on which she had numerous pigmented moles (nevi) of differing sizes, with the ointment from Example 1. The existing nevi and nevus precursors faded rapidly and receded with increasing duration of application (7 or 10 days). The color of the pigmented moles became lighter after the treatment was discontinued. After four weeks they were hardly to not at all visible. EXAMPLE 10 Topical Application in the Treatment of Nail Fungal Infections Nail fungal infections on the middle and big toes: half of the nail on the big toe infected. The treatment with conventional agents such as Lamisil had little success. The 10% artesunate petrolatum ointment from Example 2a was applied 3-4 times a week. The ointment was applied above all to the nail bed and under the nail. Already after 2 weeks a distinct improvement could be observed. After 4 weeks the discoloration on the middle toe had completely disappeared or had grown out. The necrotic nail portion on the big toe crumbled off. The treatment of the remaining nail was easier and more effective. The active agent reached the border region to the healthy portion of the nail unhindered. The nail growing in is fine, has no pale discoloration. In the case of fungal infections particularly of the nails, it can be expected that no additional systemic treatment with antimycotics will be necessary and thus not only the cost but also the risk of side effects of the antimycotic treatment will be reduced.
A method of treating a benign pigmented mole or a dermatomycosis. The method comprises locally applying to a subject in need thereof artemisinine and/or one or more structurally related compounds. Also disclosed is a plaster which comprises a topical formulation comprising artemisinine and/or one or more structurally related compounds.
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CROSS REFERENCE TO RELATED APPLICATIONS This application is a divisional of U.S. patent application Ser. No. 11/674,455, filed Feb. 13, 2007, now U.S. Pat. No. 8,093,014, which claims the benefit of U.S. Provisional Patent Application Ser. No. 60/772,584, filed Feb. 13, 2006, no expired. COPYRIGHT AND LEGAL NOTICES A portion of the disclosure of this patent document contains material which is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in the Patent and Trademark Office patent files or records, but otherwise reserves all copyrights whatsoever. FIELD OF THE INVENTION This invention pertains to the determination of post-translational modification of proteins such as phosphorylation and dephosphorylation, including methods and kits, employing elemental analysis. BACKGROUND OF THE INVENTION The methods described facilitate high-throughput assays through multiplexing assays that until now have largely been performed individually. The principal, but not exclusive, target of the method is to provide for the evaluation of agonists and antagonists to phosphorylation (kinase) and dephosphorylation (phosphatase), as these are targets for pharmaceutical drug discovery applications. Overall there are no less than 20 platform technologies available (for example, Radioactivity, Fluorescence Polarization, Time Resolved Fluorescence, Fluorescence Resonance Energy Transfer 1 , etc.), however most display important limitations for the development of a coherent screening-profiling platform. Well known drawbacks include those related to heterogeneous assay systems, limitations in ATP concentration, compound interferences and limitations of substrate size and charge. As well these methods have low level of sensitivity and are difficult to multiplex 2 , i.e. assay dozens of different kinases/phosphatases simultaneously. Thus there are many needs unfulfilled by the prior art, including but not limited to a need for a sensitive, robust and quantitative assay for protein post-translational modification. Further, there is a need for a multiplexed enzymatic assay that enables high throughput operation. Among the many advantages offered by the applicant's teaching are the following: I. The assay can be applied to any type of protein kinase; II. The assay can be applied to any type of protein phosphatase; III. The assay does not exclusively rely on the use of antibodies (although some embodiments might include antibodies); IV. The methods can be used to detect and study protein kinase antagonists and agonists; V. The methods can be used to study protein kinase signal transduction cascades; VI. The methods can be used with a number of different protein kinase buffers; VII. The assay can be supplied as a kit; VIII. The assay can be used to measure activity of multiple kinases/phosphatases in cell free systems; IX. The assay can be used to determine activity of multiple kinases/phosphatases in cellular lysates; X. The assay can be used to determine various endogenous and transfected kinase activities within intact cells. Post-translational modifications of proteins are carried out by enzymes within living cells. Known post-translational modifications include protein phosphorylation and dephosphorylation as well as methylation, prenelation, sulfation, and ubiquitination. The presence or absence of the phosphate group on proteins, especially enzymes, is known to play a regulatory role in many biochemical pathways and signal transduction pathways. Hence together, specialized kinases and phosphatases regulate enzymatic activity. A kinase function is to transfer phosphate groups (phosphorylation) from high-energy donor molecules, such as ATP, to specific target molecules (substrates). An enzyme that removes phosphate groups from targets is known as a phosphatase. The largest group of kinases are protein kinases, which act on and modify the activity of specific proteins. Various other kinases act on small molecules (lipids, carbohydrates, aminio acids, nucleotides and more) often named after their substrates and include: Adenylate kinase, Creatine kinase, Pyruvate kinase, Hexokinase, Nucleotide diphosphate kinase, Thymidine kinase. Protein kinases catalyze the transfer of phosphate from adenosine triphosphate (ATP) to the targeted peptide or protein substrate at a serine, threonine, or tyrosine residue. Protein kinases are distinguished by their ability to phosphorylate substrates on discrete sequences. Commercially available kinases can be in the active form (phosphorylated by supplier) or in the inactive form and require phosphorylation by another kinase. A protein phosphatase hydrolyses phosphoric acid monoesters at phosphoserine, phosphothreonine, or phosphotyrosine residue into a phosphate ion and a protein or peptide molecule with a free hydroxy group. This action is directly opposite to that of the protein kinase. Examples include: the protein tyrosine phosphatases, which hydrolyse phospho-tyrosine residues, alkaline phosphatase, the serine/threonine phosphatases and inositol monophosphatase. Definitions “Protein kinase or phosphatase” as used in the invention may be natural, recombinant or chemically synthesized. If either natural or recombinant, it may be substantially pure (i.e., present in a population of molecules in which it is at least 50% homogeneous), partially purified (i.e., represented by at least 1% of the molecules present in a fraction of a cellular lysate) or may be present in a crude biological sample. “Enzyme (kinase, phosphatase) assays” may target principally one of three quantities: concentration (of either the enzyme or the substrate on which it works); activity of the enzyme on the substrate or substrates; and specificity of the enzymatic activity for a given substrate or suite of substrates. The assay is of value in the determination of the impact of agonists and antagonists on the activity and specificity of the enzymatic action. Examples of the type of information that may be obtained from such assays include: I. The specificity of action on a suite of substrates can be determined if the enzyme is known to be present; II. The activity of the enzyme towards each of a suite of substrates can be determined if the concentration of the enzyme and the time of interaction is known; III. The presence of an enzyme can be determined if action on a substrate is detected; IV. The concentration of the enzyme can be determined if the concentration of the substrate and the activity of the enzyme for that substrate and the time of interaction is known. “Specific kinase assay” refers to an enzyme assay specific for individual kinases in the presence or absence of other phosphatases and kinases. “Specific phosphatase assay” refers to an enzyme assay specific for individual phosphatase in the presence or absence of other phosphatases and kinases. “Non-phosphorylated substrate” is biological material that may be phosphorylated by a protein kinase. The substrate which is targeted by kinases may be a structural protein or another enzyme which is a functional protein or a peptide or a lipid. For example, protein substrates that are typically used in an assay for specific kinase activity include milk casein; histones, isolated from calves; phosphovitin, isolated from egg yolks; and myelin basic proteins, isolated from bovine spinal cords. Production of peptides may be achieved by enzymatic digestion of full length proteins, chemical synthesis 3 or expression of a recombinant peptide. Peptide substrates may contain from about 6 to about 50 amino acids. “Element tag” or “tag” is a chemical moiety which includes any elemental atom or multitude of elemental atoms having one or many isotopes attached to a supporting molecular structure. The element tag can also comprise the means of attaching the tag to a substrate. Different element tags may be distinguished on the basis of the elemental composition of the tags. A tag may contain many copies of a given isotope and may have a reproducible copy number of each isotope in each tag. An element tag may be distinguishable from a multitude of other element tags in the same sample because its elemental or isotopic composition is different from that of other tags. For example, the element tag could be a metal-chelate polymer with an attachment group. The element can be selected from a group consisting of the noble metals, lanthanides, rare earth elements, transition elements, gold, silver, platinum, rhodium, iridium and palladium. The element can be an isotope. The element can include more than one atom of an isotope. For example, an elemental tag can be a metal-chelate polymer with an attachment group. As is known to those skilled in the art, an element tag can be an atomic part of chemical moiety, such as for example Ti in a titanium dioxide particle. A “support” is a surface which has been functionalized by, for example, pyrrole-2,5-dione (rnaleimido), sulfonic acid anion, or p-(chloromethyl) styrene. A support, for example, may be but is not limited to, a synthetic membrane, bead (polystyrene, agarose, silica, etc), planar surface in plastic microwells, glass slides, reaction tubes, etc. as is known to those skilled in the art. “Element labeled bead” is a type of support bead (polystyrene, agarose, silica, etc) which functionally incorporates or is imbibed with an element or multitude of elements with one or many isotopes. As is known to those skilled in the art, an element can be an atomic part of chemical moiety, such as for example Ti in titanium dioxide. “Uniquely labeled bead” refers to a physical entity that includes a multitude of atoms of one or more isotopes of one or more elements imbibed in a bead such that one type of said bead labeled with one or more isotopes or elements is distinguishable from other types of said beads labeled with distinguishable elements or isotopes by elemental analysis. Each uniquely labeled bead can bear a multitude of substrates specific for a given enzyme. A “substrate labeled with an element” tag is a substrate which has included an element tag which allows the substrate to be determined by elemental analysis. A “substrate labeled with a unique element tag” is a substrate labeled with an element tag that is distinguishable from a multitude of other element tags in the same sample and whose presence is indicative of the substrate specific to that tag. A “free phosphorylated substrate” is a substrate that is phosphorylated after synthesis or synthesized using phosphorylated amino acids. Phosphorylamino acids for incorporation into chemically synthesized peptides may be obtained from numerous commercial sources as is known to those skilled in the art. A “phosphorylated substrate” is distinguished from a “non-phosphorylated substrate” primarily by the presence of a phosphate group. “Metal ion coordination complex” is an association of a central metal ion and surrounding ligands, in particular transition metal, rare earth and other metal (Ga(lIl), Fe(III), Al(III), Sc(lll), Lu(Ill), Th(lIl), Zr(IV), complexes, for example, but not limited to, of iminodiacetic acid (IDA) or nitrilotriacetic acid (NTA). Metal oxide forms (such as TiO2, ZrO2, indium tin oxide) are metal compounds with coordinating properties for phosphate ions relevant to the present invention. These have been widely adopted in biology, and are gaining increasing use in biotechnology, particularly in the protein purification technique known as Immobilised Metal-ion Affinity Chromatography (IMAC). Reactions are allowed to proceed for various durations and at different temperatures. The reaction conditions vary depending on the specific kinase/phosphatase, as is known to those skilled in the art. For many mammalian kinases, the reaction is carried out at room (25° C.) or elevated temperatures, usually in the range of 20° C. to 40° C. For high-throughput applications, reaction time is minimized, and is usually from 10 minutes to 4 hours, more usually about 10 minutes to 1 hour. “Elemental analysis” is a process where a sample is analyzed for its elemental composition and sometimes isotopic composition. Elemental analysis can be accomplished by a number of methods, including but not limited to: I. Optical atomic spectroscopy, such as flame atomic absorption, graphite furnace atomic absorption, and inductively coupled plasma atomic emission, which probe the outer electronic structure of atoms; II. Mass spectrometric atomic spectroscopy, such as inductively coupled mass spectrometry, which probes the mass of atoms; III. X-ray fluorescence, particle induced x-ray emission, x-ray photoelectron spectroscopy, and Auger electron spectroscopy which probes the inner electronic structure of atoms. “Elemental analyzer” is an instrument for the quantitation of atomic composition of a sample employing one of the methods of elemental analysis. “Particle elemental analysis” is a process where an analyzed sample, composed of particles dispersed in a liquid (beads in buffer, for example), is interrogated in such manner that the atomic composition is recorded for individual particles (bead-by-bead, for example). “Solution (volume) elemental analysis” is a process where an analyzed sample is interrogated in such manner that the atomic composition is averaged over the entire volume of the sample. “Transition element” means any element having the following atomic numbers, 21-29, 39-47, 57-79 and 89. Transition elements include the rare earth elements, lanthanides and noble metals (Cotton and Wilkinson, 1972). “Affinity product” or “affinity reagent” refers to biological molecules (for example, but not limited to antibody, aptamer, lectin, sequence-specific binding peptide, etc) which are known to form highly specific non-covalent bonds with respective target molecules (peptides, antigens, small molecules, etc). Affinity reagent labeled with a unique element tag is an affinity product labeled with an element tag that is unique and distinguishable from a multitude of other element tags in the same sample. Kinase reaction buffer—There are a number of examples of reaction buffers formulated for specific kinases in the literature. The reaction generally requires the presence of an effective amount of a nucleoside triphosphate, such as ATP, usually at a concentration in the range of about 0.01-20 mM. As is known to those skilled in the art, the buffer may contain substances such as HEPES or Tris-HCI, at a concentration in the range of about 1-50 mM, at a pH of about 5-9. Individual enzymes may generally be present in an amount in the range of lpg-5 ng/μl. Cations such as Mg, Mn and Ca, at concentrations 0.1-5 mM may be employed. Other additives may include DTT at a concentration in the range of 0.1-2 mM. In some instances sodium ortho-vanadate may be used at a concentration of about 0.5-2 mM to inhibit contaminating phosphatases. Also, an inert protein may be included, such as ovalbumin, serum albumin, etc., at 0.1-5 mg/mi, to prevent non-specific binding and inactivation of low concentration assay components, especially to prevent enzyme binding to the surface. For some protein kinases, other cofactors may be required such as phospholipids, calmodulin, cAMP, phosphotidyiserine, and diolein, as is known to those skilled in the art. Phosphatase reaction buffer is a solution of Tris-HCl, at a concentration in the range of about 50-100 mM, at a pH of about 8-9.5, and 100 mM NaCl. Individual enzymes may generally be present in an amount in the range of about I pg-5 ng/pl. Cations such as Mg, Mn and Ca, at concentrations 1-5 mM may be employed. Other additives may include DTT at a concentration in the range of 0.1-2 mM. Methods of separation may include washing of the support by addition of washing buffer (may consist of a solution of 100-150 mM NaCl, 50-100 mM Tris-HCl pH 7) and aspiration of said wash buffer from container (well of a multiwell plate, microtube, etc). If assay if performed with a bead support or with element labeled beads, the method of separation may include low speed centrifugation (300-9,300×g), with or without Molecular Weight Cut Off (MWCO) filtration devices. Elution (of an element tag and/or a metal coordination complex) into solution means (preferably quantitative) solubilization of the elements comprising the tag and or metal atom(s) of the metal coordination complex, in a form to allow solution elemental analysis. Elution may include conventional elution buffers and solvents that maintain the molecular constructs intact, or may involve acid degradation or other means to convert the elements or metals of interest into solution or slurry as is known to those skilled in the art. SUMMARY OF THE INVENTION These and other features of the applicant's teachings are set forth herein. An aspect of the applicant's teachings is to provide a method for a kinase assay, comprising: incubating ATP, at least one kinase, and a free non-phosphorylated substrate labeled with an element tag, with a support having attached thereto metal ion coordination complexes under conditions to enable the kinase to phosphorylate the substrate; separating free non-phosphorylated substrate from bound phosphorylated substrate labeled with an element tag to the support; eluting the element tag associated with the resultant phosphorylated substrate into a solution; and performing solution elemental analysis of said solution. Another aspect of the applicant's teachings is to provide a method for a phosphatase assay, comprising: incubating free phosphorylated substrate labeled with an element tag with a support having attached thereto metal ion coordination complexes; separating free phosphorylated substrate from bound phosphorylated substrate labeled with an element tag attached to the metal ion coordination complexes attached to the support; incubating ADP and at least one phosphatase with the bound phosphorylated substrate labeled with an element tag attached to the metal ion coordination complexes attached to the support under conditions to enable the phosphatase to dephosphorylate the substrate; separating free non-phosphorylated substrate labeled with an element tag from bound phosphorylated substrate attached to the metal ion coordination complexes attached to the support; and measuring the tag element in a solution of the free non-phosphorylated substrate. Another aspect of the applicant's teachings is to provide a method for a phosphatase assay, comprising: incubating, in a multitude of solutions, each solution comprising a different free phosphorylated substrate labeled with an element tag, which can optionally be the same element tag for all substrates, a plurality of element labeled supports having attached thereto a metal ion coordination complex, in such manner that each type of phosphorylated substrate labeled with an element tag, which can optionally be the same element tag for all substrates, is attached to a single type of element labeled support; separating free phosphorylated substrate from the bound substrate attached to the metal ion coordination complex attached to the multitude of element labeled supports in the multitude of separate solutions; incubating the multitude of element labeled supports having attached thereto the multitude of phosphorylated substrates labeled with an element tag, which can optionally be the same element tag for all substrates, through attachment to the metal ion coordination complex that is attached to the supports in a single solution with ADP and at least one phosphatase in conditions that enable the phosphatase to dephosphorylate the phosphorylated substrates; separating free non-phosphorylated substrate from bound phosphorylated substrate labeled with an element tag, which can optionally be the same element tag for all substrates, attached to the metal ion coordination complex attached to said multitude of element labeled supports; and performing particle elemental analysis of bound phosphorylated substrate labeled with an element tag, which can optionally be the same element tag for all substrates, attached to the metal ion coordination complex attached to the multitude of element labeled supports. Another aspect of the applicant's teachings is to provide a method for a kinase assay, comprising: incubating ATP, at least one kinase, and a free metal ion coordination complex, with an immobilized non-phosphorylated substrate under conditions which enable the kinase to phosphorylate the substrate; separating immobilized phosphorylated substrate attached to the metal ion coordination complex from the free ion coordination complex and the immobilized non-phosphorylated substrate; eluting the metal ion coordination complex attached to the immobilized phosphorylated substrate into a solution; and measuring the solution by elemental analysis. Another aspect of the applicant's teachings is to provide a method for a kinase assay, comprising: incubating ATP, at least one kinase, a free metal ion coordination complex, and a multitude of non-phosphorylated substrates immobilized on element labeled supports in such manner that a single type of non-phosphorylated substrate is attached to a single type of element labeled support, in conditions to enable the kinase to phosphorylate the substrates; separating the multitude of phosphorylated substrates immobilized on element labeled supports having attached metal ion coordination complex from the free metal ion coordination complexes and the multitude of immobilized non-phosphorylated substrates; and measuring the multitude of phosphorylated substrate immobilized on element labeled supports having attached metal ion coordination complex by elemental analysis. Another aspect of the applicant's teachings is to provide a method for a kinase assay, comprising: introducing a multitude of non-phosphorylated substrates with element tags into live cells; incubating the cells having the introduced nonphosphorylated substrates with an agonist or an antagonist of kinase activity; fixing and permeabilizing the cells; incubating the cells with element-labeled antibodies directed against phosphospecific kinase substrates; separating the cells from unbound antibodies; and measuring the phosphorylated substrates with element tags and attached element-labeled antibodies by elemental analysis. Another aspect of the applicant's teachings is to provide a method for a phosphatase assay, comprising: incubating ADP and at least one phosphatase, with an immobilized phosphorylated substrate with attached metal ion coordination complexes in conditions that enable the phosphatase to dephosphorylate the substrate; separating the free metal ion coordination complex from the immobilized non-phosphorylated substrate and the immobilized phosphorylated substrate with attached metal ion coordination complex; eluting the metal ion coordination complex into a solution; and measuring the solution by elemental analysis. Another aspect of the applicant's teachings is to provide a method for phosphatase assay, comprising: incubating ADP, at least one phosphatase, and a multitude of phosphorylated substrates with attached metal ion coordination complex immobilized to element labeled supports in such manner that a single type of phosphorylated substrate is attached to a single type of element labeled support in conditions that enable the phosphatase to dephosphorylate the phosphorylated substrates; separating the free metal ion coordination complex from the multitude of non-phosphorylated substrates immobilized to element labeled supports and the multitude of immobilized phosphorylated substrate; and measuring the metal ion coordination complex attached to the multitude of phosphorylated substrate immobilized to uniquely labeled supports by elemental analysis. Another aspect of the applicant's teachings is to provide a kit for the detection and measurement of elements in a sample, where the measured elements include an element tag attached to a non-phosphorylated substrate and a metal ion coordination complex, comprising: an element tag for directly tagging nonphosphorylated substrate; non-phosphorylated substrate; a solid support; a metal ion coordination complex; and optionally, kinase; kinase buffer; and ATP. The kit can urther comprise instructions for i) directly tagging the non-phosphorylated substrate with an element tag ; ii) incubating kinase with element labeled non-phosphorylated substrate in kinase buffer, iii) attaching metal ion coordination complex to the support; iv) incubating the kinase with element labeled non-phosphorylated substrate in kinase buffer with the support having attached metal ion coordination complex; v) separating bound substrate from unbound substrate; vi) eluting the bound substrate, and vii) detecting and measuring the bound substrate by elemental analysis. Another aspect of the applicant's teachings is to provide a kit for the detection and measurement of elements in a sample, where the measured elements include element labels of uniquely labeled supports and an element of a metal ion coordination complex, comprising: a multitude of non-phosphorylated substrates; uniquely labeled supports; metal ion coordination complex; and optionally, kinase; kinase buffer; and ATP. The kit can further comprise instructions for I) immobilizing the non-phosphorylated substrates on element labeled supports in separate solutions; ii) incubating kinase in kinase buffer with the multitude of non-phosphorylated substrates immobilized on uniquely labeled supports, iii) incubating the metal ion coordination complex in the kinase buffer with the kinase and the multitude of non-phosphorylated substrates immobilized on uniquely labeled supports, iv) washing and separating bound substrate from unbound substrate; v) measuring the metal ion coordination complex bound to the multitude of phosphorylated substrate immobilized on uniquely labeled supports by elemental analysis. Another aspect of the applicant's teachings is to provide a kit for the detection and measurement of elements in a sample, where the measured elements include element tags attached to affinity products that recognize phosphorylated substrates, comprising: non-phosphorylated substrate ready to be introduced into a cell; and an element tag for directly tagging an affinity product; and optionally an affinity product. The kit can further comprise instructions for i) introducing the non-phosphorylated substrate into a cell; ii) directly tagging an affinity product that recognizes phosphorylated substrates; iii) fixing and permeabilizing the cells; iv) combining the labeled affinity product with the cells; v) separating bound affinity product from unbound affinity product, and vi) detecting and measuring the amount of the bound affinity product labeled with an element tag by particle elemental analysis. Another aspect of the applicant's teachings is to provide a kit for the detection and measurement of elements in a sample, where the measured elements include an element tag attached to a phosphorylated substrate and a metal ion coordination complex, comprising: an element tag for directly tagging phosphorylated substrate; phosphorylated substrate; a solid support; metal ion coordination complex; and optionally, phosphatase; phosphatase buffer and ADP. The kit can further comprise instructions for I) direct tagging of the phosphorylated substrate with an element tag; ii) attaching the metal ion coordination complex to the support; iii) incubating the element labeled phosphorylated substrate with the support with attached metal ion coordination complex; iv) separating bound substrate from unbound substrate; v) incubating the phosphatase in phosphatase buffer with the support with the attached metal ion coordination complex; vi) separating bound substrate from unbound substrate; vii) eluting the bound substrate, and viii) measuring the bound substrate by solution elemental analysis. Another aspect of the applicant's teachings is to provide a kit for the detection and measurement of elements in a sample, where the measured elements include an element tag attached to a phosphorylated substrate, an element of a metal ion coordination complex, and elements of uniquely labeled supports, comprising: an element tag for directly tagging phosphorylated substrate; a multitude of phosphorylated substrates; uniquely labeled supports; metal ion coordination complex; and optionally, phosphatase, phosphatase buffer and ADP. The kit can further comprise instructions for I) direct tagging the phosphorylated substrates with an element tag; ii) attaching a metal ion coordination complex to the uniquely labeled support; iii) adding element labeled phosphorylated substrates to the uniquely labeled support with attached metal ion coordination complex in separate volumes, iv) incubating the substrates; v) washing the supports; vi) combining the multitude of uniquely labeled supports having attached thereto the multitude of resultant phosphorylated substrate labeled with an element tag through coordination to the metal ion coordination complex that is attached to the supports; vii) incubating the phosphatase, the phosphatase buffer and the supports; viii) separating bound substrate from unbound substrate; and ix) measuring the phosphorylated substrate labeled with an element tag coordinated to the metal ion coordination complex attached to said multitude of uniquely labeled supports by particle elemental analysis. BRIEF DESCRIPTION OF THE DRAWINGS The invention is illustrated in the figures, which are meant to be exemplary and not limiting. FIG. 1 . Dose-dependence curve of EGFR kinase activity. Increasing amounts of EGFR-GST were incubated with 2 ug biotinylated substrate peptide (PTPI B) per reaction per well of 96-well streptavidin coated plate. All reactions were set up in triplicate. Detected signal is presented as normalized response of Ti ions to Ir internal standard. FIG. 2 . Peptide concentration dependence of EGFR kinase activity. Increasing amounts of biotinylated substrate peptide (PTP1 B) were incubated with 50 ng of EGFR-GST per reaction per well of 96-well Streptavidin coated plate. All reactions were set up in triplicate. Detected signal is presented as normalized response of Ti ions to Ir internal standard. FIG. 3 . Intracellular EGFR kinase activity in human cells. Lysates prepared from A431 and KG1-a cells were mixed with PTP1B(Tyr66) substrate linked to agarose beads in the presence of ATP and cations. Washed agarose beads with phosphorylated substrate were incubated with TiO2 particle suspension. Analysis of titanium content in solution was done by ICP-MS. Triplicate samples were set up for analysis. FIG. 4 . Schematic representation of solution ICP-MS analysis of kinase activity in cellular lysates, in accordance with the invention. FIG. 5 . Flow chart showing method of specific kinase(s) assay, in accordance with the invention. FIG. 6 . Flow chart showing method of specific phosphatase(s) assay, in accordance with the invention. FIG. 7 . Flow chart showing method of specific kinase(s) assay using uniquely labeled beads, in accordance with the invention. FIG. 8 . Flow chart showing method of specific phosphatase(s) assay using uniquely labeled beads, in accordance with the invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention comprises use of elemental tags. The choice of the element to be employed in the methods of the applicant's teaching is preferably selected on the basis of its natural abundance in the sample under investigation and whether the element is toxic to the sample under investigation. Most metals of the transition and rare earth groups are anticipated for use in applicant's teaching. It is wise to choose elements that have low or no cytotoxicity and have a low abundance in growth media and biological samples. For example, vanadium and mercury can be toxic to certain cells, while Fe, Cu and Zn can be present in high concentrations in some cell culture media. On the other hand, Pr, Ho, Tb, La, for example are normally well tolerated by mammalian cells and are not abundant in the environment. An unusual isotope composition of the tag element can be used in order to distinguish between naturally present elements in the sample and the tag material. It is advantageous if the relative abundance of the tag elements is sufficiently different from the relative abundance of elements in a given sample under analysis. By “sufficiently different” it is meant that under the methods of the present invention it is possible to detect the target elemental tag over the background elements contained in a sample under analysis. Indeed, it is the difference in inter-elemental ratios of the tagging elements and the sample matrix that can be used advantageously to analyze the sample. It is feasible to select elemental tags, which do not produce interfering signals during analysis (i.e. do not have over-lapping signals due to having the same mass). Therefore, two or more analytical determinations can be performed simultaneously in one sample. Moreover, because the elemental tag can be made containing many copies of the same atoms, the measured signal can be greatly amplified. Aspects of the Applicant's teachings may be further understood in light of the following examples, which should not be construed as limiting the scope of the present teachings in any way. Epidermal growth factor receptor (EGFR) is a 170 kDa tyrosine kinase. Ligand binding results in receptor dimerization, autophosphorylation on numerous tyrosine residues, activation of downstream signaling and lysosomal degradation. Phosphorylation of Tyr845 in the kinase domain may stabilize the activation loop, maintaining the enzyme in an active state and provide a binding surface for substrate proteins. c-Src is involved in phosphorylation of Tyr845. Phosphotyrosine 992 is a direct binding site for the PLC-g SH2 domain, resulting in activation of PLC-g mediated downstream signaling. Phosphorylation of Tyr1045 creates a major docking site for c-Cbl. Binding of c-Cbl to the activated EGFR leads to receptor ubiquitination and degradation. Phospho-Tyr1068 of activated EGFR is a direct binding site for Grb2. Phospho-tyrosine 1148 and 1173 provide a docking site for SHC. Both sites are involved in the activation of MAP kinase signaling. Phosphorylation of EGFR on serine and threonine residues attenuates EGFR kinase activity. Ser1046/1047 in the carboxy-terminal region of EGFR are sites phosphorylated by CaM kinase II. Mutations of Ser1046/1047 upregulate tyrosine autokinase activity of EGFR. EGFR is highly expressed by A431 epidermoid carcinoma cells (at least 1e6 receptors per cell) and is partly responsible for the active proliferation of these cells. EXPERIMENT 1. In one embodiment, in vitro titration assay for recombinant EGFR kinase and substrate were developed using IC P-MS. To probe activity of recombinant EGFR, expressed as a GST-kinase fusion protein (EGFR-GST Cell Signaling Tech. #7908), an ICP-MS assay was devised using a biotinylated peptide substrate PTP1B(Tyr66) (Cell Signaling Tech. #1325) and 5% TiO 2 particle suspension in water (Sigma #643114). Streptavidin coated 96-well plates (Sigma #M5432) were incubated with 2 ug biotinylated PTB1B in kinase buffer (1× Kinase Buffer: 25 mM Tris-HCl (pH 7.5), 5 mM β-glycerophosphate, 2 mM dithiothreitol (DTT), 0.1 mM Na3VO4, 10 mM MgCl2) and 200 mM ATP, to which various amounts of EGFR-GST were added. All reactions were set up in triplicate. The kinase reaction was stopped after 30 minutes incubation with 50 mM EDTA and all wells were washed 6 times with buffered saline. Thus, only phosphorylated PTP1B(Tyr66) attached to the support through biotin-streptavidin binding remained in the wells. For phosphorylation event detection, a solution of TiO 2 diluted a million-fold from the stock 5% in buffered saline was added for binding with phosphate residues on Tyr66. Finally, wells were washed 6 times with buffered saline, and filled with 80 uL concentrated HCl (SeaStar Inc) per well, and an equal volume of 1 ppb lr standard was added for further solution analysis by ICP-MS. Results are presented in FIG. 1 . The results show that GST-kinase activity follows a dose-dependence curve with the maximum activity at 50 ng of kinase per 2 microg of substrate. Antagonists and agonists of the enzyme can also be added to the incubation mix. The support can be labeled particles or beads. The active enzyme can be in the form of a cell lysate. In another embodiment, phosphatase instead of kinase is used as the active enzyme. For example, a solution of free phosphonylated substrate labeled with an element tag can be incubated with a support having attached thereto a metal ion coordination complex. Free phosphorylated substrate can be separated from the bound phosphorylated substrate by methods known to those skilled in the art. ADP and at least one phosphatase can then be incubated with the support under conditions to enable the phosphatase to dephosphonylate the substrate. The free substrate can be removed from the bound substrate and the free substrate can be analyzed by elemental analysis. Antagonists and agonists of the enzyme can also be added to the incubation mix. The support can be labeled particles or beads. The active enzyme can be in the form of a cell lysate. EXPERIMENT 2. In another embodiment, experiments were designed to probe the peptide concentration dependence of the kinase. The conditions were similar to those describe above except that the amount of GST-EGFR was kept constant at 50 ng per well, while the amounts of PTP1B substrate were varied. Results are shown in FIG. 2 . Likewise, the amount of substrate significantly influences the kinase reaction, with 1 microg substrate eliciting a response half of the maximal at 2 microg. EXPERIMENT 3. Another embodiment of the invention is related to EGFR kinase activity in human cell lines analyzed by ICP-MS. The adherent A431 cell line was cultured at 70% confluence in alpha-MEM medium (Invitrogen) supplemented with L-glutamine, penicillin-streptomycin, and 10% fetal bovine serum at 37° C. under 5% CO 2 . Cells were placed on ice and rinsed twice with cold (4° C.) phosphate buffered saline and 400 ul of cell lysis buffer (Cell Signaling #9803) plus phosphatase and protease inhibitors were added to each 100 mm plate. Plate contents were collected by scraping with a plastic cell scraper. The lysate was transferred to a 1.5 ml Eppendorf tube on ice and then clarified at 100,000×g for 15 minutes at 4° C. The suspension grown KG1-a cells were washed with cold buffer by low speed centrifugation (300×g for 10 minutes) and the cell pellet were lysed similar to A431 cells Protein concentration of lysates was determined using the NanoDrop Inc. system. Lysates from the two cell lines were adjusted with lysis buffer to the same protein concentration. KG1-a leukemia cell line does not express EGFR and was used as a negative control for the assay. A431 cells are known to synthesize large amounts of the kinase. The cell lysates were mixed with kinase buffer (Cell Signaling Tech. #9803), 200 mM ATP and agarose-substrate slurry PTP1B(Tyr66) (SignalScout EGFR-substrate on agarose, Stratagene #206307). For positive control, triplicate samples of EGFR-GST kinase (50 ng/sample as described above) were set up instead of the lysate. Negative controls contained the equivalent amount of kinase buffer instead of lysate or kinase. Incubations were carried out at 37° C. for 30 minutes, after which the agarose beads (3 um in diameter according to the manufacturer) were pelleted by low speed centrifugation (500×g, 10 min) and washed 3 times with buffered saline. A 0.0005% suspension of TiO2 particles was added to each sample and incubated for 30 minutes. Thus, the phosphorylated Tyr66 of the PTP1B-agarose substrate interacted with the surface chemistry of TiO2 and bound the titanium particles to the agarose beads. Schematic representation of this process is given in FIG. 4 and a general work flow chart is shown in FIG. 7 . Further washing of agarose beads ensures that only specifically bound titanium particles remain in the samples. Finally, pelleted material was dissolved in concentrated HCl, mixed with an equal amount of 1 ppb lr internal standard and analyzed by solution ICP-MS. Results are presented in FIG. 3 . As evident from the data, only lysates obtained from A431 cells showed a significant response even at the lowest amount of lysate tested (5 ul), while the negative KG1-a cell line did not show EGFR kinase activity at the highest loading. Therefore, the assay may be used to quantify the activity of a known kinase in cellular lysates without the need of using anti-phosphotyrosine antibodies or radioactively labeled reagents. EXPERIMENT 4. In yet a further embodiment, the invention is related to activity of phosphoinositide-3 kinase (Pl 3-kinase) and analysis of Akt phosphorylation and utilized culture conditions in which the cells were serum starved, prior to stimulation with a specific growth factor (PDGF). The Pl 3-kinase is a lipid kinase, phosphorylating the 3-OH of phosphatidylinositol-4,5-bisphosphate. In vitro substrates for Pl3K can be L-α-phosphatidyl inositol, L-α-phosphatidylethanolamine, L-α-phosphatidyl-L-serine, L-α-lysophosphatidylcholine and sphingomyelin to name a few. The generation of this signaling lipid by Pl 3-kinase is in response to growth factor tyrosine kinase receptor stimulation (for example by PDGF) recruiting Pl 3-kinase (consisting of the p85 regulatory domain and the p110 catalytic domain) to the plasma membrane, thereby activating lipid kinase activity. The signaling lipid, phosphatidylinositol-3,4,5-triphosphate (PlP3), recruits kinases that contain pleckstrin homology domains (PH) to the plasma membrane. These include Pdk1, Akt, Tec/Btk tyrosine kinases and Grp1. Pdk1 is a constitutively active kinase whose activity is regulated by localization with target proteins through recruitment to the plasma membrane, or in the case of PKC kinases, through interaction with the PlF binding domain on Pdk1. Pdk1 also activates Akt through phosphonylation. There are a number of targets for Akt, including FKHR, GSK-3, Bad and caspase-9. A role for Pl 3-kinase in cancer is suggested by studies that show that the protein levels are increased in some tumors and through identification of a mutation in the PTEN tumor suppressor gene. PTEN is a lipid phosphatase that negatively regulates the amount of PlP3 in the cell. Loss of PTEN function leads to cell proliferation and growth through enhanced stimulation of the downstream targets of the Pl 3-kinase pathway. As PlP3 is the direct product of Pl 3-kinase, inhibition of this enzyme would similarly reduce the level of PlP3 in the cell and reduce cell growth and proliferation, regardless of the status of PTEN. Inhibitors of Pl 3-kinase have been identified, the best known being wortmannin and LY294002 Wortmannin has been shown to be not specific for Pl 3-kinase. In a recent study, LY294002 was shown to inhibit one other known kinase (casein kinase II), so it may be more specific than wortmannin. Cell line and culture. A2780 ovarian cancer cell line is cultured in RPMl medium (Gibco) supplemented with L-glutamine, insulin (10 ug/ml), and 10% fetal bovine serum at 37° C. under 5% CO 2 . For kinase stimulation 23-24 hour after initiating serum-starvation, the cells are treated with PDGF BB (R&D Systems #220 BB at 10 ng/ml) or control buffer in serum- and supplement-free media with or without inhibitor (25 uM LY294002) or DMSO for 15 minutes. Once the treatment is concluded, the cells are placed on ice and rinsed twice with cold (4° C.) TBS. Cells are collected by scraping with a plastic cell scraper. The pellet is lysed in cell lysis buffer plus inhibitors (see below). The lysate is transferred to a 1.5 ml Eppendorf tube on ice and then clarified at 100,000×g for 15 minutes at 4° C. Aliquots of cell lysate containing activated kinase of interest is reacted with element-labeled specific substrates attached to a solid support. In one embodiment, to assay the activity of Pl3K the synthetic lipid biotinphosphatidylinositol 3,4,5-triphosphate (biotin-Ptdln (3,4,5)P3) from C39B6 Echelon BioSciences Inc. is reacted with a streptavidin coated 96-well plate (SigmaScreen #M5432) to produce a monolayer of substrate attached to the bottom of the wells to which cell lysates prepared as described above are added. Short incubation for 30 minutes and subsequent washes with Tris buffered saline (TBS) yield Ptdln (3,4,5)P3 phosphorylated by activated cellular Pl3K. If cells are incubated with the LY294002 inhibitor prior to PDGF stimulation, then the Ptdln (3,4,5)P3 is not phosphorylated in the designated wells. Finally, TiO2 in kinase buffer is added to all the wells and after a brief wash concentrated HCl is used to dissolve the biomolecules for solution elemental analysis, for example ICP-MS, to determine the absolute amount of titanium. EXPERIMENT 5. In another embodiment, uniquely labeled beads coated with streptavidin are reacted with biotinylted peptide substrates such that each peptide substrate corresponds to one type of labeled bead. For example, Akt substrate with sequence biotin-PRPAATF, GSK-3 substrate with sequence biotin-YRRAAVPPSPSLSRHSSPHQ(pS)EDEEE, PDK1 substrate with biotinKTFOGTPEYLAPEVR-REPRILSEEEQEMFRDFDYIADW, and PKC substrate with sequence biotin-QKRPSQRSKYL (JPT Peptide Technologies GmbH) can be used for the A2780 stimulated cell system. These labeled beads with peptide substrates in kinase buffer are incubated with cell lysates obtained as described above. After washing by low speed centrifugation (10,000 rpm 10 mm in microcentrifuge), the beads are treated with 0.0005% solution of TiO2 particles. The titanium particles bind to phosphate groups which are attached to the peptides by specific kinases present in the cell lysate. The reaction mixture with beads is once again washed by low speed centrifugation and the beads are analysed by elemental analysis particle analysis in the flow cytometric mode. Beads that carry signals of the unique elemental bead identifier together with the titanium particles indicate that the kinase of interest is present and active in the cell. If inhibitors for a specific kinase are used (LY294002 for Akt for example) during cell cultivation then there will be no concomitant Ti present for the uniquely labeled bead with the Akt substrate attached. EXPERIMENT 6. In yet another embodiment cells grown in culture are exposed to non-phosphorylated element-labeled peptides (Akt and PKA substrates, for example) conjugated with a PTD (protein transfer domain) sequence which enables the peptides to be taken up into the cytoplasm of live cells. Otherwise the element-labeled kinase substrates can be microinjected into the cells, encapsulated into lipid microsomes which are taken up by the cells or transferred into the live cells by other means known in the art. The cells are then stimulated with a specific ligand, PDGF in the example above, fixed and permeabilized in order for antibodies labeled with a different element to gain access to the phosphorylated labeled substrates in the cells. For example, an antibody or other affinity product labeled with Eu (europium) against phospho(Thr)Akt substrate (PerkinElmer AD0184) together with an antibody/affinity product to phospho(Thr)PKA substrate labeled with Sm (samarium) can be used. Single cell particle analysis by the flow elemental analysis (for example, flow-ICP-MS) instrument quantitatively detects levels of kinase activity in each cell according to their elemental signals. EXPERIMENT 7. In yet another embodiment, purified kinases or kinases in cell lysates are mixed with kinase substrates labeled with elemental tags in kinase reaction buffer. This is followed by the addition of beads with Ga3+ ions exposed on the bead surface or with titanium oxide beads that are known to bind specifically phosphate groups. Washing in buffers and low speed centrifugation will yield beads that have captured phosphorylated peptides of kinases that were active towards certain substrates. Single particle analysis by flow ICP-MS gives quantitative results of the kinase reaction. Cell Lysis buffer (example): 20 mM Tris, pH 7.5, 150 mM NaCl, 1.0% NP40(v/v), 0.5% NaDOC, 0.1 mM MgCl2, 0.2 mM AEBSF, 1.5 microg/ml Aprotinin, 1.0 microg/ml Leupeptin, 2.0 microM Pepstatin, 50 mM NaF, 1.0 mM Na3VO4. EXPERIMENT 8. Normal phosphatase function is essential for maintaining cellular homeostasis. Dysfunction lies at the basis of numerous diseases including tumorigenesis, thereby making phosphatases potential targets for therapeutic drugs. For example, the protein and lipid phosphatase PTEN has been associated with cancer. It is a tumor suppressor and its loss permits constitutive signaling through the Pl3K pathway and this may lead to the development of a tumor. In cells with low PTEN, there are elevated levels of Ptdln(3,4,5)P3 which acts as a second messenger to promote oncogenesis. PTEN hydrolyzes phosphate at the 3 position on the inositol ring of Ptdln(3,4,5)P3 and Ins(1,3,4,5)P4, however the highest catalytic activity in vitro has been observed with the negatively charged, multiply phosphorylated polymer of (Glu-Tyr)n. Protein phosphatases can be studied as purified enzymes or in the context of cell lysates. However, the cell lysis buffer in this case should not contain phosphatase inhibitors such as sodium vanadate or sodium fluoride. An excellent substrate for the mammalian PIP-lB phosphatase is the peptide from an autophosphorylation site (tyr-992) of the epidermal growth factor receptor (EGFR) -Asp-Ala-Asp-Glu-pTyr-Leu-Ile-Pro-Gln-GIn-Gly (Biomol Inc., #P323-0001). In a solid support experiment, the PIP-i B phosphorylated substrate is immobilized on a surface (microtiter plate or polystyrene bead) and reacted with the phosphatase (purified or as a cell lysate) in a phosphatase reaction buffer. Following washes, Ga 3+ coordination complex is added to the wells (see flow chart FIG. 6 ); high phosphatase activity will be detected as a low signal for Ga3+ ions, whereas low phosphatase activity will have a strong Ga signal. Embodiments when phosphorylated substrates are attached to uniquely elemental labeled beads reacted with the specific mix of phosphatases and hO 2 particles are also envisaged (included in flow chart FIG. 8 ). EXPERIMENT 9. Another embodiment is a. method for a phosphatase assay, comprising: incubating ADP and at least one phosphatase, with an immobilized phosphorylated substrate with attached metal ion coordination complex in conditions that enable the phosphatase to dephosphotylate the substrate; separating the free metal ion coordination complex from the immobilized non-phosphorylated substrate and the immobilized phosphorylated substrate with attached metal ion coordination complex; eluting the metal ion coordination complex into a solution; and measuring the solution by elemental analysis. EXPERIMENT 10. Another embodiment is a method for a phosphatase assay, comprising: incubating ADP, at least one phosphatase, and a multitude of phosphorylated substrates with attached metal ion coordination complex immobilized to element labeled supports in such manner that a single type of phosphorylated substrate is attached to a single type of element labeled support in conditions that enable the phosphatase to dephosphorylate the phosphorylated substrates; separating the free metal ion coordination complex from the multitude of non-phosphorylated substrates immobilized to element labeled supports and the multitude of immobilized phosphorylated substrate; and measuring the metal ion coordination complex attached to said residual multitude of phosphorylated substrate immobilized to uniquely labeled supports by elemental analysis. This allows the measurement of the bead's elemental signal. For example, less signals from the metal coordination complex than prior to phosphatase addition will indicate the level of enzyme activity. Kits: Also provided are kits comprising components to practice the methods of the invention. A kit is provided for the detection and measurement of elements in a sample, where the measured elements include an element tag attached to a non-phosphorylated substrate and a metal ion coordination complex, comprising: an element tag for directly tagging non-phosphorylated substrate; non-phosphorylated substrate; a solid support; metal ion coordination complex; and optionally, kinase; kinase buffer; and ATP. The kit can further comprise instructions for i) directly tagging the nonphosphorylated substrate with an element tag; ii) incubating kinase with element labeled non-phosphorylated substrate in kinase buffer, iii) attaching metal ion coordination complex to the support; iv) addition of said mixture to support with attached metal ion coordination complex vi) separating bound substrate from unbound substrate; vii) eluting the bound substrate, and viii) detecting and measuring the bound substrate by elemental analysis. The kit can further comprise a non-phosphorylated substrate, wherein the non-phosphorylated substrate is directly labeled with an element tag. The kit can further comprise a multitude of non-phosphorylated substrates directly labeled with unique element tags. The support with attached metal ion coordination complex can be a titanium oxide bead. The kit can further comprise a support with an attached metal ion coordination complex. Also provided, is a kit for the detection and measurement of elements in a sample, where the measured elements include element labels of uniquely labeled beads and an element of a metal ion coordination complex, comprising: a multitude of non-phosphorylated substrates; uniquely labeled beads; metal ion coordination complex; and optionally, kinase buffer; and ATP. The kit can further comprise instructions for i) immobilizing the non-phosphorylated substrates on element labeled beads in separate solutions; ii) incubating kinase in kinase buffer with the multitude of non-phosphorylated substrates immobilized on uniquely labeled beads, iii) incubating the metal ion coordination complex with the multitude of phosphorylated substrates immobilized on uniquely labeled beads, iv) washing and separating bound substrate from unbound substrate; v) measuring the metal ion coordination complex bound to the multitude of phosphorylated substrate immobilized on uniquely labeled beads by elemental analysis. The kit can further comprise a multitude of non-phosphorylated substrates immobilized on uniquely labeled beads. Also provided is a kit for the detection and measurement of elements in a sample, where the measured elements include element tags attached to affinity products that recognize phosphorylated substrates, comprising: non-phosphorylated substrate ready to be introduced into a cell; and an element tag for directly tagging the affinity product. The kit can further comprise instructions for i) introducing the non-phosphorylated substrate into a cell; ii) directly tagging affinity products that recognize phosphorylated substrates; iii) fixing and permeabilizing the cells; iv) combining the labeled affinity product with the cells; v) separating bound affinity product from unbound affinity product and vi) detecting and measuring the amount of the bound affinity product labeled with an element tag by particle elemental analysis. The kit can further comprise a multitude of non-phosphorylated substrates to be introduced into a cell. The non-phosphorylated substrate with or without an element tag can be in a sterile solution at a concentration compatible with microinjection into the cell. The kit can further comprise an antibody or affinity product that recognizes phosphorylated substrates, wherein the antibody or affinity product is directly labeled with an element tag. There are many antibodies or affinity products. The kit can further comprise an expression plasmid and wherein the non-phosphorylated substrate is produced by an expression plasmid transfected or electroporated into the cell. The non-phosphorylated substrate with or without an element tag can be in a liposome solution. The affinity product that recognizes the phosphorylated substrates can be selected from a group consisting of antibody, Fab′, aptamer, antigen, hormone, growth factor, receptor, protein, peptide, SH2 peptide, and nucleic acid. Also provided is a kit for the detection and measurement of elements in a sample, where the measured elements include an element tag attached to a phosphorylated substrate and a metal ion coordination complex, comprising: an element tag for directly tagging phosphorylated substrate; phosphorylated substrate; a solid support; metal ion coordination complex; optionally, phosphatase; phosphatase buffer and ADP. The kit can further comprise instructions for i) direct tagging of the phosphorylated substrate with an element tag; ii) attaching the metal ion coordination complex to the support; iii) incubating the element labeled phosphorylated substrate with the support with attached metal ion coordination complex; iv); washing of the support; v) incubating the phosphatase in phosphatase buffer with the support with the attached metal ion coordination complex; vi) separating bound substrate from unbound substrate; ix) eluting the bound substrate, and x) measuring the bound substrate by solution elemental analysis. The support with attached metal ion coordination complex can be a titanium oxide bead. The kit can further comprise a support with attached metal ion coordination complex. The kit can further comprise a phosphorylated substrate which can be directly labeled with an element tag. The kit can further comprise a multitude of phosphorylated substrates directly labeled with unique element tags. Finally, the kit can comprise instructions for the solution to be analyzed by solution elemental analysis. Also provided is a kit for the detection and measurement of elements in a sample, where the measured elements include an element tag attached to a phosphorylated substrate, an element of a metal ion coordination complex, and elements of uniquely labeled beads, comprising: an element tag for directly tagging phosphorylated substrate; a multitude of phosphorylated substrates; uniquely labeled beads; metal ion coordination complex; optionally, phosphatase; phosphatase buffer and ADP. The kit can further comprise instructions for i) direct tagging the phosphorylated substrates with an element tag; ii) attaching a metal ion coordination complex to the uniquely labeled bead; iii) adding element labeled phosphorylated substrates to the uniquely labeled bead with attached metal ion coordination complex in separate volumes, iv) incubating the substrates; v) washing the beads; vi) combining the multitude of uniquely labeled beads having attached thereto the multitude of resultant phosphorylated substrate labeled with an element tag through coordination to the metal ion coordination complex that is attached to the beads; vii) incubating the phosphatase, the phosphatase buffer and the beads; viii) separating bound substrate from unbound substrate; x) measuring the phosphorylated substrate labeled with an element tag coordinated to the metal ion coordination complex attached to said multitude of uniquely labeled beads by particle elemental analysis. The kit can further comprise a multitude of phosphorylated substrates directly labeled with the same element tag or unique element tags. The kit can further comprise a multitude of uniquely labeled beads with attached metal ion coordination complex. The nonphosphorylated substrate with or without an element tag can be attached to a protein transfer domain (PTD) in a sterile solution. The kit can comprise instructions for a cell lysate to be incubated wherein the cell lysate comprises a phosphatase. In the kits described above the element can be measured using a mass spectrometer. The element can be an isotope or ion. The element can be selected from a group consisting of the noble and transition metals, lanthanides, rare earth elements, gold, silver, platinum, rhodium, iridium and palladium. The element can include more than one atom of an isotope. The kits can further comprise standards, a dilution buffer, an elution buffer, a wash buffer and/or an assay buffer. Instructions for particle elemental analysis can also be included. The kits can also include the following reagents: (i) Protein kinase substrate labeled with element tag (ii) Lipid kinase substrate labeled with element tag (iii) Uniquely labeled beads with attached metal ion coordination complex (iv) Uniquely labeled beads attached to kinase substrate (v) Uniquely labeled beads attached to phosphatase substrate (vi) Protein phosphatase substrate labeled with element tag (vii) Lipid phosphatase substrate labeled with element While the Applicant's teachings are described in conjunction with various embodiments, it is not intended that the Applicant's teachings be limited to such embodiments. On the contrary, the Applicant's teachings encompass various alternatives, modifications, and equivalents, as will be appreciated by those of skill in the art. All references cited in the disclosure are herein incorporated by reference. Reference List 1. Noland, B. Determining phosphorylating activity of enzyme, by combining enzyme with phosphorylatable compound labeled with acceptor fluorophore, ATP analog, and donor fluorophore, and measuring fluorescence resonance energy transfer. STRUCTURAL GENOMIX INC and Noland, B. [W02004059291-A2; US20041 46961-A1; AU2003300363-A1]. 2. Xue, Q.; Gibbons, I. Multiplexed enzyme assay comprises performing enzyme reactions in presence of substrates to convert substrate to product, separating them, detecting their separation characteristic and determining amount of product. 3. Saxinger, C. Automated peptide synthesis—using novel solvent resistant substrates and novel solns. for storing protected carboxyl terminal aminoacid(s). US DEPT HEALTH & HUMAN SERVICE, US SEC OF COMMERCE, and US NAT INST OF HEALTH. [US7398458-N; WO9102714-A; AU9061 859-A; US6031 074-A]. 4. Crouch, S. P. M.; Slater, K. J. Measuring protein kinase activity, involves adding substrate to a solution with ATP and kinase, and another solution with ATP alone, and measuring ATP and/or ADP concentration using a bioluminescence reaction. 5. Hackel, P. O.; Zwick, E.; Prenzel, N.; Ullrich, A. Epidermal growth factor receptors: critical mediators of multiple receptor pathways Current Opinion in Cell Biology 1999, 11, 184-89. 6. Cooper, J. A.; Howell, B. The When and How of Src Regulation Cell 1993, 73, 1051-54. 7. Schlosser, A.; Vanselow, J. T.; Kramer, A. Mapping of phosphorylation sites by a multi-protease approach with specific phosphopeptide enrichment and nanoLC-MS/MS analysis Analytical Chemistry 2005, 77, 5243-50. 8. Meyer, T. J.; Meyer, G. J.; Pfennig, B. W.; Schoonover, J. R.; Timpson, C. J.; Wall, J. F.; Kobusch, C.; Chen, X. H.; Peek, B. M.; Wall, C. G.; Ou, W.; Erickson, B. W.; Bignozzi, C. A. Molecular-Level Electron-Transfer and Excited-State Assemblies on Surfaces of Metal-Oxides and Glass Inorganic
Methods and kits for enzymes involved in post-translational modifications are provided. The methods employ elemental analysis, including ICP-MS. The methods allow for the convenient and accurate analysis of post-translation modifications of substrates by enzymes involved in post-translational modifications, including kinase and phosphatase enyzmes.
64,521
FIELD OF THE INVENTION The present invention relates to vibrating modules that generate an alerting signal utilizing vibration, rather than calling of an audible electronic buzzer, to a user of portable equipment such as pagers, watches, portable phones or signal receivers for the visually-impaired. The portable equipments, for example pagers, use a system wherein in response to the calling signal from a caller, an alerting mechanism incorporated in the pager worn by a user produces an alarm sound, thereby letting the user know that the user is being called. This alerting means using an alarm sound has a serious disadvantage that the alarm sound may be audible to those people who happen to be near the user or may annoy them. To overcome this disadvantage, vibrating modules are being offered as mainly-non-audio alerting signal generator wherein vibration is generated instead of an alarm sound so that only the user can recognize the alerting signal. FIG. 16 is a general view of a conventional vibrating module using a cylindrical motor. In the conventional example shown in FIG. 16, an unbalanced weight 120 is attached to a shaft 970 of a cylindrical motor 900, and vibration is generated by rotation of the motor. FIG. 17 is a diagram showing a conventional vibrating module utilizing a flat motor. FIG. 17B is a vertical section view of a conventional vibrating module utilizing a flat motor, whereas FIG. 17A is a top plan of a rotor of a conventional vibrating module utilizing a flat motor. As shown in FIG. 17, a flat motor 900 is provided wherein a thin armature coil 220 is located on one side and molded with resin into a fan shape weight 120 to constitute a rotor. The flat motor 900 uses a flat rare earth magnet 110 magnetized in the direction of thickness to constitute a stator. Current supply and current switching of the armature coil 220 of the rotor is performed by a commutator 960 and a brush 950. By locating armature coils 220 on one side the, center of gravity of the rotor is located in unbalance and the armature coils 220 are rotated around the shaft 970 to operate as eccentric weights. Other example of vibrating modules not using a motor is a vibrating module in which a vibrating mass held by spring comprises a permanent magnet and an additional mass vibrates continuously (Tokkai Hei 2-71298, Tokuhyo Hei 5-500022). In any of conventional examples including the above, a ring-shaped magnet magnetized in radial direction having a pair of magnetic poles is not used. As example of a vibrating module having a plurality of anisotropic magnet pieces arranged on the circumference, there is a vibrating module that vibrates a vibrating mass held by two springs continuously in a reciprocating motion (U.S. Pat. No. 5,326,120). Conventional vibrating modules have the following disadvantages: (1) A vibrating module using a cylindrical motor has a limitation that, if the diameter of the cylindrical motor is made smaller, the unbalanced weight has to be made smaller, with the result of vibration output too weak for an alerting device to be used in practice. Furthermore, a vibrating module using a cylindrical motor is difficult to be miniaturized to a size usable in a thin card-type portable equipment. Also, since the shaft is rotated at high speed with the unbalanced weights attached thereto, too much load is applied to the bearing, thereby shortening its life. Moreover, the shaft may be deformed by a shock caused when dropped. (2) A vibrating module using a flat motor can be made thin but is difficult to provide a vibration in the direction of thickness. In addition of a relatively short life due to brush motor used, durability is so low as to be deformed by a shock caused by drop. Another disadvantage is that such vibrating module has a complicated structure and therefore is difficult to be manufactured, and is associated with high manufacturing costs. (3) In a conventional example of a vibrating module wherein a magnet is vibrated in a reciprocating motion by means of spring, a vibrating mass consisting of a permanent magnet and a weight, and current flowing in the drive coil, since the magnet is not magnetized in the radial direction, drive efficiency is low and the structure is complicated. Therefore, since the characteristics needed to be used in practice are not yet obtained, such vibrating module is not actually used in practice. (4) In the conventional vibrating module disclosed in U.S. Pat. No. 5,327,120, a plurality of anisotropic magnets that are easy to manufacture are arranged on the circumference. Therefore the dispersion of each magnet and the dispersion of dimensions and positioning by assembly are multiplied, and force applied to the magnets by electromagnetic force generated with the drive coil becomes ununiform. Disadvantageously, when the magnet and the coil are approached to a smaller interval between them for obtaining an enough alerting output, the magnet and the drive coil come into contact to each other during the use of the vibrating module in many cases. To avoid this, the gap between the magnet and the drive coil must be enlarged. If the gap is large, however, the drive efficiency decreases considerably for a magnetic circuit, and the vibrating mass cannot have the vibration amplitude large enough for providing the needed alerting output. Also, repulsion and attraction force are generated between the magnets when they are located close to each other, making the assembling work difficult. Therefore the interval between the magnets cannot be made small, so the area of the part where there is no magnet confronting a drive coil becomes large, considerably decreasing the generation efficiency of the electromagnetic force. Thus, the problems to be solved in providing a vibrating module useful in practice which have been derived from the above can be summarized as follows: 1. To obtain the needed vibration output. 2. To reduce the dispersion of quality. 3. To make a small, thin and light-in-weight body. Particularly, to make the diameter of φ 25 mm or less. 4. To provide a long life and a high reliability. 5. To provide a high shock resistance. 6. To provide a high drive efficiency (low voltage and low power consumption). 7. To provide a low manufacturing cost. SUMMARY OF THE INVENTION The present invention provides a vibrating module generating a mainly-non-audible alerting signal for portable equipment utilizing a vibrating mass supported by spring and comprising a permanent magnet and additional mass, wherein the permanent magnet has a ring shape and is magnetized in the radial direction, particularly with a radial anisotropy. Such vibrating mass is vibrated continuously in a linear vibrating motion in the resonant frequency of around 100 Hz by the current made flowing in a drive coil to generate an alerting signal, thereby structuring a vibrating module having a small and thin body, a long lifetime, a high reliability and a high shock resistance. To solve the above problems, the vibrating module according to the present invention has a structure characterized in the following points: (1) The vibrating module is structured with a vibrating mass held by spring/springs and a drive coil that generates electromagnetic force with an electric signal supplied from the drive circuit, wherein the vibrating mass is put into a continuous reciprocating motion close to a resonant frequency determined by the vibrating mass and the spring/springs and thereby transmitting the vibration of the vibrating mass to the outside, to construct a vibrating module generating an alerting signal using vibration instead of sound as main means. The friction part, such as a bearing or brush, has been eliminated by adopting this construction. (2) For the magnet that is a structure element of the vibrating mass, a radial anisotropic ring magnet is used which has been magnetized to constitute a single pair of magnetic poles in the radial direction and which is manufactured using the manufacturing method of ring-shaped radial magnet of the invention of Japanese patent application Hei 5-52473 applied by the same applicant of the present invention, to provide a vibrating module having a structure wherein the magnet and the coil are located confronting each other with a uniform interval around the circumference. (3) As a means for increasing the efficiency of the magnetic circuit of the vibrating module, the drive coil and the magnet are so arranged that the center of the height of the drive coil and the center of the height of the magnet substantially coincide with each other and the height of the drive coil Lc>the height of the magnet Lm> or Lc<Lm. (4) In order to increase the vibration force of the vibrating module, the weight of the vibrating mass needs to be increased while the vibrating mass is being prevented from coming in contact with the spring during vibration. For the shape of the vibrating mass which maximizes the weight while not contacting the vibrating mass with the spring, either the section of the vibrating mass confronting the spring has a deflection curve described as: Formula 1! Y=k×{3×X/L-4×(X/L).sup.3 } where 0≦X≦(L/2) Y=k× 3×(L-X)/L-4×{(L-X)/L}}.sup.3 ! where (L/2)<X≦L or the shape of the vibrating mass is so formed as not to contact the deflection curve of the spring given by Formula 1 except the joint part of the vibrating mass and the spring when the vibration amplitude of the vibrating mass reaches the largest designed amplitude. (5) The diameter of the spring becomes small as the vibrating module is miniaturized, and this leads to the difficulty in ensuring the effective length for obtaining the optimum resonant frequency. To ensure the effective length, the spring is given a curvature. Due to this curvature, however, a torsional motion is generated in the spring by the vibration of the spring, with the result that an abnormal vibration tends to occur in the vibrating mass. For this reason, in order to provide a simple reciprocating motion, the springs with opposite torsion polarities are arranged over and under the vibrating mass confronting each other if there are a plurality of the springs, or spring members with opposite torsion polarities are combined and integrated into a spring and arranged at least either over or under the vibrating mass in the vibrating module so that the torsional motions are compensated by each other. (6) In case that two springs are used, to make the vibrating module thin, the springs are given a three-dimensional shape so that the interval between the springs is smaller at the center part. The present invention thus structured solves the disadvantages of the conventional vibrating module for the following reasons: (1) Differently from the conventional vibrating modules using a motor shown in FIG. 16 and FIG. 17, the vibrating module according to the present invention has a structure wherein a vibrating mass is put in a continuous reciprocating motion close to the resonant frequency by means of a radial magnet, a drive coil and spring/springs. Therefore the friction parts such as bearing and brush are eliminated, a small, thin body and light weight as well as a long life and a high reliability are achieved, and the shock resistance (drop resistance) is improved. (2) By using a radial anisotropic ring magnet magnetized to constitute a single pair of magnetic poles in the radial direction, as the magnet confronts the drive coil around the circumference, the confronting area of the drive coil is larger than the conventional vibrating modules, significantly increasing the generation efficiency of electromagnetic force. As a result, a vibration output sufficient for a vibrating module is obtained while achieving a thinner body and a lower power consumption. Also, the number of the parts is reduced by use of a single magnet, thereby diminishing the parts cost and the manufacturing cost. Moreover, in comparison with the conventional vibrating modules using a plurality of magnets which are difficult to assemble because the magnets generate the repulsion and attraction force between them when coming close to each other, in the vibrating module of the present invention, this problem in assembly is removed, improving the workability with the result of possible reduction of manufacturing cost. Furthermore, in the conventional vibrating modules, the dispersion of property of each magnet and the dispersion of dimensions and positioning produced by assembly are multiplied, force applied to the magnets by electromagnetic force with the drive coil becomes nonuniform, thereby causing problems in quality. This problem is also solved in the present invention. (3) The drive coil and the magnet are so arranged that the center of the height of the drive coil and the center of the height of the magnet substantially coincide with each other and the height of the drive coil Lc>the height of the magnet Lm> or Lc<Lm. As will be described in detail for the embodiments, in the conventional vibrating modules the drive force of the drive coil reduces when the magnet is displaced and the end surface of the magnet protrudes from the end surface of the drive coil. In the present invention, by adopting the structure where the drive coil and the magnet are arranged as described above, the efficiency of the magnetic circuit of the vibrating module is increased, the above described reduction in drive force is amended, and a low power consumption is achieved while providing a sufficient vibration output. (4) In order to increase the vibration force of the vibrating module, as a shape of the vibrating mass which maximizes the weight while not contacting the vibrating mass with the spring, either the surface of the vibrating mass confronting the spring has a deflection curve described as: Formula 1! Y=k×{3×X/L-4×(X/L).sup.3 } where 0≦X≦(L/2) Y=k× 3×(L-X)/L-4×{(L-X)/L}.sup.3 ! where (L/2)<X≦L or the shape of the vibrating mass is so formed as not to contact the deflection curve of the spring given by Formula 1 except the joint part of the vibrating mass and the spring when the vibration amplitude of the vibrating mass reaches the largest designed amplitude. By adopting such shape, the weight of the vibrating mass can be increased while the vibrating mass is being prevented from contacting the spring during the operation of the vibrating module, allowing to provide a sufficient vibration output while achieving a thinner body. (5) The springs with opposite torsion polarities are arranged over and under the vibrating mass confronting each other or spring members with opposite torsion polarities are combined and integrated into a spring and arranged over or under the vibrating mass in the vibrating module so that the torsional motions are compensated by each other. Thus, the vibrating mass effectuates a stable reciprocating motion only without generating a torsional motion. (6) In case that two springs are used, to make the vibrating module thin, the springs are given a three-dimensional shape to have a smaller interval at the center part between the springs, thus allowing a thin vibrating module body. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a section view showing the structure of a vibrating module of an embodiment of the present invention. FIG. 2 is a section view showing the structure of a vibrating module of another embodiment of the present invention. FIG. 3 is a plan view showing an embodiment of the structure of the spring of the vibrating module of the present invention. FIG. 4 is a section view showing the structure of a vibrating module of another embodiment of the present invention. FIG. 5 is a schematic diagram explaining the calculation method of the deflection curve of the spring used in the vibrating module of the present invention. FIG. 6 is a schematic diagram explaining the operation of the spring and the weight used in the vibrating module of the present invention. FIGS. 7A-7D are section view showing embodiments of the structure of the vibrating mass used in the vibrating module of the present invention. FIG. 8 is a plan view showing an embodiment of the structure of the spring used in the vibrating module of the present invention. FIG. 9 is a plan view showing an embodiment of the structure of the spring used in the vibrating module of the present invention. FIG. 10 is a plan view showing an embodiment of the structure of the spring used in the vibrating module of the present invention. FIG. 11 is a plan view showing an embodiment of the structure of the spring used in the vibrating module of the present invention. FIG. 12 is a plan view showing an embodiment of the structure of the spring used in the vibrating module of the present invention. FIG. 13 is a schematic diagram explaining the positional relationship between the drive coil and the magnet used in the vibrating module of the present invention. FIG. 14 is a graph showing the relationship between the displacement of the magnet used in the vibrating module of the present invention and the electromagnetic force generated. FIG. 15 is a section view showing the structure of a vibrating module of an embodiment of the present invention. FIG. 16 is an outerward appearance view of a conventional vibrating module using a cylindrical motor. FIGS. 17A and 17B are a longitudinal section view of a conventional vibrating module using a flat motor and a top plan view of the rotor thereof. DETAILED DESCRIPTION OF THE INVENTION The embodiments of the present invention will be hereinafter described referring to the drawings. In the drawings of the embodiments, the same numeral is given to the identical part, and the same description will not be repeated for each drawing. Embodiment 1! The outer appearance of the vibrating module of embodiment 1 is substantially of a disc shape. FIG. 1 and FIG. 2 are longitudinal section views taken at the center of the vibrating module according to embodiments of the present invention. The difference of the embodiments of FIG. 1 and FIG. 2 is the three-dimensional shape of the springs 310. Referring to FIG. 1 and FIG. 2, springs 310 are joined with a vibrating mass 100 by means such as caulking and are fixedly secured to a drive coil block 200 by means such as welding. The drive coil block 200 consists of a drive coil 220 and a drive coil frame 210 made of resin holding the drive coil. A magnet 110 magnetized in the radial direction which is a constituent of the vibrating mass 100 and the drive coil 220 of the drive coil block 200 has a slight gap between them, confronting each other in the direction of radius. Drive current supplied to the drive coil 220 through a terminal 510 and the magnet generate an electromagnetic force in the longitudinal direction, and the vibrating mass vibrates in the longitudinal direction of the vibrating module close to a resonant frequency determined by the weight of the vibrating mass 100 and the springs 310. A case 410 and a case 420 contain the above mentioned drive coil block with the springs and the vibrating mass attached thereto. The terminal 510 is provided in the drive coil block 200 and connected to the end of the drive coil 220 to supply drive current to the drive coil from the outside. The vibrating mass 100 consists of a single ring magnet 110 magnetized in the radial direction attached to a weight 120 using adhesive and the like. To have an outer diameter of the vibrator of φ 25 mm or less so as to be mounted in small-size portable equipment, the magnetic circuit including the magnet must also be miniaturized. Generally the magnetic circuit loses the drive force if miniaturized, yet the needed magnetomotive force must be ensured to provide the needed vibration output even with miniaturized magnet. Therefore, the above mentioned magnet 110 require a large energy density using magnets such as centered SmCo and Nd Fe B magnets or bonded magnets consisting of rare earth magnet materials. The rare earth centered magnet has problems that it is easy to chip in the surface corner, easy to generate magnet powder, and it rusts, and is therefore preferably used with a surface coating such as plating, painting. Appropriate chamfering on the ring edge of the magnet is also preferable to avoid chipping on the edge of the magnet as well as to facilitate insertion into the weight 120. The magnet 110 is molded in a magnetic field to be oriented radially during molding, then is surface coated if necessary, and radially magnetized. To make the outer diameter of the vibrating module φ 25 mm or less, the outer diameter of the ring magnet to be used for the vibrating mass is preferably φ 20 mm or less. Thus a ring-shaped radial anisotropic, radially magnetized magnet of a small outer diameter of Φ 20 mm or less which is integrally molded is manufactured. For the method of orientation for such small-diameter radial magnet, a method of orientation of the Japanese patent application (Tokugan Hei 5-52473) of the same applicant is effective, and this method has allowed the industrial manufacturing of a small-diameter magnet having an outer diameter of Φ 20 mm or less which is used for the present invention. The magnet 110 is so magnetized that a single pair of magnetic poles is obtained as shown in FIG. 1 and FIG. 2. The vibration frequency of the vibrating module is determined by the weight of the spring 310 and the vibrating mass 100. The weight 120 supports the magnet 110 and has a purpose to adjust the weight of the vibrating mass. In order to constitute a small and thin vibrating module, material of the weight 120 needs to be a metal with a large specific gravity such as tungsten alloy or lead alloy to ensure the needed weight even with a reduced volume of the weight 120. The resonant frequency of the vibrating module of the present invention is adjusted to approximately 80 Hz to 150 Hz by means of the above described spring 310 and the vibrating mass 100. The above mentioned tungsten alloy may have a specific gravity of around 19, but is adjusted to have a specific gravity of 10 or more considering the economy because the price of tungsten is expensive. Tungsten alloy is manufactured by centering alloy consisting of either W, Ni and Cu or W, Ni and Fe. By the method of manufacturing the weight by centering, however, there is difficulty in providing accuracy in size due to contraction during centering. Therefore a finish process is conducted by sizing to ensure the accuracy of dimensions. Tungsten content is determined to be 40 to 97 wt. % considering the economy and workability in order to have a specific gravity of 10 or more. For the shape of the weight, the joint part 121 with the springs 310 has sightly larger height than main part of weight 120 as shown in FIG. 1 and FIG. 2, to allow optimum setting of the contact area with the springs. For the joint of the vibrating mass 100 and the springs 310, in the case of FIG. 1, the two springs are placed with the weight therebetween, and a pin 130 is inserted in the hole 125 provided through the center of the weight, then the pin 130 is put through a center hole 311 of the spring 310 shown in FIG. 3, and the tip of the pin is deformed by means such as caulking. In the case of FIG. 2, a protruding portion 122 is provided on the weight 120, and the protruding portion 122 of the weight 120 is put through the center hole 311 of the spring 310 shown in FIG. 3, and then the tip of the protruding portion is deformed by means such as caulking to join the vibrating mass and the spring. As means for joining the weight and the spring, other than the above mentioned caulking, a method of driving a caulking pin, a method of driving a washer, and a method of using adhesive and the like are also available. The frequency determined by the spring and the vibrating mass can be designed using a model of a beam fixed at both ends with a load added to the center and support at both ends. If the vibrating mass is lighter in weight, the springs becomes relatively thinner, causing problem in strength. The shape of the spring must be determined considering lifetime. FIG. 3 is a plan view of the spring 310 of the present invention. The center hole 311 of the spring 310 is for fixing the spring to the vibrating mass as described above, and the fixing hole 312 is for fixing the spring to the drive coil frame. The beam portion 313 is the beam of the above described model for calculation, and this abortion performs the essential function of the spring. The plan view of the spring mounted in the vibrating module is substantially the same for the embodiment of the present invention shown in FIG. 1 and for another embodiment of the present invention shown in FIG. 2. The difference between them is in the three-dimensional shape of the spring 310. Specifically, in the embodiment of the present invention shown in the longitudinal section view of FIG. 1, the interval between the upper and the lower springs 310 varies at the center and circumference with regard to the direction of radius, that is, the springs has a three-dimensional shape so that the interval is smaller at the center part of the springs 310. This shape allows to minimize the gap between the spring and the case close to zero, achieving the miniaturization of the vibrating module. In another embodiment of the present invention shown in FIG. 2, the spring 310 is in one plane, the interval between the upper and the lower spring is substantially the same at the center and circumference of the spring 310. As the vibration force of the vibrating module is proportional to the weight and amplitude of the vibrating mass and to the square of the resonant frequency, the needed designed amplitude must be ensured to provide a vibration force needed for the vibrating module. In the embodiment of FIG. 2, the intervals between the vibrating mass 100 and the spring 310, between the springs 310 and the case 410 and the case 420 must be larger than the designed amplitude of the vibration. The intervals therefore have to be set large, resulting in a large thickness of the vibrating module. In the embodiment of FIG. 1, the spring 310 has a three-dimensional shape so that the interval at the center is smaller than the interval at the circumference, allowing to reduce the interval between the spring and the case and thereby to make a thinner-body of the vibrating module. Particularly if the interval at the center part is so narrowed that the difference between the height of the joint part of the spring and the vibrating mass and the height of the joint part of the spring and the drive coil block is larger than the designed amplitude of the vibrating module, the intervals between the case 410 and the upper spring 310 and between the case 420 and the lower spring 310 at the circumference can be zero theoretically. Thus a thinner body for the vibrating module is allowed in the embodiment of FIG. 1. The drive coil block 200 consists of a drive coil 220 and a drive coil frame 210 made of resin holding the drive coil, as described earlier. In FIG. 1 the drive coil 220 and the terminal 510 are integrally formed with the drive coil frame 210, whereas in FIG. 2 the drive coil 220 is located between two drive coil frames 211 and 212 and attached thereto by means of mechanical fitting or adhesives, and the attached two drive coil frames are integrated into one unit to constitute a drive coil frame 210. In the coil frame 212 there is further provided a terminal 510 which is electrically connected to the drive coil 220. By a drive current from the outside, magnetic flux is generated in the drive coil 220. A terminal is used as current supply path to the drive coil in FIG. 1 and FIG. 2, but other means such as lead wire and flexible substrate may be used. Three terminals are provided in the embodiments of FIG. 1 and FIG. 2, but one of these terminal is for fixing the vibrating module to the substrate and therefore is not necessary for electrical purpose. Two springs 310 are joined to the drive coil block 200. For the method of joining, protruding parts are provided on the drive coil frame 210 corresponding to the fixing holes 312 of the spring. The protruding parts are put into the fixing holes 312 and heat welded or ultrasonic welded to fix the spring with the drive coil frame. For the method of fixing, other than the method above, a method whereby the drive coil frame 210 is formed with the spring 310 is inserted therein to integrate the spring with the drive coil frame and other methods such as using adhesive or mechanical fixing can be used. The vibrating module that vibrates in a linear reciprocating motion which is the purpose of the present invention is essentially constituted by the above described drive coil block 200 with the terminals 510, the vibrating mass 100 and the springs 310 only. The gap between the magnet 220 and the drive coil 110 is set to the minimum to increase electromagnetic efficiency. Consequently vibration is restricted or stopped if unexpected particles such as dust intrude or the spring comes into contact with an external object. To prevent this the cases 410 and 420 are provided. As the vibrating module of the present invention is intended for the use in thin portable equipment, the gap between the cases 410 and 420 and the magnet 110 is naturally small. Consequently if the cases 410 and 420 is made of magnetic substance, a magnetic attracting force is effected between the magnet and the cases and restricts the vibration of the vibrating mass. Therefore the cases 410 and 420 must be made of non-magnetic material. For the material of the case, for examples of metal, non-magnetic SUS materials (such as SUS 304 and SUS 316), aluminum and the like are suitable. Plastic case may also be used. Mechanical fixing such as caulking and crimping is advantageous for a metal case, but adhering is also available. For a plastic case, mechanical fixing such as welding as well as the use of adhesives are available. Embodiment 2! Another embodiment of the present invention will now be described referring to the drawing. Referring to FIG. 4, a single spring 310 is joined with a vibrating mass 100 by means such as driving a caulking pin 130 and fixedly secured to a drive coil block 200 by means such as welding. A drive coil block 200 is structured by winding a drive coil 220 around a bobbin 210 made of resin. The vibrating mass 100 is arranged around inner circumference of the drive coil block 200. The magnet 110 magnetized radially which is a constituent of the vibrating mass 100 and the drive coil 220 of the drive coil block 200 confront each other in the radial direction with a small gap between them. Electromagnetic force in the longitudinal direction is generated by the drive current supplied through a terminal 510 to the drive coil 220 and the magnet, vibrating the vibrating mass in the longitudinal direction of the vibrating module around the resonant frequency of 80 Hz to 150 Hz determined by the weight of the vibrating mass 100 and the spring 310. A case 410 and a case 420 contain the drive coil block 200, the spring and the vibrating mass. The terminal 510 is provided on the drive coil block 200, being connected to the end of the drive coil 220 to supply drive current to the drive coil from the outside. The vibrating mass 100 uses a ring magnet 110 oriented in a single radial direction and radially magnetized as described in detail for embodiment 1, which is fixed to a weight 120 using adhesive and the like. As is described in detail for embodiment 1, the resonant frequency of the vibrating module is determined by the weight of the spring 310 and the vibrating mass 100. Also, as described earlier, since the vibration force of the vibrating module is proportional to the weight, amplitude of the vibrating mass and the square of the resonant frequency, to ensure the needed weight despite a small volume for constituting a small and thin body vibrating module, the weight 120 must use a metal material with a large specific gravity and have a largest possible volume allowed in the given space. As a metal material with a large specific gravity, tungsten alloy which is described in detail for embodiment 1 is used. Now we will describe the embodiment of the present invention which is designed to maximize the volume of the vibrating mass in the space allowed while not letting the vibrating mass 100 come into contact with the spring 310, as the weight contacting the spring 310 would stop the vibration or cause an abnormal vibration having a radically changing resonant frequency. The frequency determined by the spring and the vibrating mass, which has been described in detail for embodiment 1, can be designed using a model of a beam fixed at both ends with a load added to the center or a model of a beam supported at both ends with a load added to the center of the beam. FIG. 5 is a diagram of a model of the spring of the present invention made as a beam fixed at both ends with a concentrated load 800 at the center thereof. Referring to FIG. 5, L indicates the overall length of the beam, and X indicates the length from one fixed end to the calculation point k is a constant determined by the load, the material and shape of the spring. The static deflection curve 314 of the model of the spring 310 made as a beam fixed at both ends with a concentrated load at the center is defined by Formula 1: Formula 1! Y=k×{3×X/L-4×(X/L).sup.3 } where 0≦X≦(L/2), k>0 Y=k× 3×(L-X)/L-4×{(L-X)/L}.sup.3 ! where (L/2)<X≦L, k>0 FIG. 6 is a section diagram showing the relationship between the weight and the spring of another embodiment of the present invention. The curve 123 representing the upper external shape of the section of the weight 120 in a static state is so formed as to coincide with the curve of Formula 1. The radially-magnetized magnet 110 of the present invention is arranged on the under side the weight 120 side of the curve of Formula 1, and is attached thereto without going beyond the curve of Formula 1 to constitute the vibrating mass 100. More specifically, the surface shape of the vibrating mass 100 is so formed that no portion of the vibrating mass 100 except the joint part thereof contacts the deflection curve given by Formula 1 which corresponds to the maximum amplitude designed for the spring 310 with the vibrating mass 100. Also, another curve 124 representing the lower external shape of the section of the weight 120 in a static state is so formed as to coincides with a portion of the curve defined by substituting -Y for Y in Formula 1. The lower surface of the magnet 110 is so formed as not to go beyond the curve defined by substituting -Y for Y in Formula 1. The weight 120 in a static state is joined at its vertex to the spring 310 being in static state. When a drive current is supplied to the drive coil 220 and the vibrating mass 100 is displaced to the maximum designed amplitude, in the upper direction in FIG. 6, for example, due to vibration caused by an electromagnetic force between the drive coil and the above described magnet, the weight 120 is displaced upward in FIG. 6. Referring to FIG. 6, the displaced weight is indicated by 126. If the spring displaced to the maximum designed amplitude is indicated by 315, the curve 123 representing the upper external shape of the section of the weight 120 in static state, after being displaced to the maximum designed amplitude, comes close to the spring 315. Therefore by so forming the section shape of the weight as not to go beyond the curve defined by Formula 1, the volume of the weight can be made maximum inside the space allowed. Preferably the section shape of the vibrating mass 100 consisting of the weight and the magnet approximates the shape of the curve defined by Formula 1 where Y=Y or Y=-Y while not allowing the vibrating mass except the joint part to come into contact with the spring when it is vibrating. FIG. 7 shows practical examples of the weight of the present invention. Referring to FIG. 7A, for the use with two springs as shown in embodiment 1 of the present invention, the section shape of the weight 120 is inside the shape of the deflection curve of the spring 310 defined by Formula 1 and has a portion slightly higher at the fixing part 121 with the spring 310, thereby preventing the vibrating mass 100 and the springs from coming into contact with each other and allowing an optimum contact area of the fixing part with the weight 120 and the spring 310. FIG. 7B is an example of the vibrating mass for the use with one spring as shown in embodiment 2 of the present invention, wherein the section shape of the weight 120 is inside (lowerside) the deflection curve of the spring 310 defined by Formula 1 and has a portion slightly higher at the fixing part 121 with the spring 310. FIG. 7C is an example of the vibrating mass for the use with two springs as shown in embodiment 1 of the present invention, wherein to provide a shape industrially easy to be effectuated, the section shape of the weight 120 is constituted by straight lines which do not go beyond the deflection curve defined by Formula 1 to make a cone-shaped weight. To optimize the area of the mating part 121 with the weight 120 and the spring, the weight has a flat portion. FIG. 7D is an example of the vibrating mass for the use with two springs as shown in embodiment 1 of the present invention, wherein to provide a shape easy to be industrially effectuated, the section shape of the weight 120 has a stepped shape with an envelop not exceeding the deflection curve of Formula 1, which is a shape similar to a plurality of disks stacked up. Although not shown in the drawings, one side of the vibrating mass 100 consisting of the weight 120 shown in FIG. 7C and FIG. 7D and a magnet 110 can also be used with one spring as shown in embodiment 2 of the present invention. In that case, the other side of the vibrating mass may be designed freely. In embodiment 2, the upper shape of the weight is a cone shown in the FIG. 7C of the present invention, the fixing part 121 with the spring 310 being slightly higher, while the lower shape of the weight is flat. Thus shaped weight 120 and the magnet 110 are attached to constitute a vibrating mass 100, which is fixed with the spring 310 by driving a caulking pin 130 through the hole 125 provided at the center of the weight. For the fixing method, in the same way as embodiment 1, methods such as adhesive or caulking by use of pin are also available other than driving of a caulking pin. FIG. 8 is a plan view of the spring 310 of the present invention. As described earlier, the hole at the center of the spring 310 is provided for fixing the spring with the vibrating mass, whereas the fixing holes 312 are provided for fixing the spring with the bobbin. The beam portion 313 is that portion which performs the function of the spring itself. FIG. 10 is a diagram showing the basic structure of the spring of the present invention. While the beam portions 313 of the spring is structured in a linear shape in FIG. 10, in a vibrating module with a small-diameter of Φ 25 mm or less of the present invention, this structure cannot provide the needed effective length of the beam portions of the spring. In order to adjust to the designed frequency, either the width of the beam portions have to be made smaller or the spring has to be made thinner, yet this causes the problem of strength. Therefore in the present invention as a means for providing a long effective length for the beam portion 313 of the spring, the beam portion has an angle with regard to the center direction or a curvature. FIG. 8 is an example wherein the beam portion 313 of the spring has an angle with regard to the center direction. FIG. 9 is an example wherein the beam portion 313 has a curvature. FIG. 11 is an example of fan-shaped spring which has an angle with regard to the center direction and a curvature as well, having an advantage that the effective length can be extended or set as needed easily despite its simple shape. For a method of providing a curvature in the beam portion 313 of the spring, a round spring shown in FIG. 12 can be used. However, while a round spring has a simple shape and therefore is advantageous in the manufacturing, its effective length is difficult to be extended or set as needed with the diameter being limited in the space allowed. Although not shown in the drawings, as a spring which has alleviated the disadvantage of the round spring of FIG. 12 above described in that the effective length is difficult to be extended or set as needed, an elliptical spring having beam portions 313 of elliptical shape instead of round shape may also be used. The spiral spring shown in FIG. 9 has the effective length which can be extended most and set as needed with a large freedom in design, therefore from the view point of increasing the effective length of the beam portion 313 of the spring, this is the most advantageous shape for the vibrating module with a small diameter of Φ 25 mm or less of the present invention. However, in the spiral spring, if it has a wide beam portion and a relatively small effective length, a torsional force is generated in the width direction, tending to generate abnormal vibration. To reduce the torsional force in the width direction of the beam portion of the spiral spring, the beam portion of the spring is made narrow, thick, and as long as allowed. For the process of designing a spiral spring adjusted to the resonant frequency given by the design specification, first the length of the beam portion of the spring is determined, and then the width and after that the thickness are designed. The center point 317 of the width of the beam portion of the spiral spring shown in FIG. 9 is represented by polar coordinates as the following formula: Formula 2! r=θ×a where r=distance from the center θ=rotation angle a=pitch. In order to reduce the torsional force in the width direction of the beam portion of the spiral spring and to attenuate the bad influence of the support of the spring, the length of the beam portion of the spring is designed to be θ>π/2 or preferably θ≧π. Also, in the beam portion of the spring, a tensile force is effectuated in the center direction by vibration, and due to this tensile force in the center direction, a bending force is generated in the curvature and the angled portion with regard to the center direction, and a torsional moment is generated by the bending force, causing a rotary motion in the vibrating mass. In the embodiments shown in FIG. 8 and FIG. 11, in order to prevent the above mentioned rotary motion of the vibrating mass, a pair of beams of the spring are combined which have curvatures or angles with regard to the center direction in opposite direction to each other. Referring to FIG. 8, a method of preventing torsional moment caused by bending force will now be described whereby a spring is structured by combining a pair of beams having angles in opposite direction to each other with regard to the center direction. The beams of the spring 313a and 313b have opposite angles to each other with regard to the center direction of the spring, with the center line 316 of the pair of the spring members being the symmetry axis. When a tensile force is effectuated in the center direction by vibration in each of the beam portions 313a and 313b of the spring, they are placed under a force in such direction as to approach the center line 316 respectively. Because the fixing hole 312 for fixing the spring to the drive coil frame is fixed at one end of the spring, while at the center hole of the spring which is the other end thereof the vibrating mass 100 is fixed ratably, the vibrating mass 100 causes torsional vibration (rotary vibration) if either the beam portion 313a or the beam portion 313b is provided alone. According to the present invention, because the beam portions 313a and 313b of the spring have opposite angles to each other with regard to the center direction of the spring, with the center line 316 of a pair of the spring members being the symmetry axis as described earlier, torsional motions have opposite direction for each beam, with the result of balancing the torsion forces, and generating no torsional vibration (rotary vibration) in the vibrating mass 100. As specific shape of the spring member, there are a diamond shape shown in FIG. 8, a fan shape shown in FIG. 11 and an elliptic shape not shown in the drawing. The method for reducing the torsional force in the width direction of a single spiral spring has been described earlier. In the case that two spiral springs shown in FIG. 9 are used on both sides of the vibrating mass as shown for embodiment 1, by constructing a structure wherein the directions of the spirals cross each other on both sides of vibrating mass, torsional moments in opposite directions are generated and compensate each other, causing no torque. By the above measure, torques in the vibrating mass due to the tensile force in the center direction have opposite direction to each other and thus are compensated by each other, with the result that the vibrating mass effectuates a stable simple reciprocating motion with no rotatory force generated. In FIG. 10 three beam portions of the spring are provided, but four pairs or more may be provided as shown in FIG. 3, and two pairs are also available. To obtain the same resonant frequency, however, compared with four or more pairs of the spring members, three pairs of the spring members have the advantage that the spring member can be made thicker or wider, therefore is easy to be manufactured and easy to be handled during assembling. Two pairs of spring members have the disadvantage that the rotary motion is generated. Therefore for the beam portion of the spring used in the present invention, three pairs of spring members are most advantageous. In embodiment 2 shown in FIG. 4, by using only one spring, the space inside the case 410 and the case 420 can be effectively used, thereby allowing to make a thin body of the vibrating module. Moreover the assembling can be done from one side, facilitating automated assembly. Material of spring will now be described. Assuming that the vibrating module has a frequency of 100 Hz, vibrates 10 seconds for one call, is called 10 times a day and is used for 10 years, the vibrating module vibrates 3.7×10 7 times. A material with a life enduring the fatigue of vibration repeated in this number is needed. As is apparent from the structure of the embodiments of the present invention shown in FIG. 1, FIG. 2, FIG. 4 and FIG. 11, because the gap between the spring and the magnet is made very small to make the vibrating module thin and rare earth magnet with a large energy product is used for magnet, a very strong magnetic field acts on the spring. A spring using a magnetic material is attracted to the magnet and either the spring does not vibrate or vibration is considerably affected. Therefore the spring is preferably made of a paramagnetic material or a non-magnetic material. To provide a largest possible excitation force, the weight of the vibrating mass is preferably made as heavy as possible. To have a resonant frequency of around 80 Hz to 150 Hz, which is determined by the above mentioned vibrating mass and the spring, Young's modules is preferably 12 N.m -2 or more. The case is preferably made of a corrosion resistant material withstanding common environmental conditions as the case cannot be totally sealed. Therefore the material for the spring needs to be paramagnetic or non-magnetic corrosion resistant alloy having a Young's Modules, of 12 N.m -2 or more and a magnetization ratio of 0.5 or less practically (permeability of 1.5 or less) and preferably of 5×10 -3 or less (permeability of 1.005 or less). In the present invention, springs made of SUS 304, phosphor bronze, an age-hardening Co based alloy containing Co in an amount of 25% to 50% or Co--Ni based alloy is used. Particularly a spring using an age-hardening Co based alloy containing Co in Co--Ni based amount of 25% to 50% or an alloy of Co--Ni radical has a Young's Modules of 22 N.m -2 or more, a tensile strength of 130 kgf/mm 2 or more, a fatigue limit of 75 kgf/mm 2 or more, and corrosion loss of 1 mg/cm 2 or less per hour when immersed in a chemical of halogen acid and salt, mixed hydrofloutic-nitric acid of 60° C. Therefore they are materials satisfying all the properties required for the spring of the present invention, namely high elasticity, tensile strength, fatigue strength against repeated stress, magnetic attraction to the magnet, and corrosion resistance. The composition of the age-hardening Co based alloy containing Co in an amount of 25% to 50% used in the present invention is an alloy of Co radical consisting of 25-50 wt. % of Co, 10-20 wt. % of Ni, 10-30 wt. % of Cr, 2-10 wt. % of Mo, 1-5 wt. % of W, 0.01-3 wt. % of one or more selected among Ti, Al, Mn, Si, Be and Nb, and 10 to 30 wt. % of Fe, subjected to cold working by a reduction of 60% or more, and then subjected to aging treatment at 300° to 700° C. The Co--Ni based alloy used in the present invention contains Co, Ni, Cr and Mo as main component, consisting of 20-40 wt. % of Cr+Mo, 20-50 wt. % of Ni, 25-45 wt. % of Co, 0.1-3 wt. % of each of Mn, Ti, Al and Fe, 0.1-3 wt. % of Nb, 0.01-1 wt. % of one or more rare-earth elements selected among Ce, Y and misch metal, subjected to cold working by a reduction of 60% to 90%, and then subjected to aging treatment at 500° to 600° C. The drive coil block 200 has a structure wherein a drive coil 220 is wound around a bobbin 210 made of resin as described earlier. In FIG. 4 the bobbin 210 is integrally formed with the terminal 510. The terminal 510 is electrically connected to the drive coil 220. By a drive current from the outside, magnetic flux is generated in the drive coil 220. A terminal is used as current supply path to the drive coil in FIG. 4, but other means such as lead wire and flexible substrate may also be used. A spring 310 is joined with the drive coil block 200. For the method of joining, a protruding part 211 is provided on the bobbin 210 corresponding to the fixing hole 312 of the spring 310, and the protruding part 211 is put through the fixing hole 312 and heat welded or ultrasonic welded to join the spring 310 with the bobbin 210. For the method of joining, other than the method above mentioned, a method whereby the bobbin 210, the spring 310 and the terminal 510 are integrally formed and other methods such as using adhesive or mechanical method may also be used. Because the vibrating module of the present invention is subjected to heat of 260° C. during soldering, or reflow soldering for surface mounting, of the terminal, the material of bobbin must be heat resisting resin with a softening point of 260° C. or more. The relationship between the drive coil and the magnet will now be described. FIG. 13 is a schematic diagram explaining the positional relationship between the drive coil and the magnet used for the vibrating module of the present invention. As has been described in detail for embodiment 1 shown in FIG. 1 and FIG. 2 and for embodiment 2 shown in FIG. 4, the magnet 110 is located around the inner circumference of the drive coil 220 and vibrates in the direction of the axis. In the embodiment shown in FIG. 13, while a drive current is not passed through the drive coil, the center of the height of the drive coil substantially coincides with the center of the height of the magnet, and the height of the drive coil Lc is larger than the height of the magnet Lm. FIG. 14 is a graph showing a relationship between the displacement of the magnet used in the vibrating module of the present invention and generated electromagnetic force. Referring to FIG. 14, curve A and curve B indicate the relationship between the displacement of the magnet and the resulting electromagnetic force in an example having a height of the drive coil Lc larger than the height of the magnet Lm(curve A) and in an example having a height of the drive coil Lc equal to the height of the magnet Lm(curve B) respectively. Δ1 of the horizontal axis indicates the distance of displacement from the static position of the magnet. The vertical axis is the electromagnetic force exerted on the magnet when a regular drive current is supplied to the drive coil at each displacement of the magnet. As is apparent from the result shown in FIG. 14, in the case indicated by curve A wherein the height of the drive coil Lc is larger than the height of the magnet Lm, the electromagnetic force exerted on the magnet does not decrease substantially until point C where the end face of the drive magnet confronts the end face of the coil. Even when the end face of the magnet protrudes from the end face of the drive coil, the electromagnetic force exerted on the magnet indicated by curve A for the case of Lc>Lm is always larger than the electromagnetic force exerted on the magnet indicated by curve B for the case of equal height of the drive coil and the magnet. Therefore the graph indicates that in the case of curve A, with the height of the drive coil being larger than the height of the magnet, a drive force to the vibrating mass generated by the electromagnetic force exerted on the magnet when a given drive current is supplied is larger than a drive for in the case of curve B and in the case of curve A, the vibration output of the vibrating module is more efficiently provided. In embodiment 1 to embodiment 3 which will be described later, the magnet is a movable part. In the case where the drive coil is a movable part, a large driving force is generated by providing the drive coil in such condition that the center of the height thereof substantially coincides with the center of the height of the coil of the magnet when no drive current is supplied to the drive coil, and that the height of the magnet Lm is larger than the height of the drive coil Lc. In this case, in the same way as embodiment 1, the vibrating module with a linear vibrating motion which is the purpose of the present invention can be constructed by the above described drive coil block 200 with terminal 510, vibrating mass 100, and spring 310 only, with the gap between the magnet 110 and the drive coil 220 narrowed as much as possible to improve in the electromagnetic efficiency. Consequently vibration is restricted or stopped if unexpected particles such as dust intrude or the spring 310 comes into contact with an external object. To prevent this, the cases 410 and 420 are provided. The cases 410 and 420 must be made of non-magnetic material in the same way as embodiment 1. Embodiment 3! Another embodiment of the present invention will be hereinafter described referring to the drawing. Referring to FIG. 15, a spring 310 is joined with a vibrating mass 100 by means such as welding, and is fixedly secured to a drive coil block 200 by means such as insert forming. The drive coil block 200 comprises drive coil 220 wound around a drive coil frame 210 made of resin. A magnet 110 which is a constituent of the vibrating mass 100 is located around the outer circumference of the drive coil 220, confronting the drive coil in the radial direction with a minute gap between them. An electromagnetic force is produced by a current supplied to the drive coil 220 and the magnet 110, vibrating the vibrating module in the longitudinal direction. The cases 410 and 420 contain the drive coil block 200 joined with the spring 310 and the vibrating mass 100. For the vibrating mass 100, a single ring-shaped magnet 110 is so formed in a magnetic field as to be oriented in the radial direction as described in detail for embodiment 1 and embodiment 2, and is so magnetized as to have a single pair of magnetic poles in the radial direction, and this magnet 110 and a weight 120 are fastened together by adhesive or the like to constitute a vibrating mass. As the resonance frequency of the vibrating module is determined by the spring 310 and the weight of the vibrating mass 100, the weight 120 supporting the magnet 110 has a purpose of adjusting the weight of the vibrating mass. The vibrating mass is made of metal material with a large specific gravity such as tungsten alloy or lead alloy in the same way as embodiment 1 and embodiment 2 to provide the needed weight with a small volume so that a small and thin-body vibrating module is obtained. The resonant frequency of the vibrating module of the present invention is adjusted to approximately. 80 Hz to 150 Hz by means of the spring 310 and the vibrating mass 100. The shape of the weight has a protruding contact portion with the spring 310 to allow optimum setting of the effective length of the spring. The distance between the spring 310 and the vibrating mass 100 must be larger than the designed amplitude of vibration of the vibrating module. The vibrating mass 100 and the spring 310 are joined together by laser welding from the surface of the spring 310. While the main component of the weight used for the vibrating mass 100 is tungsten having a relatively high electrical resistance in comparison with other metals and therefore is difficult to be welded by usual resistance welding, the joining method of laser welding whereby to melt and fuse the metal to be joined by heat of laser can easily weld together the weight 120 made mainly of tungsten and the spring 310. For the joining method of the weight and the spring, other than the above mentioned laser welding, other welding methods such as resistance Welding is possible provided that the welding electrode is made of appropriate material such as silver tungsten. Caulking, adhesives, caulking pin driving may also be used for joining the weight and the spring. The resonant frequency determined by the spring and the vibrating mass can be designed using a model of beams also in embodiment 3. If the vibrating mass is light in weight, the spring becomes relatively thin, causing problem in strength. The shape of the spring must be determined considering fatigue life. Therefore as described in detail for embodiment 2, material of the spring needs to be a paramagnetic or non-magnetic corrosion resistant alloy having a Young's modules of 12 N.m -2 or more and a magnetization ratio of 0.5 or less practically (permeability of 1.5 or less) and preferably of 5×10 -3 or less (permeability of 1.005 or less). In the present invention, a spring made of SUS 304, phosphor bronze, an age-hardening Co based alloy containing Co in an amount of 25% to 50% or Co--Ni based alloy is used. Particularly a spring using an age-hardening Co based alloy containing Co in an amount of 25% to 50% or Co--Ni based alloy is most suitable for the vibrating module of the present invention, as described earlier. The coil block 200 consists of the drive coil 220 directly wound around the drive coil frame 210 made of resin, as described earlier. The drive coil frame has the terminal 510 integrated therewith by insert forming for supplying drive current to the drive coil from the outside. The terminal 510 and the drive coil 220 are electrically connected to each other, and by a drive current from the outside, a magnetic field is generated in the drive coil. For the current supply path to the drive coil, other means such as lead wire and flexible substrate may also be used. The spring 310 is joined to the drive coil block 200. For the joining method, insert forming is used whereby the drive coil frame 210 made of resin is formed while the spring 310 is inserted therein to be integral therewith. In another method, a protruding portion is provided on the drive coil frame and is part through the fixing hole of the spring, and then the protruding portion is heat welded or ultrasonic welded to join the spring to the drive coil frame. Other methods such as using adhesive or mechanical mating may also be used In terms of the relationship between the magnet 110 and the drive coil 220, as described in detail for embodiment 1 and embodiment 2, while the magnet 110 is located around the outer circumference of the driving coil in the present embodiment, by locating them in such a way that the center of the height of the drive coil substantially coincides with the center of the height of the magnet and that the height of the drive coil Lc is larger than the height of the magnet Lm, the driving force by the magnet 110 and the drive coil 220 can be effectively utilized, as shown in FIG. 14. In the same manner as embodiment 1 and embodiment 2, a vibrating module vibrating in a linear reciprocation motion of the purpose of the present invention can be constructed by the above described drive coil block 200 with built-in terminal 510, the vibrating mass 100 and the spring 310, with the gap between the magnet 110 and the drive coil 220 narrowed as much as possible to improve electromagnetic efficiency. Consequently vibration is restricted or stopped if unexpected particles such as dust intrude or the spring 310 comes into contact with an external object. To prevent this, the cases 410 and 420 are provided. The cases 410 and 420 must be made of non-magnetic material in the same way as embodiment 1 and embodiment 2. Mechanical uniting such as caulking and crimping is advantageous for fixing a metal case, but adhering is also available. In another method, a protruding portion is provided on the drive coil block 200 which protrudes out of the case, and the protruding portion and the case are heat welded or ultrasonic welded. For a plastic case, mechanical mating such as heat welding or ultrasonic welding as well as the use of adhesive are also available. Although not shown in the drawings, the case 420 may be a substrate on which a driving circuit for driving the vibrating module is mounted. A catch member for fixing the driving circuit to the drive coil frame may be provided in the case 410 to secure the driving circuit substrate by the catch member. Effect of the invention! In the present invention as described above, (1) A vibrating mass comprising a radial anisotropic ring-shaped permanent magnet magnetized to constitute a single pair of magnetic poles in the radial direction is put in a reciprocating motion to generate vibration. Thereby as the magnet confronts the drive coil around the circumference, the generation efficiency of electromagnetic force is significantly increased. Moreover small number of parts used because of use of a single magnet reduces the cost of parts as well as the manufacturing cost. Furthermore, in comparison with the vibrating modules using a plurality of magnets which are difficult to assemble because the magnets generate repulsion and attraction force between them when coming close to each other, and wherein the dispersion of each magnet and the dispersion of dimensions produced during assembly are multiplied, force acting on the magnets by electromagnetic force with drive coil becomes ununiform, as a result, causing the magnet and the drive coil to come into contact to each other, these problems are solved in the present invention. (2) The drive coil and the magnet are so arranged that the center of the height of the drive coil and the center of the height of the magnet substantially coincide with each other and the height of the drive coil Lc>the height of the magnet Lm in the case of the movable magnet, or Lc<Lm in the case of the movable coil. While in the conventional vibrating modules the drive force of the drive coil is reduced when the magnet is displaced and, as a result, the end surface of the magnet protrudes from the end surface of the drive coil, in the present invention, by adopting the structure above mentioned, reduction in drive force is improved, the efficiency of the magnetic circuit of the vibrating module is increased, a low power consumption is achieved, and a sufficient vibration output owing to the increased drive force is provided. (3) For the shape of the vibrating mass, either the surface of the vibrating mass confronting a spring has a deflection curve described as: Formula 1! Y=k×{3×X/L-4×(X/L).sup.3 } where 0≦X≦(L/2) Y=k× 3×(L-X)/L-4×{(L-X)/L}.sup.3 ! where (L/2)<X≦L or the surface of the vibrating mass is so formed as not to contact the deflection curve of the spring given by Formula 1 except the joint part of the vibrating mass and the spring when the spring reaches it's largest designed amplitude. This allows to maximize the weight of the vibrating mass while the vibrating mass and the spring are being prevented from contacting each other during operation of the vibrating module, thus improving the excitation force of the vibrating module and providing a sufficient vibration output while achieving a thinner body. (4) The springs with opposite torsion polarities are arranged over and under the vibrating mass confronting each other or the spring members with opposite torsion polarities are combined and integrated into a spring and arranged in the vibrating module so that the torsional motions are compensated by each other. Thus the vibrating mass effectuates a stable reciprocating motion only without generating a torsional motion. (5) In the case that two springs are used, the springs has a three-dimensional shape so that the distance from the upper to the lower springs varies in the radial direction at the center and the circumference of the spring, being smaller at the center part, thus allowing the gap between the spring and the case to approach zero, and achieving a thinner body of the vibrating module.
A vibrating module for generating a mainly non-audible alert signal comprises a vibrating mass supported by at least one spring and having a weight and a magnet. A drive coil is supported by a coil frame for placing the vibrating mass in a continuous reciprocating motion close to a resonant frequency determined by the vibrating mass and the spring. An electrical signal supplying device supplies an electrical signal to the drive coil to vibrate the vibrating mass in a linear reciprocating motion. A vibration transmitting device transmits the vibration of the vibrating mass via the spring to an outer portion of the vibrating module to generate a mainly non-audible alert signal.
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TECHNICAL FIELD [0001] The invention relates to the field of sensing the angular orientation of a magnetic field by means of the Hall effect. In particular, the invention relates to a sensor for sensing an angular orientation of a projection of a magnetic field vector of a magnetic field into a plane and to a method for sensing an angular orientation of a projection of a magnetic field vector of a magnetic field into a plane. [0002] It relates to methods and apparatuses according to the opening clauses of the claims. Corresponding devices find application in many areas, e.g., in position sensing and in rotation speed measuring, e.g., in automotive and aircraft industry. BACKGROUND OF THE INVENTION [0003] In the state of the art, several ways of determining the angular orientation of a magnetic field using the Hall effect are known. In many cases, it is sufficient to restrict to an orientation within a plane, i.e. to determine the angular orientation of a the projection of the magnetic field into that plane. [0004] For example, it is known to use two orthogonally arranged Hall devices and convert their respective Hall voltages into a digital number using analog-digital converters. The angle representing the wanted angular orientation is then derived by calculating the inverse tangent (arc tangent, ATAN) of the ratio of these two numbers, wherein typically a digital controller such as a microcontroller computes the ATAN function using either a CORDIC algorithm or a lookup table. [0005] This solution has several rather undesirable consequences. A relatively high amount of energy is consumed, since two analog-digital converters and usually also a microcontroller are involved. And a microcontroller generally introduces a time delay, and in particular, the time needed for initializing the microcontroller will add up to the delay. Furthermore, the microcontroller is software-controlled, and in some applications such as in aircraft industry, the use of software in a sensor system requires a special and relatively tough qualification procedure. [0006] In order to be able to dispense with the analog-digital conversion of two signals, phase-sensitive systems have been suggested. They are typically configured in such a way that at the output of the sensors a sine signal is obtained the phase of which represents the angle to be measured. The advantage is that the signal can be fed to a simple phase detection circuit for obtaining the desired angle. Various methods for generating a signal the phase of which contains the desired angular information have already been proposed. [0007] E.g., in EP 2 028 450 A2, the desired signal is generated by summing up the outputs of two orthogonally arranged Hall effect devices (one of the devices being inclined with respect to the other by an angle of 90°). For accomplishing this, the Hall effect devices are provided with bias currents of sine shape which have identical amplitudes and are shifted by 90° with respect to each other. The generation of the required sine wave currents is relatively challenging and costly, and if the phase shift is not exactly 90° and/or if the amplitude of the sine waves is not equal, the outputted angular information does not precisely reflect the magnetic field orientation. [0008] Another method is disclosed in WO 2008/145 662 A1. Therein, it is suggested to provide a particular sensing structure which can be considered a circular vertical Hall device which naturally produces a sine wave output. From the sine signal, a PWM signal proportional to the angle can be readily obtained. The manufacture of the required special Hall device is relatively costly, and the time required for a measurement is relatively long. [0009] It is desirable to provide an improved way of determining the angular orientation of a magnetic field projected in a plane. SUMMARY OF THE INVENTION [0010] Therefore, one object of the invention is to create an improved way of determining the angular orientation of a magnetic field projected in a plane, in particular a way that does not have the disadvantages mentioned above. [0011] A corresponding sensor, more particularly a sensor for sensing an angular orientation of a projection of a magnetic field vector of a magnetic field into a plane, shall be provided, and in addition, the respective method shall be provided, more particularly the respective method for sensing an angular orientation of a projection of a magnetic field vector of a magnetic field into a plane. [0012] Another object of the invention is to provide a way of determining the angular orientation of a magnetic field projected in a plane which is implemented relatively easily. [0013] Another object of the invention is to provide a way of determining the angular orientation of a magnetic field projected in a plane which yields particularly accurate results. [0014] Another object of the invention is to provide a suitable sensor having a good manufacturability. [0015] Another object of the invention is to provide a particularly energy-efficient way of determining the angular orientation of a magnetic field projected in a plane. [0016] Another object of the invention is to provide a relatively simple way of determining the angular orientation of a magnetic field projected in a plane, in particular by dispensing with complex components or procedures. [0017] Another object of the invention is to provide a particularly fast way of determining the angular orientation of a magnetic field projected in a plane. [0018] Further objects emerge from the description and embodiments below. [0019] At least one of these objects is at least partially achieved by apparatuses and methods according to the patent claims. [0020] The sensor for sensing an angular orientation of a projection of a magnetic field vector of a magnetic field into a plane comprises at least a first set of N≧2 Hall effect devices, each having a detection direction and comprising two pairs of connectors, wherein, in presence of said magnetic field, a flow of an electric current between the connectors of any of said pairs of connectors allows to pick up (or measure) a Hall voltage between the connectors of the other respective pair of connectors induced by said magnetic field, unless a magnetic field component of said magnetic field along said detection direction is zero, wherein said N Hall effect devices are aligned such that their detection directions lie in said plane, and wherein at least two of said Hall effect devices have non-identical detection directions; at least one filtering-or-resonating unit comprising an input and an output, wherein a signal outputted from said output is referred to as filtered signal; at least one current source comprising an output for outputting an electrical current at its output; a wiring unit operationally connected to each of said connectors of each of said N Hall effect devices structured and configured for selectively wiring said pairs of connectors to said output of said current source or to said input of said filtering-or-resonating unit, wherein a particular way of wiring both pairs of connectors of a Hall effect device is referred to as a “wiring scheme”, wherein two wiring schemes are referred to as “orthogonal” wiring schemes if a pair of connectors connected to the current source in one of the two wiring schemes is connected to said filtering-or-resonating unit in the other of the two wiring schemes, and wherein two wiring schemes are referred to as “reverse” wiring schemes if they lead to different signs of the Hall voltage; a control unit structured and configured for controlling said wiring unit in such a way that during a first time period of a duration 0.5 Tf and in a specific sequence of said N Hall effect devices, to each of said N Hall effect devices a respective wiring scheme Wi+ is applied, i=1, . . . , N, during respective subsequent time periods of durations ti, i=1, . . . , N; and during a second time period of a duration 0.5 Tf, subsequent to said first time period of a duration 0.5 Tf, and in the same specific sequence of said N Hall effect devices, to each of said N Hall effect devices a respective wiring scheme Wi− is applied, i=1, . . . , N, during respective subsequent time periods of the same durations ti, i=1, . . . , N; wherein each of said wiring schemes Wi+ is an orthogonal and reverse wiring scheme of the respective other wiring scheme Wi−, i=1, . . . , N; an output unit operationally connected to said output of said filtering-or-resonating unit structured and configured for obtaining from a filtered signal an output signal indicative of said angular orientation and outputting said signal; wherein said filtering-or-resonating unit is structured and configured for altering an inputted signal of a fundamental frequency f=1/Tf, said inputted signal containing, in addition to said fundamental frequency, higher harmonics, in such a way that an intensity of said higher harmonics is decreased relative to an intensity of said fundamental frequency. [0030] Such a sensor makes it possible to sense an angular orientation of a projection of a magnetic field vector of a magnetic field into a plane in high precision while using relatively simple components only. Such a sensor can be constructed in a relatively simple way without lacking measuring accuracy. In addition, such a sensor can be realized in Silicon using solely CMOS processes. The use of Hall effect devices which are orthogonal to each other allows to cancel (or at least strongly reduce) offsets. Such an offset in a Hall effect device means that although no magnetic field is present (B=0), a non-zero Hall voltage is present (VHall≠0). [0031] It is well possible to realized such a sensor by means of vertical Hall effect devices. [0032] In an attempt to better understand the invention, one can say that the N Hall effect devices are read out and provided with bias current in such a way that the read out sequence of Hall voltages mimics a sine wave, the sine wave having the frequency f, and the mimicking is realized in form of a step-function, in form of a staircase signal. The filtering-or-resonating unit emphasizes the (fundamental) frequency f while suppressing other frequencies, in particular unavoidably occurring higher harmonics. And from the phase of the resulting sine or sine-like wave, the wanted angular orientation is derived, which is usually accomplished by means of a simple phase detecting. Each of said time periods of duration 0.5 T can be related to a half-wave of the sine wave, wherein said time periods do not necessarily start at 0° or 180°. [0033] The number N is positive integer, amounting to at least 2. [0034] With respect to the term 0.5 Tf, it is to be noted that this is not to be understood as 0.50000 Tf or exactly 0.5 Tf. The larger the deviation from exactly 0.5 Tf, the higher will be a distortion introduced in the signal outputted by the filtering-or-resonating unit and the output signal, respectively. Usually, for first and second time spans of 0.5 Tf, the duration will be between 0.45 Tf and 0.55 Tf or rather between 0.47 Tf and 0.53 Tf, for better results between 0.49 Tf and 0.51 Tf. [0035] Something similar applies to the durations ti, i=1, . . . , N, which are not necessarily exactly identical in the first and second time spans of 0.5 Tf, but may deviate by as much as ±5% or ±10%, preferably only up to ±2%. [0036] But the sum over all ti (i.e. for i=1, . . . , N) amounts to the before-addressed 0.5 Tf. [0037] The applied current can also be referred to as bias current. [0038] Said plane usually is a predetermined plane, usually given by the orientation in space of the sensor, or more particularly of the N Hall effect devices. [0039] In one embodiment, the sensor comprises exactly one filtering-or-resonating unit. [0040] Said fundamental frequency can usually be referred to as a filter frequency or a resonance frequency. [0041] The altering accomplished in said filtering-or-resonating unit is usually a filtering. [0042] In one embodiment which may be combined with the above-mentioned embodiment, said filtering-or-resonating unit is or comprises a band pass filter. [0043] In one embodiment which may be combined with one or more of the above-addressed embodiments, said filtering-or-resonating unit is or comprises a low pass filter, in particular, it comprises in addition an offset remover for removing any DC offsets, i.e. for removing voltages at 0 Hz. [0044] In one embodiment which may be combined with one or more of the before-addressed embodiments, said filtering-or-resonating unit comprises an amplifier, in particular an input amplifier for amplifying the Hall voltages before accomplishing the signal altering/signal filtering. [0045] In one embodiment which may be combined with one or more of the before-addressed embodiments, the sensor comprises exactly one current source or exactly two current sources, in particular exactly one current source. [0046] In one embodiment which may be combined with one or more of the before-addressed embodiments, the current outputted by the current source is a predetermined electrical current. [0047] In one embodiment which may be combined with one or more of the before-addressed embodiments, the current outputted by the current source is an adjustable electrical current. [0048] In one embodiment which may be combined with one or more of the before-addressed embodiments, to each of the N Hall effect devices, a bias current of the same amperage is applied. [0049] In one embodiment which may be combined with one or more of the before-addressed embodiments, to each of said N Hall effect device, pulses of constant current are applied. [0050] In one embodiment which may be combined with one or more of the before-addressed embodiments, constant currents are applied during measuring times, i.e. during times when a Hall voltage is fed from the respective Hall effect device to the filtering unit. [0051] Usually, the at least one current source is capable of outputting constant currents, in particular such constant currents which can be used as bias currents. [0052] In one embodiment which may be combined with one or more of the before-addressed embodiments, the current applied to the i-th of said N Hall effect devices during said first time period of duration 0.5 Tf (first half-wave)—no matter if the current is constant or time-dependent—must be the same as applied to this i-th of said N Hall effect device during said second time period of duration 0.5 Tf (second half-wave). [0053] Where the term “subsequent” and “subsequently”, respectively, is used, this usually means that something follows immediately afterwards, i.e. without or with negligible delay. [0054] With respect to said detection direction, it is to be noted that this is not a directed object, as it does not have a sense of direction like an arrow; it is rather an object like a line. [0055] Said “wiring a pair of connectors to said output of said current source” usually results in application of a current (bias current) to the respective Hall device; and the “wiring a pair of connectors to said input of said filtering-or-resonating unit” usually results in a Hall voltage being fed to filtering-or-resonating unit, for processing and finally determining the wanted angular orientation from a phase of the processed (filtered) signal. [0056] In one embodiment which may be combined with one or more of the before-addressed embodiments, in the resulting filtered signal, higher harmonics are decreased relative to the fundamental frequency f by at least 10 dB, in particular by at least 20 dB. [0057] In one embodiment which may be combined with one or more of the before-addressed embodiments, in the resulting filtered signal, higher harmonics are decreased such that a resulting intensity of any higher harmonic amounts to at most −20 dB relative to the intensity of the fundamental frequency f. [0058] In one embodiment which may be combined with one or more of the before-addressed embodiments, the attenuation by the filtering-or-resonating unit is at least 20 dB at 2 f, and in particular also at least 20 dB at f/2. An attenuation of 20 dB at 2 f will typically result in a distortion of about 0.3° in the output signal corresponding to a sensing error of 0.3°. [0059] In one embodiment which may be combined with one or more of the before-addressed embodiments, said control unit is or comprises a logic circuit. [0060] In one embodiment which may be combined with one or more of the before-addressed embodiments, in the output unit, a phase of said filtered signal is detected, such that the output unit can be considered a phase reading unit. [0061] In one embodiment which may be combined with one or more of the before-addressed embodiments, the output signal depends on a phase of said filtered signal. [0062] In one embodiment which may be combined with one or more of the before-addressed embodiments, the output signal is a PWM signal or a digital signal. [0063] In one embodiment which may be combined with one or more of the before-addressed embodiments, one of or typically each of said N Hall effect devices comprises two or more operationally interconnected Hall effect devices, in particular wherein these are interconnected in series or in parallel. This can provide an improved accuracy. In case of a parallel interwiring of more than one Hall effect devices, the Hall effect device will usually comprise an adder, for summing up Hall voltage of the interwired single Hall effect devices. [0064] In one embodiment which may be combined with one or more of the before-addressed embodiments, the N Hall effect devices are vertical Hall effect devices, in other words, their detection direction is aligned parallel to a semiconductor surface of a semiconductor device in which the are manufactured. [0065] In one embodiment which may be combined with one or more of the before-addressed embodiments, said specific sequence is a sequence related to or depending on a relative alignment of said detection directions of said Hall effect devices. [0066] In one embodiment which may be combined with one or more of the before-addressed embodiments, said durations ti, i=1, . . . , N, of said time periods are related to or depending on a relative alignment of said detection directions of said Hall effect devices. In particular, in this embodiment one can provide that said durations are related to or depending on a distribution of said detection directions when these are plotted into the positive-y half-plane of an x-y-coordinate system. [0067] In one embodiment which may be combined with one or more of the before-addressed embodiments, all said durations ti, i=1, . . . , N, are equal. [0068] In one embodiment which may be combined with one or more of the before-addressed embodiments except for the last one, in case a magnetic field to be sensed is known to be inhomogeneous (in the sense of having an angle-dependent magnetic field amplitude), the durations ti, i=1, . . . , N, are chosen so as to increase the sensing accuracy by compensating for this inhomogeneity by choosing said durations appropriately. [0069] In one embodiment which may be combined with one or more of the before-addressed embodiments, said control unit is furthermore structured and configured for controlling said wiring unit in such a way that after the before-mentioned first and second time periods of a duration 0.5 Tf, the following is accomplished: during a third time period of a duration 0.5 Tf, subsequent to said second time period of a duration 0.5 Tf, and in the same specific sequence of said N Hall effect devices, to each of said N Hall effect devices a respective wiring scheme Wi++, i=1, . . . , N, is applied during respective subsequent time periods of said same durations ti, i=1, . . . , N; and during a fourth time period of a duration 0.5 Tf, subsequent to said third time period of a duration 0.5 Tf, and in the same specific sequence of said N Hall effect devices, to each of said N Hall effect devices a respective wiring scheme Wi−−, i=1, . . . , N, is applied during respective subsequent time periods of the same durations ti, i=1, . . . , N; wherein each of said wiring schemes Wi++ is an orthogonal and reverse wiring scheme of the respective wiring scheme Wi−−, i=1, . . . , N; wherein each of said wiring schemes Wi++ is a non-orthogonal and non-reverse wiring scheme of the respective other wiring scheme Wi+ non-identical with said respective other wiring scheme Wi+, i=1, . . . , N; and wherein each of said wiring schemes Wi−− is a non-orthogonal and non-reverse wiring scheme of the respective other wiring scheme Wi− non-identical with said respective other wiring scheme Wi−, i=1, . . . , N. [0075] Typically, the sequence carried out during the first to fourth time periods of duration 0.5 Tf is repeated. [0076] In one embodiment which may be combined with one or more of the before-addressed embodiments, said specific sequence is a sequence which can be obtained by plotting said detection directions of said Hall effect devices into the positive-y half-plane of an x-y-coordinate system and ordering the Hall effect devices according to the respective angle enclosed between the detection direction of the respective Hall effect device and the positive x-axis, such that said angles constitute a monotonously increasing or monotonously decreasing series. When the Hall effect devices are ordered according either to increasing or to decreasing angles, the before-mentioned staircase signal will have a suitable form for extracting the before-mentioned sine wave. [0077] In one embodiment which may be combined with one or more of the before-addressed embodiments, said filtering-or-resonating unit has a filter frequency f at which attenuation is minimum or amplification is maximum. [0078] In one embodiment which may be combined with one or more of the before-addressed embodiments, said filtering-or-resonating unit is or comprises a bandpass filter having a quality factor Q (also sometimes simply referred to as “quality”) of about Q=π/2. Therein, n designates Archimedes' Constant, approximately 3.14. In particular, said quality factor amounts to Q=1.57±0.25, or, for better results, to Q=1.57±0.1. This way, in measurements of rotating magnetic fields such as in rotation speed measurements, the naturally occurring phase shift at frequencies near the filter frequency f can be used for reducing, in particular for compensating for a time lag of the outputting of the output signal with respect to the time when the magnetic field in fact had the angular position indicated in the output signal. Said specific sequence will in this case be chosen in dependence of the direction of rotation of the magnetic field. [0079] In one embodiment which may be combined with one or more of the before-addressed embodiments, said control unit is furthermore structured and configured for controlling said wiring unit in such a way that for at least one of said N Hall effect devices the respective pair of connectors of the respective Hall effect device, which is connected to said current source during the respective time period of duration ti, i=1, . . . , N, is wired to said current source already before the beginning of said respective time period, and that this wiring is maintained until and throughout said respective time period; and/or said wiring of the respective pair of connectors of the respective Hall effect device connected to said current source during the respective time period of duration ti, i=1, . . . , N is maintained throughout said respective time period and until after termination of said respective time period; is accomplished [0082] In particular, it will be provided that this applies for each said N Hall effect devices, and more particularly both will be accomplished for each of said N Hall effect devices. This allows to solve problems arising from switching spikes when connecting a Hall effect device to the current source and/or when disconnecting a Hall effect device from the current source. Such connecting/disconnecting may result in current spikes which reflect in the Hall voltage, such that measurement accuracy is diminished. The described embodiment suggests to make (establish) or undo the connections of a respective Hall effect device to the at least one current source at a time when no Hall voltage is fed from that respective Hall effect device to the filtering unit, or, more precisely, when no Hall signal of that respective Hall effect device contributes to the output signal. This embodiment will result in a need for the at least one current source to produce twice the current required (at minimum) when operating the sensor without the described advanced connection/delayed disconnection, which can be accomplished by a stronger current source or by a providing two current sources. [0083] In one embodiment which may be combined with one or more of the before-addressed embodiments, the sensor comprises an additional, second set of N≧2 Hall effect devices, each Hall effect device of said second set being constructed substantially identical to a respective Hall effect device of said first set, each Hall effect device of said second set being aligned the same way as said respective Hall effect device of said first set, but rotated about an axis perpendicular to said plane by substantially 180° with respect to said respective Hall effect device of said first set; wherein said control unit is furthermore structured and configured for controlling said wiring unit in such a way that the before-described application of wiring schemes to said pairs of connectors of said Hall effect devices of said first set is simultaneously applied to the respective Hall effect devices of said first set, for the same durations ti, i=1, . . . , N, and in the same specific sequence as for the respective Hall effect devices of said first set; wherein said filtering-or-resonating unit comprises a subtraction unit having two inputs, for obtaining a difference between signals fed to said inputs, wherein those pairs of connectors of the Hall effect devices of the first and second sets, respectively, which are connected to said filtering-or-resonating unit, are operationally connected to one of said inputs each. This allows for a very good offset compensation in case of strongly non-linear Hall effect devices. Accordingly, an even furtherly improved signal accuracy can be achieved. Said operational connection can be provided before or after the filtering: Either the Hall voltage signals from the Hall effect devices of the first set and the second set, respectively, are separately filtered in the described way in the filtering-or-resonating unit, and then the difference between the respective filtered signals is formed, or, more typically, firstly, the difference between the Hall voltage signals from the Hall effect devices of the first set and the second set, respectively, is obtained, and then the resulting difference signal is filtered in the described way in the filtering-or-resonating unit. Typically, the filtering-or-resonating unit comprises an adder and an inverter (the inverter at one input of the adder) for accomplishing said subtraction. [0086] In one embodiment which may be combined with one or more of the before-addressed embodiments, said output unit is furthermore structured and configured for comparing filtered signals to a non-zero constant signal and deriving from a result of said comparing an additional output signal which is indicative of an amplitude of said projection of said magnetic field vector of said magnetic field into said plane. This way, it is possible to measure an amplitude of said projection of said magnetic field into said plane. This is possible, because the comparing of the approximately sine-shaped filtered signal to a non-zero constant signal results in a pulse signal the length of which depends on the amplitude of the approximately sine-shaped filtered signal and thus on the amplitude of said projection of said magnetic field. [0087] It is to be noted the before-described way of obtaining an output signal indicative of an amplitude of said projection of said magnetic field not necessarily has to be combined with the before-described sensing of an angular orientation of said projection. [0088] In one embodiment which may be combined with one or more of the before-addressed embodiments, said output unit comprises a comparator and a phase detection unit, more particularly a latch and a comparator and a counter, in particular wherein said output unit substantially consists of a comparator and a phase detection unit, more particularly of a latch and a comparator and a counter. This is a very simple and cost-effective way of implementing the output unit, in particular an output unit outputting a digital signal. And, in addition, such an output unit responds very fast to inputted signals (filtered signals). In particular, said latch is a set-reset latch (SR latch). [0089] For a sensor with N=2 Hall effect devices, the sensor can be described as a sensor for sensing an angular orientation of a projection of a magnetic field vector of a magnetic field into a plane, wherein said sensor comprises at least a first and a second Hall effect devices each having a detection direction, said detection directions of said first and a second Hall effect devices being aligned with respect to each other in a non-parallel fashion, said Hall effect devices each comprising two pairs of connectors, wherein, in presence of said magnetic field, a flow of an electric current between the connectors of any of said pairs of connectors allows to pick up (or measure) a Hall voltage between the connectors of the other respective pair of connectors induced by said magnetic field unless a magnetic field component of said magnetic field along said detection direction is zero; at least one filtering-or-resonating unit comprising an input and an output; at least one current source comprising an output for outputting an electrical current at its output; a wiring unit operationally connected to each of said connectors of each of said Hall effect devices structured and configured for selectively wiring said pairs of connectors to said output of said current source or to said input of said filtering-or-resonating unit, wherein a particular way of wiring both pairs of connectors of a Hall effect device is referred to as a “wiring scheme”, wherein two wiring schemes are referred to as “orthogonal” wiring schemes if a pair of connectors connected to the current source in one of the two wiring schemes is connected to said filtering-or-resonating unit in the other of the two wiring schemes, and wherein two wiring schemes are referred to as “reverse” wiring schemes if they lead to different signs of the Hall voltage; a control unit structured and configured for controlling said wiring unit in such a way that for a duration of a duration Tf/4 a first wiring scheme is applied to said at least one first Hall effect device, and subsequently, for a duration of a duration Tf/4, a second wiring scheme is applied to said second Hall effect device, and subsequently, for a duration of a duration Tf/4, a third wiring scheme is applied to said first Hall effect device, and subsequently, for a duration of a duration Tf/4, a fourth wiring scheme is applied to said second Hall effect device; wherein said first and third wiring schemes are orthogonal and reverse wiring schemes; and wherein said second and fourth wiring schemes are orthogonal and reverse wiring schemes; an output unit operationally connected to said output of said filtering-or-resonating unit structured and configured for obtaining from a signal outputted from said filtering-or-resonating unit an output signal indicative of said angular orientation and for outputting said signal; wherein said filtering-or-resonating unit is structured and configured for filtering an inputted signal of a fundamental frequency f=1/Tf containing, in addition to said fundamental frequency, higher harmonics, in such a way that an intensity of said higher harmonics is decreased relative to an intensity of said fundamental frequency. [0102] Usually, the detection directions of said first and second Hall effect devices are aligned with respect to each other in a perpendicular fashion. And, usually, said first and second Hall effect devices are aligned such that their detection directions lie in said plane. [0103] Generally, the invention comprises methods with corresponding features of corresponding sensors according to the invention, and sensors with corresponding features of corresponding methods according to the invention. [0104] The advantages of the methods basically correspond to the advantages of corresponding apparatuses and vice versa. [0105] The method for sensing an angular orientation of a projection of a magnetic field vector of a magnetic field into a plane comprises the steps of a) providing at least a first set of N≧2 Hall effect devices, each having a detection direction and comprising two pairs of connectors, wherein, in presence of said magnetic field, a flow of an electric current between the connectors of any of said pairs of connectors allows to pick up (or measure) a Hall voltage between the connectors of the other respective pair of connectors induced by said magnetic field, unless a magnetic field component of said magnetic field along said detection direction is zero, wherein said N Hall effect devices are aligned such that their detection directions lie in said plane, and wherein at least two of said Hall effect devices have non-identical detection directions; b) providing at least one filtering-or-resonating unit comprising an input and structured and configured for altering an inputted signal of a fundamental frequency f=1/Tf, said inputted signal containing, in addition to said fundamental frequency, higher harmonics, in such a way that an intensity of said higher harmonics is decreased relative to an intensity of said fundamental frequency; c) providing at least one current source comprising an output and capable of outputting an electrical current at its output; wherein a particular way of wiring both pairs of connectors of a Hall effect device to said output of said current source or to said input of said filtering-or-resonating unit is referred to as a “wiring scheme”, wherein two wiring schemes are referred to as “orthogonal” wiring schemes if a pair of connectors connected to the current source in one of the two wiring schemes is connected to said filtering-or-resonating unit in the other of the two wiring schemes, and wherein two wiring schemes are referred to as “reverse” wiring schemes if they lead to different signs of the Hall voltage; d1) applying, during a first time period of a duration 0.5 Tf and in a specific sequence of said N Hall effect devices, to each of said N Hall effect devices a respective wiring scheme Wi+, i=1, . . . , N, during respective subsequent time periods of durations ti, i=1, . . . , N; and d2) applying, during a second time period of a duration 0.5 Tf, subsequent to said first time period of a duration 0.5 Tf, and in the same specific sequence of said N Hall effect devices, to each of said N Hall effect devices a respective wiring scheme Wi−, i=1, . . . , N, during respective subsequent time periods of the same durations ti, i=1, . . . , N; wherein each of said wiring schemes Wi+ is an orthogonal and reverse wiring scheme of the respective other wiring scheme Wi−, i=1, . . . , N; and e) deriving from signals outputted by said filtering-or-resonating unit in reaction to carrying out steps d1) and d2) an output signal indicative of said angular orientation. [0112] The signals outputted by said filtering-or-resonating unit can be referred to as “filtered signals”. Typically, the sequence of steps d1, d2 is repeatedly carried out, in particular subsequently. [0113] In one embodiment, the method comprises carrying out after step d2) the steps of d3) applying, during a third time period of a duration 0.5 Tf, subsequent to said second time period of a duration 0.5 Tf, and in the same specific sequence of said N Hall effect devices, to each of said N Hall effect devices a respective wiring scheme Wi++, i=1, . . . , N, during respective subsequent time periods of said same durations ti, i=1, . . . , N; and d4) applying, during a fourth time period of a duration 0.5 Tf, subsequent to said third time period of a duration 0.5 Tf, and in the same specific sequence of said N Hall effect devices, to each of said N Hall effect devices a respective wiring scheme Wi−−, i=1, . . . , N, during respective subsequent time periods of said same the same durations ti, i=1, . . . , N; wherein each of said wiring schemes Wi++ is an orthogonal and reverse wiring scheme of the respective wiring scheme Wi−−, i=1, . . . , N; and wherein each of said wiring schemes Wi++ is a non-orthogonal and non-reverse wiring scheme of the respective other wiring scheme Wi+ non-identical with said respective other wiring scheme Wi+, i=1, . . . , N; and wherein each of said wiring schemes Wi−− is a non-orthogonal and non-reverse wiring scheme of the respective other wiring scheme Wi− non-identical with said respective other wiring scheme Wi−, i=1, . . . , N. [0116] In this embodiment, typically, the sequence of steps d1, d2, d3, d4 is repeatedly carried out, in particular subsequently. Usually, said output signals will be averaged over two periods, i.e. over a duration of 2 Tf. [0117] In one embodiment which may be combined with the before-addressed embodiments, said magnetic field is a rotating magnetic field, and said filtering-or-resonating unit is or comprises a bandpass filter having a quality factor Q of substantially Q=π/2, the method comprising, [0000] in case said projection of said magnetic field vector, when plotted into said positive-y half-plane of said x-y-coordinate system, moves towards increasing angles, the step of e1) selecting said specific order such that said angles constitute a monotonously increasing series; or, in case said projection of said magnetic field vector, when plotted into said positive-y half-plane of said x-y-coordinate system, moves towards decreasing angles, the step of e2) selecting said specific order such that said angles constitute a monotonously decreasing series. [0120] This way, it can be achieved that the outputting of the output signal occurs (practically) at the same time as the sensed projection of the magnetic field in fact has the angular orientation indicated in the outputted signal. In other words, a time lag of the output signal with respect to the actual (current) magnetic field position can be reduced or even fully compensated for. [0121] The invention furthermore comprises an integrated circuit comprising at least one sensor according to one of the invention, in particular wherein said integrated circuit is manufactured using CMOS processes. [0122] The invention furthermore comprises a position sensor, in particular a sensor for sensing a rotational position of a rotatable item to which a magnet is attached. [0123] The invention furthermore comprises a rotational-speed sensor comprising at least one sensor according to the invention or an integrated circuit according to the invention. In particular, the rotational-speed sensor furthermore comprises an evaluation unit operationally connected to said output unit structured and configured for obtaining an output indicative of a speed of rotation of said projection of said magnetic field vector of said magnetic field into said plane. [0124] The invention furthermore comprises a revolution counter comprising at least one sensor according to the invention or an integrated circuit according to the invention. In particular, the revolution counter furthermore comprises an evaluation unit operationally connected to said output unit structured and configured for obtaining an output indicative of a number of rotations of said projection of said magnetic field vector of said magnetic field into said plane that have taken place from an initial point in time. [0125] Further embodiments and advantages emerge from the dependent claims and the figures. BRIEF DESCRIPTION OF THE DRAWINGS [0126] Below, the invention is described in more detail by means of examples and the included drawings. The figures show: [0127] FIG. 1 a schematic block-diagrammatical illustration of a sensor; [0128] FIG. 2 a schematic symbolic illustration of all possible wiring schemes of a Hall effect device; [0129] FIG. 3 a schematic symbolic illustration of four non-reverse wiring schemes of Hall effect device; [0130] FIG. 4 an illustration of applied bias currents and resulting Hall voltages; [0131] FIG. 5 an illustration of applied bias currents and resulting Hall voltages; [0132] FIG. 6 a schematic block-diagrammatical illustration of an improved sensor; [0133] FIG. 7 an illustration of signals usable for obtaining information about an amplitude of a magnetic field; [0134] FIG. 8 a block-diagrammatical illustration of a composed Hall effect device; [0135] FIG. 9 a block-diagrammatical illustration of a composed Hall effect device; [0136] FIG. 10 a block-diagrammatical illustration of a phase detection unit; [0137] FIG. 11 a schematized perspective view of a cross-section through a vertical integrated Hall effect device; [0138] FIG. 12 schematic symbolic illustration of four non-reverse wiring schemes applied to a vertical integrated Hall effect device. [0139] The reference symbols used in the figures and their meaning are summarized in the list of reference symbols. The described embodiments are meant as examples and shall not confine the invention. DETAILED DESCRIPTION OF THE INVENTION [0140] FIG. 1 shows schematic block-diagrammatical illustration of a sensor 1 for sensing an angular orientation of a projection B of a magnetic field into a plane, wherein said plane is the drawing plane, and wherein said angular orientation is described by an angle α. Sensor 1 comprises two Hall effect devices Sx, Sy. The devices Sx, Sy are vertical Hall effect devices, with their respective detection directions lying in said plane, running along the x-axis (Sx) and along the y-axis (Sy), respectively. The devices Sx, Sy have two pairs of connectors each, and for sensing an angular orientation, a bias current is applied to a device via the one pair of connectors, and the resulting Hall voltage is detected via the other pair of connectors. [0141] The devices Sx, Sy are operationally connected to a wiring unit W which is controlled by a control unit L. Wiring unit W applies wiring schemes to the devices Sx, Sy which determine which of the pairs of connectors is used for applying the bias current, and which for picking up the Hall voltage. Accordingly, the sensor 1 comprises a current source 2 operationally connected to wiring unit W. [0142] Wiring unit W is furthermore operationally connected to a filtering unit F which is, in the embodiment of FIG. 1 embodied as a band pass filter, so as to filter the Hall voltage signals obtained via wiring unit W from the Hall effect devices Sx, Sy. [0143] The filtered signals outputted by filtering unit F are fed into one input of a comparator 3 , the other input of comparator 3 being connected to ground potential. The signal outputted by the comparator 3 is a digital signal (digital signals are drawn as bold arrows, analogue signals are drawn as thin lines), and the phase thereof can be detected in a way known in the art. For detecting the phase, e.g., a phase detection unit 5 like depicted in FIG. 1 can be used. Phase detection unit 5 is fed with the signal outputted by the comparator 3 (which is a PWM—Pulse Width Moduldation—signal), a signal outputted by control unit L (usually a square signal) and a clock signal outputted by clock 6 . Comparator 3 and phase detection unit 5 are constituents of an output unit 4 of the sensor 1 . A signal indicative of the sought angular orientation is outputted at output 4 a of output unit 4 (“output signal”). [0144] An exemplary phase detection unit 5 as it could be used in the embodiment of FIG. 1 is block-diagrammatically illustrated in more detail in FIG. 10 . Phase detection unit 5 comprises a set-reset latch 8 and a counter 9 . Logic signals from comparator 3 and control unit L, respectively, are inputted to the two inputs of latch 8 , e.g., the signal from comparator 3 is inputted to a set (or enable) input of latch 8 , so as to trigger the on-state (or high state), and the signal from control unit L is inputted to a reset input of latch 8 , so as to trigger the off-state (or idle state), or vice versa. Both inputted logic signals have the same frequency, but their relative phase depends on (and may even represent) the sought angle α. As a result, a PWM signal having a duty cycle representative of the relative phase of the two inputted logic signals and thus representative of the sought angle α is outputted. The PWM signal outputted by latch 8 is fed into counter 9 which in addition is provided with the clock signal (cf. FIG. 1 ) having a much higher frequency, e.g. three or four orders of magnitude higher than the before-mentioned PWM signal, depending on the desired resolution. Counter 9 outputs output signals 4 a , e.g., like sketched in FIG. 10 , an eight-bit signal representative of the sought angle α. As mentioned before, other phase detection principles and implementations and in general, other output units 4 may be used. [0145] FIG. 2 is a schematic symbolic illustration of all possible schemes of a Hall effect device. The eight wiring schemes applicable to a Hall effect device are illustrated. In FIG. 2 , a Hall effect device is symbolized by a square, the direction of flow of a bias current I is symbolized by a thin arrow, and the direction of detection of a Hall voltage VHall is symbolized by a dotted arrow. These “directions” correspond of course merely to a way of wiring the Hall effect device, i.e. of making connections to the connectors of the Hall effect device. The detection direction of the Hall effect device is perpendicular to the drawing plane, and the symbol in the middle of a Hall effect device indicates whether two wiring schemes result in a Hall voltage of the same or of opposite sign. [0146] Those wiring schemes on the left hand side in FIG. 2 all result in the same sign of VHall, and accordingly, these wiring schemes are not reverse wiring schemes. The same applies to the wiring schemes on the right hand side of FIG. 2 . But any wiring scheme on the left is a reverse wiring scheme of any wiring scheme on the right in FIG. 2 . [0147] Furthermore, any wiring scheme in the top half of FIG. 2 is orthogonal to any wiring scheme in the bottom half of FIG. 2 , since the pair of connectors at which the bias current I is applied to a Hall effect device in the top half of FIG. 2 is used for outputting VHall at a Hall effect device in the bottom half of FIG. 2 and vice versa. [0148] FIG. 3 illustrates four non-reverse wiring schemes X 1 , X 2 , X 3 , X 4 of a Hall effect device (symbolized as a crossed box) in a way slightly different from FIG. 2 . The letters i and v indicate connectors connected for bias current application and Hall voltage detection, respectively, and the “+” and “−” indicate the polarization (or “direction”, cf. above). The corresponding reverse wiring schemes can be obtained by crossing the output connectors of the Hall effect device, i.e. by replacing v+ by v− and v− by v+ in FIG. 3 ; these (reverse) wiring schemes will be indicated by adding a minus, i.e. by −X 1 , −X 2 , −X 3 , −X 4 . [0149] FIG. 4 shall assist the understanding of the way of functioning of the sensor 1 of FIG. 1 and shows an illustration of Hall voltages VHall resulting when applying bias currents to the Hall effect devices Sx and Sy of FIG. 1 , and in particular the time development thereof. Therein, it is referred to the wiring schemes illustrated in FIG. 3 , wherein a wiring scheme applied to device Sx will be referred to with the letter X (X 1 , X 2 , X 3 , X 4 ), as indicated in FIG. 3 , whereas the same wiring scheme applied to device Sy is referred to with the letter Y (Y 1 , Y 2 , Y 3 , Y 4 ). The bias current applied to a Hall effect device is kept constant while feeding the corresponding Hall voltage signal to filtering unit F, and, accordingly, the bias current is applied to the Hall effect devices in form of (rectangular) current pulses, i.e. of pulses of constant current. [0150] Wiring unit W firstly applies wiring scheme X 1 , then Y 1 , then −X 2 and then −Y 2 . Thereafter, the same sequence of wiring schemes will be repeated again and again. In other words, a constant current I drawn from current source 2 will be alternately applied to devices Sx and Sy, and simultaneously, the respective device to which the bias current I is applied is connected with its other pair of connectors to filtering unit F. The Hall voltages entering filtering unit F describe a step function (drawn in solid lines in FIG. 4 ). The filtered signals outputted by filtering unit F are drawn as a dotted line in FIG. 4 . [0151] Filtering unit F has a fundamental frequency f corresponding to a period T=1/f, wherein T corresponds to 2π in FIG. 4 . Each of the wiring schemes is applied for Tf/4 before changing the wiring to the next wiring scheme. Clock 6 , together with control unit L, is operated accordingly. [0152] The applied wiring schemes are chosen in such a way that (for the particular magnetic field direction shown in the example of FIG. 1 ) in a first half-period of Tf/2, the devices Sx, Sy generate a Hall voltage of the same sign, and in a subsequently following second half-period of Tf/4, orthogonal reverse wiring schemes will be applied, wherein the sequence of Hall devices to which the wiring schemes are applied is the same in the first and the second half-period. [0153] This results in a filtered signal having the fundamental frequency f=1/Tf and being substantially sine-shaped, wherein the phase of the filtered signal is indicative of the angle α describing the angular orientation of the projection B of the magnetic field to be detected. It is furthermore remarkable that an offset usually present in a Hall effect device will be cancelled this way. [0154] Comparing the filtered signal with ground potential in comparator 3 results in a digital signal (more particularly in a square signal), and by means of this digital signal and the clock signal outputted by clock 6 and the logic signal (typically a square signal) outputted by control unit L, phase detection unit 5 (cf. also FIG. 10 ) can output a digital signal not only indicative of the angle α of the projection B of the magnetic field to be detected but directly indicating that sought angle. [0155] Usually, all three of the following signals (cf. FIGS. 1 and 10 ), the one from the comparator 3 , the one from control unit L, and the one fed from latch 8 to counter 9 , have the same frequency, namely the before-mentioned frequency f. [0156] Of course, other ways of evaluating the filtered signal are thinkable, in particular dispensing with comparator 3 and/or with latch 8 and/or counter 9 . But such ways will usually be more complicated and/or slower. [0157] When, as indicated in FIG. 4 , the connections to the current source 2 are established simultaneously with the connections to the filtering unit F, current spikes and corresponding Hall voltage spikes can occur (not shown in FIG. 4 ), in particular when initiating the connections, but also when breaking the connections. [0158] Such spikes in the voltage signals fed to filtering unit F result in inaccuracies of the detected angle α. In order to avoid such problems, it is possible to establish the connections of the devices Sx, Sy to the current source 2 already before the connections to the filtering unit F are made and/or to disconnect the current source 2 from the respective Hall effect device after the connections of that Hall effect device to the filtering unit F are broken. Accordingly, there are times when two times the bias current I is drawn. This of course requires that current source 2 can simultaneously provide two times the bias current I, or that a second current source is provided. [0159] FIG. 5 shows an illustration of applied bias currents I and resulting Hall voltages VHall suitable for accomplishing the above-described procedure for suppressing spikes and thus improving measuring accuracy, in particular the time development of I and VHall is shown. In the lower part of FIG. 5 where the applied currents I are shown, the indicated wiring schemes for Sx and Sy are put in quotes because the full wiring scheme (comprising the connections of both pairs of connectors) is of course only present during that portion of time during which also the other pair of connectors is properly connected, namely to the filtering unit F. [0160] Reading example for FIG. 5 : Whereas for Sy the connections to filtering unit F according to wiring scheme Y 1 are present from π/4 to 3π/4 (upper portion of FIG. 5 ) only, the connections to current source 2 according to wiring scheme Y 1 are present from 0 to π/2 (lower portion of FIG. 5 ). In this case, the connections for applying the bias current I are established and broken a duration of Tf/8 (corresponding to π/4) earlier and later, respectively than the connections to filtering unit F; they are present twice as long as the connections to filtering unit F are present and centered about the time the connections to filtering unit F are present. [0161] Another possible improvement which allows to achieve an excellent offset cancellation even in case of strongly non-linear Hall effect devices makes use of not only two wiring schemes (in each Hall effect device), but of four. [0162] The repeating wiring sequence in this case has a length of not only Tf, but of 2 Tf. During the first period of length Tf, the same sequence as illustrated in FIG. 4 can be used, i.e. X 1 , Y 1 , −X 2 , −Y 2 . But in the second period of length Tf, the sequence X 3 , Y 3 , −X 4 , −Y 4 is applied (cf. FIG. 3 ). The filtered signal is then an average between the first and the second period of length Tf. [0163] Of course, this embodiment can be also combined with the embodiment illustrated in FIG. 5 . [0164] Yet another possible improvement is shown in FIG. 6 . FIG. 6 shows a schematic block-diagrammatical illustration of an improved sensor 1 . In this case, an additional, second set of Hall effect device is provided: it comprises devices Sx 180 and Sy 180 . These devices are preferably constructed identical to the respective devices Sx, Sy, and they are aligned the same way as these, but rotated about an axis perpendicular to the drawing plane by 180° with respect to the corresponding other device. The additional devices Sx 180 , Sy 180 are also controlled by wiring unit W, or, as shown in FIG. 6 , by an additional wiring unit W′ which is similar to wiring unit W; both wiring units W, W′ are controlled by control unit L. Otherwise, the properties of the embodiment of FIG. 6 can be inferred from the properties of the embodiment of FIGS. 1 (and 10 ). [0165] To Sx 180 and Sx, the same wiring schemes are simultaneously applied, and to Sy 180 and Sy, the same wiring schemes are simultaneously applied. The wiring schemes may be those discussed in conjunction with FIG. 4 (X 1 , Y 1 , −X 2 , −Y 2 ) or those of the improved embodiment mentioned above (X 1 , Y 1 , −X 2 , −Y 2 , X 3 , Y 3 , −X 4 , −Y 4 ), wherein the spike-suppression idea (cf. FIG. 5 ) may of course be applied here, too. [0166] Before the VHall signals of the Hall effect devices are fed to filtering unit F, a difference between the VHall signals from the first set of devices (Sx, Sy) and the VHall signals from the second set of devices (Sx 180 , Sy 180 ) is formed using a subtraction unit 7 , e.g., embodied as an adder and an inverter, and that difference signal is then fed to filtering unit F. Due to the rotated alignment of the second two devices Sx 180 , Sy 180 , the absolute value of that difference signal will be approximately twice the absolute value derived from each of the sets of the devices, and thus, not only the signal-to-noise ratio will be improved, but much more importantly, switching noise occurring when establishing or breaking the connection to filtering unit 6 (by changing wiring schemes) will—at least to a great extent—cancel. Accordingly, an even more accurate output signal can be obtained, but at the cost of having to provide two times the bias current as compared to using only half the number of Hall effect devices. [0167] In another special embodiment which is particularly suitable when the projection B is rotating, the filtering unit substantially is a band pass filter, in particular one having a quality factor Q of preferably about π/2. [0168] In a situation where the magnetic field (and also the projection B) is rotating, like in the typical case of a permanent magnet attached to a rotating shaft, the available data (outputted by output unit 4 ) is always delayed with respect to the (current) shaft position, because the sensor's output is related to the average position of the shaft during the measurement cycle, and not to the position at the end of the measurement cycle. [0169] This lag behind becomes important when the measurement time is not short with respect to the magnet revolution period, or when the data is subsequently averaged (for instance for decreasing noise). One solution would be to correct the outputted data by evaluating the rotation speed, e.g., by taking the former position and add or subtract the shaft displacement during half an output period. This, however, requires some logic processing which costs measurement time and requires a relatively complex implementation. [0170] The proposed solution, however, is to make use of the natural phase shift generated by a band pass filter when the frequency moves away from the center frequency. And exactly this takes place when the field is rotating. The frequency of the signal at the band pass filter input decreases when the magnetic field projection B rotates in the same direction as described by the wiring sequence (in the example of FIG. 1 : x, y, −x, −y, the letters indicating the Hall effect devices Sx, Sy, the sign indicates reversed wiring schemes), and it increases when the magnet rotates in the opposite direction as described by the wiring sequence. As a consequence, the filter introduces a positive phase shift when the magnet rotates against the wiring sequence and a negative phase shift when the magnet rotates in the same sense as the wiring sequences. [0171] Thus, one can design the band pass filter in an adequate way, detect the rotating direction of the magnetic field projection and set the measurement direction (more precisely, the sequence of wiring schemes) accordingly such that the phase shift at least substantially cancels the lag described above (x, y, −x, −y; or: −y, −x, y, x). [0172] The quality factor Q of substantially π/2 allows to practically perfectly compensate for the described lag. [0173] Another aspect which is not necessarily linked to the above-described embodiments and the particular way of wiring, relates to a possibility to determine the amplitude of the projection B of the magnetic field. For explaining this in more detail, we will nevertheless refer to the embodiments above, for reasons of simplicity in particular to the embodiment of FIG. 1 . [0174] FIG. 7 is an illustration of signals usable for obtaining information about a amplitude of a magnetic field, more precisely an illustration of signals usable for determining the amplitude of a projection B of a magnetic field into a plane. Referring to FIG. 1 , it is possible to use the comparator 3 not only with one input grounded, but it is possible to apply a voltage Vc to one input. The other input receives a Hall voltage signal VHall, as is the case in FIG. 1 , in particular an at least approximately sine-shaped signal (cf. also the dotted line in FIG. 4 ). [0175] In the upper portion of FIG. 7 , the Hall voltage signal VHall is shown (having a period Tf), as is the voltage Vc. In the lower portion of FIG. 7 , the signal outputted from the comparator 3 is indicated. With Vc (Vc≠0 Volt) suitably adjusted to a voltage having an absolute value smaller than the smallest VHall signal amplitude to be expected, the duty cycle dT of the signal outputted from the comparator will depend on the before-addressed amplitude of a projection B of the magnetic field, the larger dT, the larger the amplitude of said projection B. [0176] Suitably gauging dT vs. the amplitude of said magnetic field amplitude allows to establish a magnetic field amplitude measuring device or a sensor for sensing a magnetic field amplitude of a projection of a magnetic field vector of a magnetic field into a plane and a corresponding method. [0177] As will be clear from the remarks above, this use of a comparator for determining a magnetic field amplitude of a projection of a magnetic field vector of a magnetic field into a plane can work with any Hall voltage signal (which is continuous or quasi-continuous), not only with a sine-shaped one and in particular not only with Hall voltage signals derived using wiring scheme changes like described herein before. [0178] Of course, all the concepts described above do not only work with 2 or with 4 Hall effect devices. And these do not necessarily have to be arranged with their detection directions parallel to two perpendicular directions, even though this will usually be the case. It is also possible to use three or more (and six or more) Hall effect devices and apply the same ideas as addressed above. But in this case, it is advisable to carefully select the order (sequence) in which Hall voltages are fed from the respective Hall effect device to the filtering unit. And, in addition, e.g., if the angular orientation of the Hall effect devices is not regularly spaced, it is advisable to carefully adjust the time durations during which each respective Hall effect device feeds its Hall voltage to filtering unit F. [0179] Both, order (sequence) and times shall be chosen such that the staircase signal fed to the filtering unit mimics (as close as possible) a sine signal of frequency f=1/Tf. [0180] Furthermore, it shall be mentioned that each of the Hall effect devices mentioned herein can be a simple Hall effect device or can be composed of two or more simple Hall effect devices, the latter being wired in a parallel or serial or mixed parallel-and-serial way. [0181] For a Hall effect device composed of two simple Hall effect devices wired in parallel (with respect to their current supply), this is block-diagrammatically illustrated in FIG. 8 . The composed Hall effect device 1 has its two pairs of connectors to which each of the two simple Hall effect devices are connected in parallel. [0182] FIG. 9 shows a block-diagrammatical illustration of another composed Hall effect device composed of two simple Hall effect devices. For each of the two simple Hall effect devices, a separate current supply is provided, wherein it is also possible to look upon these two separate current supplies as two components of one (composed) current supply. The voltages v− and v+, respectively, of the two simple Hall effect devices are fed to separate adders in order to provide the Hall voltage of the composed Hall effect device. [0183] In general, a Hall effect device according to the invention may of course have more than those four contacts which correspond to the before-addressed two pairs of contacts. [0184] An example is given in FIG. 9 where six contacts are present: v+ and v− (outputted from the adders) and for each simple Hall effect device, one i+ and one i− contact is provided, wherein it is also possible to short two current contacts, one of each simple Hall effect device, e.g., the two i− contacts, such that the composed Hall effect device can be considered to have five contacts. [0185] Analogously to what is shown in FIG. 9 , it is also possible to join (i.e. to short) two of the current contacts, e.g., the i− contact of the left and the i+ contact of the right simple Hall effect device, and use one (simple) current supply for supplying both simple Hall effect devices with bias current, thus realizing a composed Hall effect device comprising two simple Hall effect devices connected serially (with respect to their current supply). Otherwise, the composed Hall effect remains as depicted in FIG. 9 , including the two adders [0186] All the embodiments mentioned above can very well be realized in a single silicon chip, in particular using CMOS processes. So-called vertical integrated Hall effect devices are particularly well suited for such a realization. [0187] FIG. 11 exemplarily shows a schematized perspective view of a cross-section through a vertical integrated Hall effect device 1 . In a p-doped Silicon substrate, an n-doped well is provided, five metal contacts embodied as parallel-aligned contact lines being provided on the surface of the Silicon substrate, for applying a bias current I and picking up a Hall voltage VHall. Usually, two of the five metal contacts will be shorted, namely the outermost two, as schematically indicated by the bold lines in FIG. 11 . The arrow labelled B to the left of the vertical integrated Hall effect device 1 illustrates a magnetic field vector of a magnetic field aligned parallel to the detection direction of the vertical integrated Hall effect device 1 . [0188] According to one exemplary wiring scheme indicated in FIG. 11 , the contact in the middle is used for injecting the bias current which then flows, as visualized by the bent arrows, to both outermost contacts, a current source (only symbolically sketched in FIG. 11 ) being connected between the middlemost and the two outermost contacts. Of course it is also possible to use two separate (simple) current sources, each contacting one of the outermost metal contacts and both contacting the middlemost metal contact. As illustrated in FIG. 11 , the other two contacts are used for picking up the resulting Hall voltage (which is present if a non-zero magnetic field component exists parallel to the detection direction). [0189] FIG. 12 is a schematic symbolic illustration of four non-reverse wiring schemes applied to a vertical integrated Hall effect device. With reference to the vertical integrated Hall effect device 1 of FIG. 11 , FIG. 12 can be understood as symbolizing top views onto such vertical integrated Hall effect devices 1 . The four wiring schemes illustrated in FIG. 12 are named exactly as in FIG. 3 , confer there for details. [0190] All the embodiments described above can be used in position sensing (e.g., determining the rotational position of a rotor a motor), in rotation counting, in rotational speed sensing and for similar purposes involving a magnetic field. [0191] Aspects of the embodiments have been described in terms of functional units. As is readily understood, these functional units may be realized in virtually any number of components adapted to performing the specified functions. For example, one control unit L and only one wiring unit can be used for realizing an embodiment functioning like the one of FIG. 6 , but one could also realize it using two control units and two wiring units W, W′. [0192] Furthermore, the filtering unit F could also be realized as a lowpass filter, and possibly in addition an offset remover (for suppressing DC voltage offsets), at least in the embodiments different from the one described above for compensating for a lag in time using a band pass filter having a suitable quality factor. Generally, the main purpose of the filtering unit is to extract the sine wave of frequency f=1/Tf (having the sought phase) from the Hall voltage staircase signal. LIST OF REFERENCE SYMBOLS [0000] 1 sensor 2 current source 3 comparator 4 output unit 4 a output, output of output unit 5 phase detection unit 6 clock 7 subtraction unit 8 latch, set-reset latch 9 counter B projection of a magnetic field into a plane F filtering-or-resonating unit, filtering unit, filter I current, bias current L control unit Sx, Sy, Sx 180 , Sy 180 Hall effect devices Td duty cycle VC voltage, voltage at comparator VHall Hall voltage W wiring unit α angle
The method for sensing an angular orientation of a magnetic field includes a) providing a set of N≧2 Hall effect devices, each having a detection direction and comprising two pairs of connectors; b) providing at least one band pass filter having a fundamental frequency f=1/Tf; c) providing at least one current source for outputting an electrical current at its output; d1) applying, during a first time period of a duration 0.5 Tf and in a specific sequence of said N Hall effect devices, to each of said N Hall effect devices a respective wiring scheme Wi+, during respective subsequent time periods of durations ti; and d2) applying, during a second time period of a duration 0.5 Tf, subsequent to said first time period of a duration 0.5 Tf, and in the same specific sequence of said N Hall effect devices, to each of said N Hall effect devices a respective wiring scheme Wi−, during respective subsequent time periods of the same durations ti.
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This invention relates to instrument racks, and in particular to a foldable, expandable, and an interchangeable assembly for supporting accessories such as microphones and cables to be supported and arranged about instruments such as drum sets, and the like. BACKGROUND AND PRIOR ART Generally, many drummers use at least approximately five to approximately twelve microphone stands with boom arms. Also, the drummers need microphone cables that can be at least approximately twenty to approximately thirty feet in length for each microphone. For example, for a snare, hi-hats, three toms, a bass drum and overhead cymbals, up to nine or more individual microphone stands have been used. In addition for each microphone stand there is the requirement for individual microphone cables. For example, nine stands has required nine cables. Additionally, the traditional stands are difficult to pack up and move and further require substantial space for storage. The conventional individual stands and cables do not fold up together. Additionally, the time expense to set up and take down multiple stands and cables is an additional problem. Furthermore, the weight of the stands and cables adds a substantially extra burden for transporting and setting up the equipment. U.S. Pat. No. Des. 305,026 to Wolf; U.S. Pat. No. 4,889,303 to Wolf; U.S. Pat. No. 5,048,789 to Eason et al.; and U.S. Pat. No. 6,007,032 to Kuo, each show conventional type microphone stands. However, none of the patents allow for multiple microphones, nor provide any wrap around rack, nor support individual cables, and all suffer from all the problems described above. Some attempts have been made over the years to support multiple microphones. See for example, U.S. Pat. No. 1,045,583 to Mills; U.S. Pat. No. Des. 384,077 to Frasse; and U.S. Pat. No. 5,490,599 to Tohidi. However, these patents are generally limited to single stands for holding up several microphones. The single stand cannot support multiple microphones that must be arranged at various vertical heights and horizontally about an instrument set such as a drum set. Accessory type rails have also been proposed. See U.S. Pat. No. 4,579,229 to Porcaro et al. and U.S. Pat. No. 5,520,292 to Lombardi. However, these patented devices have rails with limited heights and lengths for directly mounting both the instruments and the microphones directly on the rails; Thus, the drummer is limited to the physical constraints of these rails for which to position both their microphones and their instruments. Both of these patents do not allow the user to customize different height and spatial type locations for their instruments and microphones. Both of these devices do not allow for extension arms with microphones to be added to the rails. Additionally, both of these devices would potentially require multiple outside cables arranged about the rails. Other patents of interest known to the subject inventor that also fail to overcome the problems described above include U.S. Pat. No. Des. 327,211 to Tarshis et al.; U.S. Pat. No. 4,703,506 to Sakamoto et al. and U.S. Pat. No. 5,058,170 to Kanamori et al. SUMMARY OF THE INVENTION The primary objective of the subject invention is to provide a single rack unit for instruments such as drums for supporting accessories such as microphone stands and cables. The secondary objective of the subject invention is to provide a single rack unit for instruments such as drums, which wraps about the instruments(such as the drum set). The third objective of the subject invention is to provide a single rack unit for instruments such as drums, which can fold up for easy storage. The invention has extension boom arms that can swing and fold parallel to the main rack unit. The main rack units arms and legs can swing in and fold up so that the entire unit is in a bundle having dimensions of approximately four feet in length, approximately ten inches high, and be approximately ten inches wide. The fourth objective of the subject invention is to provide a single rack unit for instruments such as drums that is lightweight. All the components of the single rack unit combined together can weigh approximately one fourth the weight of conventional type microphone stands and cables that are being replaced. A first preferred embodiment can include a rack having up to four or more legs, and up to three or more horizontal support bars that are pivotally attached to one another so that the rack can be easily assembled and disassembled. Fasteners such as thumbscrews can be used to tighten the legs and horizontal bars to desired positions so that the rack can be arranged about an instrument set such as a set of drums. Various novel microphone stands can be attached to the horizontal bars and legs and be further extendable and bendable to selected positions as needed. A second embodiment allows for the microphones to be easily attached to the rack by simple plug type connections such as but not limited to XLR connectors, and the like. Further objects and advantages of this invention will be apparent from the following detailed description of a presently preferred embodiment which is illustrated schematically in the accompanying drawings. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 a is a perspective view of a first embodiment of the novel microphone support rack assembled about a drum set. FIG. 1 b is an enlarged view of the sound board connection used in FIG. 1 a. FIG. 1 c is an enlarged view of a microphone mounting fitting used in FIG. 1 a. FIG. 1 d is an enlarged view of a dual pivot fitting used in FIG. 1 a. FIG. 1 e is an enlarged view of a single pivot fitting used in FIG. 1 a. FIG. 2 shows the underlying frame used in the rack of FIG. 1 a. FIG. 3 shows the frame of FIG. 2 beginning to be folded. FIG. 4 shows the frame of FIG. 2 in a final folded state. FIG. 5 a is a side view of the dual pivot fitting of FIG. 1 d along arrow V 1 . FIG. 5 b is a front view of the dual pivot fitting of FIG. 1 d along arrow V 2 . FIG. 6 a is a side view of the single pivot fitting of FIG. 1 e along arrow W 1 . FIG. 6 b is a front view of the single pivot fitting of FIG. 1 e along arrow W 2 . FIG. 7 is an enlarged view a double pivot and double telescoping microphone arm that can be used for vocals with the rack. FIG. 8 is an enlarged view of an upper microphone arm used in FIG. 1 a. FIG. 9 is an enlarged view of a lower microphone arm used in FIG. 1 a. FIG. 10 is a perspective view of a second embodiment microphone support rack. FIG. 11 is an enlarged view of a pivot support arrangement used in the rack of FIG. 10 . FIG. 12 is an enlarged view of a pivot fitting joint used in the rack of FIG. 10 . FIG. 13 is an enlarged view of a flexing microphone mount. DESCRIPTION OF THE PREFERRED EMBODIMENT Before explaining the disclosed embodiments of the present invention in detail it is to be understood that the invention is not limited in its application to the details of the particular arrangement shown since the invention is capable of other embodiments. Also, the terminology used herein is for the purpose of description and not of limitation. First Embodiment FIG. 1 a is a perspective view of a first embodiment of the novel microphone support rack 100 assembled about a conventional type drum set previously described that can include a snare, hi-hats, three toms, a bass drum and overhead cymbals. FIG. 1 b is an enlarged view of the sound board connection used in FIG. 1 a . The soundboard connection includes a multi-conductor cable 102 which can run through one opening end 101 in main horizontal longitudinal bar 110 to connect to the microphones attached to the support rack 100 . Male and female connectors 104 , 106 such as but not limited to XLR connectors, ¼ inch plugs, and the like, that can attach cable 102 to external cable 108 which can pass to conventional external equipment 109 (not shown) such as amplifiers, synthesizers, and the like. FIG. 1 c is an enlarged view of a microphone mounting fitting 210 used with the novel rack 100 in FIG. 1 a . Fitting 210 can include a main hollow cylinder portion 212 having open slit bottom 211 that allows the main horizontal longitudinal bar 110 to pass therethrough. A lower protruding double flange 216 can be adjusted apart from one another depending on the diameter of longitudinal bar 110 by an adjustable and tightenable thumb screw 217 . On top of the main hollow cylinder 212 , can be an outer telescopic tube 312 of upper microphone arm 310 pivotally attached to an upper double pivot flange 214 with an adjustable and tightenable thumb screw 215 passing therethrough(FIG. 8 shows more detail of the upper microphone arm 310 with mount hole 313 for allowing the thumb screw 215 to pass therethrough.) Screw 215 provides a pivot axis for allowing upper microphone arm 310 to be able to rotate in the both directions of arrows M 1 . FIG. 1 d is an enlarged view of a dual pivot fitting 220 (and described in greater detail in reference to FIGS. 5 a - 5 b ) used in FIG. 1 a . Fitting 220 can provide a connection point for allowing right horizontal longitudinal bar 130 to pivot and rotate in the direction of arrows H 1 to main horizontal longitudinal bar 110 . Fitting 220 also provides a connection point for allowing front right vertical leg 160 to pivot and rotate in the direction of arrows H 2 to main horizontal longitudinal bar 110 FIG. 1 e is an enlarged view of a single pivot fitting 230 (which is described in greater detail in reference to FIGS. 6 a - 6 b ) used in FIG. 1 a . Fitting 230 can provide a connection point for allowing rear right vertical leg 180 to pivot and rotate in the direction of arrows H 3 to right horizontal longitudinal bar 130 . FIG. 2 shows the underlying frame 105 used in the rack of FIG. FIG. 1 a . As described in the previous figures while keeping main horizontal bar 110 stationary, the right horizontal bar 130 can be rotated and folded in the direction of arrow H 1 , right front vertical leg 160 can be rotated and folded in the direction of arrow H 2 , and right rear vertical leg 180 can be rotated and folded in the direction of arrow H 3 . Also left horizontal bar 120 can be rotated and folded in the direction of arrow 11 , left front vertical leg 150 can be rotated and folded in the direction of arrow 12 , and left rear vertical leg 140 can be rotated and folded in the direction of arrow 13 . FIG. 3 shows the frame 105 of FIG. 2 beginning to be folded. FIG. 4 shows the frame 105 of FIG. 2 in a final folded state, after the components in FIG. 2 were folded again in the direction of arrows H 1 ′, H 2 ′, H 3 ′, I 1 ′, I 2 ′, and I 3 ′. The final folded state 100 ′ can become a bundle having dimensions of approximately four feet in length, approximately ten inches high and be approximately ten inches wide. FIG. 5 a is a side view of the dual pivot fitting 220 of FIG. 1 d along arrow V 1 . FIG. 5 b is a front view of the dual pivot fitting 220 of FIG. 1 d along arrow V 2 . Referring to FIGS. 1 d and 5 a - 5 b , dual pivot fitting 220 includes main hollow cylindrical fitting portion 222 having open slit 221 that allows an end of the main horizontal longitudinal bar 110 to pass therethrough. An upper protruding double flange 224 can be adjusted apart from one another depending on the diameter of longitudinal bar 110 by an adjustable and tightenable thumb screw 225 . On one side of the cylinder 222 , can be an end of the right horizontal longitudinal bar 130 pivotally attached to double side flanges 226 with an adjustable and tightenable thumb screw 227 . On the bottom of cylinder 222 can be the upper end of right front vertical leg 160 pivotally attached to double flanges 228 by an adjustable and tightenable thumb screw 229 . FIG. 6 a is a side view of the single pivot fitting 230 of FIG. 1 e along arrow W 1 . FIG. 6 b is a front view of the single pivot fitting 230 of FIG. 1 e along arrow W 2 . Referring to FIGS. 1 e and 6 a - 6 b , single pivot fitting 230 includes main hollow cylindrical fitting portion 232 having open slit 231 that allows an end of right horizontal longitudinal bar 130 to pass therethrough. An upper protruding double flange 234 can be adjusted apart from one another depending on the diameter of bar 130 by an adjustable and tightenable thumb screw 235 . On the bottom of cylinder 232 can the upper end of right reare vertical leg 180 pivotally attached to double flanges 236 by an adjustable and tightenable thumb screw 229 . FIG. 7 is an enlarged view a double pivot and double telescoping microphone ann 400 that can be used for vocals with the rack 100 of FIG. 1 a and the microphone mount fitting 210 of FIGS. 1 c . Referring to FIGS. 1 a , 1 c and 7 , the vertical outer telescopic tube 410 of arm 400 can attach to left horizontal bar 120 by thumb screw 215 passing through double flanges 214 and through-hole 413 in the lower end of outer telescopic tube 410 . Vertical inner telescopic tube 420 can move up and down in the direction of arrows J 3 and have an end within the upper end of outer telescopic tube 410 and be attached thereto by a clamp collar 415 and a screw 417 having a tip(not shown) which can contact an exterior lower end portion of inner telescopic tube 420 . A horizontal outer telescopic tube 430 can pivot and rotate in the direction of arrows J 2 relative to telescopic tubes 410 and 420 by a conventional type pivot clamps 450 and 460 attached to one another by thumb screws 455 similar to those previously described. A horizontal inner telescopic tube 440 can move in and out of outer telescopic tube 430 in the direction of arrows J 1 and be held to a selected position by clamp collar 435 and thumb screw 437 similar to clamp 415 and screw 417 . The outer end 447 of telescopic tube 440 can include exterior threads 447 for allowing the telescopic tube 440 to attach to a conventional microphone 3 . FIG. 8 is an enlarged view of an upper microphone arm 310 used in FIG. 1 a . Referring to FIGS. 1 a , 1 c and 8 , upper microphone arm 310 can include an outer telescopic tube 312 having a through-hole 313 in its lower end for allowing it to be pivotally attached to double flanges 214 of microphone mount fitting 210 by a thumb screw 215 . An extendable and retractable inner telescopic tube 320 has a lower end which passes into outer telescopic tube 312 , and is held to a selected position by a clamp collar 315 with a thumb screw 317 . The thumb screw can lock the inner telescopic tube 320 to a selected position to the outer telescopic tube 312 . A conventional pivot head 328 can be attached onto the outer end of inner telescopic tube 320 and be pivotally attached to a conventional microphone type clip 330 by a pivot pin 329 . Clip 330 can have a hollow cavity(not shown) for allowing a base portion of a microphone to be inserted inside, and clip 330 can rotate in the direction of arrows K 2 to inner telescopic tube 320 and outer telescopic tube 312 . FIG. 9 is an enlarged view of a lower microphone arm 350 used in FIG. 1 a , and can be similar to the double pivot and double telescoping microphone arm 400 of FIG. 7 . Referring to FIGS. 1 a , 1 c and 9 , lower microphone arm 350 can be attached to main horizontal bar 110 of rack 100 by double flanges 216 and thumb screw 217 of microphone mount fitting 210 connecting through the lower through-hole 353 which passes through a lower end portion of vertical outer telescopic tube 352 . Vertical inner telescopic tube 360 can move up and down in the direction of arrows L 1 and have an end within the upper end of outer telescopic tube 352 and be attached thereto by a clamp collar 355 and a screw 357 having a tip(not shown) which can contact an exterior lower end portion of inner telescopic tube 360 . A horizontal outer telescopic tube 370 can pivot and rotate in the direction of arrows L 2 relative to telescopic tubes 352 and 360 by a conventional type pivot clamps 392 and 396 attached to one another by thumb screw 395 similar to those previously described. A horizontal inner telescopic tube 390 can move in and out of outer telescopic tube 370 in the direction of arrows L 3 and be held to a selected position by clamp collar 375 and thumb screw 377 similar to clamp 355 and screw 357 . The outer end 387 of telescopic tube 380 can include exterior threads 387 for allowing the telescopic tube 380 to attach to a conventional screw-on microphone 3 . Some or all of the microphones 3 used in the first embodiment can be attached by the interior communication lines running through the rack 100 as shown in FIG. 1 b , so that no external lines, cables, wires, and the like are needed. The microphone fittings 210 of FIG. 1 c can be used to attach the microphone arms 310 FIG. 8, 350 FIG. 9 and 400 FIG. 7 to any of the horizontal bars 120 , 110 and 130 and to any of the vertical legs 140 , 150 , 160 and 180 of FIG. 1 a and FIGS. 2-4 either extending upward, and/or downward and/or to any side position as needed, when arranging the microphones 3 about instruments such as a drum set 1 . Second Embodiment FIG. 10 is a perspective view of a second embodiment microphone support rack 500 . FIG. 11 is an enlarged view of a pivot support arrangement 600 used in the rack 500 of FIG. 10 . FIG. 12 is an enlarged view of a pivot fitting joint 700 used in the rack of FIG. 10 . FIG. 13 is an enlarged view of a flexing microphone mount 800 . Referring to FIGS. 10-13, the second embodiment 500 includes three longitudinal horizontal bars 510 , 520 , and 530 pivotally attached to one another by a conventional type hinge arrangement. For example the hinge arrangement 600 can include a protruding portion 594 from bar 520 that passes through spaced apart flanges 592 attached to bar 530 and held together by an adjustable and tightenable thumb screw 595 which allows bars 520 and 530 to rotate and pivot to one another in the direction of arrows P 1 Similarly vertical legs 540 , 550 , 560 and 570 can be pivotally attached to horizontal bars 510 , 520 , and 530 by a hinge arrangement 700 similar to hinge arrangement 600 so that the legs( 570 for example) can pivot and rotate in the direction of arrows P 2 . A bendable goose-neck type stand 580 can connect microphone 3 to the rack 500 in the direction of arrow N by male and female connectors 575 , such as but not limited to XLR type connectors, ¼ inch plugs, and the like. Interior communication lines such as those depicted in FIG. 1 b can also pass into the rack 500 of the second embodiment, so that no external wires, lines, cables, and the like, are used in the second embodiment. Similar to the first embodiment, embodiment two can also fold up when not be used, or for transport, and the like. The components of both preferred embodiments can also be combined with one another. For example, microphone fittings 210 of FIG. 1 a can be attached to the rack 500 of FIG. 10 to supplement the microphone type connections thereon, and vice versa. Although both preferred embodiments show racks 100 and 500 using four legs and three horizontal bars, the invention can be practiced with less or more legs and bars. For example, a drummer can use double base drums, which would require four arms and four legs in the main rack. Also, the shapes of the legs and bars can also vary from being cylindrical to being rectangular, square, and the like. While the preferred embodiment is described for supporting microphones, the invention can support other components such as the instruments themselves, combinations of the microphones and the instruments, and the like. Although the preferred embodiments describe using the novel rack frame about a drum set, the invention can be used with and/or arranged about other types of instruments used in a band, an orchestra, and the like, such as but not limited to guitars, saxophones, violins, trumpets, and the like, and combinations, thereof. While the invention has been described, disclosed, illustrated and shown in various terms of certain embodiments or modifications which it has presumed in practice, the scope of the invention is not intended to be, nor should it be deemed to be, limited thereby and such other modifications or embodiments as may be suggested by the teachings herein are particularly reserved especially as they fall within the breadth and scope of the claims here appended.
A lightweight and easily erectable, collapsible and storable rack system for supporting music components adjacent to associated instruments. The racks can support microphones arranged about a drum set. The rack system includes fittings for horizontal bars that are pivotally attached to one another and foldable legs for the bars that allows for the system to be easily and neatly packed away during nonuse. Microphones can be pivotally attached to extendable arms, which in turn are pivotally attached to the horizontal bars. The arms can extend upward and downward from the bars, and be bendable to allow further versatility. Power and communication cables can also run through the legs and bars to the microphones.
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TECHNICAL FIELD The present invention relates to a facility and a method for providing a service on a mobile communication network, and more particularly to a facility and a method for performing the dynamic clustering of base stations using a centralized clustering server to support an efficient multi-BSs coordination service in a mobile communication system. The mobile communication network mentioned here refers to a mobile communication system that supports the multi-BSs coordination service. BACKGROUND ART Coordinated multi-point transmission/reception (CoMP) is already recognized as a very efficient method for extending the coverage of a high-speed data service, improving the throughput at a cell boundary, and increasing the average throughput of the system in a mobile network. In coordinated multi-point transmission/reception, it is required that clustering be performed for all network nodes that participate in the cooperation and a network node in each cluster offers the coordinated multipoint service to multiple terminals. FIG. 1 is a diagram showing a simple multi-BSs coordination service scene in a conventional mobile network. In FIG. 1 , two base stations, base station 1 and base station 2 , coordinate with each other to provide services to terminal 1 and terminal 2 at the same time. In a practical application, two or more base stations sometimes provide services to two or more terminals at the same time. 3GPP, an international standardization organization, developed the system architecture and the specifications of the second-generation and third-generation mobile communication network, and those specifications are already used today for networks that use the air interface. 3GPP is now working on establishing standards for Long Term Evolution-advanced (LTE-advanced) for a fourth-generation mobile communication network. In the standard establishment process of LTE-advanced, coordinated multi-point transmission/reception is already employed as a service of the multi-BSs coordination service. FIG. 2 is a diagram showing the frame of the multi-BSs coordination service system that performs centralized control in the conventional technology. In the description below, the LTE-advanced network established by the 3GPP standardization organization is used an example of application. The facility and the method of this network may be applied to other mobile networks that support the multi-BSs coordination service. In this typical frame, the mobile cellular network is composed of at least multiple base stations. The multiple base stations connect to one base station controller (or multiple base station controllers in an actual application), which negotiates about the key parameters of the multi-BSs coordination service. The access network connects the base station controller and the base stations to the mobile network gateway. The mobile network gateway, connected to the Internet or other servers, acts as an end node of the entire mobile access network. The mobile network gateway at least provides the information, received from other servers and the Internet, to all mobile terminals and at least performs processing, such as network registration, security, and cost calculation, for all mobile terminals. The multi-BSs coordination service has many advantages. However, for each base station to select the optimal base station cluster dynamically and individually, a large amount of data and channel state information must be shared among all base stations. This greatly increases the load of communication among base stations and, at the same time, requires the base stations to implement a complicated algorithm for selecting the optimal cluster. In addition, to select the optimal base station cluster, a large amount of information must be shared between base stations and between a base station and a terminal. This significantly consumes the signaling and resources and decreases the power of the mobile network. From another viewpoint, if static base station clustering is used in the multi-BSs coordination service such as that shown in FIG. 3 , the consumption of the signaling and resources can be saved. However, because the mobile terminal locations and the service channel state are constantly changing in a mobile network, it is difficult to satisfy all the needs of the multi-BSs coordination transmission by selecting static optimal-base station clustering. Simple static base station clustering, though simple, prevents the air interface utilization from being increased using the multi-BSs coordination service, making the multi-BSs coordination service meaningless. FIG. 3 is a diagram showing an example of static clustering in the conventional multi-BSs coordination service. In the figure, multiple base stations 1 - 30 are installed in the network, and the base stations are divided statistically into multiple base station clusters with three base stations in each cluster. When the multi-BSs coordination service is performed, only three base stations in a cluster can coordinate with each other but the coordination service cannot be performed across clusters. The advantage of this configuration is that the consumption of a base station caused by dynamic clustering is reduced. In this case, however, the performance cannot reach the optimal level. If a mobile terminal is located around the cell boundary of several base stations in the same base station cluster, the mobile terminal can receive the benefit from the multi-BSs coordination service. If a mobile terminal is located around the boundary between two base stations, for example, around the boundary between the neighboring cells of the base station 2 and the base station 4 in FIG. 3 , the base station 2 and the base station 4 cannot perform the multi-BSs coordination service because of the static clustering rule. Therefore, even if these two base stations have enough resources and good channel quality, the mobile terminal cannot receive such a service. Those situations described above are disadvantageous for optimally using the radio air-interface resources of a base station. In summary, a simpler, lower-consumption solution for selecting dynamic base station clustering is required in a mobile network that supports multi-BSs coordination transmission. The solution is required to find the optimal base station clustering result more quickly and, at the same time, to reduce the consumption of the signaling and resources for calculating base station clustering. Patent Literature 1 and Patent literature 2 disclose a method that, before the communication between a cluster, composed of multiple radio nodes, and the node at the other end of communication is started, they communicate with each other to negotiate about multi-node coordination communication. However, those nodes are all terminal nodes and the mobile communication base station does not participate in clustering. Patent Literature 3 discloses a method that the antenna units from two or more base stations configure a multi-antenna array. However, in this patent, the base station cluster is already established and a detailed clustering method is not mentioned. Patent Literature 4 discloses a method that two transmission nodes coordinate with each other to communicate with one reception node, but the detailed contents of the clustering algorithm is not mentioned. CITATION LIST PATENT LITERATURE 1 WO2008/157147A1 PATENT LITERATURE 2 US2008/0014884A1 PATENT LITERATURE 3 US2008/02060064A1 PATENT LITERATURE 4 US2008/003022A3 SUMMARY OF INVENTION Technical Problem The present invention provides a communication control device, communication control method, and system and provides a highly efficient multi-BSs coordination service using dynamic clustering in a mobile communication system. Advantageous Effects of Invention The present invention selects the optimal base station clustering, based on the communication state between a terminal and each base station, to reduce the consumption of the signaling and resources for calculating base station clustering. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram showing a conventional, simple multi-BSs coordination service scene. FIG. 2 is a diagram showing the frame of a conventional, multi-BSs coordination service system that is centrally controlled. FIG. 3 is a diagram showing an example of static clustering in the conventional multi-BSs coordination service. FIG. 4 is a diagram showing a multi-BSs coordination service system that supports centralized dynamic clustering of the present invention. FIG. 5 is a diagram showing the packet format of pilot information used for estimating channel state information. FIG. 6 is a signaling flowchart showing dynamic clustering. FIG. 7 is a flowchart showing dynamic clustering in a centralized clustering server of the present invention. FIG. 8 is a typical signaling flowchart showing the multi-BSs coordination service triggered by a terminal after the dynamic clustering of the present invention is performed. FIG. 9 is a typical signaling flowchart showing the multi-BSs coordination service triggered by a base station after the dynamic clustering of the present invention is performed. FIG. 10 is a diagram showing the basic format of the signaling transmitted between base stations in the present invention. FIG. 11 is a diagram showing an implementation example of the X2AP field of a request signaling used for coordination transmission negotiation among base stations in the present invention. FIG. 12 is a diagram showing an implementation example of the X2AP field of a response signaling used for coordination transmission negotiation among base stations in the present invention. FIG. 13 is a diagram showing the internal structure of a single-antenna base station of the present invention. FIG. 14 is a diagram showing an example of the internal structure of a multi-antenna base station of the present invention (two antennas). FIG. 15 is a diagram showing the typical structure of the internal part of the centralized clustering server of the present invention. FIG. 16 is an information flowchart showing the internal part of the centralized clustering server of the present invention. FIG. 17 is a diagram showing the typical structure of a channel state information table in the centralized clustering server of the present invention. FIG. 18 is a diagram showing an implementation example of the channel state information table in the centralized clustering server of the present invention. FIG. 19 is a diagram showing an implementation example of the interference relation map used for the dynamic clustering algorithm of the present invention. FIG. 20 is a diagram showing an implementation example after some mobile terminals have moved in the communication control system of the present invention. FIG. 21 is a diagram showing the channel state information table after some mobile terminals have moved in the communication control system of the present invention. FIG. 22 is a diagram showing the advantage comparison of the dynamic clustering algorithm of the present invention. DESCRIPTION OF EMBODIMENTS The following describes embodiments based on a 3GPP LTE-A communication system. The present invention is applicable also to other mobile communication networks that support multi-BSs coordination service. FIG. 4 is a frame diagram showing a multi-BSs coordination service system of the present invention that supports centralized dynamic clustering. This system is an example of application based on the LTE-advanced network in FIG. 2 that is defined by the 3GPP standardization organization. The centralized clustering server of the present invention may be a centralized clustering server 9 , installed standalone in the network, or a base station controller 8 added to an existing base station controller and having the dynamic clustering function. The centralized clustering server of the present invention, which will be described later, may be installed in one of these two installation modes. In the present invention, to upgrade a conventional base station, the basic single-base-station radio service or the multi-BSs coordination radio service must be supported in any case. As shown in FIG. 4 , a base station receives a channel state information vector from each terminal and transmits it to the centralized clustering server or transforms channel state information to simpler channel state information and transmits it to the centralized clustering server. The centralized clustering server uses the channel state information on each terminal, received from each base station, to perform clustering for each base station and transmits the clustering result to each base station. A base station negotiates with other base stations in the current base station cluster based on the dynamic clustering result to implement the multi-BSs coordination radio service. FIG. 5 is a diagram showing the packet format of pilot information used for estimating channel state information. For a single-antenna base station (base station 1 in the figure), a known, predefined pilot_ 1 501 must be added periodically to the downlink control channel link. The terminal can use the information in the pilot_ 1 501 to calculate the channel state information between the terminal and the base station. Other air-interface resources may be used for the transmission of downlink data 502 . For a multi-antenna base station (for example, two-antenna base stations 1 and 2 in the figure), an optional general-purpose pilot number 503 may be added and, at the same time, antenna port information 504 and general-purpose pilot information 505 may be added. A pilot_ 2 _ 1 506 and a pilot_ 2 _ 2 506 , which are transmitted from respective antennas, may be transmitted separately, and the terminal can use the information in the pilot_ 2 _ 1 506 and the pilot_ 2 _ 2 506 to calculate the channel state information between the terminal and each of the antennas of the multi-antenna base station. The contents of pilot information are a known training sequence shared in advance among all terminals and the base station. When pilot information used for channel estimation transmitted from a base station is received, the terminal compares the received pilot information with the already-shared pilot. Because the pilot contents transmitted via a radio channel and the known pilot contents locally stored in the terminal usually differ, the terminal compares the differences to estimate the channel state information. The obtained channel state information includes at least the channel attenuation state and the phase shift state from the terminal to the base station. FIG. 6 is a signaling flowchart showing dynamic clustering. First, all terminals 1 - m periodically receive pilot information from respective serving base stations 1 - n (step 601 ). After that, the terminal starts calculating the channel state information h ij (h ij indicates the channel state information between base station i and terminal j) corresponding to the base station (step 602 ). The channel state information in this case is usually expressed in complex number form. Because the calculation of channel state information based on pilot information is a known technology for those skilled in the art, the detailed description is omitted here. Next, each terminal j generates its own channel state information vector [h 1j , h 2j , . . . , h nj ] and reports the generated vector to the respective serving base station (step 603 ). Some of channel state information h ij is 0. All base stations report the respective channel state information to the centralized clustering server (step 604 ). The reported channel state information may be the original channel state information or simple channel state information. The simple channel state information in this case refers to the state information generated by taking the absolute value of the original channel state information. After receiving the reported channel state information, the centralized clustering server first updates the channel state information table (step 605 ). When the timer of dynamic clustering times out, the centralized clustering server performs dynamic clustering scheduling (step 606 ). When the scheduling is terminated, the centralized clustering server transmits the scheduling result to all base stations (step 607 ). The base station broadcasts the current cluster state to all terminals in its cell (step 608 ). A terminal or a base station, which triggers the use of the multi-BSs coordination service, follows the current clustering status (step 609 ). After that, the terminal calculates the channel state information based on the pilot information that is broadcast periodically from each base station, and provides the channel state information for the next clustering. FIG. 7 is a flowchart showing dynamic clustering in the centralized clustering server of the present invention. The centralized clustering server (communication control device) receives all simple channel state information from the base stations and updates the channel state information table (step 701 ). If clustering scheduling must be performed, the centralized clustering server configures the channel state information matrix, such as the one shown in mathematical expression 1 based on the channel state information table (step 702 ). [ MATH . ⁢ 1 ] H 11 * H 21 * … H n ⁢ ⁢ 1 * H 12 * H 22 * … H n ⁢ ⁢ 2 * … … … … H 1 ⁢ n * H 2 ⁢ n * … H nn * ( 1 ) In the expression, H* xy is a collection of simple channel state information between all mobile terminals that receive services from the base station y and the base station x. There are many collection methods. For example, when dynamic clustering scheduling is performed for each multi-BSs service time slot, the following method is used. H* xy =|h xj | where h xj is the channel state information between the mobile terminal j that receives services from the current base station y and the base station x. When the period of dynamic clustering scheduling is equal to multiple multi-BSs service time slots, H* xy can be calculated as the average or the weighted average of the absolute values of channel state information between all mobile terminals that receive services from the base station y and the base station x in this period. Based on the channel state information matrix, the centralized clustering server calculates the interference weight w xy that, between base stations, the other base station has on the terminals to which the services are provided by this base station, using mathematical expression 2 to configure the base station interference relation map (step 703 ). [MATH. 2] w xy =|H* xy | 2 +H* xy | 2   (2) The interference relation map is an undirected graph. The number of nodes in the graph matches the number of base stations participating in dynamic clustering scheduling, with each node corresponding to one of the base stations. The weight of the boundary between nodes is the interference weight w xy between the corresponding two base stations. The centralized clustering server calculates all clustering parameters Li based on the number of base stations of each cluster and arranges all clustering possibilities in the un-scheduling list in descending order of the clustering parameters (step 704 ). The calculation of the clustering parameter Li corresponding to one base station clustering possibility follows the principle defined by mathematical expression 3. [ MATH . ⁢ 3 ] Li = ∑ ab ⁢ w ab ( 3 ) In the expression, w ab is the interference weight between the base stations defined by mathematical expression 2. One of the base stations (a or b) belongs to the current base station cluster, and the other base station does not belong to the current base station cluster. The number of base stations in each base station cluster may be set in advance in the centralized clustering server or may be determined dynamically according to some principle. After that, the centralized clustering server starts dynamic clustering scheduling. The scheduling is based on assumption that the interference weight w xy among all base stations in the same base station cluster will contribute to a channel gain in the multi-BSs coordination service. However, when two base stations are not in the same base station cluster, the interference weight w xy between the two base stations will contribute to the channel interference of the multi-BSs coordination service. For example, when base station y and base station x are in the same base station cluster for h* xy , base station y and base station x can perform the multi-BSs coordination service, and all channel gains between all mobile terminals, to which base station y provides services, and base station x are the channel gain in the coordination service. When base station y and base station x are not in the same base station cluster, base station y and base station x cannot perform the multi-BSs coordination service, and all channel gains between all mobile terminals, to which base station y provides services, and base station x are all channel interference to the coordination service that is performed for each of those two base stations. Therefore, the goal of dynamic base station clustering is to find the optimal clustering method, to minimize channel interference between the base station clusters, and to maximize the channel gain. The basic scheduling process is as follows. First step 705 : Initialize un-clustered set E to all base station nodes and initialize the clustered base station set U to a null set Φ. Second step 706 : Select the clustering set θ currently having the minimum clustering parameter Li, check if θ∉U and, if the result is “yes”, pass control to the third step 707 and, if the result is “no”, pass control to the fifth step. Third step 707 : E=E−θ, U=U+θ Fourth step 708 : Select the clustering set θ, currently having the minimum clustering parameter, as efficient clustering. Fifth step 709 : Delete the clustering set θ, currently having the minimum clustering parameter, from the original un-scheduling list. Sixth step 710 : Determine if E=Φ or if the number of remaining base stations in the un-clustered set E is smaller than the number of base stations in the currently established base station cluster and, if the result is “yes”, pass control to the seventh step and, if the result is “no”, return to the second step 706 . Seventh step 711 : Terminate clustering scheduling and transmit the clustering result to all base stations. FIG. 8 is a typical signaling flowchart showing the multi-BSs coordination service triggered by a terminal after the dynamic clustering of the present invention is performed. Assume that, at some particular time, the dynamic clustering result of the base stations is already transmitted to all base stations via the centralized clustering server (step 801 ). The base station transmits the dynamic base station clustering result to a corresponding terminal (step 802 ). When the terminal determines to use the multi-BSs coordination service of the current cluster (step 803 ), the terminal transmits a message to the corresponding serving base station to trigger the multi-BSs coordination service (step 804 ). The serving base station is able to select a step for giving related permission (step 805 ). In this step, the terminal periodically reports the channel state information, generated between the terminal and all base stations in the current base station cluster, to the serving base station (step 806 ). When it is determined that the multi-BSs coordination service can be performed for the terminal, the serving base station negotiates with other base stations in the current base station cluster about the coordination transmission (step 807 ). When the negotiation is successful, the serving base station notifies the terminal about the coordination transmission key parameters (step 808 ). All base stations in the current base station cluster allocate resources and establish the related setting based on the negotiation result (step 809 ). In this way, the multi-BSs coordination service is performed between all base stations in the current base station cluster and the corresponding terminal (step 810 ). For the next dynamic clustering scheduling, the base station must periodically report simple channel state information to the centralized clustering server (step 811 ). FIG. 9 is a typical signaling flowchart showing the multi-BSs coordination service triggered by a base station after the dynamic clustering of the present invention is performed. Assume that, at some particular time, the dynamic clustering result of the base stations is already transmitted to all base stations via the centralized clustering server (step 901 ). The base station selects to transmit the dynamic base station clustering result to a corresponding terminal (step 902 ). When the serving base station determines to use the multi-BSs coordination service of the current cluster (step 903 ), the serving base station transmits a message to the corresponding terminal to trigger the multi-BSs coordination service (step 904 ). In this step, the terminal periodically reports the channel state information, generated between the terminal and all base stations in the current base station cluster, to the corresponding serving base station (step 905 ). When it is determined that the multi-BSs coordination service can be performed for the terminal, the serving base station negotiates with other base stations in the current base station cluster about the coordination transmission (step 906 ). When the negotiation is successful, the serving base station notifies the terminal about the coordination transmission key parameters (step 907 ). All base stations in the current base station cluster allocate resources and establish the related setting based on the negotiation result (step 908 ). In this way, the multi-BSs coordination service is performed between all base stations in the current base station cluster and the corresponding terminal (step 909 ). For the next dynamic clustering scheduling, the base station must periodically report simple channel state information to the centralized clustering server (step 910 ). FIG. 10 is a diagram showing the basic format of the signaling transmitted between base stations in the present invention. The signaling, an SCTP/IP data packet, may be used in both IPv4 and IPv6. In a general-purpose IP packet head 1001 , the target address is a target base station IPv4/IPv6 address 1002 and the origin address is an origin base station IPv4/IPv6 address 1003 . The general-purpose IP packet head 1001 is followed by the general-purpose SCTP packet head. The last field contains a message body 1005 conforming to the 3GPP X2AP protocol. FIG. 11 is a diagram showing an implementation example of the X2AP field 1005 of a request signaling used for coordination transmission negotiation among base stations in the present invention. The information units to be prepared include the following. 1) Message type unit 1101 . The value of this unit, defined by a standardization organization such as 3GPP, must identify a multi-BSs coordination request function. 2) X2AP protocol number corresponding to the terminal of the serving base station 1102 . This number uniquely identifies one terminal in the direction from the serving base station to the target base station. 3) Target base station number 1103 . 4) Related cell ID of target base station 1104 . 5) Multi-BSs coordination service request type 1105 (start, end, etc.). 6) Contents of request report 1106 . This field is a 32-bit bit sequence, with each bit corresponding to one piece of information content. The numeric value 1 of this bit indicates that the target base station must add corresponding information to the response message (For example, the first bit corresponds to the pre-coding option, the second bit corresponds to the output power of the coordination service, and the third bit corresponds to the modulation rate, and so on). 7) Channel state information generated between the target base station and the corresponding terminal 1108 . The optional information includes the following. 1) Information reporting period between the target base station and the serving base station 1107 . 2) Other several pieces of optional information 1109 . FIG. 12 is a diagram showing an implementation example of the X2AP field of a response signaling used for coordination transmission negotiation among base stations in the present invention. The information units to be prepared include the following. 1) Message type unit 1201 . The value of this unit, defined by a standardization organization such as 3GPP, must identify a multi-BSs coordination request function. 2) X2AP protocol number corresponding to the terminal of the serving base station 1202 . This number uniquely identifies one terminal in the direction from the serving base station to the target base station. 3) X2AP protocol number corresponding to the terminal of the target base station 1203 . This number uniquely identifies one terminal in the direction from the from the target base station to the serving base station. 4) Related cell ID of target base station 1204 . 5) Multi-BSs coordination service request type 1205 (start, end, etc.) must match the contents of the corresponding information unit in the X2AP request message. 6) Contents of response report 1206 . This field is a 32-bit bit sequence, with each bit corresponding to one piece of information content. The numeric value 1 of this bit indicates that the target base station has added corresponding information to the response message. The contents must match the contents of the corresponding information unit in the X2AP request message. The optional information includes the following. 1) Information reporting period between the target base station and the origin base station 1207 . 2) Pre-coding options 1208 . 3) Coordination transmission power 1209 . 4) Modulation rate 1210 . 5) Other several pieces of optional information 1211 . FIG. 13 is a diagram showing the internal structure of a single-antenna base station of the present invention. The internal structure of the base station mainly includes the following: high-frequency module 1322 , baseband module 1307 , high-layer signaling and control unit 1308 , network interface module 1309 connected to the access network, multi-BSs service control unit 1311 that controls communication with the multi-BSs service and the centralized clustering server, network module 1310 that communicates with the centralized clustering server, channel state information matrix 1325 , pre-coding option 1326 , and channel estimation unit 1318 . The high-frequency module 1322 includes at least one physical antenna 1301 , one or more high-frequency multiplexing units 1302 , and one or more radio frequency units 1303 . The downlink part of the high-frequency module 1322 includes a coordination pre-coding unit 1304 , a downlink pilot generation unit 1305 , at least one multi-layer mapping unit 1306 , a downlink time-division control unit 1319 , and a transmission frequency control part 1314 . The downlink part of the high-frequency module 1322 includes a coordination decoding unit 1321 , an uplink training sequence analysis unit 1305 , at least one multi-layer de-mapping unit 1316 , and an uplink time-division control unit 1320 . The baseband part includes at least one channel coding and modulation module 1312 and at least one channel decoding and demodulation module 1313 . FIG. 14 is a diagram showing an example of the internal structure of a multi-antenna base station of the present invention (two antennas). The internal structure of the base station mainly includes the following: high-frequency module 1424 , baseband module 1410 , high-layer signaling and control unit 1411 , a network interface module 1412 connected to the access network, multi-BSs service control unit 1414 that controls the communication with the multi-BSs service and the centralized clustering server, network module 1413 that communicates with the centralized clustering server, channel state information matrix 1425 , pre-coding option 1436 , and channel estimation unit 1420 . The high-frequency module 1424 includes at least two physical antennas 1401 and 1402 , one or more high-frequency multiplexing units 1403 , and one or more radio frequency units 1404 . The downlink part of the high-frequency module 1424 includes at least one coordination pre-coding unit 1405 , at least two downlink pilot generation units 1407 and 1408 , at least one multi-layer mapping unit 1409 , at least one shared pilot generation unit 1406 , at least two downlink time-division control units 1421 , and a transmission frequency control part and multi-antenna control part 1416 . The downlink part of the high-frequency module 1424 includes at least one coordination decoding unit 1423 , at least two uplink training sequence analysis units 1417 and 1418 , at least one multi-layer de-mapping unit 1419 , and at least two downlink time-division control units 1422 . The baseband part includes at least two channel coding and modulation modules 1427 and at least two channel decoding and demodulation modules 1415 . FIG. 15 is a diagram showing the typical structure of the internal part of the centralized clustering server, that is, the communication control device, of the present invention. The network interface includes an input line interface 1501 and an output line interface 1503 . At the same time, the network interface further includes a receiving buffer 1502 and a sending buffer 1504 . Each receiving buffer is connected to the input line interface 1501 and an internal bus 1514 , and each sending buffer is connected to the output line interface 1503 and the internal bus 1514 . In addition, the internal bus 1514 is further connected at least to a processor 1505 , a program memory 1506 , and a data memory 1511 . The program memory 1506 saves the functional modules to be executed by the processor 1505 , including at least a packet transmission/reception unit 1510 , a clustering control unit 1507 that mainly controls the scheduling of dynamic base station clustering, multi-BSs coordination service and clustering control signaling unit 1508 (CoMP signaling control module), and a basic control unit (basic control routine) 1509 for selecting the startup of other modules. The data memory 1511 saves a channel state information table 1512 newly added by the present invention and other several pieces of data information 1513 . The main module newly added to the program memory 1506 of the present invention is the clustering control unit 1507 . The detailed function of the clustering control unit 1507 is as follows. 1. When channel state information reports are received from the base stations, the clustering control unit 1507 updates the channel state information table 1512 with the reported channel state information. When the report from a base station is the original channel state information, the clustering control unit 1507 transforms the original channel state information to simple channel state information and, after that, saves it in the channel state information table 1512 . 2. The clustering control unit 1507 acquires the dynamic clustering scheduling timer and, when the timer times out, newly performs dynamic clustering scheduling. 3. The number of base stations in a base station cluster is set. The number of base stations may be set manually by the provider or may be set dynamically by some other method. 4. The clustering control unit 1507 performs scheduling according to the method shown in FIG. 7 when dynamic clustering scheduling is performed. 5. The clustering control unit 1507 transmits the scheduling result to all base stations after scheduling is terminated. 6. The method by which the clustering control unit 1507 communicates with other network facilities via the multi-BSs coordination service and clustering control signaling unit 1508 is as shown in FIG. 6 . In addition, the multi-BSs coordination service and clustering control signaling unit 1508 is newly added to the program memory 1506 to carry out signaling communication with other network facilities. The multi-BSs coordination service and clustering control signaling unit 1508 must at least transfer the report from each base station to the clustering control unit 1507 and, in addition, must transmit the dynamic base station clustering scheduling result of the clustering control unit 1507 to all base stations. The main module newly added to the data memory 1511 of the present invention is the channel state information table 1512 . The detail of the table is as shown in FIG. 17 . It contains information on a terminal 1701 and each base station 1702 such as the channel state information and the serving base station. The clustering control unit 1507 receives the reports from the base stations, collects the reports, and updates the table. At the same time, the clustering control unit 1507 performs dynamic base station clustering scheduling by referencing the contents of the table. FIG. 16 is an information flowchart showing the internal part of the centralized clustering server of the present invention. Simple channel state information 1601 , transmitted periodically from each base station, is received first by the input line interface 1501 and the receiving buffer 1502 and, via the bus 1514 , reaches the packet transmission/reception unit 1510 . The packet transmission/reception unit 1510 transfers the channel state information 1601 to the multi-BSs coordination service and clustering control signaling unit 1508 . After the session control is performed, the information is transmitted to the clustering control unit 1507 and then is saved in the channel state information table 1512 . If it is required to perform dynamic clustering scheduling, the clustering control unit 1507 acquires the current channel state information 1601 from the channel state information table 1512 , performs dynamic clustering scheduling, and transfers a base station clustering result 1602 to the multi-BSs coordination service and clustering control signaling unit 1508 . After the session control is performed, the information is transmitted to the packet transmission/reception unit 1510 and is transmitted via the output line interface 1503 and the output buffer 1504 . Finally, the base station clustering result 1602 is transmitted to all base stations via the network. All data and signaling flows in the centralized clustering server are controlled by the processor 1505 via a basic control unit 1509 and are transferred via the data or control bus 1514 . FIG. 17 is a diagram showing the typical structure of the channel state information table 1512 in the centralized clustering server of the present invention. The table is present in the data memory 1511 of the centralized clustering server. Each of the rows 1706 of the channel state information table 1512 , which corresponds to one mobile terminal, includes the number of the terminal 1701 . The terminal has multiple table items 1702 each of which represents the channel state information and the serving relation with each base station. Each of the table items 1702 includes simple channel state information 1704 and a serving relation 1705 with the base station corresponding to the terminal. The following describes a simple application example composed of four base stations and five mobile terminals. If each base station has only one antenna, only one terminal can be served at the same time. At the same time, assume that the network between a base station and the centralized clustering server can support dynamic base station clustering scheduling that is accurate enough to perform scheduling on a time slot basis. FIG. 18 is a diagram showing an implementation example of the channel state information table 1512 ( FIG. 17 ) in the centralized clustering server of the present invention. Each of the rows 1806 corresponds to one mobile terminal and includes the number of the terminal 1801 . The terminal has multiple table items 1802 each of which represents the channel state information and the serving relation with each base station. Each of the table items 1802 includes simple channel state information 1804 and a serving relation 1805 with the base station corresponding to the terminal. Assume that a base station 17 provides services only to a terminal 12 in one time slot. In this case, the simple channel state information matrix H, which is generated based on the contents of the channel state information table 1512 in FIG. 18 , is as follows. 2.0 0.4 0 0.9 0 2.4 0.7 0 0 0.9 2.2 0 0.8 0 1.6 2.5 The interference relation map, such as the one shown in FIG. 19 , can be generated based on this matrix. FIG. 19 is a diagram showing an implementation example of the interference relation map used for the dynamic clustering algorithm of the present invention. The generated interference relation map is an undirected graph in which each node 1901 corresponds to one base station, a side 1902 between each two nodes corresponds to the interference relation between the two base stations, and the weight is an interference weight 1903 of the two base stations. The interference relation map is generated by the clustering control unit 1507 of the centralized clustering server based on the contents of the current channel state information table 1512 . The calculation result of all current interference weights 1903 in FIG. 19 is as follows. W 12 =0.16, W 13 =0; W 14 =1.45; W 23 =1.3; W 24 =0; W 12 =1.45 Assume that the number of base stations in each base station cluster is 2. In this case, the calculation result of the clustering parameters Li of the possibilities of each base station cluster is as shown in Table 1 (arranged in ascending order). TABLE 1 Nodes Permutation Li 2, 3 1.61 1, 4 1.61 1, 2 2.75 3, 4 2.75 1, 3 3.36 2, 4 3.36 Finally, the centralized clustering server selects the two base station clusters ({2,3} and {1,4}) as the final result according to the method shown in FIG. 7 . The calculation of the clustering parameters Li for a larger number (p in this case) of base station clusters is the same method shown in FIG. 7 . The number of clustering possibilities generated in this way is C n p . The selection method is also the method shown in FIG. 7 . In the present invention, other methods may be used as the method shown in FIG. 7 for performing dynamic clustering for the base stations based on the channel state information. For example, the centralized clustering server can perform clustering based on the methods described below. Step 1: The centralized clustering server acquires all simple channel state information from the channel state information table. Step 2: The server calculates the sum S xy of the simple channel state information on each of other base stations that all terminals served in each base station have for the other base station (S xy indicates the sum of the simple channel state information that all terminals in base station x have for base station y). Step 3: The server arranges all base stations according to the number of served terminals to configure the un-clustered base station set E and initializes the clustered base station set U to an empty set. Step 4: For the current number of base station clusters (p in this case), the server selects (p−1) largest S xy base stations from the base station having the largest number of served terminals to form an efficient base station cluster, deletes p base stations in that base station cluster from the un-clustered set E, and adds those base stations to the clustered set U. Step 5: If the current un-clustered set E is an empty set or if the number of remaining base stations in the current un-clustered set E is smaller than the number of base stations in each base station cluster, control is passed to step 6 and, if not, control is returned to step 4. Step 6: The server terminates the clustering algorithm and transmits the clustering result to all base stations. In addition, the centralized clustering server can perform clustering, for example, based on the method described below. Step 1: The centralized clustering server acquires all original channel state information from the channel state information table. Step 2: For each terminal, based on the channel state information between the terminal and other non-serving base stations, the server selects (p−1) non-serving base stations, which provides the multi-BSs coordination service to the current terminal and provides the highest radio usage rate, to form the temporary optimal clustering for the current terminal. When the radio usage rate is calculated, the server first calculates the multi-BSs coordination service transmission matrix based on the attenuation and channel shift information in the original channel state information. After that, based on the transmission matrix, the server calculates the radio usage rates at which all base stations in the temporary clustering provide services to the current terminal, and calculates the sum. Step 3: The server configures all base stations into the un-clustered base station set E, initializes the clustered base station set U to an empty set, and configures all terminals into the terminal set W. Step 4: The server first selects a clustering, which occurs most as the temporary optimal clustering of all terminals in the terminal set W, as the current efficient clustering, deletes p base stations in that base station cluster from the un-clustered set E, adds those base stations to the clustered set U, and finally deletes all terminals, which select the current cluster as the temporary optimal clustering, from the terminal set W. Step 5: If the current un-clustered set E is an empty set, or if the number of remaining base stations in the current un-clustered set E is smaller than the number of base stations in each base station cluster, or if the terminal set W is an empty set, control is passed to step 7 and, if not, to step 6. Step 6: If a clustering, which occurs most as the temporary optimal clustering of all terminals in the terminal set W, can be selected, control is passed to back step 4. If there are two or more selections of temporary optimal clustering that occurs most (assume that there are T selections), the server calculates the sum of the terminal radio usage rates each corresponding to each clustering selection (S t where t is one of current T temporary optimal clustering selections), selects the temporary optimal clustering selection t having the maximum S t as the clustering that currently occurs most, and returns control to step 4. Step 7: The server terminates the clustering algorithm and transmits the clustering result to all base stations. The following describes how the present invention works in another situation, that is, when some terminals move in the communication control system. FIG. 20 is a diagram showing an implementation example after some mobile terminals have moved in the communication control system of the present invention. FIG. 21 is a diagram showing the channel state information table after some mobile terminals have moved in the communication control system of the present invention. In a particular time slot, if terminal 1 does not move and if terminal 2 , terminal 3 , and terminal 4 have moved to the respective locations in the embodiment described above as shown in FIG. 20 , then the contents of the channel state information table are changed to the contents indicated in FIG. 21 . The base station 17 provides services only to the terminal 12 , and the format of the current base station clustering is the result of dynamic clustering based on the contents of FIG. 18 . In this case, the simple channel state information matrix H, generated based on the contents of the current channel state information table in FIG. 21 , is as follows. 2.0 0.4 0 0.9 0.8 1.9 0.5 0.2 0.3 0 2.6 0.6 0.1 0.5 0.7 2.1 The interference relation map, such as the one shown in FIG. 19 , can be generated based on this matrix. FIG. 19 is a diagram showing an implementation example of the interference relation map used for the dynamic clustering algorithm of the present invention. The generated interference relation map is an undirected graph in which each node 1901 corresponds to one base station, the side 1902 between each two nodes corresponds to the interference relation between the two base stations 7 , and the weight is the interference weight 1903 of the two base stations. The interference relation map is generated by the clustering control unit 1507 of the centralized clustering server based on the contents of the current channel state information table 1912 . The calculation result of all current interference weights 1903 in FIG. 19 is as follows. W 12 =0.80; W 13 =0.09; W 14 =0.82; W 23 =0.25; W 24 =0.29; W 34 =0.85 Assume that the number of base stations in each base station cluster is 2. In this case, the calculation result of the clustering parameters Li of the possibilities of each base station cluster is as shown in Table 2 (arranged in ascending order). TABLE 2 Nodes Permutation Li 1, 2 1.45 34 1.45 1, 4 2.03 2, 3 2.03 1, 3 2.72 2, 4 2.72 Finally, the centralized clustering server selects the two base station clusters ({1,2} and {3,4}) as the final result according to the method shown in FIG. 7 . Therefore, even if terminal 1 does not change the location, that is, in the still state, in this situation, the dynamic base station clustering is changed. The dynamic base station clustering method in the present invention is based on the radio link interference among all base stations and the terminals in the current network. Therefore, when the radio channel state of one terminal is not changed but the radio channel state of another terminal is changed, the clustering result may be affected. Even when all terminal locations are not changed but there is a change in the surrounding environment (for example, an obstructing object that temporarily emerges around several terminals affects the channel state between the terminals and the related base stations), the radio channel state is changed and the clustering result is more or less affected. In contrast, the dynamic base station clustering method of the present invention allows a clustering method to be found that is always the optimal in the current channel state. FIG. 22 is a diagram showing the comparison of advantage of the dynamic clustering algorithm of the present invention. A horizontal axis 2202 indicates the reception-signal-to-noise ratio SNR in dB, and a vertical axis 2201 indicates the average capacity of the current system in bit/s/Hz. The figure has four curves, with the theoretically optimal curve at the top 2203 . The theoretical value is calculated by the Shannon channel capacity formula given below. Channel capacity/Frequency width=log(1+Signal to interference ratio) A curve 2204 indicates the average performance when the multi-BSs coordination service is performed after the dynamic clustering of the present invention is performed, a curve 2205 indicates the average performance of the multi-BSs coordination service when static clustering is performed, and a curve 2206 indicates the average performance when the multi-BSs coordination service is not performed. The dynamic clustering method of the present invention is significantly better in performance than the static clustering method and produces a value closest to the theoretically desired value, and its clustering algorithm is very simple. The curves 2204 , 2205 , and 2206 are the statistical distribution result obtained by a large number of simulations in a network composed of multiple base stations and multiple terminals. The mobile terminal of the present invention may be a mobile phone, a notebook PC having the radio online function, or other communication facilities that have the radio communication function. Advantages of the Present Invention (1) A combination of optimal base station clustering in the current network is dynamically found. (2) The parameters used for dynamic clustering scheduling are the basic channel state information reported from each terminal to the network side. Therefore, the system and method of the present invention can be supported without changing the conventional terminals. (3) Because the information reported from the mobile communication base stations to the centralized clustering server is simplified channel state information, the communication bandwidth can be saved. (4) All scheduling is a calculation carried out based on simplified real-number channel state information, the calculation is performed by four arithmetic operations and the square operation, the amount of calculation is very small, and the calculation is very suitable for implementing hardware. Therefore, dynamic clustering scheduling can be performed based on the granularity of communication time slots. (5) The clustering method is applicable to various sizes of base station clusters. (6) The amount of change in the conventional mobile communication base station and terminals is very small.
Disclosed are a communication control device, a communication control method and the system thereof, which provide efficient multi-base station joint services in a mobile communication system using dynamic clustering. Optimal base station clustering is chosen according to the communication state between a terminal and each base station. The communication control device connects with multiple base stations through a network, and clusters the multiple base stations dynamically so that the clustered multiple base stations can provide services for the mobile terminal in union. The communication control device comprises: an interface, connecting with multiple base stations, receiving channel state information related to the mobile terminal from each base station; a memory unit, storing the channel state information of the mobile terminal received from the interface; a control unit, clustering each base station dynamically according to the channel state information of the mobile terminal stored in the memory unit.
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RELATED APPLICATION [0001] This application is a divisional of U.S. application Ser. No. 14/160,006, filed on Jan. 21, 2014, which claims the benefit of U.S. Provisional Application Ser. No. 61/793,660, filed on Mar. 15, 2013, the disclosure of which is hereby incorporated by reference in its entirety. FIELD OF THE INVENTION [0002] The invention relates to heating, ventilation, air conditioning, and refrigeration (HVAC/R or, more commonly HVAC) systems. More specifically, the invention relates to a system that includes an apparatus and method for monitoring the operation of HVAC systems; acquiring, managing, sharing, and reporting data related to the HVAC systems; assessing the performance of HVAC systems; and installing, troubleshooting, and servicing the HVAC systems. BACKGROUND OF THE INVENTION [0003] HVAC systems are widely known. “Air conditioning” is a general term for a process that maintains comfort conditions in a defined area. Air conditioning includes sensible heating of the air (referred to generally as heating), sensible cooling and/or dehumidifying of the air (referred to generally as air conditioning, which can be abbreviated as A/C), humidifying the air, and cleaning or filtering the air. HVAC or air conditioning, as used herein, also includes refrigeration systems (e.g., coolers and freezers of consumer, commercial and industrial scale). Therefore, in this description, HVAC can encompass and describe any heating, ventilation, air conditioning, or refrigeration process or equipment. Also, an “A/C unit” can refer to conventional air conditioning unit, a refrigeration unit, or a heat pump. [0004] All conventional A/C or refrigeration systems share the same basic components: a compressor, a condenser coil, a metering device, and an evaporator coil. Compressors compress the gaseous refrigerant and turn it into a subcooled liquid. Condenser coils to allow the refrigerant dissipate heat and become a sub cooled liquid. Metering devices control the flow of the sub cooled refrigerant into the evaporator coil. Evaporator coils expose the refrigerant to the system load turning the refrigerant into a superheated gas. Common metering devices are capillary tubes and in new systems Thermostatic Expansion Valves (TXVs). [0005] The study of air and its properties is called psychrometrics. Typical psychrometric units of measure are dry bulb temperature, wet bulb temperature, relative humidity and enthalpy. HVAC technicians study psychrometrics to accurately predict the final properties of the conditioned air and also to determine if the conditioning equipment is performing the way it was engineered to operate. Air has mass and weight and can therefore store heat energy. The amount of heat that the air can store is dependent upon the conditions of the air. By determining the mass flow rate and understanding the properties of the air and rules of psychrometrics, the amount of heat added or removed from the air by the conditioning device can be quantified. Understanding system airflow is critical to understanding system performance. [0006] The phase change of a refrigerant (from liquid to gas and back to liquid) in a closed system is what allows the refrigerant to transfer thermal energy. To determine the phase state and energy carrying capacity of a refrigerant at any point in the system both the refrigerant pressure and temperature must be known. Pressure gauges are typically used to measure refrigerant pressures and contact thermometers are used to measure refrigerant line (tube) temperatures to infer the refrigerant temperature. [0007] Measurements as typically taken by technicians on their own mean little without knowledge of the design operation. All manufacturers of quality listed equipment have their systems tested and efficiency verified to Air-Conditioning, Heating, and Refrigeration Institute (AHRI) standards. Other independent testing laboratory standards could also be used for testing and efficiency verification. Units having an energy guide label have been tested, and their efficiency can only be guaranteed if the components are matched, the system refrigerant charge is correct, the airflow is correctly set, and the system is installed per the manufacturer's instructions including proper sizing of the equipment. [0008] To achieve the desired efficiency, all manufacturers design their equipment to operate at its rated capacity at one set of conditions at its peak performance. These conditions are known as the AHRI Standard Conditions and are as follows: Indoor air=80° F. Relative Humidity=50% Outdoor air=95° F. [0012] All equipment listed in the AHRI directory operates at rated capacity under the AHRI standard conditions. Because the AHRI standard conditions are at the high end of the normal range for human comfort, Standard Operating Conditions, or common operating conditions have been established as design conditions for the equipment in the field. Indoor air=75° F. Relative Humidity=50% Outdoor air=95° F. [0016] Under these conditions the equipment can have a slightly lower operating capacity, and the equipment will operate with different operating characteristics. Along with the standard operating conditions, conditions for airflow and coil temperatures and operating range have also been established. Most if not all manufacturers design these grades of equipment for a nominal 400 CFM airflow per ton for A/C cooling, and 450 CFM/ton for heat pumps. [0017] Government standard tests determine the energy efficiency rating of residential HVAC equipment (cite CFR). This rating is known as Seasonal Energy Efficiency Ratio, or SEER. Higher SEER ratings mean more efficient equipment. The following Tables illustrate some characteristics and nominal operating ranges for air conditioning equipment of these standard grades in certain design operating conditions: [0000] <10 SEER Equipment (R-22 Refrigerant) System Characteristics: Nominal Operating Parameters: Standard size evaporator. Evaporator designed to be 35° F. colder Standard size condenser. than return air. Fixed orifice, cap tube, or Condenser designed to be 30° F. warmer piston for metering device. than outdoor air passing over it. Design Operating Refrigerant in evaporator will boil at 40° F. Conditions: (75 indoor air − 35° design temp Indoor air: 75° F. difference = 40° F. Saturation Relative Humidity: 50%. Temperature). Outdoor air: 95° F. Refrigerant in condenser will condense at *Note: Always refer to 125° F. the manufacturer (95° outdoor air + 30° design temp specifications if possible. difference = 125° F. Saturation temperature). Evaporator airflow = nominal 400 CFM/ton. Measured superheat should = 8-10° F. Measured sub-cooling should = 6-8° F. Suction pressure should = 68.5 PSIG (+/−2 PSIG). High side pressure should = 278 PSIG (+/−2 PSIG). Suction line temperature should be 40° F. saturation + 8-10° F. superheat = 48-50° F. Liquid line temperature should be 125° F. saturation − 6-8° F. sub-cooling = 119-117° F. [0000] 10-12 SEER Equipment (R-22 Refrigerant) System Characteristics: Nominal Operating Parameters: Standard size evaporator. Evaporator designed to be 35° F. colder Larger size condenser. than return air. Metering Device = Thermal Condenser designed to be 25° F. warmer or Thermostatic Expansion than outdoor air passing over it. Valve (TXV). Refrigerant in evaporator will boil at 40° F. Design Operating (75° indoor air − design temp difference = Conditions: 40° F. Saturation Temperature). Indoor air: 75° F. Refrigerant in condenser will condense at Relative Humidity: 50%. 120° F. Outdoor air: 95° F. (95° outdoor air + 25° design temp *Note: Always refer to the difference = 120° F. Saturation manufacturer specifications temperature). if possible. Evaporator airflow = nominal 400 CFM/ton. Measured superheat should = 8-10° F. Measured sub-cooling should = 6-8° F. Suction pressure should = 68.5 PSIG (+/−2 PSIG). High side pressure should = 259.9 PSIG (+/−2 PSIG).** Suction line temperature should be 40° F. saturation + 8-10° F. superheat = 48-50° F. Liquid line temperature should be 120° F. saturation − 6-8° F. sub-cooling = 114-112° F. **The lower discharge pressure versus standard efficiency equipment provides a smaller pressure difference across the compressor, and requires less energy to operate making the system more efficient. The higher efficiency comes at the cost of poor operation when operated in low ambient conditions. Some manufacturers have incorporated a two-speed condenser fan to rectify this problem. Even so a two speed motor and the control to operate it cost more up front. The efficiency upgrade will pay for itself. [0000] 12-20+ SEER Equipment (R-22 Refrigerant) System Characteristics: Nominal Operating Parameters: Larger size evaporator. Evaporator designed to be 30° F. colder Larger size condenser. than return air. Metering Device = Condenser designed to be 20° F. warmer Thermal Expansion than outdoor air passing over it. Valve (TXV). Refrigerant in evaporator will boil at 45° F. Design Operating (75° indoor air − 30° design temp Conditions: difference = 45° F. Saturation Indoor air: 75° F. Temperature). Relative Humidity: 50%. Refrigerant in condenser will condense at Outdoor air: 95° F. 115° F. *Note: Always refer to (95° outdoor air + 20° design temp the manufacturer difference = 115° F. Saturation temperature) specifications if possible. Evaporator airflow = nominal 400 CFM/ton. Measured superheat should = 8-10° F. Measured sub-cooling should = 6-8° F. Suction pressure should = 76 PSIG (+/−2 PSIG). High side pressure should = 243 PSIG (+/−2 PSIG).** Suction line temperature should be 45° F. saturation + 8-10° F. superheat = 53-55° F. Liquid line temperature should be 115° F. saturation − 6-8° F. sub-cooling = 109-107° F. **The lower discharge in combination with high suction pressure versus standard and high efficiency equipment provides a smaller pressure difference across the compressor, and requires less energy to operate making the system more efficient. The higher operating efficiency comes at the cost of lower latent heat capability, so this system may not dehumidify as well. It will also incorporate some of same the controls that the high efficiency equipment will incorporate. [0000] 10-12 SEER Equipment (R-410a Refrigerant)* System Characteristics: Nominal Operating Parameters: Standard size evaporator. Evaporator designed to be 35° F. colder Larger size condenser. than return air. Metering Device = Condenser designed to be 25° F. warmer Thermal Expansion than outdoor air passing over it. Valve (TXV). Refrigerant in evaporator will boil at 40° F. Design Operating (75° indoor air-35° design temp difference = Conditions: 40° F. Saturation Temperature). Indoor air: 75° F. Refrigerant in condenser will condense at Relative Humidity: 50%. 120° F. Outdoor air: 95° F. (95° outdoor air + 25° design temp *Note: Always refer to difference = 120° F. Saturation temperature) the manufacturer Evaporator airflow = nominal 400 CFM/ton. specifications if Measured superheat should = 8-10° F. possible. Measured sub-cooling should = 6-8° F. Suction pressure should = 118.9 PSIG (+/−2 PSIG). High side pressure should = 416.4 PSIG (+/−2 PSIG).** Suction line temperature should be 40° F. saturation + 8-10° F. superheat = 48-50° F. Liquid line temperature should be 120° F. saturation − 6-8° F. sub-cooling = 114-112° F. *It should be noted: As far as operating conditions are concerned, the only difference in operation between R-22 unit and R-410a units is the operating pressures. **The lower discharge pressure provides a smaller pressure difference across the compressor, and requires less energy to operate making the system more efficient. The higher efficiency comes at the cost of poor operation when operated in low ambient conditions. Some manufacturers have incorporated a two-speed condenser fan to rectify this problem. Even so a two speed motor and the control to operate it cost more up front. The efficiency upgrade will pay for itself. [0000] 12-20+ SEER Equipment (R-410a Refrigerant)* System Characteristics: Nominal Operating Parameters: Larger size evaporator. Evaporator designed to be 30° F. colder Larger size condenser. than return air. Metering Device = Condenser designed to be 20° F. warmer Thermal Expansion than outdoor air passing over it. Valve (TXV). Refrigerant in evaporator will boil at 45° F. Design Operating (75° indoor air − 30° design temp Conditions: difference = 45° F. Saturation Temperature). Indoor air: 75° F. Refrigerant in condenser will condense at Relative Humidity: 50%. 115° F. Outdoor air: 95° F. (95° outdoor air + 20° design temp *Note: Always refer to difference = 115° F. Saturation temperature) the manufacturer Evaporator airflow = nominal 400 CFM/ton. specifications if Measured superheat should = 8-10° F. possible. Measured sub-cooling should = 6-8° F. Suction pressure should = 130.7 PSIG (+/−2 PSIG). High side pressure should = 389.6 PSIG (+/−2 PSIG).** Suction line temperature should be 45° F. saturation + 8-10° F. superheat = 53-55° F. Liquid line temperature should be 115° F. saturation − 6-8° F. sub-cooling = 109-107° F. *It should be noted: As far as operating conditions are concerned, the only difference in operation between R-22 unit and R-410a units is the operating pressures. **The lower discharge in combination with high suction pressure provides a smaller pressure difference across the compressor, and requires less energy to operate making the system more efficient. The higher operating efficiency comes at the cost of lower latent heat capability, this system may not dehumidify as well. It will also incorporate some of same the controls that the high efficiency equipment will incorporate. [0018] When charging a refrigeration system, the following steps should be followed: 1. Inspect filters, evaporator coils, condensers coils and blower for dirt and clean if needed. If condenser is washed, let it dry before charging. 2. Make sure evaporator airflow is correct. (Nominal 400 CFM/Ton for A/C (350 CFM/ton in humid areas) 450 CFM/ton for Heat pumps) 3. Determine type of refrigerant. 4. Determine type of metering device. 5. Measure indoor/outdoor ambient air conditions (wet bulb and dry bulb). 6. Determine proper superheat or subcooling. (Use Manufacturer's chart if available.) 7. Attach Refrigeration System Analyzer (RSA) to service valve parts. 8. Attach temperature probe (to suction line for superheat measurement, to liquid line for subcooling measurement). 9. Verify refrigerant selection in manifold. 10. Determine the charging requirements Charge directly by superheat or subcooling. Note: Watch pressures while charging by superheat and subcooling methods to assure system is operating properly. Always check evaporator and total superheat on TXV systems to assure correct TXV operation. 11. Verify system pressures and saturation temperatures are within manufacturer's design criteria. [0032] Deviation from the correct charge will have a negative impact on the performance or operation of the refrigeration system. Systems utilizing a fixed metering device without any other mechanical problems and proper airflow and load will exhibit the following symptoms if improperly charged to a low charge (undercharge): Low suction pressure. Low liquid pressure. High total superheat. Low compressor amps. Poor system performance. Coil may be freezing. Possible overheating of compressor. [0040] Systems utilizing a fixed metering device without any other mechanical problems and proper airflow and load will exhibit the following symptoms if improperly charged to a high charge (overcharge): High suction pressure. High liquid pressure. Low total superheat. Possibly higher than normal compressor amps. Poor system performance. Lack of humidity control. [0047] Systems utilizing a TXV without any other mechanical problems and proper airflow and load will exhibit the following symptoms if improperly charged to a low charge (undercharge): Evaporator superheat normal or high. Low condenser subcooling. Poor performance at full or partial load. Possible overheating of compressor. [0052] Systems utilizing a TXV without any other mechanical problems and proper airflow and load will exhibit the following symptoms if improperly charged to a low charge (undercharge): Evaporator superheat normal. High liquid pressure. High condenser subcooling. Poor performance at full or partial load. [0057] Industry studies show that approximately 70% of residential air conditioning systems are operating with refrigerant charge and airflow problems. Unlike lab testing done under a single set of closely held conditions, charging an air conditioning system in the field by a technician is often a complicated and dynamic process due to nonstandard conditions and constantly changing load conditions that technicians typically encounter. As load conditions change or vary from standard conditions inside or outside (ambient conditions) the conditioned space, so do performance and operational targets. System pressures, saturation temperatures, superheat, subcooling, airflow latent sensible split, power consumption, and work output all vary as the load and or the power supply (voltage) increases or decreases. Installation factors like line set length, lift in suction line insulation, and duct design also affect performance. Additionally as a system is serviced (particularly as refrigerant is added or removed) the operational characteristics again vary as the system reaches a new point of equilibrium which again changes the capacity and the rate which the sensible and latent load is handled. Determining when this new state of equilibrium is reached is also a challenge that can lead to excessive wait times to complete service. [0058] Due to a constantly moving target, and variables associated with the installation often not accounted for in the field, acquisition and management of the data used to resolve the target performance indicators must also be as dynamic as the system itself to more accurately evaluate the performance of the system in field practice. Managing all of the data independently and manually requires the technician to carefully and quickly gather the measurement data, use several look up tables, and make manual calculations which can result in many errors from simple transcription to that of calculation or even resulting change in load conditions faster than the data can be hand obtained. Additionally, readings and calculations are not humanly possible in real time; and the variables are changing in real time presenting, at best, a fuzzy picture of the operational performance. These problems are amplified under low load and during periods of low ambient conditions due to system characteristics and the short amount of time that the system operates to satisfy the load requirements. Manual calculation is less accurate and subject to more error and cumbersome techniques making it often impractical to do in many field installations. SUMMARY OF THE INVENTION [0059] The smart HVAC manifold system is designed to constantly and dynamically manage the data acquisition process and to measure and calculate the performance indicators and output as the load conditions and/or equipment operation change, taking into account variables in the installation that can impact performance. Both visually, and by a very specific data sets, the performance of the equipment and the installation can quickly be assessed and specific problems identified along with suggestions of typical faults or problems that may need addressed by the technician. [0060] The smart HVAC manifold system also provides a means of quickly and electronically handling the manual data acquisition process which would include component and/or brand, system model and serial numbers, equipment location (Global Positioning System (or GPS) tagging), customer name, environmental conditions that effect performance and performance measurement (weather data and elevation), and supports photo, voice and text documentation. These features streamline data acquisition, allow remote support, and minimize transcription errors also preventing data manipulation (gaming of the input of false, repeated or physically impossible data) by technicians when servicing equipment or commissioning or retro commissioning the system. [0061] The smart HVAC manifold system can quickly lead a technician in the right direction with onboard diagnostics. By making real time measurements and comparing those measurements to engineered data, the smart HVAC manifold system can help a technician isolate the potential problem and suggest possible solutions to typical charge airflow and load related problems. This approach streamlines the troubleshooting process making the technician faster and more accurate at isolating the fault in the system. [0062] Remote troubleshooting problems plague the HVAC industry today due to time consuming, frustrating, and tedious processes and the need to provide remote support to a struggling technician facing a large number of variables in assessing performance and troubleshooting substandard operation of air-conditioning equipment. The smart HVAC manifold system will allow for remote access to measurement data from anywhere in the world via a wireless internet connection. This allows for remote support from the manufacturer or a lead technician or a master technician to assist the field technician. Also the smart HVAC manifold system platform will allow for photo and/or video documentation as a “second set of eyes” at the equipment/installation site along with weather and location data providing additional information that will aid in the remote troubleshooting process. From the remote location any interested party may view (in real-time) the actual equipment performance. [0063] To achieve the best performance, test instruments used in HVAC system evaluation should be tested for accuracy or calibrated on a regular basis. Field calibration verification is often done with a pure refrigerant at a known saturation temperature or pressure and with a reference instrument or a reference measurement, such as a distilled water ice bath. The smart HVAC manifold system allows for calibration offset through the software and into the tool within a predefined limit. Sensors can be offset to a reference or averaged. Because many of the measurements are differential and not absolute, the ability to provide an averaging offset allows for higher accuracy when determining a change in temperature or enthalpy across a coil. This field calibration process also allows the tool to meet energy efficiency program requirements (programs are often run by utilities and/or their consultants) that specify a calibration verification and a calibration protocol. DESCRIPTION OF DRAWINGS [0064] FIG. 1 is a schematic illustration of an HVAC system. [0065] FIG. 2 is a block diagram illustrating a smart HVAC manifold system of the invention. [0066] FIG. 3 is a schematic illustration of a portion of the system of FIG. 2 . [0067] FIG. 4 is a block diagram illustrating another portion of the system of FIG. 2 . [0068] FIGS. 5A-5C are illustrations of display screens that may be employed by the system of FIG. 2 . [0069] FIGS. 6-13 illustrate example configurations of the system. DESCRIPTION [0070] The invention relates to HVAC systems. More specifically, the invention relates to a system that includes an apparatus and method for monitoring the operation of A/C units; acquiring, managing, sharing, and reporting data related to the A/C units; assessing the performance of A/C units; and installing, troubleshooting, and servicing the A/C units. One particular unit to which the invention relates is shown in FIG. 1 , which illustrates an air conditioning (A/C) unit 10 for providing cooled air in structure S. The structure S could be in the form of a building (air conditioning) or a cooler or refrigerated enclosure (refrigeration). Other forms of A/C units 10 include, but are not limited to: variable refrigerant flow systems (VSRs), two stage A/C systems, heat pumps, two stage heat pumps, freezers, meat cases, open cases, and low temperature refrigeration units. [0071] The A/C unit 10 shown in includes a compressor 12 , an evaporator 14 , a condenser 16 , and an expansion device 20 . The expansion device 20 may, for example, be a fixed orifice device, capillary tube device, piston device, or thermostatic expansion valve (TXV). Refrigerant flows through piping 18 in a direction indicated generally by arrows in FIG. 1 . The refrigerant flows from the compressor 12 , through the condenser 16 , through the expansion device 20 , through the evaporator 14 , and back to the compressor 12 . [0072] The compressor 12 and condenser 16 are housed, along with a fan 32 , in a housing 30 situated outside the structure S. The compressor 12 delivers high temperature, high pressure superheated refrigerant in vapor form to the condenser 16 via hot gas or discharge line 22 . The fan 32 draws ambient air 34 into the housing 30 through coils of the condenser 16 . The condenser 16 transfers heat from the heated refrigerant in the coils to the ambient air 34 , and the fan 32 discharges the heated discharge air 36 from the housing 30 . The refrigerant vapor in the condenser 16 cools as it transfers heat to the ambient air 34 . [0073] As the refrigerant cools, it changes from a vapor to a liquid by desuperheating, saturating and finally subcooling. The liquid refrigerant leaves the condenser 16 as a subcooled liquid and flows as a medium temperature, high pressure liquid through liquid line 40 to the expansion device 20 . The refrigerant undergoes a pressure drop through the expansion device 20 , which causes flashing of some of the liquid to vapor, (Flash Gas) and resulting temperature drop as some of the refrigerant changes state from liquid to vapor of the now saturated liquid refrigerant. Low pressure, low temperature saturated liquid refrigerant flows into the evaporator 14 via distributor line 42 . [0074] The evaporator 14 and expansion device 20 are housed in a forced draft unit 50 (e.g., furnace blower) situated inside the structure S. The unit 50 includes a blower 52 for inducing a draft of return air 54 into the unit. The blower 52 forces the forced air 56 through the evaporator 14 and into duct work 58 . As the forced air 56 passes through the evaporator 14 , it exchanges heat with the low pressure, low temperature refrigerant in the evaporator coils. Cooled and dehumidified supply air 60 exits the evaporator 14 and is distributed into the structure S through the duct work 58 . As the forced air 56 adds heat to the refrigerant in the evaporator 12 , the refrigerant transitions to a vapor phase, leaving the evaporator through vapor line 62 . The low pressure, low temperature superheated refrigerant in vapor line 62 refrigerant then flows into the compressor 12 to complete the cycle of refrigerant flow through the A/C unit 10 . [0075] For purposes of evaluating and testing the unit 10 , low side temperature and pressure measurement in the vapor line 62 can be performed at low side port 70 . The temperature and pressure of the refrigerant leaving entering the compressor 12 through the vapor line 62 can be measured at the low side port 70 . These measurements can be performed, for example, to check unit superheat (suction line temperature minus evaporator saturation temperature). The suction line temperature is measured at low side port 70 and the evaporator saturation temperature is approximated using measured suction line pressure (again taken at low side port 70 ) along with pressure-temperature charts/look-up tables for the particular type of refrigerant used in the unit 10 . [0076] Additionally, for purposes of evaluating and testing the unit 10 , high side temperature and pressure measurement can be performed at high side port 72 . The temperature and pressure of the refrigerant leaving the condenser 16 through the liquid line 40 can be measured at the high side port 72 . These measurements can be performed, for example to check unit sub-cooling (condenser saturation temperature minus liquid line temperature). Liquid line temperature is measured at high side port 72 and condenser saturation temperature is approximated using measured liquid line pressure (again taken at high side port 72 ) along with pressure-temperature charts/look-up tables for the particular type of refrigerant used in the unit 10 . [0077] In a single example, the superheating and sub-cooling data acquired from the unit can be used by a technician to determine whether the unit 10 is in operating normally or is in a state of overcharge or undercharge. If overcharge or undercharge is indicated, the technician can take corrective steps to bring the unit back to normal/optimal operation by adding or removing refrigerant. Such corrective actions, being unit and manufacturer specific, are far too numerous to describe in any detail greater than that which has already been described herein. [0078] The system of the invention is a smart HVAC manifold system for use in the installation, maintenance, and servicing of A/C units, particularly air conditioning and refrigeration units. The system accounts for both the mechanical refrigeration system and also measures changes in the conditioned medium along with electrical characteristics to determine the efficiency of the air conditioning process. The system can perform or assist in performing tasks, such as measuring operating parameters of the unit, measurement conditioning outside of standard conditions, measurement verification, data acquisition (including management, sharing, and reporting), and verifying, quantifying, and troubleshooting unit performance. The system is intended for use by service technicians, maintenance personal, installers, verifiers, operators, mechanics, and any other personnel that may be interested in the operation of A/C units. The scope of the invention and its associated applications will become apparent through this description of the invention and the associated figures. [0079] FIG. 2 illustrates the smart HVAC manifold system 100 . The system 100 includes an smart manifold 102 and a smart platform 104 for communicating with the manifold. In one aspect, the smart platform 104 can be a smart phone or tablet PC or other computing device. The smart platform 104 may have alternative constructions. For example, the smart platform 104 could be a tablet pc, a portable laptop computer, or even a unique, custom OEM device. In this description, for simplicity, the smart platform 104 is described and illustrated as a smart phone. [0080] The smart manifold 102 connects to an A/C unit 106 to measure data (e.g., pressures and temperatures). The unit 106 may, for example, be similar or identical to the unit 10 illustrated in FIG. 1 . Using this example to reference, the manifold 102 thus can be adapted to read high-side & low-side pressures via ports 72 and 70 , and can be adapted to read high-side & low-side temperatures in lines 62 and 40 . The unit 102 includes a plurality of connections 108 for facilitating these measurements. [0081] The smart manifold 102 is a measurement platform for passing data to the smart platform 104 . Advantageously, in a smart phone/tablet implementation of the smart platform 104 , the smart manifold 102 takes advantage of the large, high resolution screen real estate, the native GPS features, and the native communications and video system. The system 100 uses the smart manifold 102 and smart platform 104 in combination to perform measurements required for commissioning HVAC systems. Additionally, this combination provides computational power to provide an intelligent platform for simple and complex diagnostics of equipment operation and problems. The smart manifold 102 , in combination with the smart platform 104 offers a powerful communications platform to allow users to share information with consumers, owners, utilities, equipment manufacturers, and other interested parties and/or service providers. Data can be input into the application using voice to text, text, video, photo, Optical Character Recognition (OCR), on-screen or wireless input devices (e.g., Bluetooth keyboard, Bluetooth headset, mouse), and data streaming from the manifold. [0082] The smart manifold 102 includes sensors that may be wired and/or wireless. Standard core sensor technology will include pressure, and wired temperature sensors (e.g., outdoor air, liquid line, suction line, discharge line). Additional wired or wireless sensors can sense environmental and operating conditions such as wireless temperature & humidity (wet-bulb and dry-bulb; supply air and return air), equipment current, voltage, air velocity, and static pressure. The smart manifold 102 can support the following standard measurements: Low side pressure. High side pressure. Outdoor air temperature. Liquid line temperature. Suction line temperature. Discharge line temperature. The smart manifold 102 can also support the following advanced measurements: Wireless three phase/single phase compressor current. Wireless single phase indoor blower current. Wireless supply air temperatures (wet bulb and dry bulb). Wireless return air temperatures (wet bulb and dry bulb). Wireless temperature×4 (line temperatures/air temperatures). Static pressure test—airflow. Airflow measurement from TruFlow® Grid Airflow measurement from vane, hot wire or capture hood More could be added if desired/required. Compressor oil pressure. Refrigerant system vacuum during service. [0100] FIG. 3 illustrates an example embodiment of the smart manifold 102 in greater detail. The manifold 102 includes a refrigerant manifold 110 and an electronics unit 112 . The smart manifold 102 (at least the electronics unit 112 ) may be housed in an enclosure with an ingress protection rating of IP-42 to withstand light rain. The smart manifold 102 can be designed to operate in a −40° C. to +85° C. operating temperature range. [0101] The refrigerant manifold 110 is what is referred to in the art as a “three valve manifold.” The manifold 110 could have alternative configurations, such as a two-valve or four-valve configuration. All of these configurations are well known in the field of HVAC service and technology. The manifold includes a low-side port 114 and a low-side handle 116 for opening/closing a valve (not shown) associated with the low-side port. The manifold 110 also includes a high-side port 120 and a high-side handle 122 for opening/closing a valve (not shown) associated with the high-side port. The manifold further includes a refrigerant/vacuum port 124 and a refrigerant/vacuum handle 126 for opening/closing a valve (not shown) associated with the refrigerant/vacuum port. The manifold 110 also can include a low side gauge 162 and a high side gauge 164 for reading those respective pressures directly without use of the smart platform 104 . The manifold 110 can be configured such that the gauges 162 and 164 illustrate temperatures in Fahrenheit or Celsius and pressures in PSIA, PSIG, KPa, MPa, or any other desired units. The manifold 110 can include additional ports for measuring pressure, temperature, or other HVAC system operating conditions or environmental conditions. [0102] The low-side port 114 is connected to the low-side line 62 of the A/C unit 10 at the low-side port 70 via one of the connections 108 which, in this instance, includes a low-side hose 130 and a fitting 132 for connecting with the low-side port 70 . The high-side port 120 is connected to the high-side line 40 of the A/C unit 10 at the high-side port 72 via one of the connections 108 which, in this instance, includes a high-side hose 134 and a fitting 136 for connecting with the high-side port 72 . The refrigerant/vacuum port 124 is connected via a connection 108 to either a refrigerant vessel 140 or a vacuum pump 142 , depending on whether refrigerant is to be added or removed from the unit 10 . In this instance, the connection 108 includes a refrigerant hose 144 and appropriate fittings (not shown) for connecting with the refrigerant vessel 140 or vacuum pump 142 . The low-side handle 116 , high-side handle 122 , and refrigerant/vacuum handle 126 are operable in a known manner to place the manifold in a condition for measuring high-side and low-side pressures, for adding refrigerant to the unit 10 , and for removing refrigerant from the unit 10 . [0103] To obtain temperature measurements for the refrigerant in the unit 10 , the connections 108 may also include low-side and high-side temperature probes 146 for measuring one or more refrigerant line or air temperatures. The temperature probes 146 may, for example, comprise thermocouple or thermistor sensors with appropriate connectors, such as clamps, for connecting the probes directly to the low-side and high-side refrigerant lines 62 and 40 . Although the probes 146 are illustrated in FIG. 3 as leading from the refrigerant manifold 110 , the probes could lead from the electronics unit 112 . [0104] Referring to FIG. 4 , to obtain pressure measurements, the smart manifold 102 includes low-side and high-side pressure transducers 150 and 152 that are operatively connected so as to be exposed to the refrigerant line pressures via the low-side and high-side ports 114 and 120 of the refrigerant manifold 110 . Although the pressure transducers 150 and 152 are illustrated as portions of the electronics unit 112 , portions of the transducers, or even the entire transducers, could be housed in the refrigerant manifold 110 . The pressure transducers 150 and 152 are operative to convert the line pressures to digital signals representative of the sensed pressures. Those skilled in the art will appreciate that this conversion would include signal processing, such as input buffering, calibration, and analog to digital conversion (ADC). These and other such processing functions are well-known and, for simplicity, are illustrated generally as the pressure transducers 150 and 152 illustrated in FIG. 4 . [0105] To obtain temperature measurements, the smart manifold 102 includes low-side and high-side temperature transducers 154 and 156 that are operatively connected to the temperature probes 146 . Although the temperature transducers 154 and 156 are illustrated as portions of the electronics unit 112 , portions of the transducers, or even the entire transducers, could be housed in the refrigerant manifold 110 . The temperature transducers 154 and 156 are operative to apply a voltage to the thermocouples of the probes 146 and sense changes in current representative of changes in electrical resistance in the thermocouples due to temperature change. The temperature transducers 154 and 156 convert the currents to temperature indications and provide digital signals representative of the sensed temperatures. Again, those skilled in the art will appreciate that this conversion would include signal processing, such as input buffering, calibration, and analog to digital conversion. These and other such processing functions are well-known and, for simplicity, are intended to be encompassed within the temperature transducers 154 and 156 illustrated in FIG. 4 . [0106] The smart manifold 102 can be configured to include a number of ports selected to provide the desired measured conditions of the HVAC unit 10 . For example, the smart manifold 102 can include four probes for temperature, four ports for pressure, and two ports for vacuum and oil pressure as auxiliary probes. Two of the temperature ports can be used to measure discharge line temperature and the outdoor air temperature. [0107] To obtain relative humidity and temperature measurements of the conditioned medium, the smart manifold 102 can include one or more relative humidity transducers 158 that are operatively connected to one or more humidity/temperature probes 160 . Although the relative humidity transducers 158 are illustrated as portions of the electronics unit 112 , portions of the transducers, or a device to transmit their readings to the manifold. The relative humidity transducers 158 are operative to sense the relative humidity and temperature in the vicinity of the probes and provide electrical signals representative of the sensed relative humidity and temperature, which can be converted to digital signals representative of the humidity and temperature. Again, those skilled in the art will appreciate that this conversion would include signal processing, such as input buffering, calibration, and analog to digital conversion. These and other such processing functions are well-known and, for simplicity, are intended to be encompassed within the relative humidity and temperature transducers 158 illustrated in FIG. 4 . [0108] The smart manifold 102 can be adapted to include multiple configurations in which multiple pressure/temperature ports are built into the unit architecture. For example, in one construction, there can be 4 probes for temperature built into the unit as well as 4 ports for pressure, the remaining two for vacuum and oil pressure as auxiliary probes. The other two temperature ports will be to measure discharge line temperature and the outdoor air temperature. [0109] The smart manifold 102 also includes one or more memory modules 170 , one or more processing modules 172 , and one or more communications modules 174 that are operatively connected to each other, for example, via a communication and data bus 176 . As shown in FIG. 4 , the communication modules 174 can include a smart platform communications 180 , sensor communications 182 , and network communications 184 . The manifold 102 may also include a wakeup button 166 operatively connected to the processing module 172 . In the illustrated configuration, the pressure transducers 150 , 152 , and the temperature transducers 154 , 156 are also operatively connected to the bus 176 . In this manner, the processor 172 can execute instructions (e.g., applications, program files) stored in the memory module 170 . The processor 172 , e.g., a microcontroller having a processor and memory for storing firmware for controlling the processor, can read data from the memory module 170 , can manipulate the data in accordance with the executed instructions, and can write data to the memory module for storage. The processor 172 can also retrieve sensed pressure and temperature data from the transducers and can write that data to the memory module 170 at specified capture rates and durations. The processor 172 can also perform calculations, such as superheat and sub-cooling calculations. The processor 172 can also execute instructions to transmit and/or receive data via the communications module 174 . The smart manifold 102 can be configured for extended duration capture times, such as up to 99 hours (eg. 178,200 records at max 2-second capture time, 99 records at 1-hour capture time). [0110] The smart manifold 102 also includes a power module 168 that provides power for the various components of the electronics unit 112 . For simplicity, the power module 168 is illustrated as supplying power via the bus 176 , in which case the bus would be of a split design where power and data/communication signals are isolated from each other. The power module 168 could, however, supply power to the various components in any known manner. The power module 168 may include rechargeable batteries, disposable batteries, an external power supply, or a combination of these sources. [0111] The communications modules 174 supports communications between the smart manifold 102 and the smart platform 104 via the smart platform communication module 180 . The smart platform communication module 180 can be, for example, Bluetooth, Bluetooth Low Energy (e.g., Bluetooth 4.0, or “Bluetooth Smart”) and/or Wi-Fi communications, since the smart platform 104 (e.g., smart phone, tablet computer, or PC) is typically adapted for either form of wireless communication. Advantageously, as shown in FIG. 2 , the smart platform 104 also has built-in mobile communication (3G/4G or the latest standard) and communication via Wi-Fi, which gives the smart HVAC manifold system 100 the data, voice, video, and internet communication capabilities. Further, the smart platform 104 also has global positioning system GPS capabilities, which further enhances the capabilities of the system 100 . [0112] The network communication module 184 provides communication with the network 250 (see FIG. 2 ) via Wi-Fi, wired Ethernet, cellular, or satellite. The sensor communication module 182 supports wireless communication between the smart manifold 102 and any wireless sensors 186 . The wireless sensors 186 can, for example, sense low side pressure, high side pressure, outdoor air temperature, liquid line temperature, suction line temperature, discharge line temperature, compressor motor current, indoor blower current, supply air temperatures (wet bulb and dry bulb), return air temperatures (wet bulb and dry bulb), line temperatures, air temperatures, static pressure, airflow measurement, compressor oil pressure, refrigerant vacuum, local weather, weight (refrigerant scale) data, other air quality parameters (CO2 Carbon Dioxide, particulates, etc), etc. Additionally, any of these sensed conditions can be transmitted to the smart manifold 102 via one or more wired sensors 188 . [0000] Example Configuration of the Smart manifold [0113] In one example configuration of the smart manifold 102 , the processor 172 may comprise a Freescale Kinetis K20™ microcontroller, which includes a processing unit and non-volatile memory for storing firmware. The communications module 174 may comprise a single-mode Bluetooth Low Energy (BLE) radio, with an optional ZigBee™ radio, and USB On-the-Go (OTG) capabilities. In addition to on-board volatile/non-volatile memory (e.g., VRAM, NVRAM) the memory module 170 may also include an external memory card slot, such as an SD memory card slot. The power module 168 may comprise a rechargeable lithium battery, a charge management integrated controller (IC), and a wakeup button. The smart manifold 102 can include up to four each of the temperature and pressure transducers. The transducers are mounted to a refrigerant manifold 110 and the electronics are housed within an IP rated (e.g., IP-42) enclosure. The microcontroller unit (MCU) processor 172 is the primary processor within the smart manifold 102 and is responsible for performing all measurements. [0114] In this example configuration of the smart manifold 102 , the MCU executes instructions from the firmware to perform several functions. The MCU performs analog-to-digital conversions for all attached sensors and performs averaging and signal conditioning for each measurement channel. The MCU transfers all measurement data to the Bluetooth radio module and instructs the Bluetooth module to receive incoming connections and transmit measurement data. Additionally, the MCU can bring the smart manifold 102 into a sleep state when not in use and wakes up the manifold when the button is pressed. [0115] Additionally, the MCU executes instructions from the firmware to acquire and publish data from the pressure sensors and temperature sensors. To do so, the MCU executes firmware instructions to configure each analog-to-digital conversion (ADC) module to acquire a digital sample from each sensor channel, advance to the next channel after each acquisition. Each sample is converted to a floating-point value, incorporating minimum/maximum limits and calibration data in the conversion. The acquired sample is stored in a rotating buffer containing the last N samples. An averaging function is performed over the last N samples to produce a single, stable measurement value for each channel. This value is placed in the data store. [0116] Additionally, in this example, the smart manifold 102 provides all measurement data to a remote system (e.g. smartphone) via the Bluetooth communication. To do this, the MCU executes firmware instructions to convey the data to the BLE module of the communications module 174 for transmission. The BLE module runs firmware built by a special tool provided by the module manufacturer. The BLE firmware implements a GATT (Generic Attribute) profile specific to the smart HVAC manifold system 100 , which allows a BLE host to retrieve each measurement from the smart manifold 102 . To configure the firmware, the developer edits XML files describing the GATT profile for the application and the hardware configuration of the module, then runs the tool which generates the firmware image. The GATT attribute data is transferred via a universal asynchronous receiver/transmitter (UART) between the two devices using a simple serial protocol defined by the module manufacturer. The MCU does not need to manage any of the Bluetooth-specific functions; it only provides the measurement data to the BLE module. The BLE module manages all Bluetooth-specific functions and notifies the MCU when certain events occur, such as connects, disconnects, and reboots. [0117] In this example, the smart manifold 102 employs a low power management strategy in which the electronics unit 112 is powered by an internal rechargeable lithium battery. The battery is recharged through the micro-USB port and requires no MCU intervention. The MCU needs to keep itself and the Bluetooth radio in a low-power state when the device is not being used, to prevent battery drain. The MCU also needs to wake up when either the pushbutton is pressed or the Bluetooth radio wakes up from an over-the-air request. When woken up, the MCU will stay awake for as long as an active Bluetooth connection is maintained. After the connection is closed, the MCU will stay awake for a short amount of time and then go to sleep. The MCU can sleep the radio by software command and wake it up via general-purpose I/O (GPIO). [0118] The smart platform 104 can include a custom mobile application that can communicate with the smart manifold 102 for the purposes of data acquisition and analysis, as well as device calibration and other interactive functions. The communication between the smart manifold 102 and smart platform 104 can be performed via Bluetooth Low Energy (Bluetooth 4.0, or “Bluetooth Smart”) radio. Bluetooth Low Energy (BLE) radio. BLE is a new Bluetooth standard for low-power or battery-operated devices which allows rapid exchange of data using a connectionless protocol, eliminating the time required to re-establish a connection between two devices. BLE functionality is implemented in many newer smartphones and tablets such as the iPhone 4S™, iPhone 5™ iPad™ 3rd gen (Retina), Nexus7™ Galaxy S III™, and Droid Razr™. While a smart phone with a touch screen interface is described herein, the smart platform 104 could have an alternative form, such as a tablet device, a tablet PC, or a portable laptop PC and could use alternative interface, such as a keyboard, mouse, track pointer, voice recognition, gestures, etc. [0119] The smart manifold application (“manifold app”) 200 is installed on the smart platform 104 (see FIG. 2 ). The manifold app 200 communicates locally with the smart manifold 102 via communication link 202 (e.g., Bluetooth, BLE, or Wi-Fi (802.11) communication) to send and receive data and commands. This local communication function is configured to discover and list nearby devices, e.g., smart manifolds 102 , in order to allow the user to select and connect to the device. Storing identification and other data, such as manufacturer data, test data, maintenance records, previous settings, etc., the manifold app 200 can reconnect quickly to previously used devices and retrieve the data associated with the device. The manifold app 200 is also configured to display a live stream of data from the selected device and record received data to smart platform memory 204 (either internal or SD). [0120] An example of an initial screen 210 of the manifold app 200 is illustrated in FIG. 5A . The initial screen 210 may contain a smart platform status portion 212 , where data such as cellular wireless connectivity status, WiFi connectivity status, time of day, Bluetooth connectivity status, and battery charge. The initial screen can also include an application identification portion 214 for title, logo, etc. and some basic instructions to begin using the app. The initial screen 210 can also include a device list area 216 that lists the identifying information for any previously connected devices (i.e., devices that have been previously connected using that particular phone or tablet). Tapping a previously connected device (e.g., IM_X, IM_Y, of IM_Z in FIG. 5A ) will raise a “Connecting . . . ” dialog as the manifold app 200 attempts to connect to that device. The user may also delete any or all devices from the list. An instruction area 218 lists a “Discover” button allows the user to search for any active devices within range and a “Logs” button that allows the user to access previously recorded device data. [0121] A primary function of the manifold app 200 can be to discover an active device through Bluetooth. When the user presses the “Discover” button in the instruction area 218 on the main screen 210 , the app will put up a “Discovering . . . ” dialog for a few seconds, then display a list of any discovered devices. This is shown in FIG. 5B . The user can then tap one of the listed devices (e.g., IM_A, IM_B, of IM_C in FIG. 5B ), which will raise a “Connecting . . . ” dialog as the manifold app 200 attempts to connect to that device. The user can also tap “Discover” again to repeat the discovery process, in the event that the manifold app 200 failed to detect the desired device the first time. [0122] Once the manifold app 200 has connected to a Device, the app will then retrieve data from the Device and display it on the data screen. An example of a data screen 220 is illustrated in FIG. 5C . The data screen 220 may include a smart platform status area 222 that is similar or identical to the status area 212 of the initial screen 210 . An instruction area 224 lists a “List” button allows the user to go back to the device list area 216 of the initial screen 210 . The data screen 220 has a data area 226 that lists the selected device and any ID information associated with that device. The data area 226 also lists data particular to the selected device, such as low side pressure, low side temperature, low side sub-cool, high side pressure, high side temperature, and high side superheat. Calculations, such as superheat and sub-cool calculations, can be performed on the smart platform 104 via the manifold app 200 , or those calculations can be performed by the smart manifold 102 and transmitted to the smart platform. The manifold app 200 can show the data in real time or close to real time through continuous retrieval and update for as long as the data screen 220 is displayed. The user can pause updating by selecting a pop-up menu item, or disconnect from the device by pressing the “Disconnect” button on the data screen 220 . [0123] The manifold app 200 can record received data to the internal memory 204 of the smart platform 104 . Files can be named according to Device ID and time of recording. The files can be retrieved from the smart platform 104 and transmitted via any means available to the smart platform, such as a wireless cellular communications, WiFi communications, Bluetooth communications, or satellite communications. Operation of the Smart HVAC Manifold System [0124] A primary function of the smart HVAC manifold system 100 is to allow standard service procedures and to perform the basic calculations required to properly charge (add or remove refrigerant), determine capacity, Energy Efficiency Ratio and proper operation as specified by the A/C system equipment manufacturer and heat pumps using standardized charging charts/calculations for fixed type metering devices and target subcooling for thermal expansion valve (TXV) systems. [0125] To accomplish this task, the smart HVAC manifold system 100 includes a perfect charge module that looks at target output (BTUh), electrical current and refrigerant charge characteristics to determine optimum refrigerant charge. As refrigerant is added to an A/C system, the cooling output and the EER (BTUs removed/power (watts) consumed) will increase until the charge is as the optimum level. If refrigerant is added beyond the optimum level, the refrigerant will back up in the condenser causing a decrease in the EER and a decrease in cooling output in fixed orifice systems due to an increase in the suction pressure and a reduction in condenser space and increase in discharge pressure. In fixed orifice systems, target superheat will be monitored along with output to determine the optimal operation. This module will require the use of external wet bulb and dry bulb thermometers, one or more current clamps, and airflow inputs, either from the Smart manifold or through user input. [0126] The smart HVAC manifold system 100 can also include a troubleshooting module including a mode or algorithm that allows users to input information about the type of system and its components and, based on this information, will apply standardized troubleshooting algorithm(s) to help diagnose typical HVAC problems. This mode also includes basic service advice on fault remedies and tips to properly identifying problems. Examples might include considerations when installing a new TXV: bulb mounting, orientation, manufacturer nomenclature, and applications. Typical problems that can be encountered when troubleshooting can include: Refrigerant Overcharge (Fixed/TXV). Refrigerant Undercharge (Fixed/TXV). Liquid line restriction/undersized/plugged dryer (Fixed/TXV). Low evaporator airflow (Fixed/TXV). Low load (Fixed/TXV). High load (Fixed/TXV). Dirty condenser (Fixed/TXV). Low outdoor air temperature (Fixed/TXV). Inefficient compressor (Fixed/TXV). Presence of Non-condensibles (Fixed/TXV). Insufficient suction line insulation. Loose TXV bulb (TXV Only). TXV has lost its charge (TXV Only). Plugged TXV. TXV bulb poorly insulated (TXV Only). Refrigerant Flooding (via suction line temperature sensors at evaporator outlet and condenser inlet). Refrigerant Flashing (via liquid line temperature sensors located at condenser outlet and evaporator inlet). TXV Hunting (improperly varying its control position): Oversized valve. Bulb too far from outlet. Incorrect bulb charge. System under charge. Uneven loading. Poor distribution of refrigerant. High operating superheat: Low refrigerant charge. Insufficient subcooling. Improperly adjusted TXV. Excessive pressure drop in internally equalized TXV. Contamination of blocking valve. Partial loss of TXV bulb charge. Low operating superheat: Poor TXV bulb mounting. Improperly adjusted TXV. TXV Valve stuck open. Oil logging in the evaporator. Improperly adjusted TXV. [0164] The smart HVAC manifold system 100 can also include a compressor diagnostics mode that reads motor current from the common, start and run windings via optional probes that attach to the smart manifold 102 . These readings are used to diagnose typical compressor problems. [0165] The smart HVAC manifold system 100 can perform a variety of calculations related to the operation and maintenance of the A/C unit 106 . All standard calculations will include information about the standard calculations (e.g., how calculated) and their typical ranges. This information can be accessed via the smart platform 104 and can be transmitted via the network 250 using one of the various modes of transmission employed by the smart platform. The system will allow for US customary or metric (SI) units of measure. The following standard calculations can be performed: Saturation temp—low side. Saturation temp—high side. Superheat (Actual). Subcooling (Actual). The following advanced calculations can be performed: Total capacity (BTUH, KW, Tons)* Sensible capacity (BTUH, KW, Tons)* Latent capacity (BTUH, KW, Tons)* Sensible latent split (unit less ratio)* De humidification (LBS/Hr or SI equivalent)* Bypass factor (%)* Energy Efficiency Raito (EER)* *Note: These calculations require user input or advanced measurement of airflow, and voltage from line to ground, and optional probes for air conditions and current. [0177] Additionally, capacity calculations can be derived by measurements of mass flow rate of the conditioned medium at the evaporator coil and changes in enthalpy of the conditioned medium (air). The total heat added or removed can be determined using (preferably) a non-density dependent method of airflow measurement, or a density dependent method that is corrected by the apparatus, and a dry bulb and humidity sensor for the refrigerated or heated medium. [0178] When using any of the air formulas it is important to understand how to correct for changes in the air density if the air being measured is not standard air. The air constants apply to standard air at 70° F. and 14.7 Pisa, (29.92″hg.) If air being measured is outside of these parameters, it may require that the constant be recalculated. For most situations the standard air formulas can be used, but if precise measurements are desired, adjustments to the constants should be made. Remember, fans are doing work; they are moving in reality pounds of air. The amount of air they will move in CFM remains constant with a variable mass flow rate, so the cubic feet of air they will move over any given time period will remain the same. The difference is in the density of the air or the number or the pounds per cubic foot. This is important because coil selection software calculates required coil capacities based upon pounds per hour (lb/hr) of air passing through the coil, not CFM. [0000] The constant 4.5 is used to convert CFM to lbs/hr: [0000] 4.5=(60 min/hr÷13.33) or (60 min×0.075 lbs/cu ft), where: 13.33 is the specific volume of standard air (cu·ft/lb); and 0.075 is the density (lbs/cu·ft). If the air being measured is not standard air, the air density will vary with the barometric pressure and the absolute temperature. To recalculate the air density, measure the temperature and obtain the barometric pressure use the following formula: [0000] Air Density (lb/cf)=1.325× B p /T abs , where: 1.325 (Constant to keep consistent units); B p =Barometric Pressure; and Tabs=Temperature (Absolute). [0000] 1.325×29.92/(70° F.+460° F.)=0.0748˜0.075 lb/cu ft.  Example: [0000] This is how standard air density is calculated. If you were measuring air coming out of a furnace, and the air was 154° F. the air density would change as follows: [0000] 1.325×29.92/(154° F.+460° F.)=0.0645 [0000] If heated air were used in this formula, the constant would be: [0000] (60 min×0.0645 lbs/cu ft)=3.87 instead of 4.5 used for standard air. [0000] The constant used in the sensible heat formula 1.08 is used to convert CFM to lbs/hr and factor in 0.24 the specific heat of standard air (BTU/lb/° F.), where: [0000] 1.08=(0.24×60)/13.33 or 0.24×4.5 [0000] 4.5=60 min/hr÷13.33, or (60 min×0.075 lbs/cu ft) [0000] 0.24 BTU=specific heat of standard air (BTU/lb/° F.) [0000] The constant 0.68 used in the latent heat formula is used to factor out the amount of heat contained in water vapor in BTU/LB, where: [0000] 0.68=(60/13.33)×(1060/7000) or 4.5×(1060/7000); and where: 13.33 is the specific volume of standard air (cu·ft/lb). 1060=average latent heat of water vapor. (Btu/LB). 7000=grains per lb or water. 4.5=60 min/hr÷13.33 or (60 min×0.075 lbs/cu ft). [0188] The smart HVAC manifold system 100 can acquire real time data and use that data to perform performance calculations. Since HVAC systems are dynamic and conditions (e.g., load, ambient, and equipment output) are constantly changing, real time data acquisition of multiple points of data is necessary to accurately quantify performance and evaluate operation. Technicians capturing data manually are restricted by the time required to gather and interpret the measurements, record data and perform calculations before the load changes. Often systems are tested at a load condition less than full load, so conditions change faster than data can be obtained through traditional means. The system 100 can also verify measured data using algorithms that rule out data gaming and suspect or impossible measurements. The smart HVAC manifold system 100 can also perform measurement conditioning using GPS data and weather conditions available from local weather data (either automatically or via user input, as required) to apply corrections for non-standard conditions that might affect sensor accuracy or calculated accuracy if non-standard conditions were not considered. All of this can be performed in real time. [0189] The implementation of the smart device to the smart platform 104 in the smart HVAC manifold system 100 yields many features and advantages that owe to the special functionality that current smart phone/device technology employs. Referring to FIG. 2 , the smart platform 104 can communicate with a web/cloud based network 250 wirelessly via cellular communication/network connection 252 (e.g., 3G, 4G LTE, etc.), wirelessly via WiFi communication/network connection 254 over or through a WiFi enabled network, such as a local area network (LAN) 256 that acts as a gateway 258 linking the smart platform 104 to the web/cloud based network 250 . Additionally, the smart platform 104 is outfitted with hardware and software that enables the acquisition of GPS location data 260 via GPS satellites 262 . Furthermore, the smart manifold 102 can also have a connection 264 for communicating with the network 250 , e.g., via a Wi-Fi, wired Ethernet, cellular, satellite communications, or machine-to-machine (“M2M”) communications. [0190] When changes are made during the servicing of a refrigeration system, particularly when refrigerant is added or removed to obtain the correct charge, there is an impact on system performance capacity that affects the overall operation. Many system variables and indicators of correct operation are affected and take time to stabilize. A technician that is rushed to complete service or unaware of all of the variables that impact performance may not wait long enough or could wait too long for the system to reach study state conditions before evaluating the impact on the changes that have been made. If these changes are made to quickly there is a high probability of overcharging or undercharging the system leaving it with substandard operation or driving the technician to undo changes that were made. If the technician waits too long there are lost labor costs. Because of real time data acquisition, the smart HVAC manifold system 100 can assess system changes over time and indicate when a steady state condition has been achieved and the system performance then be quantified, thus saving valuable repair time and money. [0191] One advantage of the smart HVAC manifold system 100 realized through the implementation of the smart platform 104 is that manufacturer data 272 can be accessed via the network 250 and the A/C unit 106 can be tagged and identified, operating ranges and other pertinent information can be stored, and calculations/tables can be adjusted so that the unit is tuned in accordance with manufacturer specifications. The manufacturer data 272 can also include equipment specific troubleshooting data that can be used to identify problems with a specific A/C unit 106 based on manufacturer recommendations. [0192] Another advantage of the smart HVAC manifold system 100 realized through the implementation of the smart platform 104 is that the smart phone built-in camera functions of the smart platform 104 can be utilized to scan equipment label data 280 , such as bar codes or QR codes, to obtain identifying data for the A/C unit 106 . This data can be used to obtain more detailed manufacturer data 272 for the A/C unit 106 via the network 250 . Additionally, the system can allow users to tie photos to the pinned job site via the GPS module. This can allow the user to include tagged photos in reports to illustrate identified problem conditions, such as plugged coils, bad or misaligned or incorrectly tensioned belts, electrical failures, etc. Photos can also be used for equipment ID and tied together to show locations of thermostats, outdoor air controls or other remote sensors that might be tied to a unit. All photos can be location tagged via GPS for easier location by subsequent service technicians. Photos can also be tagged with unit settings and a historical data regarding the unit. [0193] The multi-platform capabilities of the smart HVAC system 100 allows for customized applications (or apps) that will allow manufacturers to collect information about the operation of the system and to see initial commissioning results for warranty purposes. Applications may be customized with a database of unit performance or go to a remote look-up table to gather performance about the equipment (e.g., the Air-conditioning, Heating and Refrigeration Institute or AHRI directory of certified product performance, see http://www.ahridirectory.org/ahridirectory/pages/home.aspx). [0194] Using the data gathered by the system 100 , graphic trending allows user to see operating characteristics of the A/C unit 10 operation and/or service over time. These operating characteristics can include: Pressure testing system integrity with time (standing pressure tests). Vacuum decay/evacuation levels with time. TXV Valve hunting. Intermittent problems. Run cycle information. Remote real time reporting/monitoring allows information to be reviewed by a lead technician, commissioning expert or appliance manufacturer, utility or other interested party for third party evaluation of performance and operating characteristics. Data can be used to verify proper operation for extended warranty, minimizing callbacks and documentation of initial startup. The user can customize the display to give the application a custom look and feel by displaying preferred data laid out in a manner suited to their liking. The user can manipulate the size, location and the screen order of objects. The user can also customize reports and add a company logo. Templates can be shared with other users. [0200] Another advantage of the smart HVAC manifold system 100 realized through the implementation of the smart platform 104 is that person-to-person communications 274 can be established over the network 250 via the cellular network connection 252 or the WiFi network connection 254 . Additionally or alternatively, the communications 274 can be established directly with the smart platform 104 establishing a direct cellular network connection 276 . Communication can be established from within the manifold app 200 or can be established with the app running in the background. The communications 274 may include text messaging, voice over internet protocol VOIP, video conferencing (2-way), email, and cellular voice and data. The communications can be used for technical support, training, and for communicating with others employing the smart HVAC manifold system 100 . [0201] These advanced communications features may enable a pay per use or a subscription service that gives users access to a group of seasoned professionals to help trouble shoot equipment problems. The service is a forum based product that has residential, commercial, industrial, and possible dealer only (eg. Trane, Carrier, Lennox) boards for users to ask questions. The service can be a moderated user community forum that is a subscription service that allows users to help each other solve problems in the field. Answers to user's questions are peer rated on a scoring system (e.g., 1 to 5 stars) that rates the quality of the answer. These professionals will be able to view the users information in real-time via their smart platform. If there are multiple answers to the questions users can sort answers by the rating of the person that answered the question. This group of professionals answering the questions can be grown from the top rated HVAC members and retired HVAC professionals that meet pre-established requirements to provide quality phone support. Support can be done via Skype®, Apple FaceTime®, text (SMS) messaging, phone or other similar medium. The service provides advanced support to technicians to provide solutions to problems that are not easily identifiable due to technician experience level or problem complexity. Service could be made available around the clock. [0202] Serving as the go-between for the local smart manifold 102 , the web/cloud-based network 250 , and the GPS location data 260 allows the smart platform 104 to facilitate combining the data to provide several advantageous features. Since the smart platform 104 communicates locally with the smart manifold 102 via Bluetooth, the GPS location data 260 can be used to associate the manifold with a geographic location. The system can thus utilize geo-tagging/time tagging for identification and recordation purposes. Additionally, since all of these functions converge at the manifold app 200 on the smart platform 104 , any data acquired by the app or entered into the app can be time-stamped and recorded in real time, and can be used, e.g., for purposes of reporting, auditing, and long term trending. [0203] The smart platform based GPS allows the technician to pinpoint the location of where the system is serviced via an online mapping service (e.g., Google maps). The GPS will show the approximate location of the technician relative to the equipment (e.g., within about 5-10 meters accuracy with full view to the sky) and allow the technician to drop a pin at the exact location if needed. The address will be automatically imported from the GPS location. When the pin is selected on the map, information about the unit including model and serial numbers, last date of service, servicing technician, unit service history, past performance will be available (i.e., if the HVAC smart manifold system 100 was utilized in commissioning or previous service of the unit). Also available will be a photo of the model and serial number tag to verify unit is the exact unit identified by the location marker. [0204] Over time, a map of A/C unit 106 installations identified by the smart HVAC manifold system 100 can be developed and used for multiple purposes, such as producing a savings calculator for equipment replacement purposes, or producing a calculator for equipment repair that estimates payback periods. Such a map could also be used to anticipate electric utility demand by geographic location. [0205] Knowing the GPS location data 260 , the manifold app 200 can access location data, such as weather and climate data, and time-stamp and associate that data with operations (e.g., tune-ups) performed on the A/C unit 106 at a site specific location. Additionally, the weather and altitude data can be used to make adjustments to calculations, for example, to air density based on the barometric pressure and altitude at the geographic location. [0206] Example configurations of the smart HVAC manifold system 100 are illustrated and described in FIGS. 8-16 . [0207] From the above description of the invention, those skilled in the art will perceive improvements, changes and modifications. Such improvements, changes and modifications within the skill of the art are intended to be covered by the appended claims.
The smart HVAC manifold system for servicing air conditioning systems is designed to dynamically manage the data acquisition process and to measure and calculate the performance indicators and output as the load conditions and or equipment operation change taking into account variables in the installation that can impact performance. Both visually and by a very specific data set the performance of the equipment and the installation can quickly be assessed and specific problems identified along with suggestions of typical faults or problems that may need addressed by the technician. The smart HVAC manifold system provides a means of quickly and electronically handling the manual data acquisition process which would include component and or system model and serial numbers, equipment location (GPS tagging), customer name, environmental conditions that effect performance and performance measurement (weather data and elevation), and supports photo, voice and text documentation. These features streamline data acquisition, allow remote support, and minimizing transcription errors and preventing data-gaming when servicing equipment, commissioning or retro commissioning the system.
90,064
FIELD OF THE INVENTION The present invention relates to a technology for measuring a lens, and more particular to a technology for measuring decenter and tilt amounts of a lens by an interferometer. BACKGROUND OF THE INVENTION For the recent years, the vigorous development of the electro-optic industry, particularly the digital camera and the cellular phone camera, has placed a larger and larger demand for the optical devices. Of the optical elements, the optical lens can be the most essential and important one. In terms of the product characteristics, the optical lens may be categorized into a refractive device (e.g. a lens and a prism), a reflective device, a diffractive device, a hybrid device, among others, which are each related to a specific material and manufacturing process. Among the optical lens, the aspherical optical devices have found more and more applications and are more and more required. This is because the aspherical lens can have a good imaging quality as compared to the spherical lens. Further, when the aspherical optical device is applied to an optical system, the number of the optical device required and the overall cost for the system may be reduced. For the manufacturing reason, the aspherical lens is prone to a decenter or tilt issue with respect to the optical axes of its two side surfaces, leading to a deviation of the optical characteristics thereof. To obviate the deficient lens products, whether the decenter and tilt issues existing on the two axes of the aspherical lens are required to be measured or inspected, so that the lens itself can be corrected in optical design or manufacturing. In this regard, how to precisely and rapidly measure the aspherical lens is apparently an important issue to the manufacturing and design of the aspherical lens. For the spherical lens, the optical axis is a line connecting the both curvature centers of the two side surfaces thereof, which is shown in FIG. 7A . For the lens with only a single spherical surface, all lines extending from the curvature center to the spherical surface can be taken as the optical axis, which is shown in FIG. 7B . For the spherical lens, the optical axis is a common line among the optical axes of the two side surfaces and thus the line connected between the two spherical curvature centers. In the spherical lens, the decenter and tilt issues do not exist between the two optical axes but only exists between the optical axes and the geometrical centerlines, which is shown in FIG. 7C . This is conventionally measured by a collimator. In the aspherical lens, a line formed by connecting the curvature centers of all the curvatures of the spherical surfaces is the optical axis and only this optical axis exists therein, which is shown in FIG. 7D . Thus, the aspherical lens is provided with an optical axis at each of the two side surfaces thereof. The two optical axes possibly do not coincide with each other due to the manufacturing error problem. Accordingly, the decenter and tilt issues exist between the two optical axes, which are shown in FIG. 7E . This is generally measured by a reflective collimator. However, the aspherical lens is mostly formed by glass molding or plastic injection and thus burrs and mouse bites might be found at the rim portion thereof, which can cause a disturbance for the rotation of the lens, required when being measured by a collimator, or an error with respect to the measurement. In view of the above, there is a need to provide a method and device for measuring the decenter and tilt amounts between the two side surfaces of the lens by using an interferometer. After a long intensive series of experiments and research, the inventor finally sets forth such method and device. As compared to the prior art, the method and device of the present invention may not only be used for the spherical lens but also for the aspherical lens, and the optical lens may be precisely and rapidly measured. SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a device for measuring a lens, comprising a first interferometer having a first optical axis and carried on a first adjustment base, a lens holder for holding the lens having a first surface having a first lens optical axis and a second surface having a second lens optical axis, and a platen having a sliding rail and carrying the first adjustment base and the lens holder thereon, wherein the lens holder is movable on the sliding rail, wherein each of the first adjustment base and the lens holder has a tetra-axis adjustment mechanism through which a relative positional relationship of the first optical axis of the first interferometer and the first lens optical axis of the first surface of the lens is adjustable. In an embodiment, the tetra-axis adjustment mechanism comprises two translation axes and two rotation axes. In an embodiment, the lens holder has a 180 degrees overturn mechanism through which the first and second lens optical axes of the first and second surfaces are calibrated in turn with respect to the first optical axis of the first interferometer. In an embodiment, the device further comprises a second interferometer having a second optical axis and disposed on a second adjustment base on the platen to measure a relative positional relationship of the second lens optical axis of the second surface and the second optical axis of the second interferometer. In an embodiment, the device is used to measure a decenter and a tilt of the lens. It is another object of the present invention to provide a method for measuring a decenter amount and a tilt amount of a lens, comprising the steps of providing an interferometer having an optical axis and the lens, wherein the lens has a first lens optical axis and a second lens optical axis, arranging the optical axis of the interferometer and the first lens optical axis of the first surface into having a first specific relative positional relationship therebetween, rotating the lens by 180 degrees, adjusting the second optical axis of the lens and the optical axis of the interferometer into having a second specific relationship therebetween and recording a first adjusted translation amount Δy, a second adjusted translation amount Δz, a first adjusted angular amount Δθ y and a second adjusted angular amount Δθ z required to be adjusted, and calculating the respective one of the decenter amount δ and the tilt amount Δθ existing between the first and second lens optical axes according to the first and second adjusted translation amounts Δy and Δz and the first and second adjusted angular amounts Δθ y and Δθ z . In an embodiment, each of the first and second specific relationships is a relationship where the optical axis of the interferometer and the first and second lens optical axes of the first and second surfaces totally coincide with each other. In an embodiment, the optical axis of the interferometer and the first and second lens optical axes of the first and second surfaces are adjusted to totally coincide with one another by observing the formed interferogram of each surface of the lens. In an embodiment, a distance between the surface of lens and the interferometer is adjusted to present the interfering fringes of the interferogram of the each surface of lens. In an embodiment, the optical axis of the interferometer and the first and second lens optical axes of the lens are adjusted to totally coincide with one another by observing whether the interfering fringes are formed as concentric rings and whether the concentric rings are positioned at a center of the interferogram. In an embodiment, the first and second specific relationships are identical to each other. In accordance with an aspect of the present invention, a method for measuring a decenter amount and a tilt amount of a lens is disclosed, which comprises the steps of providing a first interferometer having a first optical axis, a second interferometer having a second optical axis and the lens, wherein the lens has a first surface having a first lens optical axis and a second surface having a second lens optical axis, and the first and second interferometers face the first and second surfaces of the lens respectively, adjusting the first interferometer and the lens so that the first lens optical axis of the first surface and the first optical axis of the first interferometer have a first specific relative positional relationship therebetween, adjusting the second lens optical axis of the second surface of the lens and the second optical axis of the second interferometer into having a second specific relative positional relationship therebetween and recording a first adjusted translation amount Δy, a second adjusted translation amount Δz, a first adjusted angular amount Δθ y and a second adjusted angular amount Δθ z , and calculating the decenter amount δ and the tilt amount Δθ existing between the first and second lens optical axes of the first and second surfaces according to the first and second specific relative positional relationships and the first and second adjusted translation amounts Δy and Δz and the first and second adjusted angular amounts Δθ y and Δθ z . In an embodiment, each of the first and second specific relationships is a relationship where the first and second optical axes of the first and second interferometers and the first and second lens optical axes of the first and second surfaces totally coincide with one another. In an embodiment, the optical axes of the first and second interferometers and the first and second lens optical axes of the first and second surfaces are adjusted to totally coincide with one another by observing the formed interferogram of each surface of the lens. In an embodiment, a first distance between the first surface of the lens and the first interferometer and a second distance between the second surface of the lens and the second interferometer are adjusted respectively to present the interfering fringes of the interferogram of the each surface of lens. In an embodiment, the optical axes of the first and second interferometers and the first and second lens optical axes of the first and second surfaces are adjusted to totally coincide with one another by observing whether the interfering fringes are formed as concentric rings and whether the concentric rings are positioned at a center of the interferogram. In an embodiment, the first and second specific relationships are identical to each other. Other objects, features and efficacies will be further understood when the following description is read with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS The above contents and the advantages of the present invention will become more readily apparent to those ordinarily skilled in the art after reviewing the following detailed descriptions and accompanying drawings, in which: FIGS. 1A and 1B are each a diagram of an arrangement of a combination of a lens of a specific type and an interferometer when the lens is measured by the interferometer according to an embodiment of the present invention; FIGS. 2A through 2D are diagrams illustrating how to obtain a relationship of optical axes of the lens and an optical axis of the interferometer according to the present invention; FIG. 3 is a diagram of a lens measuring device with a single interferometer according to a first embodiment of the present invention; FIGS. 4A through 4D are diagrams for illustrating steps of measuring decenter and tilt amounts of the lens by using the lens measuring device shown in FIG. 3 ; FIG. 5 is a diagram of a lens measuring device with dual interferometers according to a second embodiment of the present invention; FIGS. 6A through FIG. 6C are diagrams for illustrating steps of measuring the decenter and tilt amounts of the lens by using the lens measuring device shown in FIG. 5 ; and FIGS. 7A through 7E are diagrams for illustrating the decenter and tilt existing on the optical axes of the lens according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The present invention discloses a lens measuring method and device for determining decenter and tilt amounts of a lens, which will now be described more specifically by way of the following embodiments with reference to the annexed drawings. It is to be noted that the following descriptions of preferred embodiments of this invention are presented herein for purposes of illustration and description only; it is not intended to be exhaustive or to be limited to the precise form disclosed. Referring to FIGS. 1 and 2 , which are each a diagram of an arrangement of a combination of a lens of a specific type and an interferometer when the lens is measured by the interferometer according to an embodiment of the present invention. As shown, when the lens 10 A to be measured is a convex lens, the lens 10 A has to be placed within a focus range of the interferometer 20 so that interfering bands can be generated on the lens 10 A. In the case of a concave lens, the lens 10 B has to be placed outside the focus range of the interferometer 20 so that the corresponding interfering bands can be generated on the lens 10 B. Namely, each of the lenses l 0 A, 10 B has to be placed at a proper position (the position shown in FIGS. 1A and the position shown in FIG. 1B , respectively) with respect to the interferometer 20 so that the interfering bands can be generated as a reference for the measurement scheme in this invention for the lens 10 A, 10 B. Referring to FIGS. 2A through 2D , which are diagrams illustrating how to obtain a relationship of optical axes of the lens and an optical axis of the interferometer according to the present invention. When an optical axis of one of the two surfaces of the lens coincides with an optical axis of the interferometer, the interfering fringes shown in FIG. 2A , where a spherical lens is used, and FIG. 2B , where a aspherical lens is used, and which are arranged as concentric circles with a center thereof located central to the interferogram. FIG. 2C is a diagram of interfering fringes obtained when decenter or tilt is presented between the optical axes of the spherical lens and the interferometer. FIG. 2D is a diagram of interfering fringes obtained when decenter or tilt is presented between the optical axes of the aspherical lens and the interferometer. It may be known from the above description that a relationship of the optical axes of the lens and the optical axis of the interferometer can be obtained by observing the interfering fringes of the surface of lens. Therefore, the decenter and tilt amounts of the lens can be respectively known by finding a difference between the decenter and tilt amounts of the two optical axes of the lens with respect to the optical axis of the interferometer, respectively. The following will be dedicated to the lens measuring device according to the present invention. FIG. 3 shows a lens measuring device with a single interferometer according to a first embodiment of the present invention. The lens measuring device 100 comprises an interferometer 20 , a lens 10 to be measured and a platen 40 . The interferometer 20 is mounted on an adjustment base 22 on the platen 40 . The lens is mounted on the platen 40 through a lens holder 12 . On the platen 40 , there is also a sliding rail 42 through which the lens holder 12 is movable along a straight line on the platen 40 . To make it possible to measure the two surfaces of the lens 10 by the interferometer 20 , the lens holder 12 is designed to have a 180 degrees overturn mechanism so that the two optical axes of the lens 10 can be aligned with respect to the optical axis of the interferometer 20 . In addition, to make it possible to obtain the decenter and tilt amounts of the lens by comparing the optical axis of the interferometer 20 and the optical axes of the lens 10 , each of the adjustment base 22 and the lens holder 12 is provided with a tetra-axis adjustment mechanism (not shown) so that the optical axes of the lens 10 and the interferometer 20 may be adjusted when required. In operation, one of the tetra-adjustment mechanisms may be used to adjust the adjustment base 22 or the lens holder 12 in four directions, including two translational directions and two rotative directions. When the direction of the sliding rail 42 is defined as X-axis in three dimensional space, the two translational directions are Y-axis and Z-axis directions. Thus, the relationship of the optical axis of the interferometer 20 and the optical axes of the lens 10 may be represented with two translational amounts Δy and Δz and two angular amounts Δθ y and Δθ z of the adjusted one of the two tetra-axis adjustment mechanisms. Referring to FIGS. 4A through 4D , steps for measuring the decenter and tilt of a lens by using the lens measuring device with a single interferometer shown in FIG. 3 is shown therein. As shown in FIG. 4A , the lens measuring device 100 with a single interferometer is first provided and a standard planar lens 10 ′ is provided on the lens holder 12 so that a calibrating process for the interferometer 20 may be done before the measuring process for a lens begins. In the calibrating process, the lens holder 12 is caused to move on the platen 40 backward and forward. If the same interfering fringes, which are parallel, are presented before and after the lens holder 12 and thus the standard planar lens 10 ′ moves, it means that the interferometer 20 has been finished with the calibrating process with respect to the platen 40 . Next, providing the lens 10 to be measured in place of the standard planar lens 10 ′. Then, the measuring process for the lens 10 may be launched. As shown in FIG. 4B , the optical axis of the interferometer 20 is made to coincide with the optical axis of the first surface of the lens 10 by operating the tetra-axis adjustment mechanism (not shown) on the lens holder 12 . Next, the lens 10 is caused to overturn 180 degrees by using the 180 degree overturn mechanism described above. At this time, the second surface 102 faces the interferometer 20 (as shown in FIG. 4C ). At the same time, the optical axis of the interferometer 20 still coincides with the optical axis of the first surface 101 . Referring next to FIG. 4D , the optical axis of the second surface 102 is adjusted to coincide with the optical axis of the interferometer 20 by operating the tetra-axis adjustment mechanism on the lens holder 12 . At this time, translational amounts Δy and Δz and adjusted angular amounts Δθ y and Δθ z of the tetra-axis adjustment mechanism in the Y and Z directions, respectively, required to move the optical axis of the second surface 102 from the original position when the optical axis of the first surface 101 to the final position when the optical axis of the second surface 102 coincides with the optical axis of the interferometer 20 , are recorded. With the parameters of Δy, Δz, Δθ y and Δθ z , the decenter and tilt amounts δ and θ existing between the first and second surfaces 101 , 102 can be found, wherein δ=√{square root over (δ y 2 +δ z 2 )} and Δθ=√{square root over (Δθ y 2 +Δθ z 2 )}. Referring to FIG. 5 , a diagram of the lens measuring device with dual interferometers according to a second embodiment of the present invention is shown therein. The lens measuring device 200 is identical to the lens measuring device of the above embodiment except that a second interferometer 30 further included therein. The second interferometer 30 is also mounted on the platen 40 through an adjustment base 32 . Similarly, the second interferometer 30 may also be adjusted in position, for measurement reason, with translational amounts Δy and Δz and adjusted angular amounts Δθ y and Δθ z in the Y and Z directions, respectively, of the adjustment base 32 involved. Further, the second interferometer 30 may also move forward and backward on the platen 40 . FIGS. 6A through FIG. 6C are diagrams for illustrating steps of measuring the decenter and tilt amounts of the lens by using the lens measuring device shown in FIG. 5 . At first, the lens measuring device having the two interferometers 200 shown in FIG. 5 is provided and a standard planar lens 10 ′ is provided on the lens holder 12 . As such, a calibrating process like that described with respect to FIG. 4A may be conducted. Namely, the first interferometer 20 is first calibrated with respect to the platen 40 with the second interferometer 30 being ignored. Then, the second interferometer 30 is calibrated with respect to the platen 40 . In calibrating the second interferometer 30 , the second interferometer 30 has to be translated and rotated, which have to be performed by operating the adjustment base 32 . If the same interfering fringes, which are parallel, are presented before and after the standard planar lens 10 ′ moves, it means that the interferometer 30 has been finished with the calibrating process with respect to the platen 40 . At this time, it also means that the optical axes of the first and second interferometers 20 , 30 coincide with each other. After the calibrating process, the lens 10 to be measured is provided in place of the standard planar lens 10 ′ and then the measuring process for the decenter and tilt amounts of the lens is ready to be performed. As shown in FIG. 6B , the optical axis of the first surface 101 of the lens 10 to be measured is made to coincide with the optical axis of the first interferometer 20 by using the tetra-axis mechanism (not shown) on the lens holder 12 . Next, referring to FIG. 4C where the optical axis of the lens 10 to be measured is made to coincide with the optical axis of the second interferometer 30 by using the adjustment base 32 associated with the second interferometer 30 or the tetra-axis mechanism (not shown) on the lens holder 12 . At this time, translational amounts Δy and Δz and angular amounts Δθ y and Δθ z of the tetra-axis adjustment mechanism or the adjustment base 32 in the Y and Z directions, respectively, required to make the optical axis of the second surface 102 from the original position when the optical axis of the first surface 101 coincides with the optical axis of the first interferometer 20 to the final position when the optical axis of the second surface 102 coincides with the second interferometer 30 , are recorded. With the parameters of Δy, Δz, Δθ y and Δθ z , the decenter and tilt amounts δ and θ existing between the first and second surfaces 101 , 102 can be found, wherein δ=√{square root over (δ y 2 +δ z 2 )} and Δθ=√{square root over (Δθ y 2 +Δθ z 2 )}. In the above embodiments, the decenter and tilt amounts of the lens are determined by making the optical axes of the lens coincide with the optical axis of the interferometer, which is served as a measurement basis. However, those skilled in the related art may also determine the decenter and tilt amounts of the lens by setting other measurement bases. In this regard, it is intended to cover various modifications and similar arrangements included within the spirit and scope of the appended claims which are to be accorded with the broadest interpretation so as to encompass all such modifications and similar structures. While the invention has been described in terms of what are presently considered to be the most practical and preferred embodiments, it is to be understood that the invention need not to be limited to the disclosed embodiment. On the contrary, it is intended to cover various modifications and similar arrangements included within the spirit and scope of the appended claims which are to be accorded with the broadest interpretation so as to encompass all such modifications and similar structures.
A device for measuring a lens, comprising a first interferometer having a first optical axis and carried on a first adjustment base, a lens holder for holding the lens having a first surface having a first lens optical axis and a second surface having a second lens optical axis, and a platen having a sliding rail and carrying the first adjustment base and the lens holder thereon, wherein the lens holder is movable on the sliding rail, wherein each of the first adjustment base and the lens holder has a tetra-axis adjustment mechanism through which a relative positional relationship of the first optical axis of the first interferometer and the first lens optical axis of the first surface of the lens is adjustable.
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TECHNICAL FIELD The present invention generally relates to a method and a system for modulating an information signal in a telecommunication system, for code allocation in CDMA systems using codes of different bit rates. The invention also relates to a computer program used in carrying out the method of the invention. More particularly, the invention relates to a method and a system for modulating an information signal in a telecommunication system, in which spreading codes are used for discriminating between user signals, sand codes being allocated for incoming call requests by selecting them from one or more code structures having codes of different bit rates. BACKGROUND ART There exist different channel access methods for sending and receiving digital signals. In TDMA, Tire Division Multiple Access, a channel consists of a time slot in a periodic train of time intervals over the same frequency. In FDMA, Frequency Division Multiple Access, a communication channel as a single radio frequency band. Interference with adjacent channels is limited by the use of band pass filters which only pass signal energy within the specified frequency band. In contrast, CDMA, Code Division Multiple Access, allows signals to overlap in both time and frequency. Thus, several CDMA signals can share the same frequency band, but the CDMA receiver can also operate at several frequency bands. Within the CDMA technique simultaneous connections can thus make use of a common frequency band. The selection, i.e. discrimination, between the des red signal and other signals is carried out by suitable signal processing, which is based on the desired signal being coded with a different code than other signals. The radio channels in a CDMA system are thus obtained by using different codes for each channel. Typically, the channels are obtained by using binary PN code sequences. The transmitted information in the COMA radio signal is coded (spread) by a specific spreading code in the transmitter. At the receiving end, the coded information is decoded (despread) by correlating with the same specific spreading code again or by filtering the received information in a matched filter. Second generation mobile network systems, wherein CDMA is used, such as IS-95, were primarily designed for transferring speech signals. The CDMA frequency band used in such systems was limited in comparison with the wide band CDMA system, WCDMA, which will be used in the third generation mobile system, UMTS, for transferring different services with signals of a wide spectrum of bit rates, such as speech, video and other services. In WCDMA systems, user channels can be assigned binary code sequences of varying length based on the data rate of each channel. This allows for different services, e.g. speech, video, data etc. Orthogonal codes are codes that do not correlate to each other at a given time offset. Using such codes will therefore discriminate desired channels and the use of orthogonal codes will reduce the interference. Normally, the interference will not be completely eliminated as e.g. time dispersion will partly destroy the orthogonality between signals coded with orthogonal codes. Different code structures exist, in which all available codes in a system are arranged, usually after the bit rate they provide. Examples of code structure systems used in WCDMA are e.g. the OVSF, Orthogonal Variable Spreading Factor, codes, explained in the following. One way of creating OVSF codes is by means of Walsh codes of different lengths, i.e. different spreading factors. In the international patent application WO 9503652, user channels are assigned binary Walsh code sequences of varying length based on the data rate of each channel. The lowest possible order (i.e. first order) of such a code, called a root code, has a code length of one bit, and may be equivalent to “0”. A tree of Walsh sequences may be envisioned as a set of interconnected nodes each having two branches, where all of the nodes may be traced back to the root node. Then the two branches from this root node will be connected to a pair of nodes defined by Walsh sequences “00” and “01”, which are called second order codes. This process can be continued by deriving a Walsh function matrix by branching the node “00” into the nodes “0000” and “0011”, and branching the node “01,” to “0101” and “0110” which are called third order codes. The Walsh sequence defining a node of the tree branching from a given node is not orthogonal to the Walsh sequence associated with that node. Therefore, associated nodes of different orders do not discriminate channels and branch-connected codes may not be simultaneously used. Any other Walsh sequences defining nodes not connected to the given node can be simultaneously used as codes to define other mobile channels. The amount of codes to be allocated is thus restricted, as the number of available codes for a specific code length is mathematically limited. OVSF codes are downlink channelisation codes used in WCDMA that preserves the orthogonality between channels of different rates and spreading factors. The code structure of the OVSF codes are described by means of a code tree structure, which is illustrated in FIG. 1 and will be described in more detail later on. In the code tree structure services requiring codes of greater length, like speech, are to the right of the code tree, whereas more requiring services (i.e. requiring higher data rates), like video, need codes of shorter lengths as seen to the left in the code tree. In cell able to provide different kinds of services, codes of different spreading factors and rates will be requested, corresponding to different services. Prior art solutions for allocation of codes in CDMA systems, able to provide speech and other services, in which the codes to be allocated are selected systematically, do not seem to exist as far as known. If the allocation of codes is performed by just signing the first available free code without any further rules, it represents the simplest way to allocate such code requests, the so called sequential mode. Problems in using such sequential code allocation methods in wide band systems using several code levels (orders) arise upon releasing the used codes when older calls expire, which results in holes in the code structure of busy codes. Even if the maximum total bit rate available has not been reached (i.e. there are still some free codes), new high bit rate call requests might rot be satisfied unless used lower bit rate codes are reallocated in order to free a higher bit rate code of requested level. Since reallocations need signalling between the base stations and the involved mobile stations, critical situations might arise in high load conditions. In the international patent application WO 95/03652 (QUALCOMM INCORPORATED), proposing a code allocation system for wide band CDMA systems, this problem has been discussed and the idea of minimizing the number of disqualified shorter-length codes is presented. The document states the opportunity or assigning codes that are related to busy codes, in order to minimize the fragmentation of the tree and suggest to allocate slow codes that are related to unavailable fast codes. Furthermore, reallocation is presented to increase the availability of fast codes. A precise algorithm to achieve this result as, however, not presented and the problem of future availability is not taken into account. Thus, there is a need for such an algorithm,. One object of the invention is to develop a method, which minimizes the signalling in the system when allocating codes in a multi speed system. Another object is to reduce the setup delay when allocating new calls. A third object is to develop a method, which maximizes the amount of available free codes at different levels. A fourth object is to develop a method for reallocation when no free codes are available, while minimizing the need for such reallocation. A fifth object of the invention is to develop a method attaining that a minimum of higher-rate codes become unavailable by using an algorithm to carry out the allocation of the invention. SUMMARY OF THE INVENTION The method and system of the invention is characterized by steps and means, respectively, for noting the bit rate of a code to be allocated for an incoming request, determining the availability of the different codes having the desired bit rate, and allocating a code in accordance with pre-selected rules by taking the availability of the different codes into consideration in a way leading to an optimal use of the code structure. The apparatus of the invention comprises means for performing the method of the invention. The algorithm of the invention performs the allocation method of the invention in form of a computer program in accordance with certain rules. The codes allocated for a given service request also depend on the traffic situation, the number of available codes and the requested bit rate of the code. A condition for the allocation of the code is that the traffic situation allows the allocation so that the maximum transfer capacity of the system is not exceeded. If a code system with available transfer capacity is not available, the incoming request has to be blocked. If only one free code of the requested level exists, that code is allocated for the request. If more than one free code of the requested level exist, the algorithm of the invention used for allocation of the codes, chooses the code to be allocated in accordance with pre-selected rules prioritizing some codes in front of others. If there, however, does not exist any free codes of the requested level but there are enough transfer capacity left in the system for a specific service request (some free codes), the reallocation algorithm of the invention performs a reallocation of already assigned codes to get a free code of the requested level. The incoming request is in this case assigned to a code, which is unavailable because of used related longer length codes. The reallocation of these used and already assigned codes is then carried out according to the sane rules as the allocation of a code for a new incoming request. The incoming request can be any service, used in a WCDMA system, for example speech, data, video etc. By means of the invention, an algorithm can be indicated, that, given an offered traffic statistics, minimizes the number of cases in which reallocation is needed in order to assign new codes or the total number of changes of already allocated codes. Consequently, the total signalling in the system will be decreased. In the following the invention is described by means of a block diagram and examples. The rules according to which some codes are prioritized in front of others are explained by means of the block diagram and the examples. The invention is, however, not restricted to the details of the following description, which is presented for illustrative purposes only. The idea of the invention, which is defined in the claims, can e.g. be extended to other code system, structures defining different levels of codes than the OVFS code tree, even if this particular structure is described in the Figures. BRIEF DESCRIPTION OF DRAWINGS The invention will now be described more closely with reference to the drawing, in which FIG. 1 illustrates an example of an OVSF code tree structure, FIG. 2 is a flow diagram illustrating steps of the invention, FIG. 2 b is a block diagram illustrating system sections, and FIGS. 3-7 illustrate application of the algorithm of the invention in different hypothetical situations. DETAILED DESCRIPTION QVSF codes are defined by a code structure illustrated in FIG. 1 . Each node of the tree corresponds to a code, the spreading factor (SF) and bit rate of which are defined by its SF level 1, 2, 4, 8 or 16. The code levels may also, below, generally be referred to as levels k to make the following description easier. The relationship between SF-levels and k-levels will then be such that SF-levels 1, 2, 4, 8 ard 16 correspond to k-levels 0, 1, 2, 3, 4 respectively. A code of a given level has a given length and thus corresponds to a given spreading factor and a given bit rate. The node representing the lowest SF-level, highest bit rate, and lowest k-level, is called the root, i.e. the node to the very left in FIG. 1 . One code is free, and can be assigned to an incoming call, if no code in its subtree, i.e. the subtree to which the code in question may be regarded as root, and in the branch that leads from it to the tree root, is busy. It is possible to define different levels of occupation for one code (node) A code can be busy, unavailable or free, depending on the degree of occupation. A code is busy, if the code itself, or a higher bit rate code in the path from the code to the root, already has been assigned to a downlink connection. A busy code is said to be used if it is directly assigned for a downlink connection. A code is unavailable, if one or more codes in the subtree of the code are busy. An occupation or unavailability level can be defined in this case as the fraction of the total bit rate of the subtree assigned to used codes. If the whole subtree is used, the fully unavailable code can be considered busy. All remaining codes, which are neither busy nor unavailable are free. A shorter length, or higher bit rate code from which two codes of double length descend may here be called father of these codes and the descendant codes may be called sons. Codes having the same father are brother codes. The code tree structure should be understood to imply that services requiring longer length codes, like speech, are located on the right hand side of the code tree, whereas more requiring services, like video, needing codes of shorter lengths, i.e. higher bit rates, are on the left hand side of the code tree. In order to fully appreciate nd understand the description with reference to the drawings, given further below, some shortcomings of prior art, as well as the way used by the invention to eliminate these, will be summarised in short as follows. Problems with allocation arise as older calls expire, releasing the used codes and determining holes in the tree of busy codes. Ever if the maximum total bit rate has not been reached, in such a situation new high bit rate call requests might not be satisfied unless busy codes are reallocated in order to free a subtree of suitable level. Since reallocations need signalling between the RS and the involved MSs, their number should be kept as low as possible, in order to avoid critical situations in high load conditions. The invention is based on the realisation that, as seer against the above given background, it would be of interest to indicate an allocation algorithm that, given an offered traffic statistics, minimizes the number of cases in which reallocation is needed in order to assign new codes. In the same way, once reallocation is decided, it is worth finding an algorithm that minimizes the number of total actual code changes. In accordance with the invention this new algorithm for code allocation aims at preserving the highest possible number of higher level available codes. In case of multiple choices, codes maximizing the probability, of future release of a higher level code are preferred. The algorithm is based on the following rules. Assume one code of level k has to be allocated, where k=log 2 (SF) is the base 2 logarithm of the Spreading Factor. The code to be assigned is obviously belonging to the set of free codes of level k. In this set, the codes whose father's uravailability level is higher should be preferred. This defines a new subset in which the suitable codes should be found. If more than one code exists in that set, the unavailability level of the grand-father codes, i.e. fathers of fathers should be checked, and once again higher Figures be preferred. The procedure should end when one set is found including only one code, or when the root code is reached. In that last case the first code in the resulting set will be chosen. If the incoming call leads to exceed the maximum total bit rate of the root code it shall be blocked or assigned to another code. In CDMA this can be provided by another scrambling code assigned to the If the maximum total bit rate is not exceeded, and no level k free code exists, reallocation is needed. The easiest way to reallocate consists in finding the first suitable code (not fully unavailable, busy or with busy ancestors) ard allocate it to the new call. Busy codes within its subtree will then be allocated as usual incoming calls by the allocation algorithm. The proposed reallocation algorithm does more: it aims at minimizing the number of needed reallocations, defined as changes of ongoing connections assigned codes, equivalently as number of removed codes to be reallocated as a consequence of the reallocation procedure. As a first step, the new request should be assigned to an unavailable, but not busy code. Once this code is marked as busy (used), its used descendants have to be reallocated. This operation is logically preceding the actual allocation, since only free codes should be allocated to incoming calls. The preferred code for the new allocation is the one that presents the lowest number of used codes in its subtree, i.e. the lowest number of descendants, which will assure a low number of reallocations. If more than one subtree presents the sane minimum number of assigned codes, the one with lowest unavailability level should be preferred in order to have to move lower bit-rate codes, that have a higher probability to fit in the tree without needing further reallocations. Actual reallocations of the subtree codes (codes handovers) are then performed following the same rules that apply or a new incoming call: if free codes of the corresponding level exist, according to the allocation algorithm, if no free code exists, according to the reallocation algorithm. Since codes are reallocated through the same method as used for allocation, they could in turn trigger further nested reallocation procedures, and so on. At should be noticed that through allocation and reallocation a new code request can always be satisfied, unless it exceeds the total capacity of the tree (in term of bit rate). FIGS. 2 and 2 b are a flow diagram and a system block diagram, respectively, for illustrating the principle of the invention. In step 1 an incoming request for allocation of a code for a spread information signal is received in a system section 12 for receipt of new call requests. In step 2 there is noted, in a system section 13 for noting code level of call request, a desired level k, or desired bit rate, for the signal code. The code of lowest level, i.e. the root code of the code tree, typically used in a cell of a cellular radio system, defines a total maximum transmission capacity for that cell, which should not be exceeded. Exceeding the total maximum bit rate would result in non-orthogonality between some codes and their consequent degradation. Call requests are blocked or assigned to additional code trees if the total already used bit rate plus the arriving call bit rate exceeds the total tree bit rate. In step 3 there is determined, in a system section 14 for determining excessive bit rate of new request, whether allocation of a code for the incoming request would exceed the maximum total bit rate of the root code of the code tree. If yes, a system section 15 in step 4 performs blocking of the request or assignment thereof to another code tree, if available in the system. If no, i.e. it is considered in step 3 that the maximum total bit rate is not exceeded, the flow proceeds to step 5 and a system section 16 for determining free codes of requested level. In step 5 there is thus determined whether there exist free codes of a desired level k. If no, reallocation is needed by assigning, by a system section 17 , in step 6 , a new request to an unavailable code of requested level. For this purpose, step 7 and system section 18 reallocates related higher level code(s) to release the unavailable code. In other words, the already assigned subtree codes relating to the unavailable code have to be changed to release the code of desired level k. The flow then returns to step 5 and system section 16 . In the reallocation procedure of the invention, the incoming request should be assigned to a preferred unavailable, but not busy, code in accordance with pre-selected rules, after which the used codes in its subtree have to be reallocated. The reallocation is preferably done by an algorithm which aims at minimizing the number of needed reallocations. These reallocations are defined as changes of the assigned codes of connections in progress, or equivalently as the number of removed codes to be reallocated as a consequence of the reallocation procedure. According to one embodiment of the present invention, the preferred unavailable code assigned by system section 17 in step 6 should be the one that has the lowest number of assigned codes n its subtree, i.e. the lowest number of related higher-level k codes, to prepare for a low number of reallocations, i.e. changes in the assigned codes in connections in progress. According to another embodiment, the preferred unavailable code might also be the one that has the lowest unavailability with respect to its subtree. The best mode, in which the preferred unavailable code is the one that has the lowest number of assigned codes in its subtree, minimizes the number or cases in which reallocation is needed. Reallocation of the subtree codes is then performed following the rules that apply for a new incoming request in accordance with steps 5 - 11 , i.e. if free codes of the corresponding level exist, the allocation algorithm should be used, whereas, if no free code exists, the reallocation algorithm should be used. If it is considered by system section 16 in step 5 that there is one free code of requested bit rate, that code will be allocated. If there exist more free codes of the desired level, step 8 in a system section 19 determines the availability degree for the codes of the requested level. In order to select a code, step 8 is followed by step 9 in which prioritizing of code(s) is performed by a system section 20 for prioritizing in accordance with pre-selected rules. According to these rules, the highest possible number of lower level k available codes is preserved in step 10 . Ir case several choices exist, probability of future release of a lower level code will be maximized in step 11 by a system section 22 . This can be performed in accordance with pre-selected rules as in step 9 . The prioritizing of codes preserving the highest number of free codes on lower levels in step 10 may e.g. be performed by defining a set of available codes having fathers with highest unavailability levels, and by repeating the preceding step for code levels of successively earlier generations until the root code has been reached, and finally choosing the code from the resulting subset. It should be noted that through allocation and reallocation a new code request can always be satisfied, unless it exceeds the total capacity of the tree in term of bit rate. EXAMPLES In the following examples 1-5, the invention is explained in connect on with some typical situations (cases 1-4). In all of FIGS. 3-7 , black circles represent used codes, while light grey ones represent busy, but not used codes. A code is used if a request has been assigned to it. It car be busy without being used if one or its ancestors is used. EXAMPLE 1 (Present Availability, Case 1) FIG. 3 presents a hypothetical situation, wherein OVSF codes are allocated for incoming requests. Five levels k of codes, said levels being numbered as 0, 1, 2, 3 and 4, are indicated in FIG. 3 . Free codes in the highest level are identified by capital letters A-M. An incoming request of level k=4 of the code tree of FIG. 3 , according to steps 1 and 2 of FIG. 2 is now assumed. If the maximum total bit rate or the transfer capacity or the code tree is not exceeded, as determined in step 3 , and there are free codes of the requested level as determined by step 5 , the algorithm of the invention considers, in step 8 , the unavailability level of each free code's father. The result thereof is that the unavailability level is ½ for C and zero for all the remaining free codes. This means that C will be chosen for assignment to achieve the aim in accordance with which the highest possible number or lower level available codes should be preserved as selected by step 10 . This is the best solution in term of resulting free higher bit rate codes, which, in FIG. 3 , is free codes on level k=3, 2 free codes on level k=2, 1 free code on level k=1. For the remaining possibilities to choose a higher level k code among F-M, there are 5 free codes on level k=3, 1 free code on level k=2 and 1 no free code on level k=1. For assignments A-B, there are 5 free codes on level k=3, 2 free codes on level k=2 ard 1 free code on level k=1. EXAMPLE 2 (Future Availability, Case 2) FIG. 4 presents another hypothetical situation, wherein OVSF codes are allocated for incoming requests. Five levels k of codes numbered as 0, 1, 2, 3 and 4 are indicated. Free codes in the highest level k are identified by capital letters A-E. An incoming request of level k=4 is assumed according to steps 1 and 2 of FIG. 2 . If the maximum bit rate or the transfer capacity of the code tree is not exceeded as determined by step 3 and there are free codes of the requested level as determined by step 5 , the availability degree for the free codes are determined by step e. The OVSF tree of FIG. 4 presents 5 free codes on level k=4, which are A, B, C, D and E. Codes C and D have a free father (zero unavailability), so they should be discarded to leave as much higher bit rate codes free as possible as selected by step 10 . Codes A, B and E have “half” unavailable fathers, and therefore the algorithm considers their grand-father's unavailability, which is for codes A and E and ½ for code B. This last should then be discarded by step 10 . Next, great grand-fathers (level k=1) should be considered. The ancestor of code A has unavailability 4/8, while the ancestor of code E has unavailability 7/8. Code E should then be allocated to the incoming request by step 11 . It is worth noting that codes A, B and E are equivalent from a higher level code availability point of view, in the sense that the same number of higher level free codes results from each assignment. In a preferred embodiment of the invention the allocation of a code is performed by step 11 by maximizing the probability of future release of a lower level code. The difference between codes A, B and E thus concerns the probability of a short term release of a presently unavailable lower-level code, that is maximized through the proposed choice by step 11 . EXAMPLE 3 (Reallocation, First Embodiment, Case 3) FIG. 5 presents still another hypothetical situation, wherein OVSF codes are allocated for incoming calls. An incoming request of level k=1 is row assumed to be allocated in steps 1 and 2 of FIG. 2 . If the maximum total bit rate or the transfer capacity of the code tree is not exceeded, as determined by step 3 , the availability degree of the codes of requested level is determined in step 5 . Since according to this analysis no free codes are available, a reallocation algorithm is performed according to which one of the two unavailable codes, viz. A or B, has to be chosen by step 6 to be assigned for the incoming request. Code A has two used descendants, D and E of level k=4, while code B has only one used son, C of level k=2, so code B is preferred according to the rule of the present invention saying that reallocation should be performed by minimizing the number of changes of already allocated codes and that the preferred unavailable code is the one that has the lowest number of assigned related higher-level codes. Once the choice of code B is done, the higher level code C has to be reallocated. The new situation is shown in FIG. 6 . The reallocation request for performing the reallocation of code C of level k=2 is treated as an incoming request, viz. request from step 7 to step 5 in FIG. 2 . Since no free codes are available, once again the reallocation procedure is triggered, and one of the two unavailable level k=2 codes is chosen, indifferently in this case, since they have the same unavailability. One of the related level k=4 codes then has to be moved away from the subtree of the assigned code, and in turn be allocated as an ordinary incoming request. In this last assignment the reallocation of one of the level k=4 codes is performed so that they both are in the same subtree with respect to level k=2, which is not related to the reallocated code C, and preferably also in the same subtree with respect of k=3 to leave an extra level k=3 code free. EXAMPLE 4 (Reallocation, Second Embodiment, Case 3) Instead of using the reallocation method of example 3, a different reallocation procedure is used for the same situation as in example 3. The reallocation now assumed chooses the lower unavailability level subtree. The unavailability for A is 2/8 and for B ½ (FIG. 5 ). In that case, code A would be chosen instead of code B, leading to no additional reallocation steps in addition to the reallocation of codes D and E. However, two code changes (reallocations) would hare been needed, just as in the previous case, so assuming that indirect reallocation procedures do not determine additional setup delay (this assumption is justified by the possibility the base station has to perform internally all needed reallocation, and jest at the end issue the actual code change commands to involved mobile stations), the performance of the two reallocation algorithms in the above examples 3 and 4 is the same. EXAMPLE 5 (Second Embodiment, Case 4) The second embodiment of the reallocation method of the invention is now used for the situation in FIG. 7 . As the allocating according to this embodiment is performed depending on the unavailability levels instead of the bare unweighted number of allocated codes as was done in the first embodiment in example 3, we would choose once again code A instead of B, for its unavailability level 3/8 is lower than that of code A having the unavailability level ½. Indeed, this is not the better choice in this situation, since it determines three code changes (changing of codes D, E and F in FIG. 7 ), while only two would be needed choosing code B, i.e. using the proposed, bare number of codes based, algorithm according to the first embodiment. The intention of two above examples is to illustrate how the proposed algorithm works, based on the number of used codes in the subtrees and to show that a possible alternative algorithm (based on the unavailability level of the subtrees instead) that performs in the same way in the situation depicted in example 3 may lead to additional unneeded code changes in other cases, such as in example 4. A satisfactory solution is to choose the subtree with the lowest number of used codes and if more than one subtree has the same lowest number of used codes, choosing among that subset the one that has the lowest unavailability level. Performance Evaluation Simulations have been carried out to evaluate the improvement in code allocation performance of the proposed solution of the invention. Different services have been considered, with Spreading factors ranging from 4 (384 kbps LCD (Long Constrained Delay Data) and 2048 kbps UDD (Unconstrained Delay Data)) to 128 (8 kbps Speech). Offered traffic statistics during simulation time (10000s) are reported in table 1. Five different combinations of allocation and reallocation algorithms have been tested with the same offered traffic conditions. In the following the solution of the invention is called “proposed” and the solution of prior art is caller “sequential”, referring to the sequential code allocation methods of the price art referred to in the section “Background Art”, Tables 2, 3, 4 and 5 show the simulation results (service by service) respectively using sequential allocation and reallocation, sequential allocation and proposed reallocation, proposed allocation and sequential reallocation, proposed allocation and reallocation. In the method of the sequential allocation, the first free available code is assigned without any further rules. In the first column, the number of allocations blocked due to lack of free space in the tree is reported. The number of requests that can be satisfied, eventually by reallocation follows. Since each request is served if and only if there is theoretical room in the tree (regardless of how free codes are distributed), and the offered traffic is the same (the same seeds for its random generation have been used), the number of blocked and admitted calls is the same for all cases. The simulations for the different algorithms were performed in the same conditions, not just statistically speaking, but in the same punctual conditions of tree operations. In the third column, the number of reallocations procedures can be found. Finally, in the fourth column, the total reallocations needed are presented. The number of reallocation procedures represents how many times a new code request could not be satisfied picking up directly one free code from the tree, and a call to the reallocation algorithm was therefore unavoidable. Keeping constant all other parameters, this value decreases as the performance of the allocation procedure improves. From a system point of view, the number of reallocation procedures determines an average setup delay for the incoming calls due to the need for code changes. On the other hand, assuming that all code changes can be performed simultaneously, the number of total reallocations is proportional to the generated signalling overhead. Tables 6 and 7 show the comparisons in terms of number of reallocation procedures and total reallocations using the different algorithm combinations. The improvement provided by the proposed algorithms is evident in term of both avoided reallocation procedures (and thus lower average setup delay) ard avoided code changes (and thus lower signalling overhead). The solution of the invention, when both the allocation and reallocation is performed by using the algorithms of the invention, (P.A.P.R. is used) provides a decrease of the reallocation procedure of 45% (from about 4500 to about 2500), and correspondingly a decrease of the code charges of 74% (from about 13500 to about 3500) with respect to the sequential allocation and reallocation case of prior art. The proposed allocation and reallocation algorithms of the invention determine the decrease to about one fourth of the number of code changes in a loaded system (compared to the simple sequential procedures of prior art), correspondingly reducing the involved signalling messages. This can be seen in table 8, comparing S.A.S.R. (total 13487) with P.A.P.R. (total 3507). In the sane way, the number of reallocation procedures needed is almost reduced to a half, with positive impacts on setup delays due to code changes. The cost of the solution of the invention is likely to be represented only by a slight increase on the computational complexity needed at the base station as the base station anyway has to use some algorithm for the code allocation. TABLE 1 Per service offered traffic statistics. Sym. rate Arrival Mean st. k SF [kbps] Service rate [s −1 ] time [s] 0 1 4096 LCD 2048 (4 k = 2 codes) — — 1 2 2048 — — — 2 4 1024 LCD 384-UDD 2048 0.0125 10 3 8 512 UDD 384 0.025 10 4 16 256 LCD 144 0.1 10 5 32 128 UDD 144 0.4 10 6 64 64 LCD 64-UDD 64 1.6 10 7 128 32 Speech 6.4 10 8 256 16 CCPCH — — TABLE 2 Sequential allocation and reallocation (S.A.S.R.). Blocked Admitted Reallocation Total K SF Requests Requests Procedures Reallocations 2 4 105 7 7 — 3 8 142 106 99 — 4 16 288 714 610 38 5 32 535 3426 1779 458 6 64 1065 14875 1951 1839 7 128 2073 62091 — 11152 Total 4208 81219 4446 13487 TABLE 3 Sequential allocation and proposed reallocation (S.A.P.R.). Blocked Admitted Reallocation Total K SF Requests Requests Procedures Reallocations 2 4 105 7 6 — 3 8 142 106 91 — 4 16 288 714 438 29 5 32 535 3426 1234 306 6 64 1065 14875 1798 1118 7 128 2073 62091 — 2925 Total 4208 81219 3567 4378 TABLE 4 Proposed allocation and sequential reallocation (P.A.S.R.). Blocked Admitted Reallocation Total K SF Requests Requests Procedures Reallocations 2 4 105 7 7 — 3 8 142 106 92 — 4 16 288 714 382 39 5 32 535 3426 973 443 6 64 1065 14875 1265 1742 7 128 2073 62091 — 3737 Total 4208 81219 2719 5961 TABLE 5 Proposed allocation and reallocation (P.A.P.R.). Blocked Admitted Reallocation Total K SF Requests Requests Procedures Reallocations 2 4 105 7 7 — 3 8 142 106 93 — 4 16 288 714 389 23 5 32 535 3426 896 263 6 64 1065 14875 1049 679 7 128 2073 62091 — 2542 Total 4208 81219 2434 3507 TABLE 6 Simulation results - Number of reallocation procedures. Reallocation Procedures k SF S.A.S.R S.A.P.R. P.A.S.R. P.A.P.R. 2 4 7 6 7 7 3 8 99 91 92 93 4 16 610 438 382 389 5 32 1779 1234 973 896 6 64 1951 1798 1265 1049 7 128 — — — — Total 4446 3567 2719 2434 TABLE 7 Simulation results - Total number of reallocations. Total Reallocations k SF S.A.S.R S.A.P.R. P.A.S.R. P.A.P.R. 2 4 — — — — 3 8 — — — — 4 16 38 29 39 23 5 32 458 306 443 263 6 64 1839 1118 1472 679 7 128 11152 2925 3737 2542 Total 13487 4378 5961 3507
The invention is concerned with a system for modulating an information signal in a telecommunication system. The communication system makes use of spreading codes in the modulation to discriminate between user signals. The codes are allocated for incoming requests by selection from one or more code structures having codes of different bit rates. The system is characterized by the steps of noting the bit rate of a code to be allocated for an incoming request, determination of the availability of the different codes having the desired bit rate, and allocating a code in accordance with pre-selected rules by taking the availability of the different codes into consideration in a way leading to an optimal use of the code structure(s). The apparatus of the invention comprises means for performing the system of the invention. The algorithm of the invention performs the allocation system of the invention in from of a computer program in accordance with certain rules.
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CROSS-REFERENCE TO THE RELATED APPLICATION(S) [0001] The present application is based upon and claims priority from prior Japanese Patent Application No. 2007-015299, filed on Jan. 25, 2007, the entire content of which are incorporated herein by reference. TECHNICAL FIELD [0002] The present invention relates to a game system in which a plurality of stations each having a second display unit is installed. BACKGROUND [0003] An example of conventional multi-player games, such as poker games which use cards or the like, is disclosed in WO-A1-97026061. An example of multi-player-tournament games is disclosed in WO-A1-00071218. An example of game systems for providing award to players through a network in gambling is disclosed in WO-A1-02041233. [0004] In a game in which a plurality of players participates, facial expressions of other players have an effect on psychology of players and are considerable factor in playing the game. However, when the players play the game side by side, it is difficult to directly recognize the facial expressions of other players visually. Accordingly, it is difficult to guess whether the game proceeds to be advantageous to other players, and thus it is difficult to set up a strategy, and thereby amusement in the game becomes insufficient in terms of tactically playing the game. [0005] In addition, since other players' faces cannot be seen, a player cannot have a realistic feeling that the player competes with other players, and enjoyment of participating in a multi-player game cannot be acquired sufficiently. SUMMARY [0006] One of objects of the present invention is to provide a new entertaining feature that cannot be provided by using the conventional technology. In particular, one of objects of the present invention is to provide a game system capable of increasing enjoyment of tactical play in a game and enjoyment of participating in the game. [0007] According to one aspect of the invention, there is provided a game system that provides a game in which a plurality of players participate, the game system including: a plurality of stations that are provided for each of the players to play the game; a plurality of camera devices that are respectively provided in each of the stations and capture facial images of the respective players; a plurality of display units that are respectively provided in each of the stations and display images related to the game; and a controller that operates to: control at least one of the camera devices to capture the facial images; and control at least one of the display units to display the facial images captured by the camera devices. BRIEF DESCRIPTION OF THE DRAWINGS [0008] In the accompanying drawings: [0009] FIG. 1 is a diagram showing an example of an image displayed on a liquid crystal display included in a station of a game system according to an embodiment of the present invention; [0010] FIG. 2 is a schematic perspective view showing the appearance of a game system according to the embodiment; [0011] FIG. 3 is a schematic top view of a game system according to the embodiment; [0012] FIG. 4 is a schematic perspective view showing the appearance of a station included in a game system according to the embodiment; [0013] FIG. 5 is a diagram showing an example of an image displayed on a front display; [0014] FIG. 6 is a block diagram showing the internal configuration of a game system according to the embodiment; [0015] FIG. 7 is a block diagram showing the internal configuration of a station according to the embodiment; [0016] FIG. 8 is a flowchart showing a game process according to the embodiment; [0017] FIG. 9 is a flowchart showing a game process according to the embodiment; [0018] FIG. 10 is a flowchart showing a subroutine for a process of transmitting a command for receiving a selection which is performed by a main control unit; [0019] FIG. 11 is a flowchart showing a subroutine for a selection information receiving process which is performed by a main control unit; [0020] FIG. 12 is a flowchart showing a subroutine for a process of displaying the face image of a designated player which is performed at regular time intervals by the station and the main control unit, independently of the game process shown in FIGS. 9 and 10 ; and [0021] FIG. 13 a perspective view showing the appearance of a game system according to another embodiment. DETAILED DESCRIPTION [0022] Embodiments of the present invention will now be described with reference to the accompanying drawings. [0023] FIG. 1 is a diagram showing an example of an image displayed on a liquid crystal display included in a station of a game system according to the embodiment. FIG. 2 is a schematic perspective view showing the appearance of a game system according to the embodiment. FIG. 3 is a schematic top view of a game system according to the embodiment. FIG. 4 is a schematic perspective view showing the appearance of a station included in a game system according to the embodiment. [0024] As shown in FIG. 1 , on the upper side of a liquid crystal display 10 included in a station 3 of a game system 1 (see FIG. 2 ) according to the embodiment, ten player face image display sections 76 are arranged. Alphabets of A to J displayed in the player face image display sections 76 correspond to stations 3 a to 3 j (see FIGS. 2 and 3 ) of the game system 1 . In each player face image display section 76 , a face image (hereinafter, also referred to as a face image) of a player using a corresponding station 3 is displayed. For example, in the player face image display section 76 of “A”, a face image of a man currently participating in the game is displayed. Although, in the player face image display sections 76 of “C” to “J”, the same types of face images as displayed in the player face image display section 76 of “A” are displayed, however, in FIG. 1 , the face images are omitted. In the embodiment, the face image of a player playing the game in a station 3 is not displayed in the player face image display sections 76 of the station. For example, FIG. 1 shows the liquid crystal display 10 of the station 3 b , and the face image of a player is not displayed in the player face image display section 76 of “B” corresponding to the station 3 b. [0025] In the game system 1 , faces of players playing a game in the stations 3 are captured by using cameras 16 (see FIGS. 2 and 4 ) installed to the stations 3 and the acquired images are displayed in the player face image display sections 76 of the liquid crystal display 10 of each station 3 . [0026] In the embodiment, the images captured by the cameras 16 are motion pictures. As long as a game is played in two or more stations 3 , image capturing operations performed by the cameras 16 installed to the stations 3 in which the game is played are continuously performed. In particular, from a time when coins are inserted into the station 3 to a time when all the coins are paid out or consumed in the station 3 , an image capturing operation performed by the camera 16 installed to the station 3 is performed. The image acquired by the image capturing operation is immediately displayed in the player face image display sections 76 of the liquid crystal display 10 . In addition, when it is a predetermined timing (in the embodiment, in a Hold'em Poker game, when Flop, Turn, or River, to be described later, is displayed), the face image data acquired by the image capturing operation is stored in a RAM 42 (see FIG. 6 ), to be described later. [0027] The liquid crystal display 10 serves as a second display unit according to the present invention. [0028] In an approximate center of the liquid crystal display 10 on the lower side, a special face image display section 77 is arranged. In the special face image display section 77 , the face image of a player who satisfies a predetermined condition (in the embodiment, a condition that a raise is made in Hold'em Poker) in the game is displayed in an enlarged size. In the embodiment, in the special face image display section 77 of the station 3 in which the player satisfying the predetermined condition plays the game, the face image of the player is not displayed. [0029] In the special face image display section 77 , the face image of a player designated by the player playing the game in the station 3 may be displayed. In the right end of the liquid crystal display 10 on the upper side, a player selection section 78 for selecting a player whose face image is to be displayed is arranged. The player can select a player whose face image is to be displayed by using a touch panel 11 (see FIG. 4 ) disposed above the liquid crystal display 10 . [0030] When an operation for selecting a player whose face image is to be displayed is performed, the face image of the selected player is displayed on the special face image display section 77 on the basis of the face image data stored in the RAM 42 . [0031] Next, the game system 1 according to the embodiment will be described. [0032] As shown in FIG. 2 , two main displays 2 are disposed in back-to-back arrangement in the game system 1 . Each main display 2 has a front display 21 on which information on the game (hereinafter, also referred to as game information) and the like are displayed, speakers 22 that are disposed above the front display 21 and output music or effect sounds in accordance with progress of the game, and LEDs 23 that are turned on for providing various visual effects. [0033] As shown in FIGS. 2 and 3 , ten stations 3 (in a counter clockwise direction from the lower left end in FIG. 2 , referred to as a station 3 a , a station 3 b , . . . , a station 3 i , and a station 3 j ) are disposed in the game system 1 so as to surround two main displays 2 . The description of “being disposed to surround a main display” means that a plurality of stations are installed in a range (there may be a discontinued portion) covering larger than 180 degrees to the left and right sides of the main display in which the display screen of the main display can be viewed. When two main displays are arranged in back-to-back arrangement as in the embodiment, a case where the main displays are interposed between pluralities of stations and each plurality of stations is installed in positions in which one of the display screens of the main displays can be viewed is included in the description of “being disposed to surround the main display”. [0034] According to an embodiment, the number of the stations may be two or more and is not limited to ten. [0035] As shown in FIG. 4 , on the inner side of the upper face of the station 3 , a camera 16 used for capturing an image of a player's face is disposed. [0036] In front of the camera 16 , a liquid crystal display 10 for displaying an image (see FIG. 1 ) relating to an operation, the result of a game, or the like is disposed. [0037] On the upper side of the liquid crystal display 10 , a touch panel 11 for a player to input an operation is disposed. [0038] In front of the liquid crystal display 10 , an operation button 12 for performing a payout operation and a coin insertion slot 13 for inserting a coin or medal is disposed. [0039] In the upper right end of the front side of the station 3 , a bill insertion slot 14 for inserting a bill is disposed. Below the bill insertion slot 14 , a coin payout opening 15 for paying out a player coins or medals corresponding to stored credits in a case where a payout operation is performed is disposed. [0040] In the game system 1 , Hold'em Poker is performed as a game. [0041] Here, the Hold'em Poker rule will be described. [0042] In Hold'em Poker, one set (52 cards) of playing cards excluding Joker is used. [0043] First, a dealer deals two cards to each player. Each player refers to the cards dealt to him and selects one behavior among betting chips (hereinafter, also abbreviated as “bet”), betting chips of the same amount as the former player (hereinafter, referred to as “call”), raising the bet amount (hereinafter, also referred to as “raise”), and completing a game without placing a bet (hereinafter, also referred to as “fold”). Hereinafter, this selection is called as a bet selection. [0044] Next, the dealer opens three cards (called “Flop”) from among his holding cards. In the game system 1 according to the embodiment, the Flop is display on the front display 21 , as described below. Here, each player performs a bet selection. [0045] Next, the dealer opens a fourth card (called “Turn”). Then, each player performs a bet selection. [0046] Next, the dealer opens a fifth card (called “River”). Then, each player performs a bet selection. [0047] Next, all the cards (cards dealt first) held by players remaining in the game are open (called Showdown), and each player makes a hand by combining two holding cards and three cards from among five cards of the dealer. All the bet chips are given to a player who has made the strongest hand by comparing the hands of the players. [0048] When the hands in Hold'em Poker are arranged in the order of their strength, there are royal flush, straight flush, four cards, full house, flush, straight, three cards, two pairs, one pair, and no pair. [0049] Next, images displayed on the front display 21 and the liquid crystal display 10 during a game will be described. [0050] FIG. 5 is a diagram showing an example of an image displayed on the front display. [0051] As shown in FIG. 5 , in an approximate center of the front display 21 , a dealer 30 is displayed. [0052] Below the dealer 30 , a table 31 is displayed. On the table 31 , five card images 32 representing five cards and a chip image 33 representing bet chips are displayed. [0053] In addition, below the table 31 , game information display sections 35 in which face images and game information of the players are displayed are arranged. Alphabets of A to J displayed in the game information display sections 35 correspond to stations 3 a to 3 j , and the face image of a player in the corresponding station 3 is continuously displayed in each game information display section 35 . In each game information display section 35 , the game information is displayed. The game information includes the number of bets, which have been placed until now, of each player and information on the bet selection. In addition, when a Showdown process is performed, cards dealt first to the players are displayed in the game information display sections 35 by replacing the face images. [0054] When there is a station 3 that is not used for the game, game information on a player who has a turn to perform a bet selection is displayed in the game information display section 35 corresponding to the station 3 . [0055] In the left end of the upper portion of the front display 21 , an enlarged face image displaying section 36 is arranged. In the enlarged face image displaying section 36 , the face image of a player who has a turn to receive a card or make a bet selection is displayed in an enlarged size. [0056] In the right end of the upper portion of the front display 21 , a pot display section 34 for displaying the total amount of chips currently bet is arranged. [0057] In the embodiment, although an image displayed on one front display 21 between the front displays 21 of two main displays 2 is configured to be the same as an image displayed on the other front display 21 , it may be configured that different images are displayed on the two front displays in accordance with the progress of a game. [0058] Although the face images of all the players participating in the game are configured to be continuously displayed on the front display 21 in the embodiment, the method of displaying the face images is not limited thereto. For example, the face images may be configured to be displayed only at a predetermined timing (for example, when a bet selection is made or a card is dealt) or when a predetermined condition (for example, when the amount of the pot exceeds a predetermined amount or a raise of an amount equal to or greater than a predetermined amount is made) is satisfied. In addition, for example, only the face image of a player who has a turn to receive a card or make a bet selection may be configured to be displayed, or only the face image of a player who satisfies a predetermined condition (for example, a player who makes a raise) is satisfied may be configured to be displayed. The position for displaying the face image is not limited to the example shown in FIG. 5 . [0059] Next, the image displayed on the liquid crystal display 10 will be described in detail with reference to FIG. 1 . [0060] As shown in FIG. 1 , on the upper side of the liquid crystal display 10 , ten player face image display sections 76 are arranged. In the player face image display sections 76 of each station 3 , face images of players captured by the cameras 16 installed to stations 3 other than the station 3 are displayed. [0061] In the left end of the lower portion of the player face image displaying section 76 , two card images 70 representing two cards dealt to the player at the start of the game are shown. [0062] Below the card images 70 , a bet display section 71 for displaying the current number of bets of the player is arranged. [0063] In an approximate center portion of the liquid crystal display 10 on the lower side, a special face image display section 77 for displaying the face image of a player who satisfies a predetermined condition (in the embodiment, a condition that a raise is made in Hold'em Poker) in the game or the face image of a player designated by the player playing the game in the station 3 is arranged. [0064] In the right end of the liquid crystal display 10 on the upper side, a player selection section 78 for selecting a player to be displayed in the special player face image display section 77 is arranged. The player can designate the player whose face image is to be displayed by touching a portion on the touch panel 11 corresponding to an alphabet of a station 3 in which the player whose face image is wanted to be displayed plays the game. [0065] The touch panel 11 serves as an input device according to the present invention. [0066] Below the player selection section 78 , a bet selection section 72 for selecting a “bet”, a call selection section 73 for selecting a “call”, a raise selection section 74 for selecting a “raise”, and a fold selection section 75 for selecting a “fold” are arranged for the bet selection. The player can perform the bet selection by touching a portion on the touch panel 11 corresponding to a selection section. [0067] Next, the internal configuration of the game system 1 will be described. [0068] FIG. 6 is a block diagram showing the internal configuration of the game system according to the embodiment. [0069] As shown in FIG. 6 , the game system 1 has a main control unit 40 , a plurality of stations 3 connected to the main control unit 40 , and two main displays 2 . [0070] The main control unit 40 includes a microcomputer 45 basically having a CPU 41 , a RAM 42 , a ROM 43 , a timer 90 , and a bus 44 for data transmission therebetween, as a core component. The main control unit 40 corresponds to a controller according to the present invention. In the ROM 43 , various programs, data tables, and the like for performing processes required for controlling the game system 1 are stored. The RAM 42 temporarily stores various types of data calculated by the CPU 41 and the face image data acquired by image capturing operations of the cameras 16 . The RAM 42 corresponds to a memory according to the present invention. The timer 90 measures a time. [0071] The CPU 41 is connected to an image processing circuit 47 , a voice circuit 48 , an LED drive circuit 49 , and a communication interface 50 through an I/O interface 46 . [0072] The front display 21 is connected to the image processing circuit 47 . The speakers 22 are connected to the voice circuit 48 . The LEDs 23 are connected to the LED drive circuit 49 . Ten stations 3 are connected to the communication interface 50 . [0073] The main control unit 40 also performs operations for outputting an image signal to be displayed on the front display 21 and controlling drive of the speakers 22 and LEDs 23 . [0074] Next, the internal configuration of the station 3 will be described. [0075] FIG. 7 is a block diagram showing the internal configuration of the station according to the embodiment. [0076] As shown in FIG. 7 , the station 3 includes a microcomputer 55 basically having a CPU 51 , a RAM 52 , a ROM 53 , and a bus 54 for data transmission therebetween, as a core component. [0077] In the ROM 53 , various programs, data tables, and the like required for performing processes of controlling the station 3 are stored. The RAM 52 is a memory for temporarily storing the number of credits currently stored in the station 3 or various types of data calculated by the CPU 51 . [0078] The CPU 51 is connected to a liquid crystal panel drive circuit 57 , a touch panel drive circuit 58 , a hopper drive circuit 59 , a payout completion signal circuit 60 , a coin insertion detection signal circuit 67 , a bill detection signal circuit 64 , an operation signal circuit 66 , a camera 16 , and a communication interface 61 , through an I/O interface 56 . [0079] A liquid crystal display 10 is connected to the LCD drive circuit 57 . A touch panel 11 is connected to the touch panel drive circuit 58 . A hopper 62 is connected to the hopper drive circuit 59 . A coin detecting unit 63 is connected to the payout completion signal circuit 60 . A coin insertion detecting unit 68 is connected to the coin insertion detection signal circuit 67 . A bill detecting unit 65 is connected to the bill detection signal circuit 64 . An operation button 12 is connected to the operation signal circuit 66 . [0080] The hopper 62 is disposed inside the station 3 and pays out coins from the coin payout opening 15 on the basis of a control signal output from the CPU 51 . [0081] The coin detecting unit 63 is disposed inside the coin payout opening 15 . When detecting payout of a predetermined number of coins from the coin payout opening 15 , the coin detecting unit 63 transmits a signal to the CPU 51 . [0082] When detecting insertion of a coin into the coin insertion slot 13 , the coin insertion detecting unit 68 detects the amount of the coin and transmits a detection signal indicating the detected amount to the CPU 51 . [0083] When receiving a bill, the bill detecting unit 65 detects the amount of the bill and transmits a detection signal indicating the detected amount to the CPU 51 . [0084] The operation button 12 is used for performing a payout operation in a case where payout of coins is determined. [0085] The camera 16 is used for capturing an image of a face of a player playing a game. In the embodiment, face image data acquired by an image capturing operation of the camera 16 is transmitted to the CPU 41 and the CPU 51 . [0086] Next, a process performed in the game system 1 will be described. [0087] FIGS. 8 and 9 are flowcharts showing a game process according to the embodiment. [0088] First, a process performed in each station 3 will be described. [0089] In Step S 1 shown in FIG. 8 , the CPU 51 determines whether a coin is inserted by a player. When it is determined that a coin has not been inserted, the process proceeds back to Step S 1 . On the other hand, when it is determined that a coin has been inserted, the CPU 51 adds credits corresponding to the inserted coin to the credits stored in the RAM 52 , in Step S 2 . [0090] In Step S 3 , the CPU 51 transmits a coin detection signal to the CPU 41 of the main control unit 40 . [0091] In Step S 4 , the CPU 51 receives dealing card information, which is information on two cards dealt to the player, from the CPU 41 of the main control unit 40 . The dealing card information includes numbers, alphabets, and marks. [0092] In Step S 5 , the CPU 51 displays the two cards on the liquid crystal display 10 on the basis of the dealing card information received in Step S 4 (see FIG. 1 ). [0093] In Step S 6 , the CPU 51 receives a bet selection. In this step, the player performs the bet selection on the touch panel 11 . [0094] In Step S 7 , the CPU 51 performs a process for transmitting information (hereinafter, also referred to as selection information) on the bet selection input by the player to the CPU 41 and subtracting credits corresponding to the bet chips from the credits stored in the RAM 52 . The selection information includes information on the number of chips betted by the player. [0095] When receiving the selection information, the main control unit 40 performs a process for displaying the received selection information in the game information display section 35 of the front display 21 , a process for accumulating and storing credits corresponding to the bet chips in the RAM 42 , a process for recording a face of the player, a process for determining three cards to be Flop and displaying the determined cards on the front display 21 , and a process for transmitting a direction signal for receiving a bet selection to the CPU 51 . [0096] Next, the CPU 51 receives the direction signal for receiving a bet selection from the CPU 41 (Step S 8 ), receives the bet selection (Step S 9 ), and transmits the selection information to the CPU 41 and subtracts the credits corresponding to the bet chips from the credits stored in the RAM 52 (Step S 10 ). [0097] When receiving the selection information, the main control unit 40 performs a process for displaying the received selection information in the game information display section 35 of the front display 21 , a process for accumulating and storing credits corresponding to the bet chips in the RAM 42 , a process for recording a face of the player, a process for determining a card to be Turn and displaying the determined card on the front display 21 , and a process for transmitting a direction signal for receiving a bet selection to the CPU 51 . [0098] Next, the CPU 51 receives the direction signal for receiving a bet selection from the CPU 41 (Step S 11 ), receives a bet selection (Step S 12 ), transmits the selection information to the CPU 41 , and subtracts credits corresponding to the bet chips from the credits stored in the RAM 52 (Step S 13 shown in FIG. 9 ). [0099] When receiving the selection information, the main control unit 40 performs a process for displaying the received selection information in the game information display section 35 of the front display 21 , a process for accumulating and storing credits corresponding to the bet chips in the RAM 42 , a process for recording a face of the player, a process for determining a card to be River and displaying the determined card on the front display 21 , and a process for transmitting a direction signal for receiving a bet selection to the CPU 51 . [0100] Next, the CPU 51 receives the direction signal for receiving a bet selection from the CPU 41 (Step S 14 ), receives bet selection (Step S 15 ), transmits the selection information to the CPU 41 , and subtracts credits corresponding to the bet chips from the credits stored in the RAM 52 (Step S 16 ). [0101] In Step S 17 , the CPU 51 receives information (hereinafter, also referred to as payout information) on the number of payouts from the CPU 41 . [0102] In particular, the CPU 51 receives information on the credit amount that has been accumulatively stored in the RAM 42 of the main control unit 40 from the CPU 41 . [0103] In Step S 18 , the CPU 51 pays out credits on the basis of the payout information received in Step S 17 . [0104] In particular, the CPU 51 stores the information on the credit amount accumulatively stored in the RAM 42 which has been received from the CPU 41 in the RAM 52 . Then, when the operation button 12 is pressed, the CPU 51 pays out coins corresponding to the number of credits stored in the RAM 52 from the coin payout opening 15 . [0105] After the process of Step S 18 is performed, the game process is completed. [0106] Next, a process performed by the main control unit 40 will be described. [0107] In Step S 101 , the CPU 41 receives a coin detection signal from the CPU 51 of the station 3 . [0108] In Step S 102 , the CPU 41 determines two cards to be dealt to each player by using random numbers. [0109] In Step S 103 , the CPU 41 transmits information on the cards determined in Step S 102 to the CPU 51 . [0110] In Step S 104 , the CPU 41 displays the player's face image (that is, the face image of a player who has a turn to receive a card) received from the camera 16 of the station 3 that has transmitted the card information in Step S 103 in the enlarged face image displaying section 36 of the front display 21 . [0111] After the processes of Steps S 103 and S 104 are performed for all the stations 3 , the process proceeds to Step S 105 . [0112] In Step S 105 , the CPU 41 performs a selection information receiving process. This process will be described later in detail with reference to FIG. 11 . Then, in Step S 106 , the CPU 41 displays the selection information received in Step S 105 in the game information display section 35 of the front display 21 and accumulates and stores credits corresponding to the bet chips in the RAM 42 on the basis of the received selection information. [0113] After the processes of Steps S 105 and S 106 are performed for all the stations 3 , the process proceeds to Step S 107 . [0114] In Step S 107 , the CPU 41 starts recording (capturing) the players' faces. In particular, the CPU 41 starts a process of storing the face image data of players received from the stations 3 in the RAM 42 . The CPU 41 performs a process of Step S 108 , to be described later, when five seconds elapses after the start of the recording operation, and completes the recording operation when five seconds elapses after the completion of the process of Step S 108 . In other words, the recording operation is started five seconds before the process of Step S 108 is performed, and is completed five seconds after the completion of the process of Step S 108 . [0115] In Step S 108 , the CPU 41 determines three cards by using random numbers and displays the determined cards as Flop on the table 31 of the front display 21 . [0116] In Step S 109 , the CPU 41 performs a process for transmitting a command for receiving a selection. This process will be described later in detail with reference to FIG. 10 . [0117] In Step S 110 , the CPU 41 performs the selection information receiving process. Then, in Step S 111 , the CPU 41 displays the selection information received in Step S 110 in the game information display section 35 of the front display 21 and accumulates and stores credits corresponding to the bet chips in the RAM 42 on the basis of the received selection information. [0118] After the processes of Steps S 109 to S 111 are performed for all the stations 3 , the process proceeds to Step S 112 . [0119] In Step S 112 , the CPU 41 starts the operation for recording players' faces. The CPU 41 performs a process of Step S 113 , to be described later, when five seconds elapses after the start of the recording operation, and completes the recording operation when five seconds elapses after the completion of the process of Step S 113 . In other words, the recording operation is started five seconds before the start of the process of Step S 113 , and is completed five seconds after the completion of the process of Step S 113 . When this process is performed, the face image data stored in the RAM 42 in Step S 107 is removed. [0120] In Step S 113 , the CPU 41 determines one card by using a random number and displays the determined card as Turn on the table 31 of the front display 21 . [0121] In Step S 114 , the CPU 41 performs a process for transmitting a command for receiving a selection. [0122] In Step S 115 shown in FIG. 9 , the CPU 41 performs the selection information receiving process. Then, in Step S 116 , the CPU 41 displays the selection information received in Step S 115 in the game information display section 35 of the front display 21 and accumulates and stores credits corresponding to the bet chips in the RAM 42 on the basis of the received selection information. [0123] After the processes of Steps S 114 to S 116 are performed for all the stations 3 , the process proceeds to Step S 117 . [0124] In Step S 117 , the CPU 41 starts the operation for recording players' faces. The CPU 41 performs a process of Step S 118 , to be described later, when five seconds elapses after the start of the recording operation, and completes the recording operation when five seconds elapses after the completion of the process of Step S 118 . In other words, the recording operation is started five seconds before the start of the process of Step S 118 , and is completed five seconds after the completion of the process of Step S 118 . When this process is performed, the face image data stored in the RAM 42 in Step S 112 is removed. [0125] In Step S 118 , the CPU 41 determines one card by using a random number and displays the determined card as River on the table 31 of the front display 21 . [0126] In Step S 119 , the CPU 41 performs a process for transmitting a command for receiving a selection. [0127] Next, in Step S 120 , the CPU 41 performs the selection information receiving process. Then, in Step S 121 , the CPU 41 displays the selection information received in Step S 120 in the game information display section 35 of the front display 21 and accumulates and stores credits corresponding to the bet chips in the RAM 42 on the basis of the received selection information. [0128] After the processes of Steps S 119 to S 121 are performed for all the stations 3 , the process proceeds to Step S 122 . [0129] In Step S 122 , the CPU 41 performs a Showdown process. [0130] In particular, the CPU 41 displays each two cards that have been dealt to a player using each station 3 in the game information display section 35 corresponding to the station 3 . [0131] In Step S 122 , the CPU 41 compares the hands with one another. [0132] In particular, first, the CPU 41 determines a strongest hand among hands made by combining two cards dealt to one player and three cards among five cards displayed on the table 31 of the front display 21 as the hand of the player. After the same process as that described above is performed for all the players remaining in the game, the CPU 41 compares the hands of the players to one another and determines a player whose hand is the strongest. [0133] In Step S 124 , the CPU 41 transmits the payout information to the CPU 51 . [0134] In particular, the CPU 41 transmits the information on the credit amount accumulatively stored in the RAM 42 to the CPU 51 . [0135] After the process of Step S 124 is performed, the game process is completed. [0136] FIG. 10 is a flowchart showing a subroutine for the process for transmitting a command for receiving a selection which is performed by the main control unit in Steps S 109 and S 114 shown in FIG. 8 and Step S 119 shown in FIG. 9 . [0137] In Step S 201 , the CPU 41 transmits a direction signal for receiving a bet selection to the CPU 51 . [0138] When receiving the direction signal for receiving a bet selection, the station 3 performs a process of receiving the bet selection and a process of transmitting the input selection information to the CPU 41 . [0139] In Step S 202 , the CPU 41 displays the player's face image (that is, the face image of a player who has a turn to perform a bet selection) received from the camera 16 of the station 3 that has transmitted the direction signal for receiving a bet selection in Step S 201 in the enlarged face image displaying section 36 of the front display 21 . [0140] After the process of Step S 202 is performed, the subroutine is completed. [0141] FIG. 11 is a flowchart showing a subroutine for the selection information receiving process which is performed by the main control unit in Steps S 105 and S 110 shown in FIG. 8 and Step S 115 and Step S 120 shown in FIG. 9 . [0142] In Step S 301 , the CPU 41 receives the selection information from the CPU 51 . Then, in Step S 302 , the CPU 41 determines whether the player using the station 3 has made a raise on the basis of the selection information received in Step S 301 . When it is determined that the player using the station 3 has not made a raise, this sub routine is completed. [0143] On the other hand, when it is determined that the player using the station 3 has made a raise, the CPU 41 transmits the face image data of the player received from the station 3 to the CPUs 51 of stations 3 other than the station 3 in Step S 303 . In the special face image display section 77 of the liquid crystal display 10 of the station that has received the face image data, a face image on the basis of the received face image data is displayed (see FIG. 1 ). [0144] In the embodiment, the face image of the player who has made a raise is displayed for five seconds in the special face image display section 77 . When there is a plurality of players who have made raises, the face images of the players are sequentially displayed. [0145] However, the method of displaying the face image of a player who has made a raise is not limited thereto in the present invention. For example, the face image of a player who has made a raise is displayed until the next bet selection is performed, and the display of the face image of the player may be configured to be stopped in a case where the player does not make a raise in the bet selection. The face image data of the players who have made raises is stored in a memory, and it may be configured that the face images are sequentially displayed on the basis of the stored face image data in a case where there is a plurality of players who have made raises. [0146] Next, a process of displaying the face image of a player designated by the player playing a game in the station 3 in the liquid crystal display 10 of the station 3 will be described. [0147] FIG. 12 is a flowchart showing a subroutine for a process of displaying the face image of a designated player which is performed at regular time intervals by the station and the main control unit, independently of the game process shown in FIGS. 8 and 9 . [0148] This subroutine is executed only when an input for designating a player whose face is to be displayed is performed by the player. [0149] First, in Step S 401 , the CPU 51 of the station 3 determines whether an input for designating a player whose face image is to be displayed is performed by the player. In this process, the CPU 51 determines whether an alphabet in the player selection section 78 (see FIG. 1 ) is selected through the touch panel 11 . When it is determined that an input for designating the player whose face image is to be displayed is not performed, the process proceeds back to S 401 . [0150] On the other hand, when it is determined that an input for designating the player whose face image is to be displayed is performed, the CPU 51 determines the designated player in Step S 402 . In this process, the CPU 51 determines which alphabet has been selected in Step S 401 . [0151] In Step S 403 , the CPU 51 transmits information on the designated player (hereinafter, referred to as designated player information) to the CPU 41 of the main control unit 40 . [0152] In Step S 501 , the CPU 41 of the main control unit 40 receives the designated player information from the CPU 51 of the station 3 . [0153] In Step S 502 , the CPU 41 transmits the face image data received from the station 3 in which the designated player plays a game to the CPU 51 . That is, the CPU 41 transmits the face image data obtained by the 10 seconds recording (refer to Steps S 107 and S 112 shown in FIG. 8 , and Step S 117 shown in FIG. 9 ) to the CPU 51 . [0154] Next, in Step S 404 , the CPU 51 of the station 3 receives the face image data of the designated player from the CPU 41 . [0155] Next, in Step S 405 , the CPU 51 displays the face image of the designated player on the basis of the face image data received in Step S 404 in the special face image display section 77 of the liquid crystal display 10 of the station 3 for ten seconds. [0156] In the embodiment, if the face image of a player who has made a raise is already displayed in the special face image display section 77 when an input for designating a player whose face image is to be displayed is performed by a player, the face image of the designated player is displayed preferentially. In addition, if the face image of a designated player is displayed in the special face image display section 77 when a player makes a raise, the face image of the player who has made a raise is displayed preferentially. [0157] However, according to the present invention, the method of displaying the face image of the designated player and the face image of the player who has made a raise is not limited thereto. [0158] After the process of Step S 405 is performed, this subroutine is completed. [0159] As described above, the game system 1 according to the embodiment includes a liquid crystal display 10 (second display unit) and ten stations 3 for players' playing the game each having a camera 16 for capturing an image of the face of a player playing the game. The game system 1 includes a main control unit 40 (controller) programmed to perform the following processes of “(a)” to “(c)”. [0160] (a) A process of controlling an operation for capturing image of the faces of the players playing the game in the stations 3 having the cameras 16 by using the cameras 16 . [0161] (b) A process of controlling an operation for displaying images of the players' faces captured by the cameras 16 of the stations 3 in which the game is played on the liquid crystal displays 10 of the stations 3 . [0162] (c) In a case where a predetermined condition is satisfied in at least one of the stations 3 , a process of displaying a face image of a player in the at least one of the stations 3 , in which the predetermined condition is satisfied, in the liquid crystal displays 10 of the stations 3 in which the game is played in an enlarged size. [0163] In the embodiment, when a player makes a raise, it is configured that the face image of the player is displayed on the liquid crystal display 10 in an enlarged size. However, a predetermined condition for displaying the face image of the player in an enlarged size in the present invention is not limited thereto. For example, it may be configured that the face image of a player is displayed in an enlarged size when the player makes a call or the player makes raises a predetermined number of times or more. Furthermore, it may be configured that the face image of a player is displayed in an enlarged size when the number of bets of the player exceeds a predetermined amount. [0164] In the embodiment, when a player makes a raise, the face image of the player who has made the raise is configured to be displayed on the liquid crystal displays 10 of stations 3 other than the station 3 in which the player who has made the raise plays the game in an enlarged size. However, the face image of a player who satisfies a predetermined condition may be displayed on the second display unit of the station in which the player plays the game in an enlarged size. [0165] In the embodiment, although the image capturing operations are continuously performed by the cameras 16 , however, the method of capturing images by the cameras is not limited thereto. For example, the image capturing operations may be performed only at predetermined timings (for example, at a time when a bet selection is made or a card is dealt) or only when a predetermined condition (for example, a condition that the amount of the pot exceeds a predetermined amount or a raise of an amount equal to or larger than a predetermined amount is made) is satisfied. [0166] In addition, on the liquid crystal display 10 of a station 3 , although the face images of all the players participating in the game in stations 3 other than the station are configured to be displayed in the embodiment, the face images displayed on the second display unit according to the present invention is not limited thereto. For example, only the face image of a player designated by the player using the station and the face image of a player who satisfies a predetermined condition may be configured to be displayed. Furthermore, for example, the face image of a player playing the game in the station may be configured to be displayed. [0167] In the embodiment, although the face image of a player designated by the player playing the game is displayed on the liquid crystal display 10 of the station 3 to which the selection operation is input, in the present invention, the face image of the selected player may be displayed on second display units of stations other than the station to which the selection operation is input. [0168] Although the face images are configured to be continuously displayed on the liquid crystal display 10 in the embodiment, the present invention is not limited thereto. For example, the face images may be configured to be displayed only at predetermined timings (for example, at a time when a bet selection is made or a card is dealt) or only when a predetermined condition (for example, a condition that the amount of the pot exceeds a predetermined amount or a raise of an amount equal to or larger than a predetermined amount is made) is satisfied. [0169] In the present invention, the positions in which the face images are displayed on the second display unit are not limited to those shown in the example of FIG. 1 . [0170] In the embodiment, although the face images of the players are configured to be recorded (the face image data is stored in the RAM 42 ) when Flop, Turn, or River is displayed on the front display 21 , timings for storing the face image data acquired by the image capturing operations according to the present invention is not limited thereto. For example, the face image data may be configured to be stored in a memory when a bet selection is made or a card is dealt, and the face image data may be configured to be stored in the memory when an input direction is made by the player. Furthermore, for example, the process of storing the face image data in the memory may be configured to be continuously performed. [0171] Although a case where the game system 1 has two main displays 2 disposed back to back has been described in the embodiment, the game system according to the present invention is not limited thereto. [0172] Hereinafter, an example of a game system having a configuration other than the configuration of the game system 1 will be described. [0173] FIG. 13 a perspective view showing the appearance of a game system according to another embodiment. As shown in FIG. 13 , a game system 100 has one main display, and it is configured that all the players participating in the game play the game while viewing the same main display. [0174] As described above, the present invention can be applied to a game system having one main display. [0175] In the above-described embodiment, a case where the game system has a main display as a first display unit and a plurality of the players play the game while viewing the main display has been described. However, the present invention can be applied to a game system without a first display unit. For example, the present invention can be applied to a game system including a plurality of stations each having a camera and a second display unit and the face image of a player designated by the player playing the game in the station is controlled to be displayed on the second display unit. [0176] Although a case where Hold'em Poker is played as a game has been described in the above-described embodiments, the game performed by the game system is not limited to specific a game as long as a plurality of players can participate in the game. [0177] As described above with reference to the embodiments, there is provided a game system in which the faces of the players playing the game in the stations are captured by using the cameras installed to the stations, and images of the players' faces which have been captured by the cameras are displayed on the second display units of the stations. [0178] Thus, since images of other player's faces are displayed on the second display unit of each station, each player can recognize facial expressions of other players. As a result, each player can set up a strategy on the basis of the facial expressions of other players, and it is possible to increase enjoyment of game tactics. [0179] In addition, since the images of other players are displayed on each second display unit, each player can have a realistic feeling that the player competes with the players whose face images are displayed. Consequently, it is possible to increase enjoyment of participating in the game. [0180] Accordingly, it is possible to provide an entertaining feature that has not been provided by using a conventional technology. [0181] There is also provided a game system in which the faces of the players playing the game in the stations are captured by using the cameras installed to the stations, and images of the players' faces which have been captured by the cameras are displayed on the second display units of the stations. In addition, a face image of a player using a station, in which a predetermined condition (for example, in Hold'em Poker, a raise is made) is satisfied, is displayed on the second display units of the stations in an enlarged size. [0182] Thus, since images of other player's faces are displayed on the second display unit of each station, each player can recognize facial expressions of other players. As a result, each player can set up a strategy on the basis of the facial expressions of other players, and it is possible to increase enjoyment of game tactics. [0183] In addition, since the images of other players are displayed on each second display unit, each player can have a realistic feeling that the player competes with the players whose face images are displayed. Consequently, it is possible to increase enjoyment of participating in the game. [0184] In addition, since a face image of a player in a station, in which a predetermined condition is satisfied, is displayed on the second display units of the stations in an enlarged size, a strong impression that the player satisfies the predetermined condition on other players can be made. [0185] Accordingly, it is possible to provide an entertaining feature that has not been provided by using a conventional technology. [0186] There is also provided a game system in which the faces of the players playing the game in the stations are captured by using the cameras installed to the stations, face image data representing images of the captured image of the players' faces is stored in the memory, and the face image on the basis of the face image data selected by the input from the input device is displayed on the second display unit of a station in which the input operation is performed. [0187] Thus, since the image of the player's face is displayed on the second display unit, each player can recognize facial expressions of other players. As a result, a player can set up a strategy on the basis of facial expressions of other players, and it is possible to increase enjoyment of game tactics. [0188] In addition, since the images of other players are displayed on each second display unit, each player can have a realistic feeling that the player competes with the players whose face images are displayed. Consequently, it is possible to increase enjoyment of participating in the game. [0189] The face image on the basis of the face image data stored in the memory can be frequently displayed on the second display unit, a player can frequently check the facial expression of a competitive player as is necessary. As a result, the facial expressions of various players at various timings can be checked, and it is possible to set up a precise strategy. [0190] Accordingly, it is possible to provide an entertaining feature that has not been provided by using a conventional technology. [0191] There is provided a game system having the above-described new entertaining feature that has not been in the conventional technology, that is, a game system capable of increasing enjoyment of game tactics and enjoyment of participating in the game. [0192] While the embodiments of the present invention have been described as above, the embodiments are merely detailed examples of the present invention, and therefore the present invention is not particularly limited thereto, and the design of detailed configurations of each means and the like may be changed appropriately. The advantages described in the embodiments of the present invention are merely examples of appropriate advantages that are generated from the present invention, and therefore the advantages of the present invention are not limited thereto. [0193] In the description of the present invention described above, distinctive features of the present invention have been focused for easy understanding thereof. The present invention is not limited to the embodiments described in the detailed description and may be applied to other embodiments, and the present invention can be applied to various application fields. The terms and expressions used in this specification are not for limiting the interpretation of the present invention but for precisely describing the present invention. It will be understood that those skilled in the art can easily deduce a different configuration, a system, or a method belonging to the concept of the present invention from the concept of the present invention described in this specification. Accordingly, the description of Claims should be considered to include equivalent configurations without departing from the spirit and scope of the present invention. The purpose of the abstract is to enable Patent Trademark Office, general public organizations, or a technical person or the like belonging to the technical field of the present invention who is not familiar with patents, legal terms, or professional terms to acquire the technical contents and essence of the present application in an easy manner by performing a simple research. Accordingly, the abstract is not intended to limit the scope of the present invention which should be determined by Claims. In order to sufficiently understand the object and distinctive advantages of the present invention, it is required to fully refer to disclosed documents and the like. [0194] The above-described detailed description of the present invention includes processes executed by a computer. The purpose of the descriptions and expressions as above is to enable those skilled in the art to efficiently understand the present invention. In this specification, steps used for inducing one result should be understood as processes without self contradiction. In each step, transmission, reception, record, or the like of electric or magnetic signals is performed. In the processes of the steps, although these signals are represented by bits, values, symbols, letters, terms, numbers, or the like, however, it should be considered that those representations are used only for the convenience of descriptions. Although the processes of the steps may have been described as expressions common to human behavior, basically, the processes described in this specification are performed by various apparatuses. In addition, other configurations required to perform the processes in the steps are apparent from the descriptions above.
A game system provides a game in which a plurality of players participate and includes: a plurality of stations that are provided for each of the players to play the game; a plurality of camera devices that are respectively provided in each of the stations and capture facial images of the respective players; a plurality of display units that are respectively provided in each of the stations and display images related to the game; and a controller that operates to: control at least one of the camera devices to capture the facial images; and control at least one of the display units to display the facial images captured by the camera devices.
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CROSS-REFERENCE TO RELATED APPLICATIONS [0001] Not Applicable STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT [0002] Not Applicable REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER PROGRAM LISTING COMPACT DISK APPENDIX [0003] Not Applicable BACKGROUND OF THE INVENTION [0004] This invention relates to the field of semiconductor integrated circuits, particularly to circuits useful for generating local clock signals synchronized to an external reference clock, and to semiconductor memory devices with such circuits. [0005] System specifications for double data rate dynamic random access memory(DDR DRAM) require the device in a read cycle to switch its data lines(DQ) coincident with transitions of an externally generated reference clock. The fact that the frequency of the reference clock is not known precisely presents an obstacle to meeting the above requirement. The fact that the DQ line drivers have significant delays presents another obstacle. [0006] To meet the above requirement, a DDR DRAM device typically employs a delay locked loop(DLL) to create a delayed replica clock that exactly matches the system reference clock in both frequency and phase. The DLL creates its replica clock by making a delayed copy of the reference clock. The copy has the same frequency as the reference clock because delaying a signal does not change its frequency. The DLL adjusts the delay of the copy until the copy is delayed by one or more full clock cycles from the reference clock. At this point, the reference clock and the delayed copy of the reference clock are synchronized, and the copy is then a replica of the reference clock. [0007] The following discussion describes the DLL as locked when its replica clock matches the frequency and phase of the reference clock, and describes the smallest available delay increment by which the DLL may be adjusted as the resolution of the DLL. [0008] The DLL typically taps a DQ clock signal from its delay signal path at a point preceding the replica clock by one clock input buffer delay, plus a DQ line driver delay(buffer delay). The phase of the DQ clock therefore leads the phase of the replica clock by one buffer delay. When the DLL is locked, the phase of the DQ clock signal also leads the reference clock by one buffer delay. The DQ clock may be used to trigger the DQ line drivers so that the DQ lines switch coincident with the reference clock transitions, thus meeting the above requirement. [0009] The speed with which a DLL can achieve the locked condition is an important aspect of DLL performance. At system startup, after every self-refresh, and after exiting low power modes, a DLL which locks more quickly than other designs can perform its first read sooner, improving overall performance of the device. [0010] The stability of the DLL locking in the presence of normal electrical disturbances is another important aspect of DLL performance. A design which loses lock due to a change in supply voltage or temperature cannot function until lock is regained. [0011] [0011]FIG. 1 shows prior art in delay locked loops as summarized in Keeth and Baker, ‘DRAM Circuit Design, A Tutorial,’ IEEE Press, New York, 2001 , page 143 . In FIG. 1, a shift register 120 selects the number of delay increments applied by a delay line 110 to an external reference clock 102 . Delayed clock 130 emerging from the delay line triggers output data 160 , data strobe 170 , and feeds back to phase detector 150 through delay block 140 . Delay block 140 replicates the delay of input buffer 104 . Phase detector 150 controls shift register 120 to remove any phase difference between its input signals 106 and 146 that are larger than the incremental delays controlled by its counter, as known by one skilled in the art. [0012] The FIG. 1 design uses a single delay line having the same unit delay in each stage. This approach has the disadvantage of requiring many delay stages to do its job. As a typical example, if the maximum clock period is 10 nanoseconds, and the minimum clock period is 5 nanoseconds, and the delay resolution is 100 picoseconds, the FIG. 1 design requires 50 delay stages to meet the requirements with no margin. Implementing such a large number of stages requires more device size and power consumption than necessary. [0013] The large number of stages also causes the disadvantage of slow locking. The phase detector must wait at least two clock cycles before making each decision, and each decision can only adjust total delay by a single unit delay. Thus the design of FIG. 1 moves toward locking by taking small steps, often over many steps. [0014] The design of FIG. 1 has the further disadvantage of making delay adjustments by varying the location where the clock signal enters the delay line, so the adjustments propagate through all active delay elements before evaluation at the phase detector. Adjusting at the beginning end, rather than the trailing end, of the delay line slows evaluation of the adjustment, because the design has to wait before evaluating until each adjustment propagates to the phase detector. The design must address the worst case, and pause before evaluating for the full length of the delay line. [0015] The FIG. 1 design has a further disadvantage of requiring flip-flops in the shift register outputs that control the delay line. Because the design needs flip-flops with near-zero setup time, the design operates the flip-flops close to the region where metastable operation can occur. For reliable flip-flop performance, the design must add either extra filtering circuitry, or extra setup delay. The use of flip-flops causes the device to suffer extra size or reduced performance. [0016] [0016]FIG. 2 shows further prior art, U.S. Pat. No. 6,438,067, issued Aug. 20, 2002 to Kuge et al. This patent teaches a DLL having an adjustable delay buffer and an adjustable delay line in series. Delay elements in the delay buffer provide delay increments that are smaller than those in the delay line. Reference clock 202 enters a delay buffer 204 where the delay is controlled by selectively connecting capacitive loads 222 responsive to the low-order bits of a count in counter 224 . The clock signal then enters delay line 206 , where its delay is further adjusted by passing through an adjustable number of delay elements 210 , set by the high-order bits of the same counter. Decoders 215 - 1 , . . . 215 - n select which one of delay elements 210 - 1 , . . . 210 - n admits buffered clock signal 208 into the delay line. [0017] The Kuge patent further controls the delay of each delay element 210 by varying its supply voltage on node 255 , so that a fairly small number of delay elements will suffice. At circuit startup, DLL control circuit 250 enables reference potential generating circuit 212 to adjust the supply voltage of the delay line, responsive to the output signal 240 until the remaining adjustment is within a predetermined range. Then the DLL control circuit uses gates 252 and 254 to disable voltage supply variation and enable delay line variation to further adjust DLL delay. [0018] The Kuge patent has the disadvantage of using analog voltage controls for initial steps toward lock, causing speed of locking to be less than optimal. As is known to one skilled in the art, supply voltage controls must operate more slowly than digital controls, to avoid underdamped oscillations (ringing). This approach gives a wide frequency range with a small number of delay line elements, but will have a slow initial lock. [0019] The Kuge patent has the further disadvantage of having variable size delay steps in its delay line, while the delay steps in its delay buffer are a fixed size. With both the delay buffer and delay line driven from the same counter, each counter change needs to change the total delay of both stages in a uniform fashion to be able to smoothly adjust the total delay. This is impossible since the delay of each delay line element changes with node 255 voltage, while the delay of the delay buffer step does not change. This problem will cause the DLL to have a variable locking resolution. The total delay will not change in a uniform manner as the counter is incremented and decremented. [0020] For example, when the low-order three bits of the counter contain all ones, then all seven units of capacitance in the delay buffer are switched on. When the counter increments, the capacitances are all switched out of the circuit, and one delay-line increment is added to the total delay. The delay-line increment should equal eight of the buffer capacitance units, but the delay-line increments vary significantly due to the voltage controls. When the delay line increment is less than seven of the buffer capacitance units, and the count increments across the boundary between the buffer and the delay line to call for more delay, the line delay decreases instead of increasing. When the delay line increment is more than eight of the buffer capacitance units, and the count crosses the boundary between the delay buffer and the delay line there is a large change in total delay. A gap appears every eighth count, at this boundary, in total delay values which the delay line can provide, due to the variable-voltage controls. [0021] Large temperature variations are common between quiescent conditions and full speed operation. Temperature variations cause changes in circuit delay, requiring the DLL to make small delay adjustments after the initial lock. The margin between external clock and the DQ as the temperature varies will be larger than other prior art, and the current invention, because the total delay of the delay buffer and delay line do not increment in a uniform manner over temperature changes. BRIEF SUMMARY OF THE INVENTION [0022] The current invention provides a DLL which overcomes the disadvantages of prior art circuits by providing multiple adjustable delay lines, each having separate controls and different delay resolutions. The delay lines are arranged in series so that total delay from the reference clock to the replica clock is the sum of delays imparted by each delay line. The reference clock feeds into a first delay line providing relatively coarse delay increments. Delay lines following the first delay line provide smaller delay increments, and more precise delay control. However, the first delay could have a small delay increment with the following delay lines providing a larger delay increment and still fall within the scope of the current invention. [0023] Each delay line has separate delay controls including a counter that sets the number of incremental delays applied by the delay line to the clock signal. When the delay of a delay line is adjusted, the counter of the next, higher resolution delay line is typically set at midrange, to maximize its available range of locking. [0024] A DLL typically waits two or more clock cycles between each adjustment, to allow the clock signal to stabilize, and to allow the adjusted clock timing to propagate through the delay line and back to the phase detector inputs. By having coarse delays, my DLL design can match its replica clock to the external clock more quickly than a DLL without coarse delay steps, because each initial adjustment may take larger steps toward lock. My design also locks more quickly than prior art which uses analog voltage controls, because my design does not vary the supply voltage, so it has no need to move slowly enough to avoid supply voltage oscillation. [0025] The coarse delays also permit the DLL to operate over the required frequency range using far fewer delay elements than designs having a only single delay line, giving the advantages of smaller layout and lower power consumption compared to prior art. [0026] Since the coarse delay line length is only changed during the initial lock, my DLL has a uniform delay line step for temperature transients. The uniform delay line steps enable the phase detector to keep the maximum difference between reference clock transitions and DQ transitions(margin) within the resolution of the smallest delay line element. [0027] In the current invention, each counter is typically a conventional up/down counter which increments and decrements its count responsive to pulses on UP and DN input nodes, respectively. An alternate implementation may use a counter with a single COUNT input node, in which the counter keeps track of the direction of counting, and reverses its direction at end-of-range. [0028] A separate phase detector for each delay line typically controls the counter of the delay line. The phase detector compares the reference clock with the replica clock, with resolution roughly equal to the delay elements of its delay line. Based on the phase comparison, the phase detector directs the counter to increment its count when more delay is needed, to decrement its count when less delay is needed, and to make no change when the phase difference is less than the resolution of the delay line. In the preferred embodiment, a wrap control replaces the phase detector in one of the delay lines as described more fully below. [0029] Therefore, objects and advantages of the current invention include: [0030] (a) Separate delay lines for coarse and fine resolution, each having separate controls, [0031] (b) Large range of available delay with a smaller number of delay line elements via coarse adjustments, [0032] (c) Rapid locking via coarse adjustment capability, [0033] (d) Small locking resolution via fine adjustment capability, [0034] (e) Minimized layout size and power consumption, [0035] (f) Small resolution, uniform delay step sizes over all operating conditions, [0036] (g) All-digital controls for rapid convergence and stable, robust operation over full range of temperature and manufacturing process conditions, [0037] (h) Adjusting delays at the trailing end of the delay line, obtaining the shortest signal path for each adjustment to propagate to the phase detector, and the fastest possible evaluation of each adjustment, and a constant amount time after each adjustment until the adjustment may be evaluated at the phase detector, [0038] (i) No flip flops, therefore no problem of flip flop metastability, and [0039] (j) No variable voltage supply, therefore no problem of underdamped oscillation. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING [0040] [0040]FIG. 1 shows a prior-art DLL design described in Keeth and Baker, ‘DRAM Circuit Design, A Tutorial,’ IEEE Press, New York, 2001, page 143. [0041] [0041]FIG. 2 shows a prior art DLL circuit taught by U.S. Pat. No. 6,438,067, issued Aug. 20, 2002 to Kuge. [0042] [0042]FIG. 3 shows a DLL according to the current invention, having two delay lines. [0043] [0043]FIG. 4 shows a DLL according to the current invention, having three delay lines. [0044] [0044]FIG. 5 shows the preferred embodiment of the current invention. [0045] [0045]FIG. 6 details the logic of the one-input delay block shown in FIG. 3 and FIG. 4, and the two-input delay block shown in FIG. 5. [0046] [0046]FIG. 7 shows a DDR SDRAM device. DETAILED DESCRIPTION OF THE INVENTION [0047] In FIG. 3, a buffered reference clock 302 is the input signal. For brevity, FIG. 3 does not show the reference clock input buffer. Buffered reference clock 302 connects to a first delay element in first delay line 300 , to a first input of phase detector 312 in delay line 300 , and to a first input of phase detector 332 in delay line 320 . DQ clock 350 is the output signal from the DLL. DQ clock is driven by delay line 320 , and connects further to buffer delay model 342 . A replica clock signal 340 , driven by the buffer delay model, is the feedback control signal for the loop. The replica clock connects to a second input of phase detector 312 , and to a second input of phase detector 332 . [0048] In FIG. 3 delay line 300 , the clock signal passes through delay elements 304 in series. Each delay element has an input node for receiving a clock signal, and an output node for conveying a copy of the clock signal delayed by a first delay time. The input node of each delay element in the delay line, except the first element, connects to the output of the preceding element in the delay line. The input node of the first element in the delay line connects to reference clock 302 . The output node of each delay element in the delay line, except the last, connects as described to the input node of the succeeding element. The output node of each delay element in the delay line connects further to a first input node of a separate tap gate 308 for each delay element. [0049] In FIG. 3, a conventional phase detector 312 , and counter 314 control the total delay of the clock signal by delay line 300 as follows. Phase detector 312 compares replica clock 340 to reference clock 302 . When the phase of replica clock 340 leads the phase of reference clock 302 by more than a delay of a delay element 304 , phase detector 312 issues a pulse on its UP 1 output, incrementing counter 314 , effectively increasing the delay of delay line 300 by the delay of one delay element 304 . When the phase of replica clock 340 follows the phase of reference clock 302 by more than a delay of a delay element 304 , phase detector 312 issues a pulse on its DN 1 output, decrementing counter 314 to effectively decrease the delay of delay line 300 by the delay of one delay element 304 . Nodes UP 1 and DN 1 couple to counter 314 and further to counter 334 . A pulse on either UP 1 or DN 1 sets the count of counter 334 to its midrange value. When neither action is needed, phase detector 312 issues neither signal and coarse delay line 300 is locked. After pulsing UP 1 or DN 1 , phase detector 312 waits long enough for the adjustment to propagate through the DLL and back to the phase detector inputs before repeating its compare/adjust operation. [0050] Counter 314 in FIG. 3 comprises UP 1 and DN 1 input nodes, driven as described by phase detector 312 . Counter 314 typically increments or decrements its count from a predetermined nominal delay value at system startup, but it may also begin from a random count at that time. [0051] Multi-wire bus 316 routes all bits of the count of counter 314 in parallel to a separate decoder 306 for each delay element in the first delay line. Each decoder has an output connected to a second input of tap gate 308 following its delay element. The second input of each tap gate enables and disables the tap gate for transmitting the delayed clock signal of its first input. Decoders 306 each enable a tap gate 308 only when bus 316 conveys a count that matches its position in the delay line. One of the decoders 306 enables its tap gate for each count held by counter 314 . [0052] In FIG. 3, the output signal from each tap gate 308 in the first delay line drives a separate input of first delay line output gate 310 . Decoders 306 and tap gates 308 disable all but one of the signals driving gate 310 . The enabled tap gate 308 drives its clock signal onto an input of gate 310 . Gate 310 then drives a clock signal on node 322 having a delay substantially equal to the output of the delay element driving the enabled tap gate. [0053] First delay line output clock signal 322 in FIG. 3 enters second delay line 320 , where it passes through delay elements 324 in series. Each delay element 324 has an input node for receiving a clock signal, and an output node for conveying a delayed replica of the clock signal. The input node of each delay element in the delay line, except the first element, connects to the output of the preceding element in the delay line. The input node of the first element in the delay line connects to node 322 . The output node of each delay element in the delay line, except the last, connects as described to the input node of the succeeding delay element. The output node of each delay element in the delay line connects further to a first input node of a separate tap gate 328 for each delay element. Each of the delay elements in the second delay line causes further delay by a substantially equal second delay amount, which is less than the first delay of each delay element of the first delay line. [0054] Every clock cycle, phase detector 332 compares replica clock 340 to reference clock 302 . When the phase of replica clock 340 leads the phase of reference clock 302 by more than a delay of a delay element 324 , phase detector 332 issues a pulse on its UP 2 output, incrementing counter 334 , effectively increasing the delay of delay line 320 by the delay of one delay element 324 . When the phase of replica clock 340 follows the phase of reference clock 302 by more than a delay of a delay element 324 , phase detector 332 issues a pulse on its DN 2 output, decrementing counter 334 to effectively decrease the delay of delay line 320 by the delay of one delay element 324 . When the phase of replica clock 340 is closer to reference clock 302 than the margin of phase detector 332 , phase detector 332 issues neither signal, and the loop is locked. Nodes UP 1 and DN 1 also couple to counter 334 . A pulse on either UP 1 or DN 1 initializes the count of counter 334 to its midrange value whenever delay line 300 is adjusted. Pulses on UP 2 and DN 2 then adjust the count of counter 334 to minimize the phase difference between replica clock 340 and reference clock 302 as described. The initializing of counter 334 to a mid-point value is desirable but not necessary. After pulsing UP 2 or DN 2 , phase detector 332 waits long enough for the adjustment to propagate through the DLL and back to the phase detector inputs before repeating its compare/adjust operation. [0055] All bits of the count of counter 334 are passed via multi-wire bus 336 to a separate decoder 326 for each delay element of the second delay line. Each decoder 326 has an output coupled to a second input of tap gate 328 for its delay element. The count on bus 336 causes one decoder 326 corresponding to the value of the count to activate its tap gate 328 . The output node of each tap gate 328 connects to a separate input of second delay line output gate 330 . The activated tap gate provides a path for the clock signal to exit the second delay line and drive one input of second delay line output gate 330 with a clock signal having the particular delay of the enabled tap gate of delay line 320 . Gate 330 then drives the DQ clock output signal on node 350 with substantially this same delay. The logic function of gates 308 and 310 , or gates 328 and 330 , could be implemented in many different ways without affecting the scope of this invention. [0056] [0056]FIG. 4 shows a second implementation of the current invention, in which the delay locked loop comprises three delay lines 400 , 420 and 440 connected in series. Buffered reference clock 402 is the input signal. The reference clock connects to the input node of first delay element 404 of delay line 400 , and to a first input of conventional phase detectors 412 , 432 , and 452 . Output gate 450 of third delay line 440 drives the DQ clock output on node 470 . Node 470 further couples to the input node of buffer delay model 462 , which drives replica clock 460 . The replica clock connects as a second input to each of three phase detectors 412 , 432 , and 452 . [0057] In FIG. 4, the reference clock enters delay line 400 and traverses delay elements 404 in succession, being delayed by a first delay value in traversing each element. The first delay value represents a relatively coarse fraction of the period of the input reference clock signal. Each delay element has an input node for receiving a clock signal, and an output node for conveying a delayed copy of the clock signal. The input node of each delay element in the delay line, except the first element, connects to the output of the preceding element in the delay line. The input node of the first element in the delay line connects to reference clock 402 . The output node of each delay element in the delay line, except the last, connects as described to the input node of the succeeding element. The output node of each delay element in the delay line connects further to a first input node of a separate tap gate 408 for each delay element. [0058] In FIG. 4, a conventional phase detector 412 , and counter 414 control the delay of the clock signal by the first delay line as follows. Every clock cycle, phase detector 412 compares replica clock 460 to reference clock 402 . When the phase of replica clock 460 leads the phase of reference clock 402 by more than the delay of a delay element 404 , phase detector 412 issues a pulse on its UP 1 output to increment counter 414 , thereby increasing the delay of delay line 400 by the delay of one delay element 404 . When the phase of replica clock 460 follows the phase of reference clock 402 by more that the delay of a delay element 404 , phase detector 412 issues a pulse on its DN 1 output to cause counter 414 to count down, decreasing the delay of delay line 400 by the delay of one delay element 404 . Nodes UP 1 and DN 1 couple phase detector 412 to counter 414 , and further couple to counter 434 and counter 454 . A pulse on either UP 1 or DN 1 sets counters 434 and 454 to their midrange count values. The initialization of counters 434 and 454 to a mid-point value is desirable but not necessary. After pulsing UP 1 or DN 1 , phase detector 412 waits long enough for the adjustment to propagate through the delay lines and back to the phase detector inputs before repeating its compare/adjust operation. When the phase of replica clock 460 is closer to the reference clock 402 than the phase detector margin, phase detector 412 issues neither signal and the first delay line is locked. If the reference clock has constant frequency, no further change is needed in the first delay line. [0059] Counters 414 , 434 , and 454 in FIG. 4 are conventional up/down counters, with UP 1 and DN 1 input nodes driven as described by phase detector 412 . [0060] Each bit of the count in counter 414 couples to a separate wire of counter bus 416 . Bus 416 routes all bits of the count of counter 414 in parallel to a separate decoder 406 for the output of each delay element in the first delay line. Each decoder has an output connected to a second input of tap gate 408 for its delay element. The second input of each tap gate enables and disables the tap gate for transmitting the clock signal on its first input. A decoder 406 enables a tap gate 408 only when bus 416 conveys a count that matches its position in the delay line. One decoder 406 enables its tap gate 408 for each count held by the counter. [0061] In FIG. 4, an output signal from each tap gate 408 in the first delay line connects to a separate input of first output gate 410 . Decoders 406 and tap gates 408 disable all but one of the signals driving gate 410 . The single enabled tap gate drives its delayed clock signal onto an input of gate 410 . Gate 410 then drives a clock signal on node 422 having a delay substantially equal to the output of delay element 404 driving the enabled tap gate. [0062] First delayed clock 422 connects as an input to a second delay line 420 in FIG. 4. Second delay line 420 operates in similar fashion to first delay line 400 . However, the second delay of each delay element in the second delay line is substantially less than the first delay of each delay element in the first delay line. Thus the second delay line provides a delay with finer resolution than that given by the first delay line. When the first delay line is adjusted, counter 434 of the second delay line is initialized at its mid-range value by a pulse on either the UP 1 or the DN 1 node. [0063] Delay lines 400 , 420 , and 440 are arranged in series so that the total delay from reference clock 402 to replica clock 460 is the sum of the delays from the individual delay lines, plus the delay from buffer delay model 462 . The loop is locked when all three delay lines are locked and no further changes are needed to match the phase of the replica clock with that of the reference clock. [0064] In FIG. 4, first delay line output 422 enters delay line 420 and traverses delay elements 424 in succession, being delayed by a second delay value in traversing each element. The second delay value represents a smaller fraction of the reference clock cycle time than does the first delay value. Each delay element 424 has an input node for receiving a clock signal, and an output node for conveying a delayed copy of the clock signal. The input node of each delay element in delay line 420 , except the first element, connects to the output of the preceding element in the delay line. The input node of the first element in the delay line connects to first delayed clock 422 . The output node of each delay element in the delay line, except the last, connects as described to the input node of the succeeding delay element. The output node of each delay element in the delay line connects further to a first input node of a separate tap gate 428 for that delay element. [0065] In FIG. 4, a conventional phase detector 432 , and counter 434 control the total delay of the clock signal by the second delay line as follows. Every clock cycle, phase detector 432 compares replica clock 460 to reference clock 402 . When the phase of replica clock 460 leads the phase of reference clock 402 by more than a delay of delay element 424 , phase detector 432 issues a pulse on its UP 2 output to cause counter 434 to increment its count, increasing the delay of delay line 420 by the delay of one delay element 424 . When the phase of replica clock 460 follows the phase of reference clock 402 by more than a delay of delay element 424 , phase detector 432 issues a pulse on its DN 2 output to cause counter 434 to decrement counter 434 , decreasing the delay of delay line 420 by the delay of one delay element 424 . After pulsing UP 2 or DN 2 , phase detector 432 waits long enough for the adjustment to propagate through the delay lines and back to the phase detector inputs before repeating its compare/adjust operation. When the phase of replica clock 460 is closer to reference clock 402 than the phase detector margin, phase detector 432 issues neither signal and delay line 420 is locked. If the reference clock has constant frequency, no further change is needed in delay line 420 . Whenever an adjustment of the delay line occurs, all phase detectors should be disabled, or the clocking of all counters inhibited, until the adjustment has propagated to the replica clock node. [0066] Counter 434 in FIG. 4 is a conventional up/down binary counter having UP 2 and DN 2 input nodes, UP 1 and DN 1 input nodes, and an output count bus 436 . Each bit of the count in counter 434 couples to a separate wire of count bus 436 . [0067] Bus 436 routes all bits of the count of counter 434 in parallel to a separate decoder 426 for each delay element in the second delay line. Each decoder 426 has an output connected to a second input of the tap gate 428 for its delay stage. The second input of each tap gate enables and disables the tap gate for transmitting the delayed clock signal on its first input. Each decoder 426 enables its tap gate 428 only when bus 436 conveys a count that matches its position in the second delay line. One decoder 426 enables its tap gate for each count held by the counter. The one enabled tap gate routes the delayed clock signal out of the delay line with a cumulative delay corresponding to its location in the delay line. [0068] In FIG. 4, an output node from each tap gate 428 in the second delay line connects to a separate input of second delay line output gate 430 . The single enabled tap gate drives its clock signal onto an input of gate 430 . Gate 430 then drives a delayed clock signal on node 442 , having delay substantially equal to the output of delay element 424 driving the enabled tap gate. [0069] Second delayed clock 442 connects as an input to third delay line 440 in FIG. 4. The amount of delay from each delay element in the third delay line is substantially less than the delay of each delay element in the first and second delay lines. Phase detector 452 has a resolution approximately the same as the delays in the third delay line. Thus the third delay line provides delay control with finer resolution than that given by the first and second delay lines alone. [0070] In FIG. 4, second delayed clock 442 enters third delay line 440 and passes through delay elements 444 in succession, being delayed by a substantially equal delay time in traversing each element. Each delay element 444 has an input node for receiving a clock signal, and an output node for conveying a delayed copy of the clock signal. The input node of each delay element in delay line 440 , except the first element, connects to the output of the preceding element in the delay line. The input node of the first element in the delay line connects to second delayed clock 442 . The output node of each delay element in the delay line, except the last, connects as described to the input node of the succeeding element. The output node of each delay element in the delay line connects further to a first input node of a separate tap gate 448 for each delay element. [0071] In FIG. 4, a conventional phase detector 452 , and counter 454 control the total delay of the clock signal by the third delay line as follows. Counter 454 is initialized to its midrange count by a pulse on UP 1 or DN 1 whenever coarse delay line 400 is adjusted. Another embodiment of the invention will initialize counter 454 to its midrange count whenever a pulse on UP 2 or DN 2 occurs. Every clock cycle, phase detector 452 compares replica clock 460 to reference clock 402 . When the phase of replica clock 460 leads the phase of reference clock 402 by more than the delay of a delay element 444 , phase detector 452 issues a pulse on its UP 3 output to increment counter 454 , to increase the delay of delay line 440 by the delay of one delay element 444 . When the phase of replica clock 460 follows the phase of reference clock 402 by more than the delay of a delay element 444 , phase detector 452 issues a pulse on its DN 3 output to decrement counter 454 , decreasing the delay of delay line 440 by the delay of one delay element 444 . After pulsing UP 3 or DN 3 , phase detector 452 waits long enough for the adjustment to propagate through the delay lines and back to the phase detector inputs before repeating its compare/adjust operation. When the phase of replica clock 460 is closer to reference clock 402 than the phase detector margin, the phase detector issues neither signal and the loop is locked. [0072] Each bit of the count in counter 454 couples to a separate wire of count bus 456 . Bus 456 routes all bits of the count of counter 454 in parallel to a separate decoder 446 for each delay element in the second delay line. Each decoder 446 has an output connected to a second input of tap gate 448 for the delay stage of the decoder. The second input of each tap gate 448 enables and disables the tap gate for transmitting the delayed clock signal on its first input. Each decoder 446 enables its tap gate only when bus 456 conveys a count that matches its position in delay line 440 . One decoder 446 enables its tap gate for each count held by the counter. The enabled tap gate routes the delayed clock signal out of delay line 440 at a location in the delay line where the clock signal has passed through a number of delay elements 444 equal to the count in counter 454 . [0073] In FIG. 4, an output node of each tap gate 448 in the third delay line connects to a separate input of third delay line output gate 450 . The single enabled tap gate drives its clock signal onto an input of gate 450 . Gate 450 then drives the DQ clock output signal on node 470 , the DQ clock output having a total delay substantially equal to the output of delay element 444 driving the enabled tap gate. [0074] Node 470 further drives the input node of buffer delay model 462 . Buffer delay model 462 then drives the replica clock on node 460 . [0075] [0075]FIG. 5 shows the preferred implementation of the current invention. A buffered reference clock on node 502 is the input signal. A DQ clock on node 570 is the output signal. Three delay lines, 500 , 520 , and 540 coupled in series provide a path for conveying a delayed copy of the reference clock from node 502 to node 570 . A replica clock driven on node 560 by output buffer delay model 562 is the feedback signal. Reference clock 502 connects to an input node of the first delay element of delay line 500 , and also to a first input node of conventional phase detectors 512 and 552 . Replica clock 560 connects to a second input node of phase detectors 512 and 552 . [0076] Delay lines 500 , 520 , and 540 of FIG. 5 use delay elements having two inputs. The logic design of two-input delay element 544 is shown in more detail by FIG. 6, delay element 620 . Delay element 610 corresponds to delay elements 324 or 444 . Delay elements 504 and 524 will use the NOR function shown in delay element 620 on their input structure of the delay circuit being used. These delay elements have a longer delay than delay element 544 of FIG. 5, and to one skilled in logic design can be implemented in many different ways. [0077] In FIG. 5, second delay line 520 uses a wrap control circuit 532 instead of a phase detector for controlling its counter. The wrap control steers counter 534 in the intermediate delay line via pulses on UP 2 and DN 2 lines between the wrap control and its counter, responsive to the digital count in the counter controlling the last, highest resolution delay line in the loop. The wrap control makes its decision to count up, count down, or do nothing so as to prevent counter 554 of the smallest resolution delay line from wrapping around after its count reaches either end of its range. When counter 554 reaches the minimum end of its range, the wrap control decrements medium range counter 534 by pulsing its DN 2 output, to provide less delay from the intermediate delay line 520 and increments counter 554 to increase the delay of delay line 540 by a delay of delay element 524 . This moves counter 554 away from the minimum value with no delay change in signal 560 . When counter 554 reaches the maximum end of its range, the wrap control increments counter 534 by pulsing its UP 2 output, to increase the delay from the second delay line 520 , and decrements counter 554 to decrease the delay of delay line 540 by a delay of delay element 524 . Counter 554 thus moves away from its maximum value with no delay change in signal 560 . After adjusting counter 534 and counter 554 , wrap control 532 and phase detector 552 wait long enough for the adjustment to propagate through the delay lines and back to phase detector 552 before repeating its compare/adjust operation. When counter 554 is not at the end of its numerical range, the wrap control makes no change to counter 534 . [0078] In delay line 500 , the delays of every element 504 are a relatively coarse, substantially equal fraction of the reference clock cycle time. Each delay element 504 has a first input node for receiving a clock signal, a second input node for receiving an active-low enable signal, and an output node for conveying a delayed copy of the clock signal. [0079] The first input node of each delay element in delay line 500 , except the first element, connects to the output of the preceding element in the delay line. The first input node of the first delay element in delay line 500 connects to reference clock node 502 . The second input node of each delay line 500 , except the first element, connects to the output of decoder 506 of the preceding delay stage. The second input node of the first delay element of delay line 500 is tied logically low. The output node of each delay element in the delay line, except the last, connects as described to the input node of the succeeding delay element in delay line 500 . The output node of each delay element in delay line 500 connects further to a first input node of a separate tap gate 508 for each delay element. [0080] A conventional phase detector 512 , and counter 514 control the total delay of the first delay line as follows. Phase detector 512 directly compares reference clock 502 with delayed replica clock 560 . When the phase of replica clock 560 leads the phase of reference clock 502 by more than the delay of a delay element 504 , phase detector 512 increments counter 514 by sending a pulse on its UP 1 output node to counter 514 . When the phase of replica clock 560 follows the phase of reference clock 502 by more than the delay of a delay element 504 , phase detector 512 decrements counter 514 by sending a pulse on its DN 1 output to counter 514 . A pulse on either UP 1 or DN 1 also sets the counts of counters 534 and 554 to their midrange values. After pulsing UP 1 or DN 1 , phase detector 512 waits long enough for the adjustment to propagate through the delay lines and back to the phase detector inputs before repeating its compare/adjust operation. When the delay of the first delay line is correct within the delay of a delay element 504 , phase detector 512 pulses neither UP 1 nor DN 1 , and the first delay line is locked. [0081] Counter 514 may start from a preset count at system startup, or from a random count at startup. Counter 514 may also be initialized to a preset count whenever the DLL is re-enabled. In response to the directional commands from phase detector 512 , counter 514 accumulates a digital count enumerating the number of delays 504 to be applied by delay line 500 to the reference clock. Each bit of counter 514 couples to a separate wire in count bus 516 . Bus 516 routes all bits of the count in counter 514 in parallel to each decoder 506 of first delay line 500 . Each decoder 506 has an output node 507 coupled to a second input of tap gate 508 for the delay element associated with the decoder. Decoder output node 507 further couples to the second input of the delay element of the next succeeding delay stage in delay line 500 . Each decoder 506 disables the following delay element 504 when bus 516 conveys a count equal to its sequential position in the delay line, and enables the following delay element 504 otherwise. Disabling the following delay element at the tap point disables the clock signal from propagating down the remainder of the delay line, effectively powering down all delay elements following the delay line tap point and saving power. [0082] In FIG. 5, the output node of each tap gate 508 in the first delay line connects to a separate input of first delay line output gate 510 . Decoders 506 and tap gates 508 disable all but one of the signals driving gate 510 . The single enabled tap gate drives its clock signal onto an input of gate 510 , with a delay substantially equal to the output of the delay element 504 driving the enabled tap gate. Gate 510 then drives this clock signal on node 522 . [0083] In FIG. 5, first delayed clock 522 enters second delay line 520 and passes through successive delay elements 524 , each of which imparts a fixed, substantially equal, second delay to the clock signal. The second delay represents a smaller fraction of the reference clock cycle time than does the first delay value. Each delay element 524 has a first input node for receiving a clock signal, a second input node for receiving an active-low enable signal, and an output node for conveying a delayed copy of the clock signal. [0084] The first input node of each delay element, except the first, in delay line 520 connects to the output of the preceding element in the delay line. The first input node of the first element in delay line 520 connects to first delayed clock 522 . The second input node of each delay element in delay line 520 , except the first element, couples to the output node of the decoder of the preceding delay stage in the delay line. The second input node of the first delay element in delay line 520 is coupled logically low. The output node of each delay element in the delay line, except the last, connects as described to the input node of the succeeding element. The output node of each delay element in the delay line connects further to a first input node of a separate tap gate 528 for each delay element. [0085] In delay line 520 of FIG. 5, counter 534 has input nodes UP 2 and DN 2 , driven as described by wrap control 532 . Counter 534 also has input nodes UP 1 and DN 1 , driven as described by phase detector 512 . Each bit of counter 534 couples to a separate wire of count bus 536 . Bus 536 conveys each bit of the count from counter 534 in parallel to a separate decoder 526 for each delay element of second delay line 520 . Each decoder 526 has an output node coupled to a second input node of tap gate 528 for its delay element. The second input node of each tap gate enables and disables the tap gate for transmitting the delayed clock signal on its first input node. Each decoder 526 enables its tap gate only when the count on bus 536 equals the sequential position of the decoder and its delay element in delay line 520 . Decoder output node 527 further couples to the second input of the delay element of the next succeeding delay stage in delay line 520 . Each decoder 526 disables the following delay element 524 when bus 536 conveys a count equal to the sequential position of the decoder in the delay line, and enables its delay element 524 otherwise. Disabling the following delay element prevents the clock signal from propagating down the remainder of the delay line following the tap point, saving power. For every count held by the counter, a single tap gate 528 is enabled. The output node of each tap gate 528 drives a separate input of output gate 530 of the second delay line. Decoders 526 and tap gates 528 disable all but one of the signals driving gate 530 . The single enabled tap gate drives its clock signal onto an input of gate 530 , with a delay substantially equal to the output of delay element 524 driving the enabled tap gate. The output of gate 530 then drives a clock signal having the particular delay of the enabled tap gate 528 onto node 542 . [0086] Delayed clock 542 enters third delay line 540 where it passes through successive delay elements 544 . Each delay element 544 delays the clock signal by a substantially equal amount, which is less than the delays of delay elements 524 . Delay lines 500 , 520 , and 540 can be sequentially placed in any order without affecting the functionality of the present invention. [0087] Each delay element 544 has a first input node for receiving a clock signal, a second input node for receiving an active-low enable signal, and an output node for conveying a delayed copy of the clock signal. The first input node of each delay element in delay line 540 , except the first element, connects to the output of the preceding element in the delay line. The first input node of the first element in the delay line connects to second delayed clock 542 . The second input node of each delay element in delay line 540 , except the first element, connects to the output of decoder 546 of the preceding delay stage in the delay line. The second input node of the first delay element in delay line 540 connects logically low. The output node of each delay element in the delay line, except the last, connects as described to the input node of the succeeding element. The output node of each delay element in the delay line connects further to a first input node of a separate tap gate 548 for that delay element. [0088] Delay line 540 of FIG. 5 is controlled by a conventional phase detector 552 , and counter 554 . Phase detector 552 compares input reference clock 502 to delayed replica clock 560 , and sends commands to counter 554 by pulsing the UP 3 and DN 3 lines connecting these two blocks. When the phase of replica clock 560 leads the phase of reference clock 502 by more than a delay of delay element 544 , phase detector 552 pulses the UP 3 line to increment counter 554 , increasing the delay provided by the third delay line by the delay of one delay element 544 . When the phase of replica clock 560 trails the phase of reference clock 502 by more than a delay of delay element 544 , phase detector 552 pulses the DN 3 line to decrement counter 554 , decreasing the delay of the third delay line by effectively removing the delay of one delay element 544 . After pulsing UP 3 or DN 3 to adjust counter 554 , phase detector 552 waits long enough for the adjustment to propagate through the delay lines and back to the inputs of phase detector 552 before repeating its compare/adjust operation. When no change is needed, phase detector 552 sends no pulses and the loop is locked. [0089] Counter 554 in FIG. 5 starts, after an adjustment of delay line 500 , with a preset count in the middle of its numerical range, driven as described by phase detector 512 via nodes UP 1 and DN 1 . Counter 554 accumulates a count as directed by the pulses on its UP 3 and DN 3 input lines. Should this count reach either end of its numerical range, wrap control 532 adjusts counter 554 away from the end of its numerical range and moves counter 534 one step in the opposite direction with the sum of the delays of delay lines 520 and 540 remaining the same. Each bit of the count in counter 554 couples to a separate wire of count bus 556 . Bus 556 routes each bit of the count in parallel to each decoder 546 in the third delay line, and to wrap control 532 of the second delay line. Each decoder 546 has a single output which drives a second input of a separate tap gate 548 coupled to the decoder and to the output of its associated delay element. Each decoder 546 enables its tap gate 548 only when the count on bus 556 is equal to its sequential position in the third delay line. Each value of the count in counter 554 activates one tap gate 548 , to route the clock signal out from delay line 540 after the clock signal has passed through the number of delay elements 544 indicated by the count in counter 554 . [0090] Each output from tap gates 548 drives a separate input of output gate 550 of delay line 540 . Since only one of the tap gates 548 is active, the clock signal passing through the active tap gate 548 drives output gate 550 with the particularly delayed copy of the reference clock signal at the active tap gate 548 . The output of gate 550 drives this delayed clock signal onto node 570 , the DQ output clock. [0091] Node 570 further connects to the input of output buffer delay model 562 , which delays the clock signal by an amount equal to the input and DQ buffer delay. Buffer delay model 562 then drives the replica clock on node 560 . The DQ clock output thus precedes the replica clock by one buffer delay. When the loop is locked and the delayed replica clock on node 560 has the same phase as input reference clock 502 , then the DQ outputs transition coincident with the clock, as required. [0092] A DDR SDRAM device 700 as shown in FIG. 7 comprises at least one array of memory cells 720 for retaining data, with support circuitry for reading, writing, and testing. DDR SDRAM device 700 has a write cycle for writing data from data ports 776 to memory array 720 , and a read cycle for reading data from the array to the data ports. Address latches 710 receive signals from address ports 702 , comprising row address, column address, and command data. Address latch signals couple to row decoders 712 , column select 716 , and controls 714 , respectively. Controls 714 obtain a reference clock and control signals such as chip-select, read/write, and test from external ports 704 , and commands from the address latches to operate row decoders 712 , column select/sense amp 716 , and data path circuits 718 . Controls 714 typically contain a DLL to set the timing of local clock signals on the device. Row decoders 712 select a row 722 of memory cells for access, responsive to the row address and section signals from the controls. Column-select and sense amplifier 716 selects bitlines 724 for access, and performs read/write operations via the selected bitlines. Data buffers 728 receive write data signals from data ports 776 , and convey the write data to the memory array via a data bus 726 , data path logic 718 , column-select/sense amp 716 , and bitlines 724 . Bitlines 724 convey read data signals from the memory array to column-select/sense amp block 716 , and thence to data path logic 718 , the data bus 726 , data buffers 728 , and data ports 776 . [0093] The current invention overcomes the disadvantages of prior art circuits by providing a hierarchy of adjustable, all-digital delay lines having unique controls. Control of delay lines is performed by counter controls, counter, and decoders disposed for each delay line. The counter controls may comprise a phase detector or wrap-control as described. This topology and the design elements that render it stable and small are unique aspects of the current invention providing a novel improvement to speed, size, and stability in delay locked loop design. [0094] Though the above description discloses many details, these details should not be understood to limit the current invention. Obvious changes, such as implementing the tap gates and output gate of each delay line using NOR gates instead of NAND gates, or switching the coarse/fine order of adjustable delay lines, while retaining the structure, function, and/or methods of the current invention, would fall within the scope of the patent rights claimed by the inventor. Therefore the scope of the current invention should be limited only by the appended claims and their legal equivalents.
A delay locked loop for generating a replica clock signal synchronized to an externally generated clock signal comprises a succession of separately controlled delay lines. Each of the delay lines has different delay resolution.
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CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of Korean Patent Application No. 10-2007-0033469, filed on Apr. 4, 2007, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety. BACKGROUND [0002] 1. Field [0003] The present disclosure relates to a method of keyword advertisement, and more particularly, to determining cost-per-click for keyword advertisement. [0004] 2. Discussion of the Related Technology [0005] In a cost per click (CPC, or cost-per-click) computing method, advertisers are required to input each bid amount suitable for a desired rank. Also, when a bid environment is changed due to new advertisement submission and an advertisement display rank is changed, advertisers are required to set a new bid amount for a desired rank. Advertisers are also required to monitor if the advertisement display rank is changed, and a revised bid amount is manually submitted for a desired advertisement display rank. [0006] The discussion in this section is to provide general background information, and does not constitute an admission of prior art. SUMMARY [0007] One aspect of the invention provides a method of computing a cost-per-click for a keyword advertisement, which comprises: receiving a plurality of submissions of proposed keyword advertisements for an identical keyword, each submission comprising an advertisement content and a willing cost-per-click; analyzing the advertisement content of each submission based on relevance of the advertisement content of the submission to the identical keyword, thereby generating a first index for each submission; performing a mathematical operation using the willing cost-per-click and the first index so as to generate a second index for each submission; ordering the second indexes of the plurality of submissions so as to generate rankings of the plurality of submissions, wherein each of the plurality of submissions for the identical keyword has a rank; and computing a cost-per-click for at least part of the plurality of submissions, wherein a first computed cost-per-click for a first submission having a first rank is computed using the second index of a second submission having a second rank that is immediately next to the first rank. [0008] In the foregoing method, the advertisement content may comprise information that is to be displayed on a search result page in response to a search using the keyword. The advertisement content may comprise information contained in a webpage, an anchor tag of which is placed on a search result page in response to a search using the keyword. The willing cost-per-click may be an amount that an advertiser of a proposed keyword advertisement is willing to pay for a click-through of an anchor tag associated with the proposed keyword advertisement that is placed on a search result page in response to a search using the keyword. The first index may be a value indicative of the degree of relevance of the advertisement content of the submission to the keyword. [0009] Still in the foregoing method, analyzing comprises counting the keyword and its derivative terms in the advertisement content, wherein the more the keyword and its derivative terms are, the higher the first index is. The mathematical operation may comprise at least one selected from the group consisting of a summation of the first index and the willing cost-per-click, a multiplication of one or more predetermined coefficients with at least one of the first index and the willing cost-per-click, a multiplication of the first index and the willing cost-per-click, a division of the first index by the willing cost-per-click, a division of the willing cost-per-click by the first index, a deduction of the first index from the willing cost-per-click, and deduction of the willing cost-per-click from the first index. The method may further comprise sending a first computed cost-per-click to a first advertiser of the first submission. The method may further comprise receiving an acceptance of the first computed cost-per-click from the first advertiser, conducting a keyword advertisement for the first advertiser, and charging to the first advertiser at the first computed cost-per-click. [0010] Yet in the foregoing method, the first computed cost-per-click may be between the willing cost-per-click of the first submission and the willing cost-per-click of the second submission. The first computed cost-per-click is not greater than the willing cost-per-click of the first submission. The first computed cost-per-click may be greater than the willing cost-per-click of the second submission as a function of the willing cost-per-click of the second submission. The first rank may be immediately higher than the second rank. The keyword may comprise one or more word. [0011] Further in the foregoing method, the method may further comprise providing historical data of clicking-throughs for at least part of the proposed keyword advertisements, and analyzing the historical data so as to modify the first index for the at least part of the proposed keyword advertisements. Each submission may further comprise a desired rank, wherein the method may further comprise determining whether the desired rank is higher or lower than the rank of the submission generated by ordering the second indexes, wherein if the desired rank is higher than the rank of the submission generated by ordering, the cost-per-click is not computed for the particular submission. [0012] Another aspect of the invention provides a method of computing a cost-per-click for a keyword advertisement, which comprise: receiving a plurality of submissions of proposed keyword advertisements for an identical keyword, each submission comprising a willing cost-per-click and an address of a webpage that is to be displayed on a search result page in response to a search using the keyword; providing historical data of clicking-throughs for at least part of the proposed keyword advertisements that have been previously serviced; analyzing the historical data so as to generate a first index for the at least part of the proposed keyword advertisements; performing a mathematical operation using the willing cost-per-click and the first index so as to generate a second index for each submission; ordering the second indexes of the plurality of submissions so as to generate rankings of the plurality of submissions, wherein each of the plurality of submissions for the identical keyword has a rank; and computing a cost-per-click for one or more of the plurality of submissions, wherein the cost-per-click of a first one of the plurality of submissions having a first rank is computed using the second index of a second one of the plurality of submissions having a second rank that is immediately next to the first rank. [0013] In the foregoing method, analyzing the historical data may comprise ranking the numbers of clicking-throughs for the at least part of the proposed keyword advertisements, wherein the first index is generated based on the ranking of the numbers. The greater the number is, the higher the first index is. The first index may be generated further based on the degree of relevance of the advertisement content of the submission to the keyword. The mathematical operation may comprise at least one selected from the group consisting of a summation of the first index and the willing cost-per-click, a multiplication of one or more predetermined coefficients with at least one of the first index and the willing cost-per-click, a multiplication of the first index and the willing cost-per-click, a division of the first index by the willing cost-per-click, a division of the willing cost-per-click by the first index, a deduction of the first index from the willing cost-per-click, and deduction of the willing cost-per-click from the first index. [0014] Still in the foregoing method, the first computed cost-per-click may be between the willing cost-per-click of the first submission and the willing cost-per-click of the second submission. The first computed cost-per-click is not greater than the willing cost-per-click of the first submission. The first rank may be immediately higher than the second rank. Each submission may further comprise a desired rank, wherein the method may further comprise determining whether the desired rank is higher or lower than the rank of the submission generated by ordering the second indexes, wherein if the desired rank is higher than the rank of the submission generated by ordering, the cost-per-click is not computed for the particular submission. [0015] An aspect of the present invention provides a method and system for automatically controlling a cost-per-click. Another aspect of the present invention also provides a method and system for automatically controlling a cost-per-click which determines an advertisement display rank and whether to display an advertisement using a desired advertisement display rank received by an advertiser, and thereby may guarantee the advertisement to be displayed to a rank equal to or higher than a rank desired by an advertiser, depending on an advertising bid situation. [0016] Another aspect of the present invention also provides a method and system for automatically controlling a cost-per-click, which calculates a ranking index, which may be changed according to an advertising bid environment, using bid data received by an advertiser, and determines the bid amount based on the ranking index, thereby automatically controlling the cost-per-click. [0017] Another aspect of the present invention also provides a method and system for automatically controlling a cost-per-click which uses a maximum cost per click and a quality index (QI) to calculate a maximum ranking index for determining a rank for each advertisement, and thereby enabling quality of an advertisement to be guaranteed. [0018] Another aspect of the present invention also provides a method and system for automatically controlling a cost-per-click which determines a range of the cost-per-click based on a ranking index of a corresponding rank between a maximum ranking index of a corresponding advertisement and a maximum ranking index of a subsequent rank, and thereby enabling an advertiser to pay a more reasonable cost-per-click. [0019] According to an embodiment of the present invention, there is provided a method of automatically controlling a cost-per-click, the method including: receiving a maximum CPC and a desired advertisement display rank from an advertiser; calculating a maximum ranking index for each advertisement using the maximum CPC; determining an advertisement display rank according to the maximum ranking index for each advertisement and the desired advertisement display rank; comparing a maximum ranking index of a corresponding rank and a maximum ranking index of a subsequent rank, and calculating a ranking index or an adjusted ranking index of a corresponding rank; and automatically controlling the cost-per-click based on the adjusted or calculated ranking index of the corresponding rank. [0020] According to an aspect of the present invention, the determining of the advertisement display ranking includes: comparing the desired advertisement display rank and the advertisement display rank ordered according to the maximum ranking index for each advertisement, and excluding a corresponding advertisement from the advertisement display rankings according to an advertisement display on/off display command; and determining the advertisement display rank according to the maximum ranking index for each advertisement after excluding the corresponding advertisement from the advertisement display rank. [0021] According to another aspect of the present invention, the ranking index of the corresponding rank is included in a range which is equal to or greater than the maximum ranking index of the subsequent rank and equal to or less than the maximum ranking index of the corresponding rank, and the comparing and calculating sums the maximum ranking index of the subsequent rank and a value obtained by multiplying a set or adjusting rate and a difference between the maximum ranking index of the corresponding rank and the maximum ranking index of the subsequent rank, to calculate the ranking index of the corresponding rank. [0022] According to still another aspect of the present invention, the automatically controlling determines a value as the cost-per-click, the value being obtained by dividing the calculated ranking index of the corresponding rank into a quality index for each advertisement. Also, when the cost-per-click has an amount with a non-zero digit in a number's place which is less than a predetermined number's place, the amount is rounded up, and when the rounded-up cost-per-click is less than a reference amount, the reference amount is applied as the cost-per-click. [0023] According to another aspect of the present invention, there is provided a system for automatically controlling a cost-per-click, the system including: a bid data input unit receiving a maximum CPC and a desired advertisement display rank from an advertiser; a maximum ranking index calculation unit calculating a maximum ranking index for each advertisement using the maximum CPC; an advertisement display rank determination unit determining an advertisement display rank according to the maximum ranking index for each advertisement and the desired advertisement display rank; a ranking index calculation unit comparing a maximum ranking index of a corresponding rank and a maximum ranking index of a subsequent rank, and calculating a ranking index of the corresponding rank; and a cost-per-click control unit automatically controlling the cost-per-click based on the calculated ranking index of the corresponding rank. A method of automatically controlling a cost-per-click according to an embodiment of the present invention may be performed by a system for automatically controlling a cost-per-click. BRIEF DESCRIPTION OF THE DRAWINGS [0024] The above and/or other aspects and advantages of the present invention will become apparent and more readily appreciated from the following detailed description, taken in conjunction with the accompanying drawings of which: [0025] FIG. 1 is a flowchart illustrating a method of automatically controlling a cost-per-click according to an embodiment of the present invention; [0026] FIG. 2 is a flowchart illustrating an operation of determining an advertisement display rank according to an embodiment of the present invention; [0027] FIG. 3 illustrates an example of receiving a maximum cost per click and a desired advertisement display rank from an advertiser according to an embodiment of the present invention; [0028] FIG. 4 illustrates an example of determining an advertisement display rank according to a maximum ranking index for each advertisement according to an embodiment of the present invention; [0029] FIG. 5 illustrates an example of controlling a cost-per-click based on a ranking index obtained from a maximum ranking index according to an embodiment of the present invention; and [0030] FIG. 6 is a block diagram illustrating a system for automatically controlling a cost-per-click according to an embodiment of the present invention. DETAILED DESCRIPTION OF EMBODIMENTS [0031] Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. [0032] When a rank is not changed after a new advertisement is bid on, advertisers may want a cost-per-click which is less than the bid amount. For example, when a bid amount of 150 is suggested to be the second rank and the third rank bidder offered a bid amount of 100, the second rank advertiser may desire to pay an amount between 100 and 150, not a full bid amount of 150, as a cost-per-click to maintain a current ranking. That is, when a bid amount is set to display an advertisement to a desired rank, the advertiser may need to pay an amount much greater than a minimum cost-per-click required to maintain a desired rank. [0033] FIG. 1 is a flowchart illustrating a method of automatically controlling a cost-per-click according to an embodiment of the present invention. [0034] In operation S 101 , a maximum cost per click or willing cost-per-click and a desired advertisement display rank are received from an advertiser. The maximum CPC is a maximum amount paid per click to display an advertisement to the desired advertisement display rank inputted by the advertiser. The willing cost-per-click is an amount that an advertiser of a proposed keyword advertisement is willing to pay for a click-through of an anchor tag associated with the proposed keyword advertisement that is placed on a search result page in response to a search using the keyword. In one embodiment, based on the maximum CPC of a subsequent rank and the difference between the maximum CPC of one advertiser and the maximum CPC of a subsequent rank, the cost-per-click of the advertiser can be adjusted. [0035] The desired advertisement display rank is any one of a desired ranking and desired ranking range of an advertisement the advertiser desires to expose. Also, the desired advertisement display rank may further include an advertisement display on/off display command according to the desired advertisement display rank. The maximum CPC and desired advertisement display rank are described in greater detail with reference to FIG. 3 . [0036] In operation S 102 , a maximum ranking index for each advertisement is calculated using the maximum CPC inputted by the advertiser. The maximum ranking index for each advertisement may be obtained by multiplying the maximum CPC and a quality index (QI) for each advertisement. In a CPC accounting method, when the QI for each advertisement is low even when the advertiser sets the maximum CPC high, the maximum ranking index may not be high. Accordingly, the advertiser may be required to improve the QI. The QI for each advertisement may be a numerical value of advertising evaluation factors associated with advertising quality, for example, a Click Through Rate (CTR) of the advertisement, degree of association between a search keyword and an advertising copy, degree of association between the search keyword and an advertising site, and the like. [0037] In operation S 103 , an advertisement display rank is determined according to the maximum ranking index for each advertisement and the desired advertisement display rank. [0038] When determining the advertisement display rank using the maximum ranking index for each advertisement calculated in operation S 102 , whether to display the advertisement may be determined according to the desired advertisement display rank inputted by the advertiser. That is, the advertisement display rank is ordered according to the maximum ranking index for each advertisement, a desired advertisement display rank for each advertisement is compared, and thus it may be determined whether to include the advertisement in the advertisement display rank according to the advertisement display on/off display command. The desired ranking for each advertisement is inputted by the advertiser for each ranking. The determining of the advertisement display rank in operation S 103 is described in greater detail with reference to FIGS. 2 and 4 . [0039] In operation S 104 , a maximum ranking index of a corresponding rank and a maximum ranking index of a subsequent rank are compared according to the advertisement display rank determined in operation S 103 , and a ranking index of the corresponding rank is calculated. The ranking index of the corresponding rank may be calculated in descending order of the determined advertisement display rank, although not limited thereto. In this instance, the ranking index of the corresponding rank may be calculated without considering a maximum ranking index of an advertisement excluded from the advertisement display ranking according to the advertisement display on/off display command. [0040] The ranking index of the corresponding rank may be obtained by summing the maximum ranking index of the subsequent rank and a value. The value is obtained by multiplying a set rate and a difference between the maximum ranking index of the corresponding rank and the maximum ranking index of the subsequent rank. The set rate may be set, by the advertiser or the system for automatically controlling a cost-per-click, to be within a range of 0 to 100% of the difference between the maximum ranking index of the corresponding rank and the maximum ranking index of the subsequent rank. Also, the ranking index of the corresponding rank has a same value as the maximum ranking index of the corresponding rank when a rank is the lowest one of the advertisement display ranking. [0041] When the set rate is 0%, the ranking index of the corresponding rank is equal to the maximum ranking index of the subsequent rank. When the set rate is 100%, the ranking index of the corresponding rank is equal to the maximum ranking index of the corresponding rank. Accordingly, the set rate may be included in a range which is equal to or greater than the maximum ranking index of the subsequent rank and equal to or less than the maximum ranking index of the corresponding rank. An example of calculating the ranking index of the corresponding rank is described in greater detail with reference to FIG. 5 . [0042] In operation S 105 , the cost-per-click is automatically controlled based on the calculated ranking index of the corresponding rank calculated in operation S 104 . In this instance, the cost-per-click may be obtained by dividing the calculated ranking index of the corresponding rank into a QI for each advertisement. When the cost-per-click has an amount with a non-zero digit in a number's place which is less than a predetermined number's place, the amount is rounded up, and when the rounded-up cost-per-click is less than a reference amount, the reference amount is applied as the cost-per-click. [0043] For example, when the cost-per-click is 113.6 Korean won and a non-zero digit in a number's place which is less than a one's place is rounded-up, the cost-per-click is controlled to be 120 Korean won. Also, when a reference amount is 130 Korean won, a final cost-per-click is 130 Korean won. For the above-calculation with respect to the cost-per-click, any one of rounding up, rounding off, and rounding down is used. An example of calculating the cost-per-click based on the ranking index of the corresponding rank is described in greater detail with reference to FIG. 5 . [0044] FIG. 2 is a flowchart illustrating an operation of determining an advertisement display rank according to an embodiment of the present invention. [0045] An operation of determining the advertisement display rank in operation S 103 is illustrated in FIG. 2 . In brief, the advertisement display rank may be determined according to the maximum ranking index for each advertisement and the desired advertisement display rank. [0046] In operation S 201 , to determine the advertisement display rank using the maximum ranking index for each advertisement, a corresponding advertisement may be excluded from the advertisement display ranking according to the advertisement display on/off display command inputted by the advertiser. The maximum ranking index for each advertisement is calculated in operation S 102 . The desired advertisement display rank and the advertisement display rank ordered according to the maximum ranking index for each advertisement are compared. When the ordered advertisement display rank is not included in the desired advertisement display rank or desired ranking range, whether to display the advertisement may be determined according to the advertisement display on/off display command. [0047] For example, when the advertisement display rank is third and the advertiser inputs “second/on” or “second or higher/on” as the desired advertisement display rank condition, a corresponding advertisement may not be displayed and may be excluded from the advertisement display ranking, since the ordered advertisement display rank is not included in the desired advertisement display rank or desired ranking range and an advertisement display on display command is set. Although the advertisement display on/off display command may be interpreted differently from the above description, the advertisement display on display command indicates the advertisement is exposed, and an advertisement display off display command indicates the advertisement is excluded. That is, whether to display the advertisement may be determined depending on the desired advertisement display rank inputted by the advertiser and advertisement display on/off display command. [0048] In operation S 202 , the advertisement display rank is determined according to the maximum ranking index for each advertisement, after excluding the corresponding advertisement using the desired advertisement display rank and advertisement display on/off display command. In this instance, rankings of advertisements in subsequent ranks of the corresponding advertisement, excluded from the advertisement display ranking ordered according to the maximum ranking index for each advertisement, may rise. The advertisement excluded from the advertisement display ranking may be listed on a ranking list according to the maximum ranking index for each advertisement, but may not be actually included in the advertisement display ranking. An example of the determining in operation S 201 and operation S 202 is described in detail with reference to FIG. 4 . [0049] FIG. 3 illustrates an example of receiving a maximum CPC and a desired advertisement display rank from an advertiser according to an embodiment of the present invention. [0050] The maximum CPC is a maximum amount per click paid by the advertiser to display an advertisement. A difference between a maximum CPC of a subsequent rank and the maximum CPC is controllable to be within a range of 0 to 100% of the maximum CPC. For example, when a first advertiser's maximum CPC is 100, a second advertiser may input the second advertiser's maximum CPC from 100 to 200. When the difference between the maximum CPC of the subsequent rank and the maximum CPC exceeds a certain limit, a goal of advertising bid may not be achieved. Accordingly, a range of the difference is limited. The range may vary depending on a situation of system, popularity of advertisement, a number of advertisers that desire to bid, maximum CPC, and the like. [0051] The desired advertisement display rank is a rank which is set to display the advertisement to a rank desired by the advertiser. A desired ranking range may refer to a range from a lowest display rank desired by the advertiser to a higher display rank than the lowest display rank. For example, when the advertiser desires to display the advertisement to a third position, the desired ranking range is to be specified as “third or higher”. Also, an advertisement display on/off display command may be used to determine whether to exclude the advertisement from the advertisement display ranking by comparing the desired advertisement display rank and the advertisement display rank ordered according to the maximum ranking index for each advertisement. [0052] As illustrated in FIG. 3 , an advertiser of an advertisement A and an advertiser of an advertiser D input 200 as a maximum CPC, and an advertiser of an advertisement C inputs 300 as a maximum CPC. As described above, the advertiser of the advertisement C may input 200 through 400 as the maximum CPC so that an advertisement with the maximum CPC of 200 is to be a subsequent rank. The maximum CPC of 200 through 400 is a range where 0 to 100% of the maximum CPC is added to the maximum CPC of 200. In FIG. 3 , it is indicated that the advertisement A is displayed only when a rank ordered according to a maximum ranking index is second or higher. Also, it is indicated that the advertisement C is displayed only when the ranking ordered according to the maximum ranking index is first. [0053] Also, it is indicated that an advertisement E is displayed only when the ranking ordered according to the maximum ranking index is fourth or lower. Specifically, the advertisement E is not displayed when the ranking ordered according to the maximum ranking index is third or higher. However, whether to display the advertisement may not be actually determined only based on data illustrated in FIG. 3 , and may be determined according to the desired advertisement display rank and maximum ranking index for each advertisement. The desired advertisement display rank and maximum ranking index for each advertisement are calculated using the maximum CPC. Although the advertisement display on/off display command may be interpreted differently from the above description, an advertisement display on display command indicates the advertisement is exposed, and an advertisement display off display command indicates the advertisement is excluded. [0054] FIG. 4 illustrates an example of determining an advertisement display rank according to a maximum ranking index for each advertisement according to an embodiment of the present invention. [0055] In a table 401 , the maximum ranking index is calculated by multiplying a QI of a corresponding advertisement and a maximum CPC inputted by an advertiser, and the calculated maximum CPC is ordered in descending order. A rank in the table 401 is not an actual advertisement display rank, and may be controlled according to a desired advertisement display rank. As illustrated in the table 401 , even though the advertiser input a high maximum CPC, since the QI of the corresponding advertisement affects the maximum ranking index, the maximum ranking index may not be determined only based on the maximum CPC. Accordingly, to raise the maximum ranking index which affects an actual rank, setting the maximum CPC high or improving the QI may be required. [0056] In a table 402 , an actual advertisement display rank after determining whether to display the advertisements by considering the desired advertisement display rank and the advertisement display rank ordered based on the table 401 is illustrated. The desired advertisement display rank is inputted by the advertiser. [0057] In principle, the actual advertisement display rank may be determined according to the maximum ranking index. The maximum ranking index is obtained by multiplying the QI of the advertisement and the maximum CPC inputted by the advertiser. Accordingly, the actual advertisement display rank is determined in an order of the advertisement C, advertisement D, advertisement B, advertisement A, and advertisement E which are ordered according to the maximum ranking index in the table 401 . However, whether to display the advertisement may be determined according to the desired advertisement display rank inputted by the advertiser, and may be examined in descending order, respectively. [0058] In the table 402 , since a desired advertisement display rank of the advertisement C, that is, first-ranked advertisement, is “first/on”, the advertisement C is displayed and the actual advertisement display rank may be maintained. Also, a desired advertisement display rank of the advertisement D, that is, second-ranked advertisement, is “second or higher/on”, and a desired advertisement display rank of the advertisement B, that is, third-ranked advertisement, is “third or higher/on”, and thus the advertisement D and the advertisement B are displayed since each desired ranking range is satisfied. Also, the actual advertisement display rank may be maintained. [0059] However, a desired advertisement display rank of the advertisement A, that is, fourth-ranked advertisement, is “second or higher/on”, and thus the advertisement A is not displayed since the desired ranking range is not satisfied. The advertisement A may be excluded from the actual advertisement display ranking. Also, although the advertisement E, that is, fifth-ranked advertisement, corresponds to a subsequent rank of the advertisement A, the advertisement E may raise to the fourth-ranked advertisement, since the advertisement A is excluded from the actual advertisement display ranking. In this instance, since a desired advertisement display rank of the advertisement E is “third or higher/off”, the fourth-rank is not included in the range of ‘third or higher’. Accordingly, the advertisement E is not excluded from the actual advertisement display ranking, and a rank of the advertisement E is fourth. [0060] Thus, the advertisement C, advertisement D, advertisement B, and advertisement E are actually displayed in the order of the advertisement C, advertisement D, advertisement B, and advertisement E. Also, since the advertisement A is not exposed, an advertiser of the advertisement A is required to re-input the maximum CPC to display the advertisement A to a desired rank. When it is assumed that a new bid is added, the maximum ranking index is determined according to a bid amount, and thus an advertisement display rank may be automatically controlled according to the above-described operations. [0061] FIG. 5 illustrates an example of controlling a cost-per-click based on a ranking index obtained from a maximum ranking index according to an embodiment of the present invention. [0062] A table 501 illustrates the cost-per-click and a ranking index of a corresponding rank. The cost-per-click and the ranking index of the corresponding rank are obtained from a determined advertisement display rank and maximum ranking index for each advertisement. The maximum ranking index for each advertisement is calculated using a maximum CPC, and the cost-per-click is calculated based on the ranking index. [0063] The ranking index of the corresponding rank may be determined by comparing a maximum ranking index of the corresponding rank and a maximum ranking index of a subsequent rank in descending order of the determined advertisement display rank. In this instance, a maximum ranking index of an advertisement excluded from the advertisement display ranking is not compared. [0064] The ranking index of the corresponding rank may be determined by summing the maximum ranking index of the subsequent rank and a value. The value is obtained by multiplying a set rate and a difference between the maximum ranking index of the corresponding rank and the maximum ranking index of the subsequent rank. A method of determining the ranking index of the corresponding rank may be represented as, [0000] RI ( i )={Max RI ( i+ 1)+(Max RI ( i )−Max RI ( i+ 1))* x %}  [Equation 1] [0065] where RI(i) denotes the ranking index of the corresponding rank, Max RI(i) denotes the maximum ranking index of the corresponding rank, Max RI(i+1) denotes the maximum ranking index of the subsequent rank, and x % denotes the set rate. The set rate may be set, by an advertiser or the system for automatically controlling a cost-per-click, to be within a range of 0 to 100% of the difference between the maximum ranking index of the corresponding rank and the maximum ranking index of the subsequent rank. In FIG. 5 , the set rate is 20%. [0066] When Equation 1 is applied, a ranking index of an advertisement C, that is, first-ranked advertisement, may be determined by summing a maximum ranking index of an advertisement D, that is, second-ranked advertisement, and a value. The value is obtained by multiplying the set rate and a difference between a maximum ranking index of the advertisement C and the maximum ranking index of the advertisement D. Equation 1 is applied to Equation 2. The ranking index of the advertisement C may be represented as RI(1), which is calculated by, [0000] R   I  ( 1 ) =  { Max   R   I  ( 2 ) + ( Max   R   I  ( 1 ) - Max   R   I  ( 2 ) * 20  % } =  { 800 + ( 900 - 800 ) * 20  % } =  820 [ Equation   2 ] [0067] A ranking index of the advertisement D and a ranking index of an advertisement B, that is, third-ranked advertisement, may be represented as RI(2) and RI(3), respectively. In the same way as the method of determining the ranking index of the corresponding rank, when Equation 1 is applied, the ranking index of the advertisement D and the ranking index of the advertisement B may be calculated by, [0000] R   I  ( 2 ) =  { Max   R   I  ( 3 ) + ( Max   R   I  ( 2 ) - Max   R   I  ( 3 ) * 20  % } =  { 750 + ( 800 - 750 ) * 20  % } =  760 [ Equation   3 ] R   I  ( 3 ) =  { Max   R   I  ( 4 ) + ( Max   R   I  ( 3 ) - Max   R   I  ( 4 ) * 20  % } =  { 450 + ( 750 - 450 ) * 20  % } =  510 [ Equation   4 ] [0068] Equation 1 may not be applied to an advertisement which is the lowest one of the advertisement display ranking, since a maximum ranking index of a subsequent rank of the advertisement does not exist. Accordingly, a ranking index of the lowest rank may be the same as the maximum ranking index of the corresponding advertisement. Thus, a ranking index of the advertisement E, that is, the lowest ranked-advertisement, may be 450 which is the same as the maximum ranking index of the advertisement E. Also, the ranking index of the advertisement E may be represented as RI(4). [0069] The ranking index of the corresponding rank may be included in a range which is equal to or greater than the maximum ranking index of the subsequent rank, and equal to or less than the maximum ranking index of the corresponding rank. That is, as long as a new bid having an amount greater than the maximum ranking index of the corresponding rank is not suggested, an existing advertiser is required to pay a cost-per-click based on the ranking index within the range, in order to maintain a desired rank. Also, the existing advertiser is not required to pay a bid amount corresponding to the maximum ranking index of the corresponding rank, which is advantageous in terms of cost. Accordingly, the ranking index of the corresponding rank is a relative value, not an absolute value. When a new advertiser inputs a maximum CPC and desired advertisement display rank to bid, a maximum ranking index is calculated, and thus an existing advertisement display rank changes and ranking index may change. [0070] In the example above, it may be assumed that an advertisement F is newly bid on. The advertisement F has a ranking index greater than the ranking index of the advertisement B and a maximum ranking index less than the maximum ranking index of the advertisement B. The maximum ranking index of the advertisement F is calculated using a maximum CPC of the advertisement F inputted by the advertiser. When the advertisement display rank is determined using the maximum ranking index without considering the desired advertisement display rank, the advertisement F corresponds to the ranking index of the advertisement B and advertisement E. Accordingly, the ranking index of each of the advertisement B and advertisement E automatically changes. In this instance, Equation 1 is applied. Thus, the ranking index may flexibly change according to a bid environment change and the cost-per-click is controlled. [0071] Also, the advertiser may determine the cost-per-click based on the ranking index of the corresponding rank. Here, the cost-per-click may be determined by dividing the ranking index of the corresponding rank into a QI for each advertisement. A method of calculating the cost-per-click may be represented as, [0000] BA  ( i ) =  R   I  ( i ) / Q   I  ( i ) =  { Max   R   I  ( i + 1 ) + ( Max   R   I  ( i ) - Max   R   I  ( i + 1 ) ) * x   % } / Q   I  ( i ) [ Equation   5 ] [0072] where BA(i) denotes a cost-per-click of the corresponding rank, QI(i) denotes a QI for each advertisement of the corresponding rank, RI(i) denotes a ranking index of the corresponding rank, Max RI(i) denotes a maximum ranking index of the corresponding rank, Max RI(i+1) denotes a maximum ranking index of the subsequent rank, and x % denotes the set rate. [0073] Accordingly, the cost-per-click for each advertisement of the corresponding rank may be calculated by, [0000] BA (1)= RI (1)/ QI (1)=820/3=273.3 [0000] BA (2)= RI (2)/ QI (2)=760/4=190 [0000] BA (3)= RI (3)/ QI (3)=510/5=102 [0000] BA (4)= RI (4)/ QI (4)=450/5=90  [Equation 6] [0074] In this instance, when the cost-per-click has an amount with a non-zero digit in a number's place which is less than a predetermined number's place, the amount may be rounded up, and when the rounded-up cost-per-click is less than a reference amount, the reference amount is applied as the cost-per-click. In a table 502 , a non-zero digit in a number's place which is less than a one's place is rounded-up. When the rounded-up cost-per-click is less than 100 which is the reference amount, 100 is applied as the cost-per-click. Accordingly, the cost-per-click for each advertisement is 280, 190, 110, and 100. When a new bid amount is suggested, the cost-per-click for each advertisement may be changed and the ranking index may also be changed, as described above. [0075] FIG. 6 is a block diagram illustrating a system 601 for automatically controlling a cost-per-click according to an embodiment of the present invention. [0076] The system 601 for automatically controlling a cost-per-click may include a bid data input unit 602 , a maximum ranking index calculation unit 603 , an advertisement display rank determination unit 604 , a ranking index calculation unit 605 , and a cost-per-click control unit 606 . [0077] The bid data input unit 602 may receive a maximum CPC and a desired advertisement display rank from an advertiser. The maximum CPC and desired advertisement display rank are bid data. [0078] The maximum ranking index calculation unit 603 may calculate a maximum ranking index for each advertisement by multiplying the maximum CPC received by the bid data input unit 602 and a QI of a corresponding advertisement. [0079] The advertisement display rank determination unit 604 may determine an advertisement display rank according to the maximum ranking index for each advertisement and the desired advertisement display rank. The maximum ranking index for each advertisement is calculated by the maximum ranking index calculation unit 603 . In this instance, the desired advertisement display rank and the advertisement display rank ordered according to the maximum ranking index for each advertisement are compared. Also, after excluding a corresponding advertisement from the advertisement display rank according to an advertisement display on/off display command, the advertisement display rank may be determined. [0080] The ranking index calculation unit 605 may compare a maximum ranking index of a corresponding rank and a maximum ranking index of a subsequent rank, and calculate a ranking index of the corresponding rank. The ranking index of the corresponding rank may be calculated in descending order of the determined advertisement display rank. A maximum ranking index of an advertisement excluded from the advertisement display ranking according to an advertisement display on/off display command may be excluded when comparing. [0081] A method of calculating a ranking index of the corresponding rank may be obtained by summing the maximum ranking index of the subsequent rank and a value. The value is obtained by multiplying a set rate and a difference between the maximum ranking index of the corresponding rank and the maximum ranking index of the subsequent rank. In this instance, the ranking index calculation unit 605 may apply a same value as the maximum ranking index of the corresponding rank when a rank is the lowest one of the advertisement display ranking. [0082] The cost-per-click control unit 606 may automatically control the cost-per-click by dividing the calculated ranking index of the corresponding rank into a QI for each advertisement. [0083] The method of automatically controlling a cost-per-click according to the above-described embodiment of the present invention may be recorded in computer-readable media including program instructions to implement various operations embodied by a computer. The media may also include, alone or in combination with the program instructions, data files, data structures, and the like. Examples of computer-readable media include magnetic media such as hard disks, floppy disks, and magnetic tape; optical media such as CD ROM disks and DVD; magneto-optical media such as optical disks; and hardware devices that are specially configured to store and perform program instructions, such as read-only memory (ROM), random access memory (RAM), flash memory, and the like. The media may also be a transmission medium such as optical or metallic lines, wave guides, and the like, including a carrier wave transmitting signals specifying the program instructions, data structures, and the like. Examples of program instructions include both machine code, such as produced by a compiler, and files containing higher level code that may be executed by the computer using an interpreter. The described hardware devices may be configured to act as one or more software modules in order to perform the operations of the above-described embodiments of the present invention. [0084] According to an embodiment of the present invention, there is provided a method and system for automatically controlling a cost-per-click which sets a rank and automatically retrieves a cost-per-click for the rank when bidding. [0085] Also, according to an embodiment of the present invention, there is provided a method and system for automatically controlling a cost-per-click which determines an advertisement display rank and whether to display an advertisement using a desired advertisement display rank received by an advertiser, and thereby may guarantee the advertisement to be displayed to a rank equal to or higher than a rank desired by an advertiser, depending on an advertising bid situation. [0086] Also, according to an embodiment of the present invention, there is provided a method and system for automatically controlling a cost-per-click which calculates a ranking index, which may change according to an advertising bid environment, using bid data received by an advertiser, determines the cost-per-click based on the ranking index, and thereby may automatically control the cost-per-click. [0087] Also, according to an embodiment of the present invention, there is provided a method and system for automatically controlling a cost-per-click which uses a maximum CPC and a QI to calculate a maximum ranking index for determining a rank for each advertisement, and thereby may enable quality of an advertisement to be guaranteed. [0088] Also, according to an embodiment of the present invention, there is provided a method and system for automatically controlling a cost-per-click which determines a range of the cost-per-click based on a ranking index of a corresponding rank between a maximum ranking index of a corresponding advertisement and a maximum ranking index of a subsequent rank, and thereby may enable an advertiser to pay a more reasonable cost-per-click. [0089] Although embodiments of the present invention have been shown and described, the present invention is not limited to the described embodiments. Instead, it would be appreciated by those skilled in the art that changes may be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Disclosed is a method of computing a cost-per-click for a keyword advertisement. The method comprises receiving a plurality of submissions of proposed keyword advertisements for an identical keyword. Each submission comprises an advertisement content and a willing cost-per-click. The advertisement content of each submission or historical data is analyzed so as to generate a first index for each submission. A mathematical operation using the willing cost-per-click and the first index is performed so as to generate a second index for each submission. The second indexes of the submissions are ordered so as to generate rankings of the submissions. A cost-per-click for each submission is computed. A first computed cost-per-click for a first submission having a first rank is computed using the second index of a second submission having a second rank that is immediately next to the first rank.
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BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flattening method and a flattening apparatus, and more particularly to a flattening method and a flattening apparatus for flatly processing a surface (surface to be processed) of a workpiece, such as a simple substrate consisting of SiC or GaN, a bonded substrate (epitaxial substrate) having a layer of SiC or GaN, or a substrate for use in MEMS (micro electro mechanical system). 2. Description of the Related Art With the recent progress toward higher integration of semiconductor devices, the circuit interconnects are becoming finer and the distance between adjacent interconnects is becoming smaller. Especially when forming a circuit pattern by optical lithography with a line width of not more than 0.5 μm, a stepper requires a high flatness of imaging surface because of the small depth of focus. A CMP apparatus for carrying out chemical mechanical polishing (CMP) is known as a means for flattening a surface of such a semiconductor substrate. SiC, GaN, etc. are becoming increasingly important as a material for semiconductor devices. As a new processing method for flatly processing with high precision a surface of SiC or GaN, a CARE (catalyst-referred etching) method has been proposed which utilizes a catalytic action, capable of a chemical reaction, to etch a surface of a workpiece. The CARE method comprises immersing a workpiece in a processing solution containing hydrohalic acid, such as hydrofluoric acid; placing a platinum, gold or ceramic solid catalyst in contact with or close proximity to a surface (surface to be processed) of the workpiece so as to cause molecular dissociation of hydrogen halide at the surface of the catalyst, thereby generating a halogen radical; and dissolving a halogen compound, which has been produced by chemical reaction between the halogen radical and a surface atom of the workpiece, in the processing solution. The surface of the workpiece is processed (etched) in this manner (see e.g., Japanese Patent Laid-Open Publication No. 2006-114632). BRIEF SUMMARY OF THE INVENTION The CARE method, which carries out removal processing (etching) of a surface of a workpiece, e.g., composed of SiC or GaN, has the advantageous features that it can process a surface (surface to be processed) of a workpiece with higher precision as compared to conventional processing methods such as CMP and can obtain a processed surface having high flatness and, in addition, can process the workpiece without leaving damage in the processed surface. However, the CARE method, in which removal processing (etching) of a surface of a workpiece progresses through dissolution in a processing solution of a halogen compound produced by chemical reaction between a halogen radical and a surface atom of the workpiece, has the drawback that the processing rate is significantly low as compared to grinding, CMP, etc. which are commonly used in the manufacturing of a semiconductor device. Thus, high-throughput processing is difficult with the CARE method. The present invention has been made in view of the above situation in the related art. It is therefore an object of the present invention to provide a flattening method and a flattening apparatus which, by utilizing the advantages of the CARE method and making up for the disadvantages, can perform removal processing of a surface of a workpiece at a sufficient processing rate and can provide a processed surface having enhanced flatness without leaving damage in the processed surface. In order to achieve the object, the present invention provides a flattening method comprising at least two surface removal steps and at least two cleaning steps, the final surface removal step being a catalyst-referred etching step comprising immersing a workpiece in a processing solution containing at least one of hydrohalic acid, hydrogen peroxide water and ozone water, and bringing a surface of a catalyst platen into contact with or close proximity to a surface to be processed of the workpiece to process the surface to be processed, said catalyst platen having in a surface a catalyst selected from the group consisting of platinum, gold, a ceramic solid catalyst, a transition metal, glass, and an acidic or basic solid catalyst. The “surface removal step” is the step of processing and removing a surface portion of a workpiece, such as a substrate, and the “cleaning step” is the step of removing particulate contaminants, organic contaminants, metal contaminants, etc. from the surface of the workpiece before or after the surface removal step. The cleaning step also includes the step of removing an oxide film remaining on the surface of the workpiece after the surface removal step. According to this flattening method, after carrying out at least one surface removal step to enhance the flatness of a surface to be processed of a workpiece, CARE processing, which can flatly process the surface (surface to be processed) of the workpiece with high precision, is carried out in the final surface removal step. This makes it possible to process the workpiece at a sufficient processing rate while gradually enhancing the flatness of the surface to be processed and finally create a damage-free, very flat processed surface. The processing solution may also contain a wetting improver for improving wetting of the catalyst platen. Nitric acid or ethanol may be used as the wetting improver. When processing is carried out using hydrofluoric acid as a processing solution and platinum as a catalyst, because of poor wetting of a surface of platinum with hydrofluoric acid, it is difficult to efficiently supply the processing solution (hydrofluoric acid) to the catalyst surface which serves as a processing reference surface. In such a case, efficient supply of the hydrofluoric acid processing solution to the catalyst surface becomes possible by adding a wetting improver to the processing solution. Preferable examples of the wetting improver include nitric acid and ethanol. The processing solution may also contain a buffering agent for pH adjustment. The processing solution may also contain an organic alcohol or an inorganic acid. Methanol or ethanol may be used as the organic alcohol, and sulfuric acid or nitric acid may be used as the inorganic acid. The processing solution may also contain a buffering agent. A buffering agent is a solution which prevents a change in the pH of the processing solution even when a small amount of an acid or base is added to the processing solution. Especially when processing GaN, because of the formation of its oxide Ga 2 O 3 which is soluble in an acid or a base, it is necessary to keep the processing solution at a pH around 7 so as to prevent dissolution of Ga 2 O 3 in the processing solution. The pH of the processing solution can be adjusted by adding a pH-adjusted buffering agent to the processing solution. Further, a buffering agent has the property of consuming H + ions or OH + ions generated, and therefore can shorten the active distance of H + ions or OH + ions in the vicinity of an acidic or basic solid catalyst. Thus, the use of a buffering agent can cause H + ions or OH + ions to be present only in close proximity to a solid catalyst, making it possible to more flatly process a workpiece. The present invention also provides a flattening method comprising at least two surface removal steps and at least two cleaning steps, the final surface removal step being a catalyst-referred etching step comprising immersing a workpiece in a processing solution containing a buffering agent, and bringing a surface of a catalyst platen into contact with or close proximity to a surface to be processed of the workpiece to process the surface to be processed, said catalyst platen having in the surface a catalyst selected from the group consisting of platinum, gold, a ceramic solid catalyst, a transition metal, glass, and an acidic or basic solid catalyst. At least one of the surface removal steps other than the final surface removal step may be grinding, lapping, CMP or light irradiation catalyst-referred etching of the surface to be processed of the workpiece, the light irradiation catalyst-referred etching corresponding to said catalyst-referred etching step as carried out under light irradiation. For example, it is possible to first carry out a surface removal step by grinding or lapping which, though the processing accuracy is not so high, can be carried out at a relatively high processing rate, and also carry out, according to necessity, CMP or light irradiation catalyst-referred etching, i.e., catalyst-referred etching carried out under light irradiation, and lastly carry out the catalyst-referred etching step as the final surface removal step. This flattening process can flatten a surface to be processed, having relatively large initial irregularities, of a workpiece into a processed surface having a desired flatness in a shorter time. The grinding may be carried out by, for example, electrolytic in-process dressing (ELID) mirror grinding. CMP or light irradiation catalyst-referred etching, i.e., catalyst-referred etching carried out under light irradiation, though inferior to catalyst-referred etching in terms of the flatness of a processed surface, can perform surface removal processing at a higher processing rate as compared to catalyst-referred etching. Accordingly, by carrying out catalyst-referred etching after carrying out CMP or light irradiation catalyst-referred etching, the overall processing rate can be increased. At least one of the cleaning steps may be SPM (sulfuric acid-hydrogen peroxide mixture) cleaning, aqua regia cleaning or hydrofluoric acid cleaning. A surface to be processed of a workpiece can be cleaned by aqua regia cleaning when the surface to be processed is contaminated with platinum, by SPM cleaning when the surface to be processed is contaminated with organic matter or with a metal other than noble metals, or by hydrofluoric acid cleaning when an oxide film is formed in the surface to be processed. At least one of the cleaning steps may be rinsing of the workpiece in a cleaning unit. At least one of the cleaning steps may be rinsing of the workpiece carried out around the catalyst platen. The present invention also provides a flattening apparatus comprising at least two surface removal processing units and at least two cleaning units, the surface removal processing unit for carrying out the final surface removal processing being a catalyst-referred etching unit comprising: a catalyst platen having in a surface a catalyst selected from the group consisting of platinum, gold, a ceramic solid catalyst, a transition metal, glass, and an acidic or basic solid catalyst; a holder for holding a workpiece and bringing a surface to be processed of the workpiece into contact with or close proximity to the surface of the catalyst platen; a processing solution supply section for supplying a processing solution, containing at least one of hydrohalic acid, hydrogen peroxide water and ozone water, to between the catalyst platen and the workpiece held by the holder and kept in contact with or close proximity to the surface of the catalyst platen; and a drive section for moving the catalyst platen and the workpiece, held by the holder and kept in contact with or close proximity to the surface of the catalyst platen, relative to each other. The present invention also provides a flattening apparatus comprising at least two surface removal processing units and at least two cleaning units, the surface removal processing unit for carrying out the final surface removal processing being a catalyst-referred etching unit comprising: a catalyst platen having in a surface a catalyst selected from the group consisting of platinum, gold, a ceramic solid catalyst, a transition metal, glass, and an acidic or basic solid catalyst; a holder for holding a workpiece and bringing a surface to be processed of the workpiece into contact with or close proximity to the surface of the catalyst platen; a processing solution supply section for supplying a processing solution containing a buffering agent to between the catalyst platen and the workpiece held by the holder and kept in contact with or close proximity to the surface of the catalyst platen; and a drive section for moving the catalyst platen and the workpiece, held by the holder and kept in contact with or close proximity to the surface of the catalyst platen, relative to each other. Preferably, a plurality of through-holes is formed in the catalyst platen. A processing solution can be uniformly supplied through the through-holes to the surface of the catalyst platen, whereby an entire surface to be processed of a workpiece can be processed more uniformly. Preferably, a plurality of concentric grooves is formed in the surface of the catalyst platen. A processing solution can be held in the grooves provided in the surface of the catalyst platen, thus allowing the processing solution to be present between a workpiece and the catalyst platen. The holder preferably has a retainer ring, made of the same material as the surface of the catalyst platen, for preventing escape of the workpiece. When the holder having the retainer ring is used, there is a case where the retainer ring contacts the catalyst platen and is chipped off, and the retainer ring chip adheres to the surface of the catalyst platen. Even in such a case, the retainer ring chip, because of the same material as the surface of the catalyst platen, will not adversely affect the removal processing reaction. In a preferred aspect of the present invention, the flattening apparatus further comprises a conditioning section for carrying out conditioning of the surface of the catalyst platen. Specific examples of the conditioning section include: a pure water jet nozzle for jetting pure water toward the catalyst platen while causing cavitation or applying ultrasonic waves as necessary; a light irradiator for applying light to the catalyst platen to remove a broken piece or an organic contaminant from the surface of the catalyst platen by photoelectrochemical etching; and an electrolytic removal apparatus which includes an electrode disposed opposite the catalyst platen and removes a broken piece or an organic contaminant from the surface of the catalyst platen by applying a voltage between the catalyst platen and the electrode. A broken piece which has been separated from the catalyst platen can be removed, e.g., by filtration. At least one of the surface removal processing units other than the surface removal processing unit for carrying out the final surface removal processing may be a grinding unit, a lapping unit, a CMP unit, or a light irradiation catalyst-referred etching unit having the same construction as said catalyst-referred etching unit but additionally comprising a light source. According to the present invention, after carrying out at least one surface removal step to enhance the flatness of a surface to be processed of a workpiece, CARE (catalyst-referred etching) processing, which can flatly process the surface (surface to be processed) of the workpiece with high precision, is carried out in the final surface removal step. This makes it possible to process the workpiece at a sufficient processing rate while gradually enhancing the flatness of the surface to be processed and finally create a damage-free, very flat processed surface. The present invention thus makes it possible to increase the throughput while fully enjoying the merits of CARE. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a plan view showing the overall construction of a flattening apparatus according to an embodiment of the present invention; FIG. 2 is a vertical sectional front view schematically showing a CARE unit used as a final surface removal processing unit in the flattening apparatus of FIG. 1 ; FIG. 3 is a plan view of a catalyst platen for use in the CARE unit of FIG. 2 ; FIG. 4 is an enlarged view of a portion of FIG. 3 ; FIG. 5 is a plan view of another catalyst platen; FIG. 6 is a cross-sectional view showing the catalyst platen shown in FIG. 5 as mounted to a rotating body; FIG. 7 is a graph showing the results of total reflection X-ray fluorescence analysis of platinum contamination as measured on a sample after CARE processing and on the processed sample after cleaning with aqua regia; FIG. 8 is a graph showing the results of total reflection X-ray fluorescence analysis of platinum contamination as measured on a sample after CARE processing, on the processed sample after cleaning with SPA and on the processed sample after additional cleaning with hydrofluoric acid (HF); FIGS. 9A and 9B are graphs showing the results of X-ray photoelectron spectroscopy of iron contamination as measured on a sample after CARE processing and on the processed sample after cleaning with SPM; FIG. 10 is a graph showing the results of X-ray photoelectron spectroscopy of a surface of an SiC sample after light irradiation CARE processing; FIG. 11 is a graph showing the results of X-ray photoelectron spectroscopy of the surface of the processed SiC sample of FIG. 10 as measured after cleaning the sample with hydrofluoric acid; FIGS. 12A through 12D are diagrams illustrating the concept of CARE processing of a workpiece with the use of a processing solution containing a buffer solution (buffering agent); FIG. 13 is a diagram schematically showing a CARE unit (light irradiation CARE unit) provided with a light source; FIG. 14A shows a phase-shifting interference microscopic image of a surface of a sample (GaN wafer) before CARE processing, FIG. 14B shows a phase-shifting interference microscopic image of the surface of the sample after carrying out CARE processing using a processing liquid (ultrapure water) not containing a buffer solution (buffering agent), and FIG. 14C shows a phase-shifting interference microscopic image of the surface of the sample after carrying out CARE processing using a processing solution containing a buffer solution (buffering agent); FIG. 15 shows XPC O1s spectra for a GaN substrate having a vapor-deposited platinum film on a back surface and for a GaN substrate having no platinum film on a back surface, as measured before and after carrying out light irradiation of the substrates while immersing the substrates in ultrapure water; and FIG. 16A shows a phase-shifting interference microscopic image of a surface of a sample (GaN substrate), having no vapor-deposited platinum film on a back surface, before light irradiation CARE processing, FIG. 16B shows a phase-shifting interference microscopic image of the surface of the sample (GaN substrate) of FIG. 16A after light irradiation CARE processing, and FIG. 16C shows a phase-shifting interference microscopic image of a surface of a sample (GaN substrate), having a vapor-deposited platinum film on a back surface, after light irradiation CARE processing. DETAILED DESCRIPTION OF THE INVENTION Preferred embodiments of the present invention will now be described with reference to the drawings. The following description illustrates the case of using hydrofluoric acid (HF) as a processing solution and platinum as a catalyst, and processing and removing a surface (surface to be processed) of a substrate, such as an SiC wafer, into a desired flatness. FIG. 1 is a plan view showing the overall construction of a flattening apparatus according to an embodiment of the present invention. As shown in FIG. 1 , the flattening apparatus of this embodiment includes a generally rectangular housing 1 whose interior is divided by partition walls 1 a , 1 b , 1 c into a loading/unloading section 2 , a surface removal processing section 3 and a cleaning section 4 . The loading/unloading section 2 , the surface removal processing section 3 and the cleaning section 4 are independently fabricated and independently ventilated. The loading/unloading section 2 includes at least two (three in this embodiment) front loading sections 20 each for placing a substrate cassette storing substrates (workpieces). The front loading sections 20 are arranged side by side in the width direction (perpendicular to the long direction) of the flattening apparatus. Each front loading section 20 can place an open cassette, a SMIF (standard manufacturing interface) pod or a FOUP (front opening unified pod). The SMIF and FOUP are closed containers which can house a substrate cassette and can keep an interior environment independent of the exterior environment. A traveling mechanism 21 , extending along the line of the front loading sections 20 , is provided in the loading/unloading section 2 . On the traveling mechanism 21 is provided a first transport robot 22 as a first transport mechanism, which is movable along the direction in which substrate cassettes are arranged. The first transport robot 22 can reach the substrate cassettes placed in the front loading sections 20 by moving on the traveling mechanism 21 . The first transport robot 22 has two hands, an upper hand and a lower hand, and can use the two hands differently, for example, by using the upper hand when returning a processed substrate to a substrate cassette and using the lower hand when transporting an unprocessed substrate. The loading/unloading section 2 is an area which needs to be kept in the cleanest environment. Accordingly, the interior of the loading/unloading section 2 is constantly kept at a higher pressure than any of the outside of the apparatus, the surface removal processing section 3 and the cleaning section 4 . Furthermore, a filter-fan unit (not shown) having an air filter, such as an HEPA filter or a ULPA filter, is provided above the traveling mechanism 21 for the first transport robot 22 . Clean air, from which particles, vapor and gas have been removed, continually blows off downwardly through the filter-fan unit. The surface removal processing section 3 is an area where removal processing of a surface (surface to be processed) of a substrate is carried out and, in this embodiment, includes therein a lapping unit 30 A as a first surface removal processing unit, a CMP unit 30 B as a second surface removal processing unit and two catalyst-referred etching (CARE) units 30 C, 30 D as third (final) surface removal processing units. As shown in FIG. 1 , the lapping unit 30 A, the CMP unit 30 B and the CARE units 30 C, 30 D are arranged along the long direction of the flattening apparatus. The lapping unit 30 A includes a platen 300 A having a lapping surface, a top ring 301 A for detachably holding a substrate and pressing the substrate against the platen 300 A, a lapping liquid supply nozzle 302 A for supplying a lapping liquid, such as a diamond slurry or a colloidal silica slurry, to the platen 300 A, and a pure water supply nozzle 303 A for supplying pure water to the surface of the platen 300 A. During lapping in the lapping unit 30 A, the lapping liquid (slurry) is supplied from the lapping liquid supply nozzle 302 A onto the platen 300 A, and a substrate as a workpiece is held by the top ring 301 A and pressed against the platen 300 A to carry out lapping of the surface of the substrate. The lapping unit (first surface removal processing unit) 30 A is mainly directed to obtaining a large processing amount while enhancing the flatness of a substrate surface in the process of flattening, e.g., a substrate surface having relatively large initial irregularities into a desired flatness. The lapping unit 30 A can therefore be omitted when a surface to be processed of a substrate does not have large initial irregularities. Though in this embodiment the lapping unit 30 A is used as a first surface removal processing unit, it is also possible to use, instead of the lapping unit 30 A, a grinding unit, such as an electrolytic in-process dressing (ELID)-mirror grinding unit, which can obtain a considerably larger processing amount than the CARE units 30 C, 30 D. The CMP unit (second surface removal processing unit) 30 B includes a polishing table 300 B having a polishing surface, a top ring 301 B for detachably holding a substrate and pressing the substrate against the polishing table 300 B to polish the substrate, a polishing liquid supply nozzle 302 B for supplying a polishing liquid or a dressing liquid (e.g., water) to the polishing table 300 B, a dresser 303 B for carrying out dressing of the polishing surface of the polishing table 300 B, and an atomizer 304 B for spraying a mixed fluid of a liquid (e.g., pure water) and a gas (e.g., nitrogen gas) in a mist form onto the polishing surface of the polishing table 300 B from one or a plurality of nozzles. A polishing cloth, abrasive grains (fixed abrasive grains), or the like, constituting a polishing surface for polishing a substrate surface, is attached to the upper surface of the polishing table 300 B of the CMP unit 30 B. During polishing in the polishing unit 30 B, a polishing liquid is supplied from the polishing liquid supply nozzle 302 B onto the polishing surface of the polishing table 300 B, and a substrate as a workpiece is held by the top ring 301 B and pressed against the polishing surface to carry out polishing of the surface of the substrate. The CMP unit (second surface removal unit) 30 B is to enhance the flatness of a substrate surface while processing the substrate at a higher processing rate, i.e., obtaining a larger processing amount, than the CARE units 30 C, 30 D. Thus, the CMP unit 30 B, when used in combination with the above-described lapping unit (first surface removal processing unit) 30 A, can effectively flatten a substrate surface having relatively large initial irregularities into a desired flatness. Depending on the degree of surface irregularities of the substrate to be processed, etc., however, the use of the CMP unit 30 B may be omitted. Though in this embodiment the CMP unit 30 B is used as a second surface removal processing unit, it is also possible to use, instead of the CMP unit 30 B, a light irradiation catalyst-referred etching unit (light irradiation CARE unit) which has the same construction as the CARE unit 30 C or 30 D shown in FIGS. 2 through 4 but additionally includes a light source for applying light, preferably ultraviolet light, to a surface of a substrate held by a substrate holder and which, upon removal processing of a substrate surface, applies light to the substrate surface to activate it, so that the substrate surface can be processed at a higher processing rate than the CARE unit. It is also possible to use the light irradiation catalyst-referred etching unit (light irradiation CARE unit) shown in FIG. 13 . As shown in detail in FIG. 2 , the CARE units (third surface removal processing units) 30 C, 30 D each include a processing tank 124 , a catalyst platen 126 rotatably disposed in the processing tank 124 , and a substrate holder 130 for detachably holding a substrate (workpiece) 128 with its surface (surface to be processed) facing downwardly. The substrate holder 130 is made of, e.g., SiC which has excellent processability, chemical resistance and temperature resistance. It is also possible to use rigid PVC (polyvinyl chloride) or PEEK (polyether ether ketone) for the substrate holder 130 . The substrate holder 130 is coupled to the front end of a vertically-movable rotating shaft 132 which is disposed parallel to and eccentrically with respect to the axis of rotation of the catalyst platen 126 . The substrate holder 130 is supported (by a ball bearing) pivotably with respect to the rotating shaft 132 , so that the substrate holding surface of the substrate holder 130 can follow the surface of the catalyst platen 126 and the workpiece 128 can make plane contact with the catalyst platen 126 . In this embodiment, surface removal processing of the substrate 128 , such as an SiC wafer, in the CARE units 30 C, 30 D is carried out by using, e.g., hydrofluoric acid (50% HF) as a processing solution and using the catalyst platen 126 , e.g., composed of a 28 mm-thick molybdenum substrate 140 and a 1 mm-thick platinum sheet 142 as a catalyst attached to the substrate 140 . It is also possible to use a molybdenum or molybdenum alloy plate as the catalyst platen 126 , without providing a platinum sheet as a catalyst, and use the molybdenum or molybdenum alloy plate as a catalyst. Further, hydrohalic acid other than hydrofluoric acid, such as hydrochloric acid, may also be used as a processing solution. The processing solution used preferably contains as an additive a wetting improver for improving wetting of the surface of the catalyst platen. The wetting improver is a compound having a hydrophilic group and a hydrophobic group in the molecule and, when added to the processing solution, can improve wetting of the catalyst platen with the processing solution. This can increase the efficiency of supply of the processing solution to between a substrate (workpiece) and the catalyst platen, enabling stable surface removal processing. The processing solution may also contain as an additive a buffering agent for pH adjustment. By adjusting the pH of the processing solution with a buffering agent, a substrate (workpiece), in its area other than the removal processing reaction area, can be prevented from dissolving in the processing solution. Further, H + ions or OH − ions, which are active species generated at the surface of the catalyst platen, can be quickly deactivated, thereby limiting the removal processing reaction to the close vicinity of the surface of the catalyst platen. This can enhance a flatness of a processed surface of a substrate (workpiece). The processing solution may also contain an organic alcohol, such as methanol or ethanol, or an inorganic acid, such as sulfuric acid or nitric acid. F atoms or OH radicals generated at the surface of the catalyst platen are very active, and have a very short life, i.e., promptly lose their activity. There is therefore a case where a sufficient processing rate cannot be obtained. In such a case, by adding an alcohol such as ethanol or an inorganic acid such as nitric acid to the processing solution to cause the additive to react with F atoms or OH radicals, it becomes possible to secondarily generate organic radicals or nitrate radicals which have a longer life than F atoms or OH radicals, thereby increasing the processing rate. The above-described additives (wetting improver, pH adjuster, organic alcohol, inorganic acid) may be used either singly or in a combination of two or more. Further, the processing solution may also contain a buffering agent (buffer solution) capable of preventing a change in the pH of the processing solution. A heater 170 , embedded in the substrate holder 130 and extending into the rotating shaft 132 , is provided as a temperature control mechanism for controlling the temperature of the substrate 128 held by the substrate holder 130 . Above the processing tank 124 is disposed a processing solution supply nozzle 174 for supplying the processing solution (hydrofluoric acid), which is controlled at a predetermined temperature by a heat exchanger 172 as a temperature control mechanism, into the processing tank 124 . Furthermore, a fluid passage 176 as a temperature control mechanism for controlling the temperature of the catalyst platen 126 is provided in the interior of the catalyst platen 126 . Though the heater 170 as a temperature control mechanism for controlling the temperature of the substrate 128 , the heat exchanger 172 as a temperature control mechanism for controlling the temperature of the processing solution, and the fluid passage 176 as a temperature control mechanism for controlling the temperature of the catalyst platen 126 are used in this embodiment, it is possible to omit all of the temperature control mechanisms or to employ any one of them. As is known by the Arrhenius equation, with reference to a chemical reaction, the higher the reaction temperature, the higher is the reaction rate. Thus, by controlling at least one of the temperature of the workpiece 128 , the temperature of the processing solution and the temperature of the catalyst platen 126 so as to control the reaction temperature, the processing rate can be adjusted or changed in such a manner as to stabilize the processing. As shown in FIGS. 3 and 4 , a plurality of concentric grooves 144 are formed over three groove formation areas 146 a , 146 b , 146 c in the surface of the platinum (catalyst) layer 142 of the catalyst platen 126 . In this embodiment, the width of the groove formation area 146 b , lying in the middle of the three groove formation areas, is smaller than the diameter of the substrate 128 held by the substrate holder 130 . This allows two ends of the substrate 128 , held by the substrate holder 130 , to lie in the flat area between the groove formation areas 146 a and 146 b and in the flat area between the groove formation areas 146 b and 146 c , respectively, so that the ends of the substrate 128 , held and being rotated by the substrate holder 130 , will not be caught in a groove 144 . When the use of a thin platinum (catalyst) layer 142 is intended, the depth of the grooves formed in the layer should necessarily be small accordingly. When the width, the depth and the pitch of the grooves are made small, however, the fluidity of a fluid will become poor and a large attraction (adsorption) power will be generated between a substrate and the catalyst. It is therefore desirable that the depth D of the grooves be made as small as possible within the acceptable range of adsorption power. As shown in phantom line in FIG. 3 , when using a substrate holder provided with a retainer ring 148 surrounding the circumference of the substrate 128 , the overall width of the groove formation areas 146 a , 146 b , 146 c is made smaller than the diameter of the retainer ring 148 so that two ends of the rotating retainer ring 148 are allowed to lie in the flat areas outside the groove formation areas 146 a , 146 c and will not be caught in a groove 144 . In this case, in order to prevent end portions, etc. of the substrate 128 from being caught in a groove 144 , the grooves 144 have not a rectangular but an r-shaped cross-section, as shown in FIG. 4 . The grooves may have any tapered cross-section. The pitch (groove pitch) of the grooves 144 is preferably as small as possible in order to efficiently supply the processing solution to the area of contact (processing area) between the catalyst platen 126 and the substrate 128 . In this embodiment, as shown in FIG. 4 , the groove pitch P is set about 3 to 5 mm, and the groove depth D is set about 0.5 to 1.0 mm. To make the platinum catalyst layer 142 thin, the groove depth D is preferably made small to such an extent as not cause unacceptable attraction between the platinum layer 142 and the substrate 128 . When the large number of concentric grooves 144 are provided in the surface of the platinum (catalyst) layer 142 of the catalyst platen 126 as in this embodiment, it is preferred to pivot the substrate 128 with the substrate holder 130 in order to enhance the uniformity of processing amount in the entire surface to be processed of the substrate 128 . Instead of the concentric grooves, eccentric grooves or a spiral groove may also be employed. When the processing solution (hydrofluoric acid) is supplied from the processing supply nozzle 174 to the catalyst platen 126 , the processing solution is held in the grooves 144 provided in the surface of the catalyst platen 126 . While pressing the substrate (workpiece) 128 , held by the substrate holder 130 , against the surface of the platinum (catalyst) layer 142 of the catalyst platen 126 at a predetermined pressure and allowing the processing solution to be present in the area of contact (processing area) between the substrate 128 and the platinum (catalyst) layer 142 of the catalyst platen 126 , the catalyst platen 126 and the substrate 128 are rotated, thereby flatly processing (etching) the surface (lower surface) of the substrate 128 such as an SiC wafer. Instead of pressing the substrate 128 , held by the substrate holder 130 , against the platinum (catalyst) layer 142 of the catalyst platen 126 at a predetermined pressure, it is also possible to keep the substrate 128 in close proximity to the platinum (catalyst) layer 142 in carrying out removal processing (etching) of the surface of the substrate 128 . When using a substrate holder having the retainer ring 148 for preventing escape of a substrate, it is preferred that at least that portion of the retainer ring 148 , which is to face the catalyst platen 126 , be made of the same material as the surface material of the catalyst platen 126 . For example, when platinum is used as the surface material (catalyst) of the catalyst platen 126 , that portion of the retainer ring 148 , which is to face or contact the catalyst platen 126 , is preferably made of platinum. Similarly, when iron is used as the surface material of a catalyst platen, that portion of the retainer ring, which is to face or contact the catalyst platen, is preferably made of iron. There is a case where the surface material of the retainer ring 148 contacts the catalyst platen 126 and is chipped off, and the retainer ring chip adheres to the surface of the catalyst platen 126 . Even in such a case, if the surface material of the retainer ring is made of the same material as the surface material of the catalyst platen 126 , processing can be continued without loss of the catalytic effect of the catalyst platen 126 . The surface material of the retainer ring 148 may also be an alloy rich in the same metal as the surface metal of the catalyst platen 126 . For example, when iron is used as the surface metal of the catalyst platen, the surface material of the retainer ring may be an iron-rich alloy, such as carbon steel or stainless steel. It is also possible to use a catalyst platen 200 which, as shown in FIGS. 5 and 6 , has a large number of through-holes 200 a in its area which is to contact the substrate (workpiece) 128 held by the substrate holder 130 shown in FIG. 2 . As with the above-described catalyst platen 126 , the catalyst platen 200 may be composed of a molybdenum substrate and a platinum sheet as a catalyst attached to the substrate. In this embodiment, the through-holes 200 a are formed in equally-spaced lattice positions in the catalyst platen 200 . The lattice spacing is, for example, 5 mm and the diameter of the through-holes 200 a is, for example, 1 mm. The lattice spacing and the hole diameter of the through-holes 200 a are preferably as small as possible. The provision of the uniformly distributed though-holes 200 a in the catalyst platen 200 enables uniform processing of the entire surface of the substrate (workpiece) 128 . A recess 200 b is formed in the lower surface of the catalyst platen 200 and, when the catalyst platen 200 is mounted on the upper surface of a rotating body 202 , a processing solution reservoir 204 is formed between the catalyst platen 200 and the rotating body 202 . The catalyst platen 200 has a vertical through-hole in the center, and a rotary joint 206 is mounted to the through-hole. The rotary joint 206 is connected to the processing solution supply nozzle 174 shown in FIG. 2 , for example. In this embodiment, processing of the substrate (workpiece) 128 is carried out in the following manner: While rotating the catalyst platen 200 together with the rotating body 202 , the processing solution is supplied through the rotary joint 206 into the processing solution reservoir 204 between the catalyst platen 200 and the rotating body 202 , and the processing solution is spouted from the through-holes 200 a . This manner of processing can prevent the substrate (workpiece) 128 from sticking to the catalyst platen 200 and, at the same time, can replace the processing solution remaining in the through-holes 200 a. The pressure of the processing solution spouting from the through-holes 200 a is preferably much lower than the pressure of the substrate (workpiece) 128 on the catalyst platen 200 . In consideration of the strength of the catalyst platen, it is also possible to form radial grooves extending from the center of the catalyst platen so that the processing solution will be supplied through the grooves to below the through-holes. As shown in FIG. 1 , each of the CARE units 30 C, 30 D is provided with a pure water jet nozzle 150 as a conditioning section for carrying out conditioning of the surface of the catalyst platen 126 by jetting pure water toward the surface platinum (catalyst) layer 142 of the catalyst platen 126 while causing cavitation or applying ultrasonic waves, as necessary. It is also possible to use as a conditioning section a light irradiator for applying light to the catalyst platen to remove a broken piece or an organic contaminant from the surface of the catalyst platen by photoelectrochemical etching, or an electrolytic removal apparatus which includes an electrode disposed opposite the catalyst platen and electrolytically removes a broken piece or an organic contaminant from the surface of the catalyst platen by applying a voltage between the catalyst platen and the electrode. A broken piece, which has been separated from the catalyst platen 126 , can be removed, e.g., by filtration. Between the lapping unit 30 A, the CMP unit 30 B and the cleaning unit 4 is disposed a first linear transporter 5 as a second (translatory) transport mechanism for transporting a substrate between four transport positions (first transport position TP 1 , second transport position TP 2 , third transport position TP 3 and fourth transport position TP 4 in order of distance from the loading/unloading section 2 ) along the long direction of the apparatus. A reversing machine 31 for reversing a substrate received from the first transport robot 22 is disposed above the first transport position TP 1 of the first linear transporter 5 , and a vertically-movable lifter 32 is disposed below the reversing machine 31 . Further, a vertically-movable pusher 33 is disposed below the second transport position TP 2 , a vertically-movable pusher 34 is disposed below the third transport position TP 3 , and a vertically-movable lifter 35 is disposed below the fourth transport position TP 4 . Beside the CARE units 30 C, 30 D and adjacent to the first linear transporter 5 is disposed a second linear transporter 6 as a second (translatory) transport mechanism for transporting a substrate between three transport positions (fifth transport position TP 5 , sixth transport position TP 6 and seventh transport position TP 7 in order of distance from the loading/unloading section 2 ) along the long direction of the apparatus. A vertically-movable lifter 36 is disposed below the fifth transport position TP 5 , a pusher 37 is disposed below the sixth transport position TP 6 , and a pusher 38 is disposed below the seventh transport position TP 7 . Further, a pure water replacement section 160 including a tub and a pure water nozzle is disposed between the CARE unit 30 C and the pusher 37 , and a pure water replacement section 162 including a tub and a pure water nozzle is also disposed between the CARE unit 30 D and the pusher 38 . As will be understood from the use of a slurry or the like in surface removal processing, the surface removal processing section 3 is the dirtiest area. In this embodiment, therefore, discharge of air is carried out around a removal processing site, such as a platen, so as to prevent particles in the surface removal processing section 3 from flying to the outside. Further, the internal pressure of the surface removal processing section 3 is made lower than the external pressure of the apparatus and the internal pressures of the neighboring cleaning section 4 and loading/unloading section 2 , thereby preventing particles from flying out. A ventilation duct (not shown) and a filter (not shown) are usually provided respectively below and above a removal processing site, such as a platen, so as to create a downward flow of cleaned air through the ventilation duct and the filter. The cleaning section 4 , which is an area for cleaning a substrate, includes a second transport robot 40 , a reversing machine 41 for reversing a substrate received from the second transport robot 40 , three cleaning units 42 , 43 , 44 for cleaning the substrate, a drying unit 45 for rinsing the cleaned substrate with pure water and then spin-drying the substrate, and a movable third transport robot 46 for transporting the substrate between the reversing machine 41 , the cleaning units 42 , 43 , 44 and the drying unit 45 . The second transport robot 40 , the reversing machine 41 , the cleaning units 42 to 44 and the drying unit 45 are arranged in a line along the long direction of the apparatus, and the third transport robot 46 is movably disposed between the first linear transporter 5 and the line of the second transport robot 40 , the reversing machine 41 , the cleaning units 42 to 44 and the drying unit 45 . A filter-fan unit (not shown) having a clean air filter is provided above the cleaning units 42 to 44 and the drying unit 45 , and clean air, from which particles have been removed by the filter-fan unit, continually blows downward. The interior of the cleaning unit 4 is constantly kept at a higher pressure than the surface removal processing section 3 to prevent inflow of particles from the surface removal processing section 3 . In this embodiment, the first and second cleaning units 42 , 43 are chemical cleaning units which cleans a substrate by immersing the substrate in a chemical solution, such as aqua regia, SPM (sulfuric acid-hydrogen peroxide mixture) or hydrofluoric acid, and the third cleaning unit 44 is a pure water cleaning unit which cleans a substrate by supplying pure water to the substrate. In particular, the first cleaning unit 42 uses hydrofluoric acid as a cleaning chemical and the second cleaning unit 43 uses aqua regia as a cleaning chemical. As shown in FIG. 1 , a shutter 10 , located between the reversing machine 31 and the first transport robot 22 , is provided in the partition wall 1 a surrounding the surface removal processing section 3 . The shutter 10 is opened when transferring a substrate between the first transport robot 22 and the reversing machine 31 . Further, a shutter 13 located at a position facing the CMP unit 30 B and a shutter 14 located at a position facing the CARE unit 30 C are provided in the partition wall 1 b surrounding the surface removal processing section 3 . Processing for flattening a surface of a substrate by the flattening apparatus having the above construction will now be described. One substrate is taken by the first transport robot 22 out of a substrate cassette mounted in one of the front loading sections 20 , and the substrate is transported to the reversing machine 31 . The reversing machine 31 180° reverses the substrate and then places the substrate on the lifter 32 at the first transport position TP 1 . The top ring 301 A of the lapping unit 30 A receives the substrate from the lifter 32 , and the lapping unit 30 A carries out lapping of the surface of the substrate. In particular, in the lapping unit 30 A, lapping of the substrate surface is carried out, e.g., at a processing rate of not more than several tens of μm/h while supplying a lapping liquid, such as a diamond slurry or a colloidal silica slurry, to the platen 301 A, thereby removing the substrate surface in an amount corresponding to a thickness of about 10 μm and flattening the substrate surface. In this case, the depth of damage in the substrate surface after processing is about 1 μm. The substrate surface is then rinsed with pure water, as necessary. The substrate after lapping is transferred to the pusher 33 at the second transport position TP 2 , and is then transported to the third transport position TP 3 by horizontally movement of the first linear transporter 5 . The top ring 301 B of the CMP unit 30 B receives the substrate from the pusher 34 at the third transport position TP 3 , and the CMP unit 30 B carries out chemical mechanical polishing of the surface of the substrate. In particular, in the CMP unit 30 B, chemical mechanical polishing of the substrate surface is carried out, e.g., at a processing rate of not more than several μm/h while supplying a polishing liquid, e.g., containing colloidal silica, to the polishing table 300 B, thereby removing the substrate surface in an amount corresponding to a thickness of about several μm and further flattening the substrate surface. In this case, the depth of damage in the substrate surface after processing is about 10 nm. The substrate surface is then rinsed with pure water, as necessary. The substrate after CMP is transferred to the lifter 35 at the fourth transport position TP 4 . The second transport robot 40 receives the substrate from the lifter 35 and transports the substrate to the reversing machine 41 . The reversing machine 41 180° reverses the substrate and then transports it to the first cleaning unit (chemical cleaning unit) 42 . The first cleaning unit 42 carries out hydrofluoric acid cleaning of the substrate by immersing the substrate in hydrofluoric acid, for example. The substrate after the hydrofluoric acid cleaning is transported by the third transport robot 46 to the third cleaning unit (pure water cleaning unit) 45 , where the substrate is cleaned with pure water. Thereafter, the substrate is returned by the third transport robot 46 to the reversing machine 41 . When chemical cleaning of the substrate is not necessary, the substrate, which has been 180° reversed by the reversing machine 41 , is transported by the third transport robot 46 to the third cleaning unit (pure water cleaning unit) 45 , where the substrate is cleaned with pure water, and the substrate is then returned by the third transport robot 46 to the reversing machine 41 . The reversing machine 41 180° reverses the substrate. The second transport robot 40 receives the reversed substrate from the reversing machine 41 and places the substrate on the lifter 36 at the fifth transport position TP 5 . The second linear transporter 6 moves horizontally to transport the substrate on the lifter 36 to one of the sixth transport position TP 6 and the seventh transport position TP 7 . The substrate holder 130 of the CARE unit 30 C or 30 D receives the substrate from the pusher 37 or 38 , and the CARE unit 30 C or 30 D carries out CARE (catalyst-referred etching) processing of the surface of the substrate. In particular, in the CARE unit 30 C or 30 D, CARE processing of the substrate surface, which utilizes the catalytic action on SiC by the surface platinum layer 142 of the catalyst platen 126 , is carried out, e.g., at a processing rate of not more than 100 nm/h while supplying a processing solution, e.g., comprising hydrofluoric acid, to the catalyst platen 126 , thereby removing the substrate surface in an amount corresponding to a thickness of about several tens of μm. In this case, the depth of damage in the substrate surface after processing is zero. For the substrate which has undergone CARE processing in the CARE unit 30 C, hydrofluoric acid remaining on the substrate surface after CARE processing is replaced with pure water in the pure water replacement section 160 , and the substrate is then returned to the sixth transport position TP 6 . For the substrate which has undergone CARE processing in the CARE unit 30 D, hydrofluoric acid remaining on the substrate surface after CARE processing is replaced with pure water in the pure water replacement section 162 , and the substrate is then returned to the seventh transport position TP 7 . The substrate after pure water replacement is then moved by the second linear transporter 6 to the fifth transport position TP 5 . There is a case where the surface of the substrate after CARE processing can be roughened when the surface with hydrofluoric acid attached is exposed to light of an excitation wavelength. In such a case, it is desirable to attach a UV blocking film to windows facing the transport path from the CARE unit 30 C to the pure water replacement section 160 and the transport path from the CARE unit 30 D to the pure water replacement section 162 . The second transport robot 40 takes the substrate out of the fifth transport position TP 5 and transports the substrate to the reversing machine 41 . The reversing machine 41 180° reverses the substrate and then transports it to the first cleaning unit 42 . The third transport robot 46 transports the substrate form the first cleaning unit 42 to the second cleaning unit 43 , where the substrate is cleaned by immersing it in aqua regia. The aqua regia cleaning of the substrate is carried out a plurality of times, as necessary. The third transport robot 46 transports the substrate after aqua regia cleaning to the third cleaning unit (pure water cleaning unit) 44 , where the substrate is cleaned with pure water. The third transport robot 46 transports the substrate after pure water cleaning to the drying unit 45 , where the substrate is rinsed with pure water and then rotated at a high speed to spin-dry the substrate. The first transport robot 22 receives the substrate after spin-drying from the drying unit 45 and returns the substrate to the substrate cassette mounted in the front loading section 20 . Methods for detecting the end point of CARE processing in the CARE units 30 C, 30 D include (a) a method of detecting the end point from the processing time, (b) a method of detecting the end point from a change in the electric current of a drive motor for rotationally driving a catalyst platen, (c) a method of detecting the end point from a change in the concentration of a processing solution, (d) a method of detecting the end point by measuring the processing surface with an in-situ optical monitor (e.g., photoluminescence method), (e) a method comprising taking a substrate out of a processing solution, and detecting the end point (either in situ or ex situ) by using a device such as a TEM, (g) a method of detecting the end point from a change in the weight of a substrate (workpiece) before and after processing, etc. The end point of CARE processing can also be detected by an SEM for a patterned substrate such as an SiC wafer. When the crystallinity of a processed surface is of importance, it is preferred to use the photoluminescence method which can determine the crystallinity. The photoluminescence method is easy to operate because it can be carried out at atmospheric pressure. According to this embodiment, using the lapping unit 30 A as a first surface removal processing unit, lapping of a substrate surface to enhance the flatness of the surface is first carried out, e.g., at a processing rate of not more than several tens of μm/h, thereby removing the substrate surface in an amount corresponding to a thickness of about 10 μm (the depth of damage in the substrate surface after processing is about 1 μm); using the CMP unit 30 B as a second surface removal processing unit, CMP processing of the substrate surface to further enhance the flatness of the surface is carried out, e.g., at a processing rate of not more than several μm/h, thereby removing the substrate surface in an amount corresponding to a thickness of about several μm (the depth of damage in the substrate surface after processing is about 10 nm); and using the CARE unit 30 C or 30 D as a third (final) surface removal processing unit, CARE processing of the substrate surface to enhance the flatness of the surface is lastly carried out, e.g., at a processing rate of not more than 100 nm/h, thereby removing the substrate surface in an amount corresponding to a thickness of about several tens of nm (the depth of damage in the substrate surface after processing is zero). This processing method thus makes it possible to process a substrate (workpiece) at a sufficient processing rate while gradually enhancing the flatness of the surface (surface to be processed) of the substrate and finally create a damage-free, very flat processed surface. Depending on the type of the workpiece, the state of the processed surface, etc., one of lapping (first surface removal processing) and CMP (second surface removal processing) may be omitted. In the case of CARE processing of SiC, dissolved C (carbon) is present in a processing solution after processing and the carbon needs to be treated. A method for treating the carbon comprises irradiating the processing solution after use with UV light at a position opposite a substrate holder on a catalyst platen and/or in a circulation line to break the chemical bond, and allowing carbon to precipitate at a different place. The carbon concentration of the processing solution in a processing tank can thus be decreased. Further, it is preferred to provide a filter in a circulation line or piping for the processing solution so as to filter out carbon and other possible impurities that will adversely affect CARE processing. When flatly processing a surface of a substrate, an SiC wafer, by CARE using hydrofluoric acid as a processing solution and platinum as a catalyst as in this embodiment, the processed surface of the substrate will be contaminated with platinum. The platinum contaminant can be removed by aqua regia cleaning carried out by immersing the substrate in aqua regia. FIG. 7 shows the results of total reflection X-ray fluorescence (TRXF) analysis of platinum contamination as measured on an SiC wafer sample after CARE processing and on the processed sample after cleaning with aqua regia. The CARE processing was carried out by using hydrofluoric acid as a processing solution and platinum as a catalyst under the processing conditions shown in Table 1 below. The aqua regia cleaning was carried out by immersing the sample in a 3:1 mixed solution (aqua regia) of hydrochloric acid (60%) and nitric acid (60%) at 60° C. for 10 minutes, followed by rinsing of the sample with ultrapure water for one minute. The above cleaning operation was repeated a plurality of times. The TRXF measurement was carried out under the measurement conditions shown in Table 2 below. TABLE 1 Sample: n-type 4H—SiC 2 inch wafer Plane direction: 8° off Si plane Resistivity: 0.01-0.05 Ocm Catalyst platen: 300 mm Pt platen Processing time: 30 hrs TABLE 2 Voltage applied: 40 kV Electric current: 40 mA Incidence angle of incident X-ray: 0.050 deg Incidence time of incident X-ray: 100 sec As can be seen from FIG. 7 , platinum contamination was observed on the sample after CARE processing; and the platinum contamination decreased with the repetition of the aqua regia cleaning of the sample. For comparison, the same SiC wafer sample was CARE-processed in the same manner as described above, and the processed sample was subjected to SPM cleaning and further to hydrofluoric acid cleaning. The SPM cleaning was carried out by immersing the sample in a 4:1 mixed solution of sulfuric acid (98%) and hydrogen peroxide water (30%) for 10 minutes, followed by rinsing of the sample with ultrapure water for one minute. The hydrofluoric acid cleaning was carried out by immersing the sample in hydrofluoric acid (50% HF) for 10 minutes, followed by rinsing of the sample with ultrapure water for one minute. FIG. 8 shows the results of TRXF analysis of platinum contamination on the sample after CARE processing, on the processed sample after SPA cleaning and on the processed sample after the additional HF cleaning. As can be seen from FIG. 8 , the platinum contaminant on the sample after CARE processing cannot be removed by SPM cleaning nor by hydrofluoric acid cleaning. In this embodiment, the surface of SiC is processed (etched) by CARE using hydrochloric acid as a processing solution and platinum as a surface catalyst of a catalyst platen. It is also possible to process (etch) a surface of Si, SiC, GaN, sapphire, ruby or diamond by CARE using hydrohalic acid, such as hydrofluoric acid or hydrochloric acid, as a processing solution and platinum, gold, a ceramic solid catalyst, molybdenum or a molybdenum alloy as a catalyst. Further, it is possible to process (etch) a surface of Si, SiC, GaN, sapphire, ruby or diamond by CARE using hydrogen peroxide water or ozone water as a processing solution and a transition element, such as Fe, Ni, Co, Cu, Cr or Ti, as a surface catalyst of a catalyst platen. For example, in the CARE units 30 C, 30 D shown in FIGS. 2 through 4 , it is possible to process (etch) a surface of a substrate, such as an SiC wafer, by supplying hydrogen peroxide water as a processing solution from the processing solution supply nozzle 174 to a catalyst paten 126 wholly made of iron which itself has a catalytic action. When processing a surface of a substrate, such as an SiC wafer, by CARE using hydrogen peroxide water as a processing solution and iron as a catalyst, the processed surface of the substrate will be contaminated with iron and an oxide film will be formed in the processed surface of the substrate. FIGS. 9A and 9B show the results of X-ray photoelectron spectroscopy (XPS) of iron contamination as measured on an SiC wafer sample after CARE processing and on the processed sample after cleaning with SPM, FIG. 9A showing the XPS data at the Fe2p core level for the sample after CARE processing and FIG. 9B showing the XPS data at the Fe2p core level for the sample after SMP cleaning. The CARE processing was carried out by using hydrogen peroxide water as a processing solution and iron as a catalyst under otherwise the same processing conditions as indicated in Table 1 above, and the SPM cleaning was carried out in the same manner as described above with reference to the TRXF analysis of platinum contamination. As clearly shown in FIG. 9A , a signal at the Fe2p core level was detected for the sample after CARE processing, whereas no signal at the Fe2p core level was detected for the sample after SPM cleaning as will be appreciated from FIG. 9B . This indicates that the iron contaminant on the sample after CARE processing was completely removed by the SPM cleaning. The surface removal process for SiC generally passes through the stage of oxidation of the surface and the stage of removal of the oxide film. Accordingly, an oxide film may remain on a surface of a workpiece after processing. Especially in a light irradiation CARE process in which processing of a workpiece is carried out while irradiating the surface to be processed of the workpiece with ultraviolet light, due to promoted oxidation of the surface to be processed by the UV irradiation, an oxide film is likely to remain on the processed surface. FIG. 10 shows the results of X-ray photoelectron spectroscopy of a surface of an SiC sample after light irradiation CARE processing, and FIG. 11 shows the results of X-ray photoelectron spectroscopy of the surface of the processed SiC sample as measured after cleaning the sample with hydrofluoric acid. The light irradiation CARE processing was carried out for 6 hours by using hydrogen peroxide water as a processing solution and quartz glass as a catalyst and irradiating the surface to be processed of the sample with ultraviolet light during processing. The hydrofluoric acid cleaning was carried out by immersing the sample after the light irradiation CARE processing in 50% hydrofluoric acid solution for 10 minutes. FIG. 10 shows the peak at 103.6 eV, indicating the presence of SiO 2 oxide film, in addition to the peak (101.3 eV) indicating the Si—C bond of the sample material. On the other hand, FIG. 11 shows no peak concerning SiO 2 and a larger peak value concerning Si—C bond. The comparative data clearly demonstrates the fact that the hydrofluoric acid cleaning can fully remove the oxide film remaining on the surface of the SiC sample after light irradiation CARE processing. Also in the case of CARE processing of an SiC workpiece as carried out by using hydrogen peroxide water as a processing solution and iron as a catalyst, it is considered, in view of the removal processing principle, that an oxide film will remain on the surface of the workpiece after processing. Thus, also in this case, it is preferred to carry out hydrofluoric acid cleaning of the workpiece after removal processing. As will be appreciated from the above, when using hydrogen peroxide water as the processing solution supplied from the processing solution supply nozzle 174 and a catalyst platen wholly made of iron having a catalytic activity as the catalyst platen 126 in the CARE units 30 C, 30 D shown in FIGS. 2 through 4 , it is preferred to use a hydrofluoric acid cleaning unit, which cleans a substrate by immersing it in hydrofluoric acid, as the first cleaning unit 142 of the flattening apparatus shown in FIG. 1 as in the above-described embodiment, and to use an SPM cleaning unit, which cleans a substrate by immersing it in SPM, as the second cleaning unit 43 . By subjecting a substrate after CARE processing to hydrofluoric acid cleaning in the first cleaning unit 42 and then to SPM cleaning in the second cleaning unit 43 , an iron contaminant on the surface of the substrate and an oxide film formed in the substrate surface can be removed. When hydrogen peroxide water or ozone water is used as a processing solution, it is possible to use as a surface catalyst of a catalyst platen, beside the above-described transition metals, a noble metal such as platinum or gold, a ceramic metal oxide or a glass-type metal oxide. The ceramic metal oxide is exemplified by alumina, and the glass-type metal oxide is exemplified by sapphire (Al 2 O 3 ), quartz (SiO 2 ) and zirconia (ZrO 2 ). Further, when hydrogen peroxide water or ozone water is used as a processing solution, it is also possible to use an acidic or basic solid catalyst as a surface catalyst of a catalyst platen. The acidic or basic solid catalyst is exemplified by a non-woven fabric, a resin or a metal having an ion exchange function. Preferable examples of such materials having an ion exchange function include a non-woven fabric composed of polyethylene fibers, resins such as fluororesin and PEEK, and oxidation-resistant metals such as Pt and Au. For example, an ion exchange function can be imparted to a non-woven fabric of polyethylene fibers by graft polymerization. In this case, the etching rate of a workpiece can be increased by increasing the ion exchange capacity of a solid catalyst. Examples of other usable solid acid catalysts include a solid acid comprising silica-alumina with H 2 SO 4 , H 3 PO 4 , or the like adsorbed on it, inorganic salts such as a metal sulfate and a metal phosphate, and oxides such as Al 2 O 3 , ThO 2 , Al 2 O 3 —SiO 2 and TiO 2 —SiO 2 . Examples of solid base catalysts include a solid base comprising silica gel with NaOH, KOH, Na, K or the like adsorbed on it, inorganic salts such as Na 2 CO 3 , Ba 2 CO 3 and Na 2 WO 4 , and oxides such as CaO, MgO, SrO, MgO—SiO 2 and MgO—Al 2 O 3 . Contamination (especially organic contamination) of a surface of a platen or the presence of an oxide film in the surface of the platen will affect wettability of the platen surface. In order to improve wettability of a surface of a catalyst platen, the following treatments of the catalyst platen can be carried out before or during processing: (1) Treatment to Improve Wettability of Catalyst Platen Carried Out Before Processing: A catalyst platen before processing is subjected to chemical cleaning (e.g., with SPM) or ultraviolet irradiation. The chemical cleaning can remove an organic contaminant from the platen surface, thereby improving wettability of the platen surface. The ultraviolet irradiation will oxidize the surface of the platen, when it is made of, e.g., iron, thereby improving wettability of the surface. The ultraviolet irradiation treatment is applicable to catalyst platens other than a platinum platen. (2) Treatment to Improve Wettability of Catalyst Platen Carried Out During Processing: Ultraviolet light is applied to a surface portion, which is different from the portion facing a top ring, of a catalyst platen during processing to form an oxide film in the platen surface, thereby improving wettability of the platen surface. Owing to the improved wetting of the paten surface with a plating solution, organic matter which adheres to the platen surface during processing will be removed. This further enhances wettability of the platen surface and makes the surface more hydrophilic. If a surface oxide film of, e.g., an iron platen is removed during processing, the ultraviolet irradiation can form a surface oxide film again to improve wettability of the platen surface. In the above-described embodiments, CARE processing in the CARE unit 30 C or 30 D is carried out in a piece-by-piece manner by pressing one substrate, held by the substrate holder 130 , against the catalyst platen in each operating cycle. A catalyst platen is generally costly. Further, the surface conditions of a catalyst platen affect the processing performance. Accordingly, and also with a view to increasing the throughput, it is preferred to simultaneously process a plurality of substrates, e.g., four substrates, by simultaneously pressing the plurality of substrates, held by one substrate holder, against a catalyst platen. It is also possible to use a CARE unit which includes a plurality of substrate holders which each hold one substrate. Prior to CARE processing, a substrate (workpiece) is preferably subjected to wet cleaning to clean a surface (surface to be processed). A surface of a substrate may be contaminated with particles, an organic substance and/or a metal. Non-scrub cleaning, such as water jet cleaning (hydrofluoric acid cleaning when using colloidal silica), is suited for particle contamination, SPM (sulfuric acid-hydrogen peroxide mixture) cleaning is suited for organic contamination, and SPM cleaning or hydrofluoric acid cleaning is suited for metal contamination. A surface of an SiC substrate per se does not change by such cleaning, and only a contaminant can be removed. FIGS. 12A through 12D illustrate the concept of CARE processing of a workpiece with the use of a processing solution containing a buffer solution (buffering agent). As shown in FIG. 12A , when an acidic solid catalyst 416 is immersed in a processing solution 412 b , hydrogen ions (H + ) 416 a are generated at a surface of the acidic solid catalyst 416 , and the hydrogen ions 416 a leave the surface of the acidic solid catalyst 416 . The processing solution 412 b contains a buffering agent 480 dissolved therein, and the hydrogen ions 416 a , which have left the surface of the acidic solid catalyst 416 , promptly react with the buffering agent 480 and become inactive, as shown in FIG. 12B . Thus, the hydrogen ions 416 a are present only on or in the close vicinity of the surface, serving as a processing reference surface, of the acidic solid catalyst 416 . When the acidic solid catalyst 416 is brought into contact with or close proximity to the surface to be processed of a workpiece 414 in the processing solution containing the buffering agent 480 , as shown in FIG. 12C , surface atoms of the workpiece 414 at the contact portion are dissolved by chemical reaction in the processing solution 412 b . When the acidic solid catalyst 416 is separated from the surface to be processed of the workpiece 414 , as shown in FIG. 12D , the hydrogen ions 416 a generated at the surface of the acidic solid catalyst 416 do not act on the surface of the workpiece 414 anymore whereby the dissolution reaction stops. Thus, the surface to be processed of the workpiece 414 is processed only when the acidic solid catalyst 416 is in contact with or in close proximity to the surface to be processed. Examples of solid acid catalysts include a solid acid comprising silica-alumina with H 2 SO 4 , H 3 PO 4 , or the like adsorbed on it, inorganic salts such as a metal sulfate and a metal phosphate, and oxides such as Al 2 O 3 , ThO 2 , Al 2 O 3 —SiO 2 and TiO 2 —SiO 2 . Examples of solid base catalysts include a solid base comprising silica gel with NaOH, KOH, Na, K or the like adsorbed on it, inorganic salts such as Na 2 CO 3 , Ba 2 CO 3 and Na 2 WO 4 , and oxides such as CaO, MgO, SrO, MgO—SiO 2 and MgO—Al 2 O 3 . When a processing solution does not contain a buffer solution (buffering agent), i.e., when a buffering agent is not present in the processing solution, hydrogen ions diffuse in the processing solution even after they leave a surface of an acidic solid catalyst. Hydrogen ions can therefore be present also in those places which lie at a distance from the surface of the acidic solid catalyst. Accordingly, when the acidic solid catalyst is brought into contact with or close proximity to the surface to be processed of a workpiece in the processing solution, surface atoms of the surface to be processed, not only those lying in the vicinity of the surface of the acidic solid catalyst but also those lying at a distance therefrom, will be dissolved by chemical reaction in the processing solution. Thus, hydrogen ions act not only on raised portions of the surface to be processed but on recessed portions as well, whereby the surface to be processed will be processed isotropically and flattening of the surface will not progress. A phosphate buffer solution is an exemplary buffer solution (buffering agent). Other buffer solutions, such as an acetate buffer solution and a citrate buffer solution, may also be used insofar as it reduces a change in the pH of the processing solution. When a buffer solution is used as an additive in a processing solution, the processing solution preferably is ultrapure water or an aqueous solution containing an oxidizing agent, such as ozone water, hydrogen peroxide water or an aqueous potassium persulfate solution. The concentration of buffering agent in a processing solution is preferably such as to adjust the pH of the processing solution to a predetermined value. When processing a GaN substrate, for example, the pH of a processing solution is preferably adjusted to around 7 (6.5 to 7.5). FIG. 13 schematically shows a CARE unit (light irradiation CARE unit) provided with a light source. The CARE unit (light irradiation CARE unit) includes a vessel 484 for filling it with a processing solution 482 , e.g., containing a buffer solution (buffering agent), a platen 488 coupled to the upper end of a rotating shaft 486 and rotatably disposed in the vessel 484 , and a holder 492 for detachably holding a workpiece 490 , such as a GaN substrate, with its surface to be processed facing downwardly. The holder 492 is secured to the lower end of a rotating shaft 494 . A light source 496 is provided below the platen 488 . The platen 488 is comprised of an acidic solid catalyst having high light transmissivity, such as quartz, so that light, e.g., ultraviolet light, from the light source 496 passes through the platen 488 and applied to the lower surface (surface to be processed) of the workpiece 490 . The platen 488 may also be comprised of sapphire, zirconia, or the like, having high light transmissivity. Using the CARE unit (light irradiation CARE unit) shown in FIG. 13 , processing of a GaN wafer (sample) was carried out for 3 hours under ultraviolet irradiation. FIG. 14A shows a phase-shifting interference microscopic image of the surface of the sample before processing, FIG. 14B shows a phase-shifting interference microscopic image of the surface of the sample after carrying out processing using a processing liquid (ultrapure water) not containing a buffer solution (buffering agent), and FIG. 14C shows a phase-shifting interference microscopic image of the surface of the sample after carrying out processing using a processing solution (pure water) containing a buffer solution (phosphate buffer solution at a pH of 6.8). FIG. 14A shows surface roughness as observed on the surface of the sample before processing. As will be appreciated from comparison between FIG. 14B and FIG. 14C , the processing of the sample carried out using the processing solution containing the buffer solution (buffering agent) reduced the surface roughness to a much larger extent as compared to the processing carried out using the processing liquid containing no buffer solution (buffering agent). When a substrate, such as a semiconductor wafer, is irradiated with light having a larger energy than the band gap of the substrate material, electrons in the valence band are excited and electron-hole pairs are generated. Oxidation of the substrate surface occurs through the holes of the valence band generated by the light irradiation. When the electron-hole pairs generated by light adsorption recombine and disappear, an oxidation reaction will not occur at the substrate surface. The recombination should therefore be prevented in order to progress the surface oxidation. In this regard, when platinum (Pt) is allowed to be in electrical contact with the substrate, electrons in the conducting band are accumulated in the platinum, and electron exchange will take place between the platinum and a solution. This can prevent recombination of the electron-hole pairs generated. An experiment on photooxidation of a surface of a GaN substrate was conducted to confirm the effect of electrical contact of platinum with the substrate. A 500-nm thick platinum film was formed by electron beam deposition on the back (000-1) surface of an n-type GaN (0001) substrate, thereby preparing a test sample in which the substrate is in electrical contact with the platinum layer. The same GaN substrate but with no platinum film formed on the back surface was used as a comparative sample. Light (UV light) irradiation was carried out for 3 hours on the respective substrate which was kept immersed in ultrapure water. FIG. 15 shows XPC O1s spectra for the GaN substrate sample and the comparative sample, as measured before and after the light irradiation. It is apparent from the data in FIG. 15 that for the comparative sample having no platinum film, there is no change in the O1s peak intensity before and after the light irradiation, whereas the O1s peak intensity of the sample having the platinum film is larger after the light irradiation. The data thus demonstrates that surface photooxidation occurs only in the GaN substrate having the platinum film on the back surface. A light irradiation CARE processing experiment was conducted using, as a sample, a GaN substrate having a vapor-deposited platinum film on the back surface and using, as a comparative sample, a GaN substrate with no platinum film formed on the back surface. Processing was carried out for 3 hours by immersing the respective substrate in phosphate buffer solution at a pH of 6.86 while irradiating the substrate surface with ultraviolet light. FIG. 16A shows a phase-shifting interference microscopic image of the surface of the comparative sample (GaN substrate), having no vapor-deposited platinum film on the back surface, before the light irradiation CARE processing, FIG. 16B shows a phase-shifting interference microscopic image of the surface of the comparative sample after the light irradiation CARE processing, and FIG. 16C shows a phase-shifting interference microscopic image of the surface of the sample (GaN substrate), having the vapor-deposited platinum film on the back surface, after the light irradiation CARE processing. As can be seen from comparison between FIGS. 16A and 16B , there is no significant change in the morphology and the micro roughness of the surface of the comparative sample, having no platinum film, before and after the processing, indicating no significant progress of processing. In contrast, as can be seen from comparison between FIG. 16A and FIG. 16C , scratches present in the substrate surface before processing are not found in the surface of the sample, having the platinum film, after the processing, and the micro roughness value 6.497 nm rms before processing decreased to 0.804 nm rms after processing. The comparative data thus demonstrates significant flattening by the CARE processing of the surface of the sample having the platinum film. Besides platinum, it is possible to use other metals, such as Ti, Ni, Cr, etc. as a metal for contact with a substrate, though the use of platinum is preferred in the interface between a processing solution and a metal. A metal (platinum) film may be formed on a substrate by any known vapor deposition method, such as vacuum deposition, electron beam evaporation, sputtering, etc. While platinum is preferably vapor-deposited on substantially an entire back surface of a substrate, it is possible to vapor-deposit platinum on part of the back surface. Further, it is not always necessary to form a metal (platinum) film on a back surface of a substrate. Thus, any method that can ensure electrical contact between a substrate and a metal, such as the use of a substrate holder made of a metal, may be used. It is also possible to apply a platinum coating to an inner side of a retainer of a substrate holder so that the coating will contact the edge of a substrate. While the present invention has been described with reference to the embodiments thereof, it will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described above, but it is intended to cover modifications within the inventive concept.
A flattening method, by utilizing the advantages of the CARE method and making up for the disadvantages, can perform removal processing of a surface of a workpiece at a sufficient processing rate and can provide a processed surface having enhanced flatness without leaving damage in the processed surface. A flattening method comprises at least two surface removal steps and at least two cleaning steps, the final surface removal step being a catalyst-referred etching step comprising immersing a workpiece in a processing solution containing at least one of hydrohalic acid, hydrogen peroxide water and ozone water, and bringing a surface of a catalyst platen into contact with or close proximity to a surface to be processed of the workpiece to process the surface, said catalyst platen having in a surface a catalyst selected from the group consisting of platinum, gold, a ceramic solid catalyst, a transition metal, glass, and an acidic or basic solid catalyst.
85,442
BACKGROUND OF THE INVENTION This invention relates to an improvement in the compression of delta coded sequences representative of successive scan lines of a continuous tone image. In the prior art, J. S. Wholey (IRE Transactions on Information Theory, April 1961, pages 99-104) pointed out that compression would result if the binary threshold-encoded elements of successive scan lines of graphical images were applied to a predictive encoder. Wholey further pointed out, at page 100, that a run-length code could always be found for coding the predictor output. It is to be recalled that the generic predictive encoding compression technique was introduced by P. Elias (IREa Transactions on Information Theory, March 1955, at pages 16-33). Relatedly, R. E. Graham in U.S. Pat. No. 2,905,756, "Method and Apparatus for Reducing Television Bandwidth" Sept. 22, 1959) applied predicitive encoding to the threshold-encoded elements of successive television scan lines. The term "threshold encoding" was taken to mean resolving each picture element independently as having either a black or a white picture value. The question naturally arises as to how may one encode images having tones between black and white. If a scan represents continuum of values, then differential encoding can be used. Relatedly, Armin H. Frei in "An Adaptive dual mode Coder/Decoder for Television Signals", IEEE Trans. on communications Technology, December 1971, pages 933-944, points out at page 934 that early attempts to encode video information consisted in sampling the video signal at the Nyquist rate and in coding 64 gray levels by means of 6 binary digits per pel. Later, differential PCM was introduced and where the video waveform was relatively smooth, it was feasible to operate a coder in the delta mode producing one bit per pel. SUMMARY OF THE INVENTION It is accordingly an object of this invention to devise a system for compressing gray scale imagery to less than one bit per picture element. This object is achieved by a system for compressing delta modulation image information by first predictive and then run-length encoding. Delta modulation techniques produce binary data representing gray scale images at exactly one bit per picture element. For example, a delta coded 1 bit indicates that the gray level is increasing, while a 0 is indicative that the level is being reduced. In most areas of a typical image, the gray level does not change rapidly. Therefore, adjacent delta modulation bits in a line tend to be complementary. A prediction is based upon the preceding bit and the two bits vertically adjacent to the preceding bit and the prediction bit. If the prediction is correct, a 0 is recorded. If the prediction bit is incorrect, a 1 is recorded. The resultant recorded bits comprise substantial strings of zeros and are then run-length encoded. In particular, the invention resides in an apparatus for compressing an mxn array of delta coded points obtained from the delta coding of the successive scan lines of a continuous tone image. The location of each point in the array is defined as an ordered pair (i,j) over the range 0≦i≦m and 0≦j≦n. The apparatus comprises means (1,3) for generating the delta coded values x of the array in row major order; an exhaustive non-linear predictor stage (14), responsive to the delta coded values xfor predicting a value x at array location (i,j) based upon previous values x 1 ,x 2 ,x 3 at corresponding locations (i-1,j-1), (i-1,j), (i,j-1) according to the relation: x = x.sub.3 x.sub.2 +x.sub.3 x.sub.1 +x.sub.1 x.sub.2 ; means (25) for correlating the actual value x and the predicted value x according to the relation y=x⊕x; and means (29) for variable length encoding runs of like consecutive values of y. As is apparent, the delta coding produces binary data representing gray scale pels at exactly one bit per pel. The resulting array of delta coded points is compressed by redistributing the statistics of run lengths such as to increase the expectancy of longer runs. This "predictive encoding" is followed by any suitable form of variable length coding in order to achieve compression. Since each delta coded point represents 1 bit per pel, compression to less than that amount results from the apparatus and method of the invention. BRIEF DESCRIPTION OF THE DRAWING FIGS. 1A and B are logical block diagrams representatively embodying the invention and respectively depicting gray scale image compression and expansion. FIGS. 2 and 3 show third- and fifth-order pel prediction patterns according to the invention. FIGS. 4A and B illustrate logical embodiments of the third- and fifth-order pel predictors. DESCRIPTION OF THE PREFERRED EMBODIMENT In encoding a gray scale image to exactly one bit per picture element using delta modulation, how can one compress such bit streams? Delta modulation involves incrementing or decrementing the present encoded gray level by some amount based upon a comparison with the actual gray level. The method involves an approximation of the actual image in that the gray scale image is not exactly reproducable from the encoded data. Some sophisticated techniques allow the encoded gray level to be incremented or decremented by a variable amount based upon the value of the present pel and some number of previous pels or even pels on the previous raster scan line of the image. The issue of compression is resolvable by identifying further redundancy at the output of the delta encoder. It was unexpectedly observed that if one examined the encoded data set from a delta encoder in a bit plane format, then one could invariably discern the pattern of the original image. In this regard, a bit plane format refers to the original image with each gray value replaced with a black or a white picture element, depending on the output of the delta modulator. This fact alone implies that there are still redundancies in the encoded data set. There are two primary sources of redundancy. First, a sequence of 1's or 0's indicates an edge in the original gray scale image. The edge is likely to repeat itself in the next scan line. A predictor that looks at the previous scan line can take advantage of this. It is this edge information that may be discerned by eye in the Δ coded output. Secondly, there exists a high a priori probability that two adjacent pels in a rastered scan line will be delta coded as complements of each other. This is due to the fact that the expected value of a gray scale picture element is close to the gray value of the previous picture element. As is apparent, a delta modulator tends to flip back and forth between zero and one in regions of uniform gray level. As a result of these considerations, it was theorized that those predictor/run-length encoder which were developed for "sparse" black/white images would be applicable to delta modulator outputs if modified to accommodate the expectation of alternating 1's and 0's. One example of predictor/run-length encoders developed for "sparse" black/white images may be found in Kobayashi and Bahl, "Image Data Compression By Predictive Coding", IBM Journal of Research and Development, March 1974, pages 164-179, especially at page 165. Another example of such a "sparse" system may be found in R. B. Arps, U.S. Pat. No. 3,813,4185, "System for Compression of Digital Data," filed Jan. 5, 1972. Referring now to FIG. 1A, there is shown a logical embodiment of gray scale image compression. A source 1 of gray scale image data in raster order is applied to a delta modulator encoder 3. Any analog-to-digital converter which would supply a numerically coded equivalent to a gray scale value for each consecutive picture element scanned in row major order would be sufficient. The delta modulation encoder 3 shown, for example, in H. R. Schindler, U.S. Pat. No. 3,699,566, "Delta Coder," issued Oct. 17, 1972, describes the type of digital encoding which encodes only the variation in the level between two successive sampling instants. In addition to the delta coder shown in FIG. 1 of the Schindler reference, a delta decoder is set forth in FIG. 3. As Schindler points out, a delta modulation system is one in which each sample is compared to a reference and the relative magnitude is encoded as one of only two binary levels. The sample magnitude is compared to the previously considered level. The binary level is indicative of whether the input is being approximated by positive or negative steps. Accordingly, the encoder sends a binary 1 in the case of the negative-going approximation and binary 0 in the case of a positive-going approximation. For a constant input, that is, one with successive differences of zero, the encoder will characteristically produce an alternating output 101010, this corresponds to regions of constant tone, i.e. constant gray level. The bit stream output x from delta coder 3 is applied to predictor stage 14 over path 5. The output of stage 14 consists of a so-called correlated error image x⊕x. It is applied over path 27 to run-length encoder 29. Note, it is to be understood that the function of the predictor stage is to change the statistical distribution of run lengths in the correlated error image x⊕x by increasing the frequency of long runs of zeros. The runs of consecutive zeros can then be conveniently compressed with a suitable run-length encoder. The predictor stage comprises a line store A formed from a shift register serially storing n+1 bits of delta coded data, where n is the number of bits in a raster scan line. The line store is tapped at predetermined points along its extent so that its contents may be applied to predictor 15. Parenthetically, predictor 15 may be either of the three-pel or five-pel variety as logically embodied in FIGS. 4A and B. The correlated error image is formed by exclusive OR gate 25 from the joint input of each delta coded bit x on path 5 and its predicted value x on path 16. Referring now to FIG. 1B there is shown the logical embodiment of a gray scale image expander. The compressed error image is applied in raster scan order to run-length decoder 33. This yields the expanded correlated error image x⊕x. This is applied to the predictor stage 36 over path 35. The output of predictor stage 36 in raster scan line order is the delta coded values x applied to delta decoder 45 over path 43. Delta decoder 45 integrates successive delta values in order to provide gray scale image data. Now, the output from the delta decoder as shown in FIG. 3 of the Schindler patent may be converted into a binary digital value for storage, for example, in a serially readable buffer. Both the analog-to-digital encoding and buffering are incorporated in element 47. In this regard neither source 1 nor sink 47 constitute elements of this invention. Referring again to FIG. 1A, consideration should be given to the nature of the predictor stage 14 and the run-length encoder 29. The predictive stage utilizes an nth order exhaustive, causal predictor which looks at adjacent points of previous scan lines and preceding points of present scan lines to predict the binary value that delta coder 3 ought to generate. This is compared with the actual delta coder binary x Exclusive OR gate 25. If the prediction is in error, that is, if x and x mismatch, than a binary 1 is transmitted on path 27. If there is a match, then a binary 0 is applied to path 27. If the prediction algorithm is accurate for a substantial fraction of the time, then long runs of zeros can be expected on path 27. Run-length encoder 29 and decoder 33 may be of the extended run-length code variety such as, for example, shown respectively in FIGS. 2 and 4 of R. B. Arps, U.S. Pat. No. 3,813,485. This run length encoder is of the type which uses variable length words, with subword length L related to a dual-based counting system such that L=log 2 (p+r) bits, where p equals the number of states in the lower order subwords; and r equals the number of states in successive higher and highest order subwords. Alternatively, the run lengths may be Huffman encoded according to the Kobayashi et al reference at pages 174-179. This run length encoder is of the type where the length of the instantaneous Hoffman integer valued code word is inversely proportional to the logarithm of the frequency of occurrence of runs of any given length. Given that the delta coded output of 1 bit per picture element, it can now be seen that by predictive coded results in a larger number of long run lengths. It is possible to take advantage of the compression efficiency of run-length encoding. A compression of between 1.5 and 2.0 is achievable using the method and apparatus of this invention. Illustratively, without the invention pq bits of memory would be required to store a p×q two-dimensional array of delta coded points. Utilizing the invention, only pq/2 bits of memory are needed. Referring now to FIG. 2 taken together with FIG. 1A, attention is first directed to the reference pel pattern. For a three-pel predictor, according to this invention, x 1 and x 2 refer to the delta coded values in the ith - 1 scan line respectively in the j-1 and j pel positions while x 3 and x in the ith scan line represent the delta coded values of the j-1 and j pel positions. It is a significant aspect of the invention, that x is related to x 1 , x 2 , and x 3 according to the relation: x = x.sub.3 x.sub.2 +x.sub.3 x.sub.1 +x.sub.1 x.sub.2. As s shown on the accompanying table, each of the pel patterns 2A-H defined by elements x 1 x 2 x 3 have associated therewith a corresponding predictive value. Now, in relating the reference pel pattern to the values contained in line store 17, it will be observed that x 3 is the delta coded value obtained from the immediate preceding clocking cycle, while x 1 x 2 are contained in the appropriate positions in the immediately preceding raster scan line. Referring now to FIG. 4A, there is shown a logical embodiment for the three-pel predictor 15 and its connection to line store 17. Referring now to FIG. 3, disclosing a fith-order pel predictor, there is shown a reference pel pattern and the relationship between the predicted value x and x 1 , x 2 , x 3 , x 4 , and x 5 . The reference pel pattern discloses that three pels, x 1 , x 2 , and x 4 from the ith - 1 scan line, in pel positions j-1, j, and j+1, together with delta coded values x 5 and x 3 of the ith scan line in pel positions j-2 and j-1, respectively, are used to predict x. As a consequence of the higher order prediction, the population of 1's in the error image should be even further reduced. Reference should be made to FIG. 4B for a logical embodiment of the five-pel predictor according to the invention. Parenthetically, x is related to x 1 . . . x 5 according to the relation: x = x.sub.3 x.sub.2 +x.sub.1 x.sub.2 (x.sub.4 x.sub.5)+x.sub.1 x.sub.3 (x.sub.4 x.sub.5)+(x.sub.2 +x.sub.3)x.sub.1 (x.sub.4 x.sub.5)+x.sub.4 x.sub.5 (x.sub.2 x.sub.3 +x.sub.2 x.sub.3). It will be understood that the predictor stage 14, run-length encoder 29, run-length decoder 33, and predictor stage 36 are synchronous clock driven elements. Thus, during any given clock cycle, a predicted value x is generated on line 16 and compared with the delta coded value x on line 5 through Exclusive OR gate 25 with the appropriate correlated error image being applied to run-length encoder on line 29 via path 27. Of some interest is the fact that the ability to compress and expand delta coded information is limited to a small subset of casual predictor algorithms. Thus, the predictor pattern shown on FIG. 3B of Arps is not operative for error-free compression and expansion with the delta coded gray scale image information. While the preferred embodiment of the invention including both the method and apparatus have been illustrated and described, different implementations of the disclosed techniques may be preferred by others, and since modifications will naturally occur to those skilled in this art, the invention should not be circumscribed by the disclosed embodiments but, rather, should be viewed in light of the following claims.
In a continuous tone image approximated by a two-dimensional array of gray scale coded points, more than one bit per picture element is required. Compression coding consists firstly of delta coding sequences representative of the successive scan lines of the continuous tone image and secondly applying them to a predictive encoder having a particular transfer function and thirdly run-length encoding the error image. Central to the invention is the observation that delta coded sequences of gray scale pel values along a given scan line having a high expectancy of alternating, i.e. 101010. Also, the gray scale trend in the ith scan line is expected to be the same as the trend of the ith - 1 scan line. Relatedly, gray scale image expansion is achieved by applying the compressed image to a run-length decoder, a predictor stage, and delta decoder.
16,544
This application is a division of application Ser. No. 07/951,166, filed Sep. 25, 1992, now U.S. Pat. No. 5,289,414. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high speed comparator used in microprocessor cache memories and translation look-aside buffer (TLB) devices. 2. Description of the Prior Art In conventional microprocessors, plural bit comparators are used for cache memory tagging and for TLBs. One example of a conventional 24-bit comparator used as a cache memory tag unit is shown in FIG. 14. The tag memory 1401 is accessed by the input address PA 1410 (PA represents physical address), which is decoded by the decoder 1402. When the word line WL 1411 voltage is HIGH, the data stored in the memory cell array selected by the HIGH word line WL 1411 is output to the bit line pair thereof. When the sense enable line SEN 1412 becomes HIGH, the data from the tag memory is read out as address B [23:0] by the sense amplifier 1403. Here, [23:0] indicates that there are 24 bit lines 0, 1, 2, . . . , 23 for address B. Each bit in address A [23:0] 1413 from the central processing unit (CPU) and B [23:0] is compared in the coincidence circuit 1404 for detecting whether the bit line signal from address A and the corresponding bit line signal from address B coincide with each other, or not. The coincidence circuit 1404 is formed by an exclusive NOR (XNOR; logical inverse of the exclusive logical sum) gate, and the coincidence/non-coincidence of all corresponding bits is detected by the AND circuit 1405. The hit signal line HIT 1414 becomes HIGH when all bit lines are coincident, and LOW when one or more bit lines is non-coincident. The cache memory RAM controls data input/output using this bit line signal. The precharge/equalization circuit 1406 is controlled by the precharge enable PCEN 1415 and equalize enable EQEN 1416 signals to precharge and equalize the bit line pairs when the tag memory is not accessed. An N-channel MOSFET device is used as the precharge circuit to increase the speed of the read and precharge/equalization operations. The write circuit 1407 for writing data W [23:0] 1418 is controlled by the write enable WEN 1417 signal. A differential sense amplifier using a bipolar transistor with a high transconductance (gm) is used as the sense amplifier circuit 1403 to achieve a high read speed in the memory circuit. An example of this differential sense amplifier is shown in FIG. 15. Referring to FIG. 15, the bit line pair B 1511 and NB 1512 are the inputs to the emitter follower circuits 1501, 1502. Two NPN transistors 1503, 1504 form the differential sense amplifier. The current-switching N-channel MOSFET 1505 operates only when the sense enable signal 1515 is HIGH, and operates then as a constant current supply device. A load resistance 1506, 1507 is provided for each differential sense amplifier, and data is output to the data output 1516. In general, a circuit built with bipolar transistors has a low input impedance. A high base current is output when the bipolar transistor is saturated, and the load on the circuit connected to the base, i.e., the bit line, increases. As a result, there is the danger of the wrong data being written to the memory cell when there is much noise signal in the power supply or ground line because there will be a significant voltage drop even with the HIGH bit line during memory reading. Since the emitter follower circuit has a high input impedance, low output impedance, and high current gain as shown in FIG. 15 (1501, 1502), the emitter follower circuit is used to avoid this by reducing the bit line load. In addition, because a voltage that is the internal voltage Vbe between the base and emitter less than the bit line voltage is input to the base of the NPN transistor in the differential sense amplifier, the differential sense amplifier NPN transistor is not as easily saturated. With the prior art as described above, three steps must be completed before the bit signal is generated, specifically, (1) tag reading, (2) per-bit coincidence/non-coincidence comparison of the address B [23:0] read from the tag memory and the address A [23:0] from the CPU, and (3) coincidence/non-coincidence comparison of all bits. As a result, this increases the time required between reading from the tag memory and hit signal generation. In particular, the number of gates and the delay time both increase because the multiple-bit data signal is compacted to a 1-bit signal in steps (2) and (3). Furthermore, the addition of an emitter follower circuit increases the number of bipolar transistors, and thus increases the size of the sense amplifier. The effective size of bipolar transistors requiring a separation area between other bipolar transistor cannot be reduced as much as MOSFET devices can, even when the degree of integration increases, and it therefore becomes impossible to keep the memory cells and sense amplifiers proportionally reduced sized. As a result, it is not possible to provide a large-scale sense amplifier for each bit in a TLB or tag memory requiring simultaneous reading of many bits. SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a high speed comparator featuring a sense function and comparison function achieved in a small hardware. A comparator according to the present invention compares, in response to an activation signal, the voltages of first and second signals in complement with the voltages of third and fourth signals in complement, and according to one embodiment comprises: a first bipolar transistor for receiving the third signal to a base thereof; a second bipolar transistor for receiving the fourth signal to a base thereof; a first FET for receiving the second signal to a gate thereof, the first bipolar transistor and the first FET being connected in series to form a first current path; a second FET for receiving the first signal to a gate thereof, the second bipolar transistor and the second FET being connected in series to form a second current path, the first current path and the second current path connected in parallel; a switching FET having a drain connected to emitters of the first and second bipolar transistors and a source connected to ground, and being turned on during when the activation signal is in a first state; a load resistor means connected to a junction of drains of the first and second FETs; and a precharge means for precharging collectors of the first and second bipolar transistors during when the activation signal is in a second state. In operation, when the first and third signals are in the same state and, at the same time, the second and fourth signals are in the same state, the junction produces a first level signal, and when the first and third signals are in the opposite state and, at the same time, the second and fourth signals are in the opposite state, the junction produces a second level signal. A comparator according to another embodiment of the present invention comprises: an exclusive NOR comprising first, second, third and fourth inputs for receiving the first, third, second and fourth signals, respectively, and first and second outputs, the first and second outputs are connected when the first and third signals are in the same state, and the first and second outputs are disconnected when the first and third signals are in the opposite state; an exclusive OR comprising fifth, sixth, seventh and eighth inputs for receiving the first, fourth, second and third signals, respectively, and third and fourth outputs, the third and fourth outputs are connected when the first and third signals are in the opposite state, and the third and fourth outputs are disconnected when the first and third signals are in the same state; a first bipolar transistor having base and collector connected to the first and second junctions, respectively; a second bipolar transistor having base and collector connected to the third and fourth junctions, respectively; a switching FET having a drain connected to emitters of the first and second bipolar transistors and a source connected to ground, and being turned on during when the activation signal is in a first state; a first load resistor means connected to the second junction; and a second load resistor means connected to the fourth junction. In operation, when the first and third signals are in the same state and, at the same time, the second and fourth signals are in the same state, the first and second bipolar transistors are turned on and off, respectively, and when the first and third signals are in the opposite state and, at the same time, the second and fourth signals are in the opposite state, the first and second bipolar transistors are turned off and on, respectively. A comparator according to yet another embodiment of the present invention comprises: an exclusive OR comprising first, second, third, and fourth inputs for receiving the first, fourth, second and third signals, respectively, and first and second outputs, the first and second outputs are connected when the first and third signals are in the opposite state, and the first and second outputs are disconnected when the first and third signals are in the same state; a switching FET means for connecting the first junction to ground and the second junction to a voltage source in response to the activation signal; and a current mirror coupled to the switching FET means for producing a current corresponding to the connection and disconnection of the exclusive OR. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will become more fully understood from the detailed description given below and the accompanying diagrams wherein: FIG. 1 is a circuit diagram of a 1-bit comparator according to the first embodiment of the invention; FIG. 2 is a timing chart of a 1-bit comparator according to the first embodiment of the invention; FIGS. 3a, 3b and 3c are each a circuit diagram of a 1-bit comparator according to a modification of the first embodiment of the invention; FIG. 4 is a circuit diagram of a circuit diagram of a 1-bit comparator according to the second embodiment of the invention; FIG. 5 is a time chart of a 1-bit comparator according to the second embodiment of the invention; FIG. 6 is a circuit diagram of a 1-bit comparator according to a modification of the second embodiment of the invention; FIG. 7 is a circuit diagram of a 1-bit comparator according to the third embodiment of the invention; FIG. 8 is a timing chart of a 1-bit comparator according to the third embodiment of the invention; FIG. 9 is a circuit diagram of a 1-bit comparator according to the fourth embodiment of the invention; FIG. 10a is a circuit diagram of a 1-bit comparator according to the fifth embodiment of the invention; FIG. 10b is a timing chart of a 1-bit comparator according to the fifth embodiment of the invention; FIG. 11a is a circuit diagram of a 1-bit comparator according to a first modification of the fifth embodiment of the invention; FIG. 11b is a timing chart of a 1-bit comparator according to the first modification shown in FIG. 11a; FIG. 11c is a circuit diagram of a 1-bit comparator according to a second modification of the fifth embodiment of the invention; FIG. 12 is a circuit diagram of comparators and tag memory of a cache memory according to the sixth embodiment of the invention; FIG. 13 is a circuit diagram of comparators and tag memory of a cache memory according to the seventh embodiment of the invention; FIG. 14 is a circuit diagram of comparators and tag memory of a cache memory according to prior art; and FIG. 15 is a circuit diagram of a sense amplifier according to prior art. DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of a comparator according to the present invention are described below with reference to the accompanying figures, of which FIG. 1 is a circuit diagram of a 1-bit comparator used in the cache memory comparators according to the first embodiment of the invention. This comparator compares one bit signal, e.g., NB 112, in the address read from the tag memory with one bit signal, e.g., NA 114, in the address from the CPU. It is noted that "N" in NA and NB represents logic "NOT". Referring to FIG. 1, a differential sense amplifier is formed by two NPN transistors 101, 102 of which a bit line pair B 111 and NB 112 are the base inputs, respectively. A current switching N-channel MOSFET 103 is ON only when the sense enable signal EN 115 is HIGH, and operates as a constant current supply. Two other N-channel MOSFETs 104 and 105 control the collector current of the NPN transistors 101 and 102, respectively. The gate inputs to these MOSFETs 105 and 104 are respectively the address input line A 113 and the inverted address input line NA 114, which is the logic inversion signal of the address input line A 113. Transistors 101 and 102 and MOSFETs 104 and 105 form an XOR gate. Other components of this embodiment are the load resistor 106, HIT output line 116, and P-channel MOSFETs 107 and 108 for precharging the collector voltage of the NPN transistors 101 and 102 when the precharge enable PC 117 signal is LOW. It is to be noted that the precharge enable PC 117 signal and the sense enable signal EN 115 are the same phase, and a common signal can be used. The operation of the 1-bit comparator shown in FIG. 1 is to detect signal coincidence between line A 113 and line B 111 (or between line NA 114 and line NB 112). When both lines A 113 and B 111 carry a LOW level signal, lines NA 114 and NB 112 will eventually carry a HIGH level signal. In this case, transistor 101 closes and MOSFET 104 opens and, at the same time, transistor 102 opens and MOSFET 105 closes. Thus, there will be no current path established between resistor 106 and MOSFET 103. Thus, the voltage level of the output HIT 116 is HIGH, indicating that a coincidence of the signal between line A 113 and line B 111 (or between line NA 114 and line NB 112) is obtained. However, when lines NA 114 and NB 112 carry different level signals, it is so detected that a non-coincidence is obtained. For example, when line A 113 carries HIGH and B 111 carries LOW, line NA 114 will carry LOW and line NB 112 will carry HIGH. In this case, transistor 101 closes and MOSFET 104 closes and, at the same time, transistor 102 opens and MOSFET 105 opens. Thus, there will be a current path established between resistor 106 and MOSFET 103 through MOSFET 105 and transistor 102. Thus, the voltage level of the output HIT 116 is grounded through the established current path and MOSFET 103. Thus, output HIT 116 produces a LOW level signal indicating that a non-coincidence of the signal between line A 113 and line B 111 (or between line NA 114 and line NB 112) is obtained. When a coincidence is obtained, the output HIT 116 produces a HIGH level signal, but when a non-coincidence is obtained, the output HIT 116 is grounded to produce a LOW level signal. The operation for detecting the coincidence and non-coincidence is further described below with reference to the timing chart shown in FIG. 2. It is to be noted that the voltage waveforms shown in FIG. 2 correspond to the signals carried by the signal lines of the same reference numbers in FIG. 1. (1) Coincidence When a HIGH level signal (V DD ) is output to address input line A 113, a LOW level signal (V SS ) is output to the address inversion signal input line NA 114. When the word line WL is HIGH, HIGH and LOW level signals are output to the bit lines B 111 and NB 112, respectively. The comparator starts operating when the sense enable signal EN 115 becomes HIGH, that is during a period T1. Before the period T1, a transient current caused by parasitic capacity discharge is produced, and thus the voltage of the HIT output line 116 drops slightly. Also, before the period T1, by the precharge signal PC 117 having a similar waveform to that of the sense enable signal EN 115, MOSFETs 107 and 108 provides a predetermined voltage to each junctions of between transistors 101 and 104 and between transistors 102 and 105, so that the transistors 101 and 104 on one side of the XOR gate balances with the transistors 102 and 105 on the other side thereof. During period T1, there is no current from the collector of the NPN transistor 101 to which the base input is the HIGH bit line B 111 because the N-channel MOSFET 104 is OFF. Thus, during the period T1, since both signals NA 114 and NB 112 are LOW level signal, the voltage of the output line HIT 116 is maintained HIGH because there is no establishment of a current path. (2) Non-Coincidence When a LOW level signal is output to address input line A 113, a HIGH level signal is applied to the address inversion signal input line NA 114. Then, when the word line WL becomes HIGH, HIGH and LOW level signals are applied to the bit lines B 111 and NB 112, respectively. Because the N-channel MOSFET 104 is ON at this time, there is a current path from the collector to the NPN transistor 101 to which the base input is the HIGH bit line B 111. As a result, a constant current flows to the load resistance 106. Thus, the voltage of the HIT output line 116 becomes LOW. It is to be noted that the output LOW voltage is a voltage divided by the resistance component of the MOSFET and NPN transistor. If an inverter circuit or similar device having a logic threshold shifted lower than one-half the power supply voltage is used, there will be sufficient LOW output signal from the circuit. Discharge of the parasitic capacity causes the collector voltage to drop in the NPN transistor for which the current path from the collector has been opened. Because equality of the collector voltage and base voltage of two NPN transistors is a prerequisite condition of comparison, operation during the next cycle will not be correct without any balancing operation. P-channel MOSFETs 107 and 108 are therefore provided as precharge circuits for precharging the collector voltage to HIGH during the sense amplifier standby state. FIGS. 3a-3c show modifications of the comparator shown in FIG. 1. FIG. 3a is a circuit in which the P-channel MOSFETs 301 and 302 are provided in place of N-channel MOSFETs 104 and 105 for forming the collector current control circuit. FIG. 3b is a circuit in which both the N-channel MOSFETs 104 and 105 and P-channel MOSFETs 301 and 302 are used for forming a collector current control circuit. Note that like parts are indicated by like reference numbers in FIGS. 1 and 3. With these circuits current flows to the collector of the NPN transistor 101 when the address input line A 113 is LOW, i.e., when the address inversion signal input line NA 114 is HIGH, and the collector current of the other NPN transistor 102 flows when the address input line A 113 is HIGH, thus resulting in the same operation as the construction shown in FIG. 1. It should also be noted that this construction also helps reduce the cell area because the P-channel MOSFETs 301, 302 can be formed in the N-type impurity area of the collector. In the device shown in FIG. 3c, the address signal is read from the memory cell 304 of the memory circuit 303. In this case the precharge circuit is shared by the N-channel MOSFETs 104,105. This is because the address input lines A 113 and NA 114 are precharged by the precharge/equalization circuit 305 during when the comparator and memory circuit are not accessed, resulting in such that the collector voltage of the NPN transistors 101, 102 is HIGH because the N-channel MOSFETs 104 and 105 are ON. It is to be noted that if the address input lines A 113 and NA 114 are HIGH during precharging, it is possible to connect the sense amplifier 306. As described hereinabove, an exclusive NOR (XNOR) gate is formed by the differential sense amplifier 101 and 102 and collector current control MOSFETs 104 and 105 (and/or 301 and 302) in the present embodiment of the invention. The sense amplifier and comparator are thus effectively combined or integrated formed, and reading and comparison are performed simultaneously to shorten the required read/comparison time. SECOND EMBODIMENT FIG. 4 is a circuit diagram of a 1-bit comparator used in the cache memory comparators according to the second embodiment of the invention. This comparator compares one bit in the address read from the tag memory with one bit in the address from the CPU. This embodiment of the invention increases the input impedance of the differential circuit by providing a MOSFET of which the gate inputs are the bit line pair, and the source and drain are connected to the base and collector of an NPN transistor. Note that like parts are indicated by like reference numbers in FIGS. 1 and 4. The second embodiment of FIG. 4 differs from the first embodiment in that the N-channel MOSFETs 401, 402 are further provided. The N-channel MOSFETs 401, 402 have their gate inputs connected to the bit line pair B 111, NB 112, and the drain and source thereof connected to the collector and base of the differential sense amplifier, respectively. Other than the point that the base current is supplied to the NPN transistor, the configuration of the second embodiment is identical to that of the first embodiment shown in FIG. 1. The voltage waveforms of each signal line in the 1-bit comparator are shown in FIG. 5. Except for an initial transient voltage drop, the HIT output line 116 is HIGH when the input signal is coincident, and LOW when not coincident as with the waveforms of the first embodiment shown in FIG. 2. Unlike in the first embodiment, the input impedance of the differential sense amplifier 101, 102 is high, and the HIGH bit line voltage does not drop because the NPN transistor base current is supplied through the MOSFET (FIG. 5). As a result, there is virtually no danger of memory circuit operating errors resulting from the noise signal. FIG. 6 is a modification of the second embodiment in which P-channel MOSFETs 601, 602 are used in place of N-channel MOSFETs 401 and 402 to form the collector base current supply MOSFET. In this case too, a strong base current is supplied to the NPN transistor 101 when the memory data is HIGH, i.e., the inverted bit line NB 112 is LOW, as with the 1-bit comparator shown in FIG. 4. This device therefore functions in the same way as the 1-bit comparator shown in FIG. 4. Furthermore, it should also be noted that this construction also helps reduce the cell area because the P-channel MOSFETs 601, 602 can be formed in the N-type impurity area of the collector. It is to be noted that even if the memory cell contents are output to the bit line, the comparator will not act effectively unless the bit line-source voltage of the P-channel MOSFETs 601, 602 exceeds the threshold voltage Vt, that is unless the MOSFET operating condition Vgs≧Vt (where Vg is the bit line voltage and Vs is the source voltage) is satisfied. As a result, this non-operating time increases if the bit line is precharged to V DD . TO achieve a high speed comparison mode, it is sufficient to lower the precharge voltage to V DD -Vt or less. As described hereinabove, an exclusive NOR (XNOR) gate is formed by the differential sense amplifier and collector current control MOSFET in the present embodiment of the invention. The sense amplifier and comparator are thus effectively integrated, and the read/comparison operations can be completed in a short time. In addition, the base current of the NPN transistor is supplied through the MOSFET of which the gate inputs are the bit lines. Stable operation of the memory circuit can be achieved with a small hardware configuration because the MOS circuit changes the impedance without using an emitter follower circuit. Furthermore, saturation of the NPN transistors can be prevented because the NPN transistor collector-base is clamped by the MOSFET threshold voltage Vt. Finally, this embodiment is described with the base current supply MOSFET added to the comparator shown in FIG. 1, but the same effect can be obtained by adding this MOSFET to the comparator shown in FIG. 3. THIRD EMBODIMENT Referring to FIG. 7, a third embodiment of a comparator according to the present invention is shown, wherein a 1-bit comparator is used in the cache memory comparators for comparing one bit in the address read from the tag memory with one bit in the address from the CPU. Referring to FIG. 7, an XNOR gate 701 is formed by four N-channel MOSFETs F1, F2, F3 and F4. Gates of MOSFETs F1 and F2 are connected to address line A 713 and bit line B 711, respectively, and gates of MOSFETs F3 and F4 are connected to inverted address line NA 714 and inverted bit line NB 712, respectively. MOSFETs F1 and F2 are connected in series and MOSFETs F3 and F4 are connected in series. The sources of MOSFETs F1 and F3 are connected to a junction J1 and further to the base of transistor 703. The drains of MOSFETs F2 and F4 are connected to a junction J2 and further to the collector of transistor 703. Similarly, an XOR gate 702 is formed by four N-channel MOSFETs F5, F6, F7 and F8. Gates of MOSFETs F5 and F6 are connected to address line A 713 and inverted bit line NB 712, respectively, and gates of MOSFETs F7 and F8 are connected to inverted address line NA 714 and bit line B 711, respectively. MOSFETs F5 and F6 are connected in series and MOSFETs F7 and F8 are connected in series. The sources of MOSFETs F5 and F7 are connected to a junction J3 and further to the base of transistor 704. The drains of MOSFETs F6 and F8 are connected to a junction J4 and further to the collector of transistor 704. The NPN transistors 703, 704 forms a differential sense amplifier. The current-switching N-channel MOSFET 705 is ON only when the sense enable signal EN 715 is HIGH. When the current-switching N-channel MOSFET 705 is ON, it functions as the constant current supply to the differential sense amplifier. Load resistors 706, 707 are provided for the differential sense amplifiers, and the result is output to the HIT output line 716. The operation of the 1-bit comparator shown in FIG. 7 is described below with reference to the timing chart shown in FIG. 8. It is to be noted that the voltage waveforms shown in FIG. 8 correspond to the signals carried by the signal lines of the same reference numbers in FIG. 7. (1) Non-Coincidence When a LOW level signal is applied to address input line A 713, a HIGH level signal is applied to the inverted address input line NA 714. Then, when the word line WL becomes HIGH, HIGH and LOW level signals are applied to the bit lines B 711 and NB 712, respectively. The XNOR gate 701 and XOR gate 702, both formed by pass transistor logic circuits, become OFF and ON, respectively, and the base current is supplied to the NPN transistor 704. When the sense enable signal EN 715 becomes HIGH, the differential sense amplifier starts operating, and the collector current of the NPN transistor 704 flows. A voltage drop in the load resistor 707 occurs, and the output line 716 becomes LOW. It is to be noted that the output LOW voltage is a voltage divided by the resistance component of the MOSFET and NPN transistor. If an inverter circuit or similar device having a logic threshold shifted lower than one-half the power supply voltage is used, there will be sufficient LOW output signal from the circuit. (2) Coincidence When a HIGH level signal is applied to address input line A 713, a LOW level signal is applied to the inverted address input line NA 714. Then, when the word line WL becomes HIGH, HIGH and LOW level signals are applied to the bit lines B 711 and NB 712, respectively. The XNOR gate 701 and XOR gate 702, both formed by pass transistor logic circuits, become ON and OFF, respectively. The differential sense amplifier starts operating when the sense enable signal EN 715 becomes HIGH, a transient current caused by parasitic capacity discharge is emitted, and the voltage of the HIT output line 716 drops slightly. However, the base current is not supplied to the NPN transistor 704 and there is no constant collector current path because the XOR gate 702 is OFF. When the initial discharge is completed, the HIT output line 716 voltage does not drop any further, and is raised to the power supply voltage V DD by the load resistor 707 again. As described hereinabove, the present embodiment of the invention forms XOR and XNOR gates from pass transistor logic circuits, which are then combined with differential sense amplifiers to form a comparator. By thus effectively integrating a sense amplifier and comparator, reading and comparison operations can be simultaneously performed, and the read/comparison time can be shortened. Furthermore, because the NPN transistor base current is supplied through the MOSFET devices, the input impedance of the differential sense amplifier increases. Thus, there is no drop in the HIGH bit line voltage, and there is no danger of the memory circuit storing false data because of noise signal. In addition, the base voltage of the NPN transistors 703, 704 is clamped at a voltage less than the collector voltage by the voltage of the serial MOSFET devices in the pass transistor logic circuit, and an NPN transistor saturation prevention circuit can be achieved using small MOSFET devices, eliminating the need for emitter follower circuits requiring a large area. The present embodiment of the invention can therefore achieve a high speed comparator in a small hardware package for use in translation look-aside buffers and tag memory devices of cache memories requiring simultaneous reading of plural bits. FOURTH EMBODIMENT FIG. 9 is a circuit diagram of a 1-bit comparator used in the cache memory comparators according to the fourth embodiment of the invention. This comparator compares one bit in the address read from the tag memory with one bit in the address from the CPU. In this embodiment, the P-channel MOSFETs F1', F2', F3', F4', F5', F6', F7' and F8' are used to form the XNOR gate 901 and XOR gate 902 of the pass transistor logic circuit. As with the 1-bit comparator shown in FIG. 7, the base current is not supplied to the NPN transistor 704 when the voltages of the bit line pair B 711, NB 712 and address input line pair A 713, NA 714 are coincident, and the base current is supplied when the voltages are non-coincident. As a result, this comparator operates identically to the 1-bit comparator shown in FIG. 7. Furthermore, it should also be noted that this construction also helps reduce the cell area, because the P-channel MOSFETs can be formed in the N-type impurity area of the collector, and thus an element separation area between the NPN transistor and P-channel MOSFET is not needed. It is to be noted that even if the memory cell contents are output to the bit line, the operating conditions of the P-channel MOSFET devices of which the gate input is the bit line pair will not be satisfied and the comparator will not function unless the bit line-collector voltage exceeds the threshold voltage Vt of the P-channel MOSFETs, that is unless the MOSFET operating condition Vbc=Vgs≧Vt (where Vb is the voltage of one of the bit lines, Vc is the collector voltage, and Vgs is the gain-source voltage of the P-channel MOSFET) is satisfied. As a result, this non-operating time increases if the bit line is precharged to V DD , but a high speed comparison mode can be achieved by lowering the precharge voltage to V DD -Vt or less. As described hereinabove, an XOR gate and XNOR gate are formed by the pass transistor logic circuit, and the comparator is formed by combining these with a differential sense amplifier. The sense amplifier and comparator are thus effectively integrated, and the read/comparison time can be shortened by performing both operations simultaneously. In addition, because the base current of the NPN transistor is supplied through the MOSFET devices, the input impedance of the differential sense amplifier rises, there is no danger of the memory circuit storing false data, and a bipolar transistor saturation prevention circuit can be formed using small MOSFET devices. The present embodiment of the invention can therefore achieve a high speed comparator in a small hardware package for use in translation look-aside buffers and tag memory devices of cache memories requiring simultaneous reading of plural bits. FIFTH EMBODIMENT FIG. 10a is a circuit diagram of a 1-bit comparator used in the cache memory comparators according to the fifth embodiment of the invention. This comparator compares one bit in the address read from the tag memory with one bit in the address from the CPU. In this embodiment, an XOR gate 1001 is formed by first, second, third, and fourth N-channel MOSFETs F11, F12, F13 and F14 which have their gates connected to lines A 1013, NB 1012, NA 1014 and B 1011, respectively. A junction J11 between sources of MOSFETs F11 and F13 is connected to ground through a switching MOSFET 1006, and a junction J12 between drains of MOSFETs F12 and F14 is connected to a voltage source through a switching MOSFET 1004. The first and second junctions J11 and J12 are connected when the signals on lines A 1013 and B 1011 are in the opposite state, and are disconnected when the signals on lines A 1013 and B1011 are in the same state. N-channel MOSFET devices 1002 and 1003 form a current mirror circuit which receives the discharge current from XOR gate 1001 as a reference input current. P-channel MOSFET 1004 is provided for the current switch which turns on when the sense enable signal EN 1015 becomes HIGH. A precharge circuit 1005 is provided for the HIT output line 1016. N-channel MOSFET 1006 is provided for turning off the current mirror circuit. The operation of the fifth embodiment of FIG. 10a is as follows. When the comparator is in the stand-by state, the sense enable signal EN 1015 becomes LOW. Thus, at the initial state, the HIT output line 1016 is precharged to HIGH by the precharge circuit 1005, and at the same time, the current mirror circuit is turned off by the LOW level signal applied to line L1 connected to the gates of the N-channel MOSFET devices 1002 and 1003. When the voltages at the bit line pair B 1011 and NB 1012, and address input line pair A 1013 and AN 1014 reach the required level, the sense enable signal EN 1015 becomes HIGH. Then the voltages at the bit line pair are compared with the voltages at the address input line pair. As shown in FIG. 10b, when the voltages are non-coincident, the XOR gate 1001 closes. Thus, discharge current from the XOR gate 1001 is supplied to the drain of N-channel MOSFET 1002, providing reference current to the current mirror circuit. Thus, a current flows through the drain of the N-channel MOSFET 1003. Since the drain of the N-channel MOSFET 1003, i.e., the output of the current mirror circuit, is connected to the HIT output line 1016, the current flowing through the drain of the MOSFET 1003 causes the discharge of the HIT output line 1016, which then result in the LOW level. On the other hand, when the voltages are coincident, the XOR gate 1001 closes to maintain the LOW level signal at the gates of MOSFETs 1002 and 1003. Thus, the HIT output line 1016 is maintained HIGH. According to this embodiment, since the HIT output line 1016 can be discharged with only one MOSFET 1003, it is possible to speed up the detection of the non-coincident and coincident. Referring to FIG. 11a, a first modification of the fifth embodiment is shown. According to the first modification, the P-channel MOSFET 1004 for the current switch is replaced with N-channel MOSFET 1101, and the current mirror circuit is formed by P-channel MOSFETs 1102 and 1103. The operation of the modification of FIG. 11a is shown in FIG. 11b. Referring to FIG. 11c, a second modification of the fifth embodiment is shown. According to the second modification, the current mirror circuit is formed by NPN transistors 1104 and 1105. SIXTH EMBODIMENT FIG. 12 is a circuit diagram of the tag memory area of a cache memory device according to a sixth embodiment of the invention. The output leads of twenty-four 1-bit comparators described in any of the first to fifth embodiment are connected in a wired OR configuration to form a 24-bit comparator. Thus, if any one or more of the HIT output line is grounded to produce a LOW level signal, all the remaining HIT output lines will also be grounded, resulting in a LOW level signal from HIT output 1214. Thus, HIT output 1214 produces a HIGH level signal only when all the HIT output lines from the twenty-four 1-bit comparators produce HIGH level signals. Thus, the OR gate for taking a logic OR of twenty-four HIT output lines can be easily formed without using any logic gates, such as AND logic 1405 shown in FIG. 14. Referring to FIG. 12, the tag memory 1201 is accessed by the input address PA 1210, which is decoded by the decoder 1202. When the word line WL 1211 voltage is HIGH, the data stored in the memory cell array selected by the HIGH word line WL 1211 is output to the bit line pair thereof as address B [23:0]. When the sense enable line SEN 1212 becomes HIGH, each bit in address A [23:0] 1213 from the central processing unit (CPU) and B [23:0] is compared for coincidence/non-coincidence by the 1-bit comparators 1203. Each of the 1-bit comparator 1203 is described in any of the first to fifth embodiments above, and is formed by combining or integrating a sense amplifier and coincidence/non-coincidence detection circuit. According to the 1-bit comparator of the first and second embodiments described above, a precharge signal is necessary, but it is possible to use the sense enable signal SEN 1212 as well. By connecting the output leads of each of the 1-bit comparators 1203 in a wired OR configuration, a 24-bit comparator 1204 is constructed. Wired OR connection of the output leads is possible because each 1-bit comparator detects the voltage drop of the load resistor as the output voltage. The voltage of the output line HIT 1214 is LOW if a non-coincident result is obtained for any one bit, but is HIGH when all bits are coincident. The precharge/equalization circuit 1205 precharges and equalizes the bit line pair during tag memory non-access periods as controlled by the precharge enable PCEN signal 1215 and the equalization enable signal EQEN 1216. An NPN transistor is used as the precharge circuit for high speed reading and bit line precharging and equalization. The write circuit 1206 for writing data W [23:0] 1218 is controlled by the write enable signal WEN 1217. It is to be noted that the hardware configuration required to achieve this embodiment is smaller because the plural input AND circuit, as required in the prior art device as shown in FIG. 14, for generating the logical product of the coincidence/non-coincidence result signals for each bit is not required. In addition, high speed coincidence/non-coincidence detection is possible because the delay time of the AND circuit is eliminated. SEVENTH EMBODIMENT FIG. 13 is a circuit diagram of a physical address cache memory system according to the seventh embodiment of the present invention. In this embodiment the physical address PA read by the tag memory and the physical address converted by the translation look-aside buffer (TLB) are compared by the multiple bit comparator described in the sixth embodiment above. Referring to FIG. 13, a given word is selected by the tag memory 1301 according to a specific number of bits in the logical address PA 1311 from the CPU, and physical address B [23:0] is output to the bit line pair from the memory cell array. When a stored data address in the CAM (content-addressable memory) area of the translation look-aside buffer content-addressable memory (TLB CAM) 1302 is matched by selected bits in the logical address PA 1311, one bit in the coincident signal line 1312 becomes HIGH, and the physical address A [23:0] from the TLB RAM 1303 is output. The comparator 1304 described in the third embodiment above compares the two physical addresses A [23:0] and B [23:0] when the sense enable signal SEN 1313 is HIGH. If the two physical addresses are coincident, the output line HIT 1314 is HIGH; otherwise the output line HIT 1314 is LOW. It is to be noted that what bits in the logical address PA are used by the CAM and tag memory is dependent upon the set number and line size of the cache memory. The hardware configuration required to achieve this embodiment can be made smaller because the plural input AND circuit for generating the logical product of the coincidence/non-coincidence result signals for each bit is not required. In addition, high speed coincidence/non-coincidence detection is possible because the delay time of the AND circuit is eliminated. A comparator according to the various embodiments of the invention as described hereinabove offers a number of advantages, as follows. (1) A high speed comparison operation can be achieved by effectively integrating the sense amplifier and the comparator. (2) A high speed, multiple bit comparison operation can also be achieved in a relatively small hardware area because a wired OR gate that eliminates the need for the AND gate required in the prior art can be formed. (3) Sense amplifier input impedance conversion and bipolar transistor saturation prevention can also be achieved with a relatively small hardware configuration. (4) In addition, the operation of the memory circuit can be stabilized. As a result, a comparator according to the present invention can thus be used with great effectiveness in semiconductor integrated circuit devices. The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
A comparator for comparing the voltages of an address pair signals in complement with the voltages of bit pair signals in complement includes a pair of transistors for receiving the bit pair signals and a pair of MOSFETs for receiving the address pair signals. One transistor and one MOSFET are connected in series to define a first current path and other transistor and other MOSFET are connected in series to define a second current path. When the address signal and the bit signal are the same, both the first and second current paths close, but when they are different, either the first or the second current path opens to permit a current to pass therethrough. By detecting the current in the path, the coincidence and non-coincidence between the address pair signals and bit pair signals are detected.
42,843
RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Patent Applications Ser. No. 61/168,537, filed Apr. 10, 2009, entitled “HAMSTRING STRETCHING DEVICE,” and U.S. Provisional Patent Application No. 61/222,850, filed Jul. 2, 2009, entitled “HAMSTRING STRETCHING DEVICE” which are hereby incorporated by reference in their entirety. FIELD OF THE INVENTION [0002] This invention relates to exercise and medical devices for stretching muscles, and more particularly to a device for stretching the back and leg muscles. BACKGROUND [0003] The hamstring muscle group comprises three muscles: the semitendinosus, the semimembranosus, and the biceps femoris. The hamstring muscle group acts upon both the hip and knee joints. The hamstrings play an important role in walking, running, jumping, and controlling some movement of the trunk of the body. [0004] Many people suffer from tightness of the hamstrings. Tightness of the hamstrings can be caused by genetic factors (some people are naturally born with shorter hamstring muscles), back problems can also cause the sciatic nerve to become compressed which can cause the hamstring muscles to tighten, and lack of stretching before physical activity can also cause tightness in the hamstring muscles. Furthermore, sedentary lifestyles and/or desk jobs that involve sitting for long periods of time can also contribute to tightness in the hamstring muscles. [0005] Tightness in the hamstring muscles can cause decreased physical performance and can make the muscles more susceptible to tearing during physical activities. Furthermore, the tightness in the hamstring muscles can also lead to postural problems and/or back problems by causing the hips and/or the pelvis to rotate to position that can compress nerves and/or put strain on other muscle groups. Pain in the back and knees are also a common result. [0006] Stretching of the back and hamstring muscles can increase flexibility and blood flow to these muscles groups and can help to alleviate pain and/or stiffness caused by tightening of the hamstring muscles. SUMMARY [0007] An apparatus that facilitates the stretching and exercising of the hamstring and back muscles is provided. The apparatus described herein can be used for stretching to improve flexibility, to warm up muscles before physical activity, and/or for physical rehabilitation. The apparatus includes a set of hand grips and a set of foot plates. A user grasps the hand grips and positions the arches of his or her feet above the foot plates. The apparatus includes a user actuated drive mechanism for moving a set of hand grips along the shaft toward the foot plates. The user maintains a grip of the hand grips as the hand grips move along the shaft toward the foot plates, thereby stretching the hamstring and back muscles of the user. [0008] According to an embodiment, an exercise device for stretching the hamstring and muscles is provided. The device includes a support shaft. a set of foot plates disposed at one end of the support shaft, a set of hand grips slideably disposed on the support shaft and being moveable upward along the shaft away from the foot plates and moveable downward along the shaft toward the foot plates, and a user-actuated drive mechanism comprising a ratchet for moving the hand grips and ratchet downward along the support shaft toward the foot plates when the user-actuated drive mechanism is activated. [0009] According to another embodiment, an exercise device for stretching the hamstring and back muscles is provided. The device includes a support shaft, a set of foot plates disposed at one end of the support shaft, a set of hand grips slideably disposed on the support shaft and being moveable upward along the shaft away from the foot plates and moveable downward along the shaft toward the foot plates, and a user-actuated drive mechanism comprising a motor for moving the hand grips downward along the support shaft toward the foot plates when the user-actuated drive mechanism is activated. [0010] According to yet another embodiment, a method of stretching the hamstring and back muscles using an apparatus that includes a user actuated drive mechanism and a hand grip slideably disposed on a shaft, and a foot rest disposed at one end of the shaft, the user actuated drive mechanism being configured to move the hand grip along the shaft toward the foot rest when the drive mechanism is activated by the user. The method includes positioning the footplate of the device under the arches of the user's feet while maintaining the position of the legs relatively straight, grasping the hand grips of the apparatus, squeezing the hand grip of the apparatus to actuate the drive mechanism, causing the drive mechanism to move the hand grip along the shaft towards the foot plates, thereby stretching the back and hamstring muscles of the user. [0011] Other features and advantages of the present invention should be apparent from the following description which illustrates, by way of example, aspects of the invention. BRIEF DESCRIPTION OF THE DRAWINGS [0012] The details of the present invention, both as to its structure and operation, may be gleaned in part by study of the accompanying drawings, in which like reference numerals refer to like parts, and in which: [0013] FIG. 1 illustrates an apparatus for stretching the hamstring and back muscles according to an embodiment; [0014] FIG. 2 illustrates a ratchet-like structure that can be used to move the grip along the shaft of the apparatus illustrated in FIG. 1 according to an embodiment; [0015] FIG. 3 illustrates the grip and ratchet system of the apparatus illustrated in FIG. 1 according to an embodiment; [0016] FIG. 4 illustrates the footplate and main plate of the apparatus illustrated in FIG. 1 according to an embodiment; [0017] FIG. 5 illustrates the shaft of the apparatus illustrated in FIG. 1 according to an embodiment; [0018] FIG. 6 illustrates the handle and top end cap of the apparatus illustrated in FIG. 1 according to an embodiment; [0019] FIG. 7 is flow chart illustrating a method of stretching muscles using the apparatus illustrated in FIGS. 1-6 according to an embodiment; [0020] FIG. 8 illustrates an alternative implementation of the apparatus illustrated in FIG. 1 that includes a motor for moving the grip along the shaft of the apparatus according to an embodiment; [0021] FIG. 9 is a logical block diagram of a motor component that can be used with the apparatus illustrated in FIG. 8 according to an embodiment; and [0022] FIG. 10 is a flow chart of a method of stretching the back and hamstring muscles using the apparatus illustrated in FIGS. 8 and 9 according to an embodiment. DETAILED DESCRIPTION [0023] The following detailed description is directed to certain specific embodiments of the invention. However, the invention can be embodied in a multitude of different systems and methods. In this description, reference is made to the drawings wherein like parts are designated with like numerals throughout. [0024] FIGS. 1 to 10 of the drawings illustrate embodiments of an exercise/medical apparatus 10 . FIGS. 2 to 6 illustrate specific individual components 11 , 12 , 13 , 14 , 15 of the apparatus in more detail. FIG. 7 is a flow chart that illustrates a method of stretching the hamstring and back muscles using the apparatus 10 . FIG. 9 illustrates an alternative embodiment of the apparatus 10 that includes a motor. FIG. 8 is a block diagram of a motor component that can be used with the embodiment of the apparatus illustrated in FIG. 8 . FIG. 10 is a flow chart that illustrates a method for stretching the hamstring and back muscles using the motorized embodiment of apparatus 10 illustrated in FIG. 8 . It will be understood that in one embodiment the reverse side of the apparatus 10 is identical in structure and appearance. [0025] As best illustrated in FIG. 1 , the apparatus 10 basically comprises a long center shaft 14 . According to an embodiment, the length of the shaft can be in the range of 30 and 40 inches. In other embodiments, the length of the shaft can be selected to fit the size of the user. In one embodiment, the shaft is extendable and retractable in order to change the length of the device for users of different sizes. [0026] The adjoining parts 11 , 12 , 13 , 15 connect to the shaft. Foot plate 13 and handle 15 are stationary and affixed to proximate opposite ends of the main shaft 14 allowing them to perform as end caps, handles, and/or hooks. [0027] Ratchet 11 grip 12 attach to the shaft in a manner allowing for vertical motion up and down the shaft. When all parts are assembled as in FIG. 1 , squeezing the grip 12 causes the combination of the ratchet 11 and the grip 12 to travel along the shaft 14 towards the foot rest 13 . [0028] FIG. 2 details a ratchet-like structure 11 used to move the grip 12 up and down the shaft 14 . A large spring 19 is placed between the palm grip 21 and the finger grip 22 portions of the grip 12 . This spring is compressed upon squeezing of the palm 21 and finger 22 grips together. This motion actuates the ratchet to moves the grip 12 and ratchet 11 structures downward along the shaft 14 . The ratchet 11 moves through the use of springs 18 , 19 and metal plates which lock in place due to the angle they are placed against the shaft. Squeezing the grip changes the angle of the metal plates and compresses the main spring 19 allowing the ratchet to creep slightly down the shaft. Upon release of the grip, the metal plates return to the locking angle thereby holding the ratchet in place. In one embodiment, the ratchet is of the type described in U.S. Pat. No. 4,926,722, hereby incorporated by reference. According to an embodiment, the trigger 20 is pulled to release ratchet system allowing the ratchet system to slide up and down the shaft freely. The trigger 20 can be used to position the ratchet 11 and grip 12 back to a starting position along the shaft 14 . [0029] FIG. 3 details the grip and ratchet system 11 , 12 that moves down the shaft 14 . The palm grip 21 is fixed in position relative to the finger grip 22 , which is moveable. The finger grip 22 is squeezed toward the palm grip 21 in order to actuate the movement of the grip and ratchet system. The finger grip 22 is hollow and thereby able to pass over the outside of the palm grip 21 as it is being squeezed. Upon release of the finger grip 22 , the spring-like part 19 pushes the finger grip 22 back into place. [0030] Alternatively, different types of mechanisms can be used to allow the user to move the grip towards the foot plate. For example, indentations or teeth can be formed in the shaft for use with a ratchet or gear mechanism or the shaft can be threaded to allow for a screw type movement of the grip. [0031] FIG. 4 details the footplate 13 to be placed under the feet of a user thereby providing the leverage necessary to operate the apparatus. The footplate 13 is secured to the bottom of the shaft 14 . In one embodiment the footplate 13 is comprised of two basic sections, the main plate 23 and the bottom end cap 24 to be made of nonslip material. Alternatively, in other embodiments, other shapes and configurations (e.g., straps) can be used to provide allow the user to apply a restraining force against the shaft. [0032] FIG. 5 details the shaft 14 upon which the apparatus operates. The shaft can be a single or multiple solid structure 16 . According to other embodiments, other cross sectional shapes for the shaft can also be used (e.g., circular). [0033] In an embodiment, the shaft 16 is marked with progress lines for the purpose of tracking performance. A performance/progress tracking part (not shown) is attached to the shaft 14 and moves down the shaft 14 when pushed by the grip 11 and ratchet 12 motion. According to an embodiment, the progress tracker can maintain its position along the shaft 14 even after the trigger 20 is used to release the ratchet 11 and grip 12 . The progress tracking part can be used to provide feedback to the user regarding how far along the shaft the position of the grips has been [0034] FIG. 6 details the handle 15 , also referred to as the top end cap 25 . The handle 15 is attached to the top of shaft 14 . The handle 15 is used for carrying and aesthetic purposes only. The handle 15 is fixed in place and provides no working mechanism or functional purpose during actual use. [0035] FIG. 7 illustrates a method of stretching the muscles of the hamstring and back muscles using the apparatus described above in FIGS. 1-6 . To use the device, a person places the footplate under the arches of their feet (step 700 ). The left hand is placed on one grip and the right hand on the other (step 710 ). With knees held straight or as close to straight as possible, the person squeezes the grip with one hand (step 720 ). This squeeze actuates the movement of the ratchet system downward along the shaft. The ratchet system holds it position along the shaft. In an embodiment, the ratchet system holds its position along the shaft with a locking angle which prevents movement up or down the shaft. With each additional squeeze of the grip, the ratchet moves further and further down the shaft towards the footplate creating a stretching effect on the back of the legs including the hamstring muscles and in the muscles of the lower back (step 730 ). The trigger 20 is pulled to release ratchet system allowing the ratchet system to slide up and down the shaft freely and to return the ratchet 11 and the grip 12 to starting position along the shaft (step 740 ). [0036] FIG. 8 illustrates an alternative embodiment of the apparatus illustrated in FIG. 1-6 that includes a motor component 811 for moving the grip 12 along the shaft 14 . Like the embodiments illustrated in FIGS. 1-6 , the motorized embodiment of the apparatus illustrated in FIG. 8 includes a user-actuated drive mechanism. The user-actuated drive mechanism in FIG. 8 uses a motor component 811 to move the grip 12 along the shaft 14 instead of the ratchet mechanism 11 used in the embodiment illustrated in FIG. 1 . [0037] The finger grip 22 of the motorized embodiment illustrated in FIG. 8 is squeezed toward the palm grip 21 in order to actuate the motor component 811 , causing the movement of the grip 12 and motor component 811 along the shaft 14 . According to an embodiment, the motor 811 component and the grip 12 continue to move downward along the shaft while the user continues squeezes the grip 12 and stops when the user releases the grip 12 . In some embodiments, the motor is configured to move the grip structure downward along the shaft in a stepwise motion similar to that of the embodiment of FIG. 1 that includes the ratchet 11 . For example, in some embodiments, the grip can include a button that is pressed when the grip 12 configured to cause the motor to move one step downward along the shaft each time that the user squeezes the grip with his or her hand. [0038] According to an embodiment, the motor can engage with a gear or set of gears that mesh with the indentations or teeth formed along the shaft in order to move the motor component 811 and the grip 12 along the shaft 14 . Alternatively, the shaft can be threaded to allow for a screw type movement motor component 811 and grip 12 along the shaft 14 . According to some embodiments, a release similar to trigger 20 can be included to cause the motor component 811 to move freely along the shaft to allow the grip slide up and down the shaft freely. For example, the release can be configured to cause the motor component to disengage from the indentations, teeth, or threads with which the motor component engages to move the grips 12 and the motor component 811 along the shaft. The release mechanism can be used to allow the user to move the grips back up shaft to “reset” the device for use in another stretching session. [0039] FIG. 9 is a logical block diagram of the motor component 811 according to an embodiment. The motor component includes a motor 910 , a button 905 , and a power supply 915 . [0040] According to an embodiment, the motor 910 can be a direct current (DC) motor or an alternating current (AC) motor depending upon the type of power supply 915 selected. [0041] According to an embodiment, the button 905 is disposed between the power supply 915 and the motor 910 . In some embodiments, the button 905 can be integrated into the grip 12 so that when a user squeezes the finger grip 22 the button 905 is depressed to complete the circuit between the power supply 915 and the motor 910 . According to some embodiments, the grip 12 can have a button 905 on each side of the finger grips 22 so that if the finger grip 22 on either side of the grip 12 is depressed, the motor 910 is activated. [0042] In an embodiment, power supply 915 can be an internal power source, such as a battery, for powering the motor 910 . In some embodiments, the internal power source comprises a rechargeable battery pack that placed in a battery compartment of the apparatus 10 (not shown). In some embodiments, the rechargeable battery pack can be charged while installed in the battery compartment of the apparatus 10 by coupling a power cord to the to the apparatus 10 that provides power to the battery pack from an external power source, such as the electrical mains used to provide power to many homes and businesses. According an alternative embodiment, the battery pack may be removable for replacement and/or to be recharged using an external battery charger. In an alternative embodiment, the apparatus 10 can be connected to an external power supply to provide power to the motor 910 via power cord coupled to the motor component 811 . [0043] FIG. 10 illustrates a method of stretching the muscles of the hamstring and back muscles using the motorized version of the apparatus described above. To use the device a person places the footplate under the arches of their feet (step 1000 ). The left hand is placed on one grip and the right hand on the other (step 1010 ). With knees held straight or as close to straight as possible, the person squeezes the grip with one hand (step 1020 ). Squeezing the grip causes a button in the grip be depressed, completing a circuit to activate the motor, and the motor moves the grip downward along the shaft. With each additional squeeze of the grip, the motor moves further and further down the shaft towards the person's feet creating a stretching effect on the back of the legs and lower back (step 1030 ). In some alternative embodiments, motor component is configured to move downward along the shaft as long as the user continues to squeeze the finger grip 22 , and releasing the finger grip causes the motor to stop. As described above, some embodiments of the motorized version of the device can include a release similar to trigger 20 that can be used to cause the motor to move freely along the shaft to allow the grip slide up and down the shaft freely. The release mechanism can be used to allow the user to move the grips 12 back up shaft to “reset” the device for use in another stretching session. When the release is actuated, the grip can slide up and down the shaft freely (step 1040 ). According to alternative embodiments, the grip may include a switch or button that, when activated, causes the motor to move the grip assembly to back up the shaft rather than using a release mechanism to disengage the motor from the shaft. [0044] The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles described herein can be applied to other embodiments without departing from the spirit or scope of the invention. Thus, it is to be understood that the description and drawings presented herein represent a presently preferred embodiment of the invention and are therefore representative of the subject matter which is broadly contemplated by the present invention. It is further understood that the scope of the present invention fully encompasses other embodiments that may become obvious to those skilled in the art and that the scope of the present invention is accordingly not limited.
An apparatus that facilitates the stretching and exercising of the hamstring and back muscles is provided. The apparatus can be used for stretching to improve flexibility, to warm up muscles before physical activity, and/or for physical rehabilitation after injury. The apparatus includes a set of hand grips and a set of foot plates. A user grasps the hand grips and positions the arches of his or her feet above the foot plates. The apparatus includes a user actuated drive mechanism for moving a set of hand grips along the shaft toward the foot plates. The user maintains a grip of the hand grips as the hand grips move along the shaft toward the foot plates, thereby stretching the hamstring and back muscles of the user.
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FIELD OF THE INVENTION This invention relates to photothermographic materials and in particular to post-processing stabilization of dry silver systems. BACKGROUND OF THE ART Silver halide photothermographic imaging materials, especially "dry silver" compositions, processed with heat and without liquid development have been known in the art for many years. Such materials are a mixture of light insensitive silver salt of an organic acid (e.g., silver behenate), a minor amount of catalytic light sensitive silver halide, and a reducing agent for the silver source. The light sensitive silver halide is in catalytic proximity to the light insensitive silver salt such that the latent image formed by the irradiation of the silver halide serves as a catalyst nucleus for the oxidation-reduction reaction of the organic silver salt with the reducing agent when heated above 80° C. Such media are described in U.S. Pat. Nos. 3,457,075; 3,839,049; and 4,260,677. Toning agents can be incorporated to improve the color of the silver image of photothermographic emulsions as described in U.S. Pat. Nos. 3,846,136; 3,994,732 and 4,021,249. Various methods to produce dye images and multicolor images with photographic color couplers and leuco dyes are well known in the art as represented by U.S. Pat. Nos. 4,022,617; 3,531,286; 3,180,731; 3,761,270; 4,460,681; 4,883,747 and Research Disclosure 29963. A common problem that exists with these photothermographic systems is the instability of the image following processing. The photoactive silver halide still present in the developed image may continue to catalyze print-out of metallic silver even during room light handling. Thus, there exists a need for stabilization of the unreacted silver halide with the addition of separate post-processing image stabilizers or stabilizer precursors to provide the desired post-processing stability. Most often these are sulfur containing compounds such as mercaptans, thiones, thioethers as described in Research disclosure 17029. U.S. Pat. No. 4,245,033 describes sulfur compounds of the mercapto-type that are development restrainers of photothermographic systems as do U.S. Pat. Nos. 4,837,141 and 4,451,561. Mesoionic 1,2,4-triazolium-3-thiolates as fixing agents and silver halide stabilizers are described in U.S. Pat. No. 4,378,424. Substituted 5-mercapto-1,2,4-triazoles such as 3-amino-5-benzothio-1,2,4-triazole as post-processing stabilizers are described in U.S. Pat. No. 4,128,557; 4,137,079; 4,138,265, and Research Disclosure 16977 and 16979. Some of the problems with these stabilizers include thermal fogging during processing or losses in photographic sensitivity, maximum density or, contrast at stabilizer concentrations in which stabilization of the post-processed image can occur. Stabilizer precursors have blocking or modifying groups that are usually cleaved during processing with heat and/or alkali. This provides the remaining moiety or primary active stabilizer to combine with the photoactive silver halide in the unexposed and undeveloped areas of the photographic material. For example, in the presence of a silver halide precursor in which the sulfur atom is blocked upon processing, the resulting silver mercaptide will be more stable than the silver halide to light, atmospheric and ambient conditions. Various blocking techniques have been utilized in developing the stabilizer precursors. U.S. Patent No. 3,615,617 describes acyl blocked photographically useful stabilizers. U.S. Pat. Nos. 3,674,478 and 3,993,661 describe hydroxyarylmethyl blocking groups. Benzylthio releasing groups are described in U.S. Pat. No. 3,698,898. Thiocarbonate blocking groups are described in U.S. Pat. No. 3,791,830, and thioether blocking groups in U.S. Pat. Nos. 4,335,200, 4,416,977, and 4,420,554. Photographically useful stabilizers which are blocked as urea or thiourea derivatives are described in U.S. Pat. No. 4,310,612. Blocked imidomethyl derivatives are described in U.S. Pat. No. 4,350,752, and imide or thioimide derivatives are described in U.S. Pat. No. 4,888,268. Removal of all of these aforementioned blocking groups from the photographically useful stabilizers is accomplished by an increase of pH during alkaline processing conditions of the exposed imaging material. Other blocking groups which are thermally sensitive have also been utilized. These blocking groups are removed by heating the imaging material during processing. Photographically useful stabilizers blocked as thermally sensitive carbamate derivates are described in U.S. Pat. Nos. 3,844,797 and 4,144,072. These carbamate derivatives presumably regenerate the photographic stabilizer through loss of an isocyanate. Hydroxymethyl blocked photographic reagents which are unblocked through loss of formaldehyde during heating are described in U.S. Pat. No. 4,510,236. Development inhibitor releasing couplers releasing tetrazolylthio moieties are described in U.S. Pat. No. 3,700,457. Substituted benzylthio releasing groups are described in U.S. Pat. No. 4,678,735; and U.S. Pat. Nos. 4,351,896 and 4,404,390 utilize carboxybenzylthio blocking groups for mesoionic 1,2,4-triazolium-3-thiolates stabilizers. Photographic stabilizers which are blocked by a Michael-type addition to the carbon-carbon double bond of either acrylonitrile or alkyl acrylates are described in U.S. Pat. Nos. 4,009,029 and 4,511,644, respectively. Heating of these blocked derivatives causes unblocking by a retro-Michael reaction. Various disadvantages attend these different blocking techniques. Highly basic solutions which are necessary to cause deblocking of the alkali sensitive blocked derivatives are corrosive and irritating to the skin. With the photographic stabilizers which are blocked with a heat removable group, it is often found that the liberated reagent or by-product, for example, acrylonitrile, can react with other components of the imaging construction and cause adverse effects. Also, inadequate or premature release of the stabilizing moiety within the desired time during processing may occur. Thus, there has been a continued need for improved post-processing stabilizers that do not fog or desensitize the photographic materials, and stabilizer precursors that release the stabilizing moiety at the appropriate time and do not have any detrimental effects on the photosensitive material or user of said material. SUMMARY OF THE INVENTION According to this invention, the incorporation of omega-substituted-2-propioamidoacetyl or omega-substituted-3-propioamidopropionyl stabilizer precursors of Formula I, below, and/or α-amidoacetyl or α-amidopropionyl derivatives of Formulas II and III, below, into the photothermographic emulsion layer or a layer adjacent to the emulsion layer stabilizes the silver halide for improved post-processing stabilization without desensitization or fogging the heat developable photographic material and process. The general formulae I, II and III describes such compounds thereof: ##STR1## wherein A represents a residue of a post-processing stabilizer, AH, in which a hydrogen atom of the post-processing stabilizer has been replaced by the remainder of the structure shown in Formula I; R 1 , R 2 , and R 3 are independently hydrogen or methyl, with the proviso that R 1 can also represent an aryl group when R 2 and R 3 are hydrogen; R 4 and R 5 independently represent an alkyl group, a cyclo-alkyl group, an aryl group or R 4 and R 5 taken together with the carbon atom to which they are joined form a ring of 4 to 12 atoms (preferably 5 or 6 carbon atoms); R 6 and R 7 are independently hydrogen or lower alkyl, preferably C-1 to C-4 alkyl; R 8 is any organic group such as alkyl groups (e.g., of 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and inclusive of cycloalkyl of 3 to 20 carbon atoms, preferably 5 to 8 carbon atoms), aryl groups (e.g., up to 7 ring atoms) and heterocyclic groups (preferably of C, S, N, O and Se atoms with up to 7 ring atoms); n is 0 or 1; x represents an oxygen, nitrogen, or sulfur atom; and G represents an organic ballasting group (e.g., alkyl group of up to 20 carbon atoms, aryl group of up to 20 carbon atoms, and mixed alkyl and aryl groups of up to 30 carbon atoms). In this application: "alkenyl" and "alkenylene" mean the monovalent and polyvalent residues remaining after removal of one and at least two hydrogen atoms, respectively, from an alkene containing 2 to 20 carbon atoms; functional groups which may be present are one or more aryl, amide, thioamide, ester, thioester, ketone (to include oxo-carbons), thioketone, nitrile, nitro, sulfide, sulfoxide, sulfone, disulfide, tertiary amine, ether, urethane, dithiocarbamate, quaternary ammonium and phosphonium, halogen, silyl, silyloxy, and the like, wherein the functional gorups requiring substituents are substituted with hydrogen, alkyl, or aryl groups where approprite; additionally, the alkenyl and alkenylene residues may contain one or more catenary S, O, N, P, and Si heteroatoms; "alkyl" and "alkylene" mean the monovalent and polyvalent residues remaining after removal of one and at least two hydrogen atoms, respectively, from a linear or branched chain hydrocarbon having 1 to 20 carbon atoms, functional groups and catenary heteroatoms which may be present are the same as those listed under the "alkenyl" definition; "aryl" and "arylene" mean the monovalent and polyvalent residues remaining after removal of one and at least two hydrogen atoms, respectively, from an aromatic compound (single ring and multi- and fused-cyclic) having 5 to 12 ring atoms in which up to 5 ring atoms may be selected from S, Si, O, N, and P heteroatoms, functional groups which also may be present are the same as those listed under the "alkenyl" definition; "azlactone" means 2-oxazolin-5-one groups of Formula IV and 2-oxazin-6-one groups of Formula V. ##STR2## "Michael reaction" means the catalyzed or uncatalyzed addition of a "Michael donor," illustrated by a nitrogen nucleophile (VI) in the equation below, to an alkenyl azlactone "Michael acceptor" (VII) to form a "Michael adduct" reaction product (VIII): ##STR3## "Michael donor" means the nucleophilic reactant in a Michael reaction; "Michael acceptor" means the electrophilic reactant in a Michael reaction; "azlactone ring opening reaction" means the catalyzed or uncatalyzed addition reaction of a nucleophile, HXG (wherein X =O, S, NH, or NR and R means independent selections of alkyl and/or aryl groups), as illustrated by an HXG nucleophile in the equation below, to an azlactone (IV) to provide the α-amidoacetyl derivative (IX) ##STR4## The compositions of Formula I are formally the products of a ring-opening reaction of an azlactone Michael adduct of Formula X by an HXG nucleophile as shown in the equation below. The azlactone Michael adducts of Formula X are described extensively in pending application File No. 45053USA1A (U.S. Ser. No. 07/500,768 filed Mar. 29, 1990 in the name of Dean M. Moren) and the compositions of Formula I are described in detail in application File No. 45466 (U.S. Ser. No. 07/575,835 filed Aug. 31, 1990 in the name of Larry R. Krepski, et al.) USA5A. ##STR5## wherein A, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X, G and n are as described above. The compositions of Formulae II and III are the products of ring-opening reactions of azlactones of Formulae XI and XII, respectively, by HXG nucleophiles as shown in the equation below. Reaction conditions for these azlactone ring opening reactions are described in detail in application File No. 45466USA5A. ##STR6## wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , X, G and n are as described above. DETAILED DESCRIPTION OF THE INVENTION The addition of the novel omega-substituted-2-propioamidoacetyl or omega-substituted-3-propioamidopropionyl stabilizer precursors of Formula I, and/or the α-amidoacetyl and/or α-amidopropionyl compositions of Formulae II and III into the photothermographic emulsion layer or layer adjacent to the emulsion layer provides the photoactive silver halide emulsion with improved post-processing stability without desensitizing or fogging said emulsion. In general Formula I, A represents the residue of a "primary" post-processing stabilizer, AH, in which the hydrogen atom has been replaced by the propioamidoacetyl or propioamidopropionyl group. The propioamidoacetyl or propioamidopropionyl group acts as a blocking group to block the activity of the primary stabilizer AH. If AH is left unblocked and added to the photographic emulsion at the same molar equivalent concentration as the composition of Formula I, AH desensitizes said emulsion. In addition to functioning as a blocking group for the "primary" post-processing stabilizer AH, the propioamidoacetyl or propioamidopropionyl functionality of the composition of Formula I has another function and that is to act as a "secondary" stabilizer for the image. The α-amidoacetyl and α-amidopropionyl compositions of Formulae II and III also act as "secondary" stabilizers. While not wishing to be bound by any particular reaction mechanism or explanation for the observed stabilization effect of the compositions of Formula I, it is possible that the combination of processing heat and the photothermographic environment causes release of the "primary" stabilizer AH from the composition of Formula I through a retro-Michael reaction. When AH is liberated in this retro-Michael reaction, the "secondary" stabilizer which is the composition of Formula II is also liberated in situ. It is thus possible by the present invention to provide secondary stabilization of the image by a composition of Formula II which is generated in situ by the decomposition of the composition of Formula I, or independently by the addition of the compositions of Formula II and/or III to the photothermographic imaging material. Suitable primary stabilizers are well known in the art such as nitrogen-containing substituted or unsubstituted heterocyclic rings; such as benzimidazole, benzotriazole; triazoles; tetrazoles; imidazoles; various mercapto-containing substituted or unsubstituted compounds; such as mercapto triazoles, mercapto tetrazoles; thio-substituted heterocycles; or any such compound that stabilizes the said emulsion but at such concentrations desensitizes the initial sensitometric response if left unblocked. Many of such compounds are summarized in Research Disclosure 29963 from March, 1989 entitled "Photothermographic Silver Halide Systems". Specific examples of the novel ring-opened azlactone-based stabilizer precursors and ring-opened azlactones are shown below, which, however, does not limit the compounds to be used in the present invention. ##STR7## The general synthesis of the stabilizer precursors is described in the patent application entitled "Azlactone Michael Adducts", FN 45053USA1A. Specific synthesis examples of the compounds according to the present invention are set forth below. In all cases, structures of the compounds were confirmed by spectral analysis, including IR, proton and carbon NMR spectroscopy. SYNTHESIS EXAMPLE 1 Synthesis of Compound I-A A mixture of VDM (2-vinyl-4,4-dimethylazlactone) (13.9 g, 0.10 mole) and 1-phenyl-1H-tetrazole-5-thiol (17.8 g, 0.10 mole) was heated at 100° C. overnight, then phenol (9.4 g, 0.10 mole) was added and the mixture heated at 70° C. for 22 hours. Since IR analysis indicated some residual azlactone absorbance at around 1800cm -1 , DBU (0.3 g) was added to reaction mixture and heating continued at 90° C. for 23 hours to complete the reaction. The product was recrystallized from aqueous ethanol. SYNTHESIS EXAMPLE 2 Synthesis of Isomers I-B and I-C A mixture of VDM (13.9 g, 0.10 mole) and benzotriazole (11.9 g, 0.10 mole) was heated at 100° C. overnight, then phenol (9.4 g, 0.10 mole) and DBU (0.2 g) were added and heating continued for 24 hours at 100° C. Recrystallization from aqueous ethanol gave the product as a mixture of 1-N-alkylated and 2-N-alkylated isomers in about a 4 to 1 ratio. Synthesis of Isomers I-E and I-F A mixture of VDM (13.9 g, 0.10 mole) and benzotriazole (11.9 g, 0.10 mole) were heated at 100° C. for 24 hours, then cyclohexanol (10.0 g, 0.10 mole) and DBU (0.3 g) were added and the mixture heated at 70° C. for 2 hours and then at 100° C. for 20 hours. Recrystallization from ethylacetate-toluene gave the product as a mixture of 1-N-alkylated and 2-N-alkylated isomers. SYNTHESIS EXAMPLE 3 Synthesis of Compound I-D VDM (13.9 g, 0.10 mole) and benzimidazole (11.8 g, 0.10 mole) were heated at 100° C. overnight. After cooling, tetrahydrofuran (50 ml) was added to dissolve the product, then water (10 ml) was added and the mixture allowed to stand at room temperature overnight. Evaporation of the solvent and recrystallization of the residue from aqueous ethanol gave the desired product. SYNTHESIS EXAMPLE 4 Synthesis of Compound I-G VDM (6.95 g, 0.05 mole), 4-methyl-5-trifluoromethyl-4H-1,2,4-triazolin-3(2H)-thione (9.1 g, 0.05 mole), and 1,8-diazabicyclo [5.4.0.] undec-7-ene (DBU) (0.3 g) were heated at 60° C. for 40 hours, then 1-butanol 7.4 g (0.05 mole) and DBU (0.3 g) were added and the mixture heated at 100° C. for 40 hours. Recrystallization from aqueous ethanol gave the desired product. SYNTHESIS EXAMPLE 5 Synthesis of Compound I-H To a mixture of VDM (13.9 g, 0.10 mole) and phenol (9.4 g, 0.10 mole) was added 0.3 g of DBU. After a brief exotherm, the material crystallized. Recrystallization from aqueous ethanol gave the desired product. SYNTHESIS EXAMPLE 6 Synthesis of Compound I-I To a mixture of VDM (13.9 g, 0.10 mole) and 2,2,2-trifluoroethanol (10.0 g, 0.10 mol) was added 0.3 g of DBU. After a brief exotherm, the product crystallized. Recrystallization from aqueous ethanol gave the desired product. The amounts of the above described compounds according to the present invention which are added can be varied depending upon the particular compound used and upon the photothermographic emulsion-type. However, they are preferably added in an amount of 10 -3 to 100 mol, and more preferably from 10 -2 to 20 mol, per mol of silver halide in the emulsion layer. The photothermographic dry silver emulsions of this invention may be constructed of one or more layers on a substrate. Single layer constructions must contain the silver source material, the silver halide, the developer and binder as well as optional additional materials such as toners, coating aids and other adjuvants. Two-layer constructions must contain the silver source and silver halide in one emulsion layer (usually the layer adjacent the substrate) and some of the other ingredients in the second layer or both layers. Multicolor photothermographic dry silver constructions contain sets of these bilayers for each color. Color forming layers are maintained distinct from each other by the use of functional or non-functional barrier layers between the various photosensitive layers as described in U.S. Pat. No. 4,460,681. The silver source material, as mentioned above, may be any material which contains a reducible source of silver ions. Silver salts of organic acids, particularly long chain (10 to 30, preferably 15 to 28 carbon atoms) fatty carboxylic acids are preferred. Complexes of organic or inorganic silver salts wherein the ligand has a gross stability constant between 4.0 and 10.0 are also desirable. The silver source material constitutes from about 5 to 30 percent by weight of the imaging layer. The second layer in a two-layer construction or in the bilayer of a multi-color construction would not affect the percentage of the silver source material desired in the photosensitive single imaging layer. The organic silver salt which can be used in the present invention is a silver salt which is comparatively stable to light, but forms a silver image when heated to 80° C. or higher in the presence of an exposed photocatalyst (such as silver halide) and a reducing agent. Suitable organic silver salt include silver salts of organic compounds having a carboxy group. Preferred examples thereof include a silver salt of an aliphatic carboxylic acid and a silver salt of an aromatic carboxylic acid. Preferred examples of the silver salts of aliphatic carboxylic acids include silver behenate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartarate, silver furoate, silver linoleate, silver butyrate and silver camphorate, mixtures thereof, etc. Silver salts which are substituted with a halogen atom of a hydroxyl group can also be effectively used. Preferred examples of the silver salts of aromatic carboxylic acid and other carboxyl group-containing compounds include silver benzoate, a silver substituted benzoate such as silver 3,5-dihydroxybenzoate, silver o-methylbenzoate, silver m-methylbenzoate, silver p-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate, silver p-phenyl benzoate, etc., silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitate, a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione or the like as described in U.S. Pat. No. 3,785,830, and silver salt of an aliphatic carboxylic acid containing a thioether group as described in U.S. Pat. No. 3,330,663, etc. Silver salts of compounds containing mercapto or thione groups and derivatives thereof can be used. Preferred examples of these compounds include a silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver salt of 2-mercaptobenzimidazole, a silver salt of 2-mercapto-5-aminothiadiazole, a silver salt of 2-(S-ethylglycolamido) benzothiazole, a silver salt of thioglycolic acid such as a silver salt of a S-alkyl thioglycolic acid (wherein the alkyl group has from 12 to 22 carbon atoms) as described in Japanese patent application No. 28221/73, a silver salt of a dithiocarboxylic acid such as a silver salt of dithioacetic acid, a silver salt of thioamide, a silver salt of 5-carboxylic-1-methyl-2-phenyl-4-thiopyridine, a silver salt of mercaptotriazine, a silver salt of 2-mercaptobenzoxazole, a silver salt as described in U.S. Pat. No. 4,123,274, for example, a silver salt of 1,2,4-mercaptothiazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4-thiazole, a silver salt of thione compound such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione as disclosed in U.S. Pat. No. 3,301,678. Furthermore, a silver salt of a compound containing an imino group can be used. Preferred examples of these compounds include a silver salt of benzothiazole and a derivative thereof as described in Japanese patent publications Nos. 30270/69 and 18146/70, for example, a silver salt of benzothiazole such as silver salt of methylbenzotriazole, etc., a silver salt of a halogen substituted benzotriazole, such as a silver salt of 5-chlorobenzotriazole, etc., a silver salt of carboimidobenzotriazole, etc., a silver salt of 1,2,4-triazole, of 1-H-tetrazole as described in U.S. Pat. No. 4,220,709, a silver salt of imidazole and an imidazole derivative, and the like. It is also found convenient to use silver halfsoaps, of which an equimolar blend of silver behenate and behenic acid, prepared by precipitation from aqueous solution of the sodium salt of commercial behenic acid and analyzing about 14.5 percent silver, represents a preferred example. Transparent sheet materials made on transparent film backing require a transparent coating and for this purpose the silver behenate full soap, containing not more than about four or 5 percent of free behenic acid and analyzing about 25.2 percent silver may be used. The method used for making silver soap dispersions is well known in the art and is disclosed in Research Disclosure April 1983 (22812) ibid October 1983 (23419) and U.S. Pat. No. 3,985,565. The light sensitive silver halide used in the present invention can be employed in a range of 0.0005 mol to 5 mol and, preferably, from 0.005 mol to 1.0 mol per mol of organic silver salt. The silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide, etc. The silver halide used in the present invention may be employed without modification. However, it may be chemically sensitized with a chemical sensitizing agent such as a compound containing sulphur, selenium or tellurium etc., or a compound containing gold, platinum, palladium, rhodium or iridium, etc., a reducing agent such as a tin halide, etc., or a combination thereof. The details of these procedures are described in T. H. James "The Theory of the Photographic Process", Fourth Edition, Chapter 5, pages 149 to 169. The silver halide may be added to the emulsion layer in any fashion which places it in catalytic proximity to the silver source. The silver halide and the organic silver salt which are separately formed in a binder can be mixed prior to use to prepare a coating solution, but it is also effective to blend both of them in a ball mill for a long period of time. Further, it is effective to use a process which comprises adding a halogen-containing compound in the organic silver salt prepared to partially convert the silver of the organic silver salt to silver halide. Methods of preparing these silver halide and organic silver salts and manners of blending them are described in Research Disclosures, No. 170-29, Japanese patent applications Nos. 32928/75 and 42529/76, U.S. Pat. No. 3,700,458, and Japanese patent applications Nos. 13224/74 and 17216/75. The use of preformed silver halide emulsions of this invention can be unwashed or washed to remove soluble salts. In the latter case the soluble salts can be removed by chill-setting and leaching or the emulsion can be coagulation washed, e.g., by the procedures described in Hewitson, et al., U.S. Pat. No. 2,618,556; Yutzy et al., U.S. Pat. No. 2,614,928; Yackel, U.S. Pat. No. 2,565,418;; Hart et al., U.S. Pat. No. 3,241,969; and Waller et al., U.S. Pat. No. 2,489,341. The silver halide grains may have any crystalline habit including, but not limited to cubic, tetrahedral, orthorhombic, tabular, laminar, platelet, etc. Photothermographic emulsions containing preformed silver halide in accordance with this invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds, or combinations of these. Suitable chemical sensitization procedures are described in Shepard, U.S. Pat. No. 1,623,499; Waller, U.S. Pat. No. 2,399,083; McVeigh, U.S. Pat. No. 3,297,447; and Dunn, U.S. Pat. No. 3,297,446. The light-sensitive silver halides can be spectrally sensitized with various known dyes including cyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes. Useful cyanine dyes include those having a basic nucleus, such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus. Useful merocyanine dyes which are preferred include those having not only the above described basic nuclei but also acid nuclei, such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malonitrile nucleus and a pyrazolone nucleus. In the above described cyanine and merocyanine dyes, those having imino groups or carboxyl groups are particularly effective. Practically, the sensitizing dye to be used in the present invention is properly selected from known dyes as described in U.S. Pat. No. 3,761,279, 3,719,495 and 3,877,943, British Pat Nos. 1,466,201, 1,469,117 and 1,422,057, Japanese Patent Application (OPI) Nos. 27924/76 and 156424/75, and so on, and can be located in the vicinity of the photocatalyst according to known methods used in the above-described examples. These spectral sensitizing dyes are used in amounts of about 10 -4 mol to about 1 mol per 1 mol of photocatalyst. The reducing agent for silver ion may be any material, preferably organic material, which will reduce silver ion to metallic silver. Conventional photographic developers such as phenidone, hydroquinones, and catechol are useful but hindered phenol reducing agents are preferred. The reducing agent should be present as 1 to 10 percent by weight of the imaging layer. In a two-layer construction, if the reducing agent is in the second layer, slightly high proportions, of from about 2 to 15 percent tend to be more desirable. A wide range of reducing agents have been disclosed in dry silver systems including amidoximes such as phenylamidoxime, 2-thienylamidoxime and p-phenoxyphenylamidoxime, azine, e.g., 4-hydroxy-3,5-dimethoxybenzaldehyde azine; a combination of aliphatic carboxylic acid aryl hydrazides and ascorbic acid, such as 2,2-bis(hydroxymethyl)propionyl-beta-phenyl hydrazide in combination with ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, a reductone and/or a hydrazine, e.g., a combination of hydroquinone and bis(ethoxyethyl)hydroxylamine, piperidinohexose reductone or formyl-4-methylphenyl hydrazine, hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenyl hydroxamic acid, and beta-alanine hydroxamic acid; a combination of azines and sulphonamidophenols, e.g., phenothiazine and 2,6-dichloro-4-benzenesulphonamidophenol; alphacyanophenylacetic acid derivatives such as ethyl-alpha-cyano-2-methylphenylacetate, ethyl alphacyanophenylacetate; bis-beta-naphthols as illustrated by 2,2'-dihydroxy-1,1'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, and bis(2-hydroxy-1-naphthyl)methane; a combination of bis-beta-naphthol and a 1,3-dihydroxybenzene derivative, e.g., 2,4-dihydroxybenzophenone or 2'4'-dihydroxyacetophenone; 5-pyrazolones such as 3-methyl-1-phenyl-5-pyrazolone; reductones as illustrated by dimethylamino hexose reductone, anhydro dihydro amino hexose reductone, and anhydro dihydro piperidone hexose reductone; sulphonamidophenol reducing agents such as 2,6-dichloro-4-benzensulphonamidophenol, and p-benzenesulphonamidophenol; 2-phenylindane-1,3-dione and the like; chromans such as 2,2-dimethyl-7-t-butyl-6-hydroxychroman; 1,4-dihydro-pyridines such as 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine; bisphenols e.g., bis(2-hydroxy-3-t-butyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4-ethylidene -bis(2-tert-butyl-6-methylphenol), and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane; ascorbic acid derivatives, e.g., 1-ascorbylpalmitate, ascorbylstearate and unsaturated aldehydes and ketones, such as benzyl and diacetyl; 3-pyrazolidones and certain indane-1,3-diones. The literature discloses additives, "toners", which improve the image. Toner materials may be present, for example, in amounts from 0.1 to 10 percent by weight of all silver bearing components. Toners are well known materials in the photothermographic art as shown in U.S. Pat. Nos. 3,080,254; 3,847,612 and 4,123,282. Examples of toners include phthalimide and N-hydroxyphthalimide; cyclic imides such as succinimide, pyrazoline-5-ones, and a quinazolinone, 3-phenyl-2-pyrazoline-5-one, 1-phenylurazole, quinazoline, and 2,4-thiazolidinedione; naphthalimides, e.g., N-hydroxy-1,8-naphthalimide; cobalt complexes, e.g., cobaltic hexamine trifluoroacetate; mercaptans as illustrated by 3-mercapto -1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N-(aminomethyl)aryl dicarboximides, e.g. (N-dimethylaminomethyl)phthalimide, and N-(dimethylaminomethyl)naphthalene-2,3-dicarboximide; and a combination of blocked pyrazoles, isothiuronium derivatives and certain photobleach agents, e.g., a combination of N,N'-hexamethylene bis(1-carbomoyl-3,5-dimethylpyrazole), 1,8-(3,6-diazaoctane)bis(isothiuronium trifluoroacetate) and 2-(tribromomethylsulfonyl)benzothiazole); and merocyanine dyes such as 3-ethyl-5[(3-ethyl-2-benzothiazolinylidene)-1-methylethylidene]-2-thio-2,4-oxazolidinedione; phthalazinone, phthalazinone derivatives or metal salts or these derivatives such as 4-(1-naphthyl)phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone, and 2,3-dihydro-1,4-phthalazinedione; a combination of phthalazinone plus sulphinic acid derivatives, e.g., phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, and tetrachlorophthalic anhydride; quinazolinediones, benzoxazine or naphthoxazine derivatives; rhodium complexes functioning not only as tone modifiers but also as sources of halide ion for silver halide formation in situ, such as ammonium hexachlororhodate (III), rhodium bromide, rhodium nitrate and potassium hexachlororhodate (III); inorganic peroxides and persulphates, e.g., ammonium peroxydisulphate and hydrogen peroxide; benzoxazine-2,4-diones such as 1,3-benzoxazine-2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione, and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidines and asym-triazines, e.g., 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, and azauracil, and tetrazapentalene derivatives, e.g, 3,6-dimercapto-1,4-diphenyl-1H,4H-2,3a,5,6a-tetrazapentalene, and 1,4-di(o-chloro-phenyl)3,6-dimercapto-lH,4H-2,3a,5,6a-tetrazapentalene. A number of methods have been proposed for obtaining color images with dry silver systems. Such methods include incorporated coupler materials, e.g., a combination of silver benzotriazole, well known magenta, yellow and cyan dye-forming couplers, aminophenol developing agents, a base release agent such as guanidinium trichloroacetate and silver bromide in poly(vinylbutyral); a combination of silver bromoiodide, sulphonamidophenol reducing agent, silver behenate, poly(vinylbutyral), an amine such as n-octadecylamine and 2-equivalent or 4-equivalent cyan, magenta or yellow dye-forming couplers; incorporating leuco dye bases which oxidizes to form a dye image, e.g., Malachite Green, Crystal Violet and pararosaniline; a combination of in situ silver halide, silver behenate, 3-methyl-1-phenylpyrazolone and N,N'-dimethyl-p-phenylenediamine hydrochloride; incorporating phenolic leuco dye reducing agents such as 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-4,5-diphenylimidazole, and bis(3,5-di-tert-butyl-4-hydroxyphenyl)phenylmethane, incorporating azomethine dyes or azo dye reducing agents; silver dye bleach process, e.g., an element comprising silver behenate, behenic acid, poly(vinylbutyral), poly(vinylbutyral)peptized silver bromoiodide emulsion, 2,6-dichloro-4-benzenesulphonamidophenol, 1,8-(3,6-diazaoctane)bis-isothiuronium-p-toluene sulphonate and an azo dye was exposed and heat processed to obtain a negative silver image with a uniform distribution of dye which was laminated to an acid activator sheet comprising polyacrylic acid, thiourea and p-toluene sulphonic acid and heated to obtain well defined positive dye images; and incorporating amines such as aminoacetanilide (yellow dye-forming), 3,3'-dimethoxybenzidine (blue dye-forming) or sulphanilide (magenta dye forming) which react with the oxidized form of incorporated reducing agents such as 2,6-dichloro-4-benzene-sulphonamido-phenol to form dye images. Neutral dye images can be obtained by the addition of amines such as behenylamine and p-anisidine. Leuco dye oxidation in such silver halide systems are disclosed in U.S. Pat. Nos. 4,021,240, 4,374,821, 4,460,681 and 4,883,747. Silver halide emulsions containing the stabilizers of this invention can be protected further against the additional production of fog and can be stabilized against loss of sensitivity during keeping. Suitable anti-foggants and stabilizers which can be used alone or in combination, include the thiazolium salts described in Staud, U.S. Pat. No. 2,131,038 and Allen U.S. Pat. No. 2,694,716; the azaindenes described in Piper, U.S. Pat. No. 2,886,437 and Heimbach, U.S. Pat. No. 2,444,605; the mercury salts described in Allen, U.S. Pat. No. 2,728,663; the urazoles described in Anderson, U.S. Pat. No. 3,287,135; the sulfocatechols described in Kennard, U.S. Pat. No. 3,235,652; the oximes described in Carrol et. al., British Patent No. 623,448; nitron; nitroindazoles; the polyvalent metal salts described in Jones, U.S. Pat. No. 2,839,405; the thiuronium salts described by Herz, U.S. Pat. No. 3,220,839; and palladium, platinum and gold salts described in Trivelli, U.S. Pat. No. 2,566,263 and Damschroder, U.S. Pat. No. 2,597,915. Stabilized emulsions of the invention can contain plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton, U.S. Pat. No. 2,960,404; fatty acids or esters such as those described in Robins, U.S. Pat. No. 2,588,765 and Duane, U.S. Pat. No. 3,121,060; and silicone resins such as those described in DuPont British Patent No. 955,061. The photothermographic elements can include image dye stabilizers. Such image dye stabilizers are illustrated by U.K. Patent No. 1,326,889; Lestina et al. U.S. Pat. Nos. 3,432,300 and 3,698,909; Stern et al. U.S. Pat. No. 3,574,627; Brannock et al. U.S. Pat. No. 3,573,050; Arai et al. U.S. Pat. No. 3,764,337 and Smith et al. U.S. Pat. No. 4,042,394. Photothermographic elements containing emulsion layers stabilized according to the present invention can be used in photographic elements which contain light absorbing materials and filter dyes such as those described in Sawdey, U.S. Pat. No. 3,253,921; Gaspar U.S. Pat. No. 2,274,782; Carroll et a]., U.S. Pat. No. 2,527,583 and Van Campen, U.S. Pat. No. 2,956,879. If desired, the dyes can be mordanted, for example, as described in Milton and Jones, U.S. Pat. No. 3,282,699. Photothermographic elements containing emulsion layers stabilized as described herein can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al., U.S. Pat. No. 2,992,101 and Lynn, U.S. Pat. No. 2,701,245. Emulsions stabilized in accordance with this invention can be used in photothermographic elements which contain antistatic or conducting layers, such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk, U.S. Pat. Nos. 2,861,056, and 3,206,312 or insoluble inorganic salts such as those described in Trevoy, U.S. Pat. No. 3,428,451. The binder may be selected from any of the well-known natural or synthetic resins such as gelatin, polyvinyl acetals, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyolefins, polyesters, polystyrene, polyacrylonitrile, polycarbonates, and the like. Copolymers and terpolymers are of course included in these definitions. The preferred photothermographic silver containing polymer is polyvinyl butyral, butethyl cellulose, methacrylate copolymers, maleic anhydride ester copolymers, polystyrene, and butadiene-styrene copolymers. Optionally these polymers may be used in combination of two or more thereof. Such a polymer is used in an amount sufficient to carry the components dispersed therein, that is, within the effective range of the action as the binder. The effective range can be appropriately determined by one skilled in the art. As a guide in the case of carrying at least an organic silver salt, it can be said that a preferable ratio of the binder to the organic silver salt ranges from 15:1 to 1:2, and particularly from 8:1 to 1:1. Photothermographic emulsions containing the stabilizer of the invention can be coated on a wide variety of supports. Typical supports include polyester film, subbed polyester film, poly(ethylene terephthalate)film, cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polycarbonate film and related or resinous materials, as well as glass, paper metal and the like. Typically, a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an alphaolefin polymer, particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like. The substrate with backside resistive heating layer may also be used in color photothermographic imaging systems such as shown in U.S. Pat. No. 4,460,681 and 4,374,921. Photothermographic emulsions of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type descirbed in Benguin, U.S. Pat. No. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in Russell, U.S. Pat. No. 2,761,791 and Wynn British Patent No. 837,095. The present invention will be i]]ustrated in detail in reference to the following examples, but the embodiment of the present invention is not limited thereto. EXAMPLE 1 A dispersion of silver behenate half soap was made at 10% solids in toluene and acetone by homogenization. To 127g of this silver half soap dispersion was added 252g methyl ethyl ketone, 104g isopropyl alcohol and 0.5g of polyvinylbutyral. After 15 minutes of mixing 4 ml of mercuric bromide 0.36/10 ml methanol) were added. Then 8.0 ml of calcium bromide 0.236 g/10ml methanol) was added 30 minutes later. After two hours of mixing, 27.0 g of polyvinylpyrrolidone was added, and 27.0 g of polyvinylbutyral was added one hour later. To 32.1 g of the prepared silver premix described above was added 2.0 ml of the sensitizing dye A (0.045 g/50ml of methanol) shown below. ##STR8## After 20 minutes, a yellow color-forming leuco dye solution was added as shown below. ______________________________________Component Amount______________________________________Leuco Dye B 0.275 gTribenzylamine 0.24 gPhthalazinone 0.14 gTetrahydrofuran 6.0 ml______________________________________ The leuco dye is disclosed in U.S. Pat. No. 4,883,747 and has the following formula: ##STR9## After sensitization with the dye and the addition of the leuco base dye solution, Compound I-A was added in the amounts of 0.2 ml or 0.5 ml at a concentration of 0.2 g/5 ml of methanol to 9.9 g aliquot of the yellow coating solution. The resulting solutions were coated along with a solution not containing any stabilizer precursor at a wet thickness of 3 mils and dried at 82° C. in an oven for 5 minutes onto a vesicular polyester base. A topcoat solution was coated at a wet thickness of 3 mils over the silver halide layer and dried at 82° C. in an oven for 5 minutes. The topcoat solution consisted of 7% polyvinyl alcohol in an approximate 50:50 mixture of water and methanol and 0.06% phthalazine. The samples were exposed for 10 -3 seconds through a 47B Wratten filter and a 0 to 3 continuous wedge and developed by heating to approximately 138° C. for 6 seconds. The density of the dye was measured using a blue filter of a computer densitometer. Post-processing stability was measured by exposing imaged samples to 1,200 ft-candles of illumination for 6 hours at 65% relative humidity and 26.7° C. The initial sensitometric data are shown below: ______________________________________ Dmin Dmax Speed.sup.1 Contrast.sup.2______________________________________Control (0.0 ml) 0.11 2.46 1.77 5.090.2 ml I-A 0.12 2.55 1.70 5.900.5 ml I-A 0.13 2.54 1.72 5.78______________________________________ .sup.1 Log exposure corresponding to density of 0.6 above Dmin. .sup.2 Average contrast measured by the slope of the line joining density points 0.3 and 0.9 above Dmin. The post-processing print stability results are shown below: ______________________________________ .increment.Dmin .increment.Dmax______________________________________Control (0.0 ml) +0.48 -0.020.2 ml I-A +0.46 -0.031.0 ml I-A +0.38 -0.02______________________________________ A 20% improvement in the post-processing Dmin was observed vs. unstabilized control with little effect on initial sensitometric responses. EXAMPLE 1A Comparison To 9.9 g of the silver halide coating solution as described in Example 1 was added 1.0 ml of 1-phenyl-5-mercapto-tetrazole (PMT) at a concentration of 0.1 g/5 ml methanol. The silver solutions and topcoats were coated, exposed and processed as described in Example 1. The initial sensitometric data are shown below. ______________________________________ Dmin Dmax Speed.sup.1 Contrast.sup.2______________________________________Control (0.0 ml) 0.14 2.52 1.73 5.010.5 ml PMT 0.12 1.02 2.36 0.36______________________________________ .sup.1 Log exposure corresponding to density of 0.6 above Dmin. .sup.2 Average contrast measured by the slope of the line joining density points 0.3 and 0.9 above Dmin. The post-processing print stability was measured as described in Example 1 and the results are shown below. ______________________________________ .increment.Dmin .increment.Dmax______________________________________Control (0.0 ml) +0.50 -0.061.0 ml PMT +0.18 -0.11______________________________________ At these concentrations of PMT, significant desensitization of the silver halide emulsion has occured for post-processing Dmin improvements. In Example 1, PMT was successfully blocked to minimize any desensitization effects but still allowed release of some PMT for the Dmin post-processing improvements. EXAMPLE 2 A magenta color-forming silver halide dispersion was prepared by using 502 g of the silver half soap dispersion of Example 1 and adding 0.4 g of polyvinylbutyral. After 15 minutes of mixing, a 0.5 g/9.75g mercuric acetate in methanol solution and a 0.55 g/18.4g calcium bromide in methanol solution were added. Then an additional 0.55 g/18.4g calcium bromide in methanol solution was added 30 minutes later. After 45 minutes of mixing 49.8g of polyvinylbutyral was added. To 35.8 g of the prepared silver premix described above was added 1.4 ml of the sensitizing dye c (0.021 g/100 ml of methanol) shown below. ##STR10## After 30 minutes, a magenta color-forming leuco dye solution was added as shown below. ______________________________________Component Amount______________________________________Leuco Dye .sub.-- D 0.593 gPhthalazinone 0.901 gTetrahydrofuran 47.6 gVAGH (Union Carbide) 2.2 gPolyvinylbutyral 10.2 g______________________________________ The leuco dye is disclosed in U.S. Pat. No. 4,795,697 and has the following formula. ##STR11## A topcoat solution was prepared consisting of 24.0% polystyrene resin in approximately 52% tetrahydrofuran, 17% toluene, 2% acetone and 5% methanol. To 10.0g of magenta silver coating solution was added 0.67 ml or 1.0 ml of the isomer mixture, compounds I-B and I-C, at a concentration of 0.3 g/3ml of methanol and 2 ml of tetrahydrofuran, or 0.65 ml of benzotriazole (BZT) at a concentration of 0.1 g/5ml of methanol. The magenta silver layer and topcoat were coated simultaneouosly at a wet thickness of 2 mils, respectively and dried for 5 minutes at 82° C. The samples were exposed for 10 -3 seconds through a 58 Wratten filter and a 1 to 3 continuous wedge and developed by heating to approximately 138° C. for 6 seconds. The density of the dye for each sample was measured using a green filter of a computer densitometer. Post-processing stability was measured by exposing imaged samples to 1200 ft-candles of illumination for 7 hours at 65% relative humidity and 26.7° C. The initial sensitometric data are shown below. ______________________________________ Dmin Dmax Speed.sup.1 Contrast.sup.2______________________________________Control (0.0 ml) 0.08 1.92 1.93 2.030.65 ml BZT 0.08 0.20 -- --0.67 ml I-B + I-C 0.08 1.98 1.98 2.031.0 ml I-B + I-C 0.08 1.89 2.02 2.01______________________________________ .sup.1 Log exposure corresponding to density of 0.6 above Dmin. .sup.2 Average contrast measured by the slope of the line joining density points 0.3 and 0.9 above Dmin. The post processing print stability was measured and the results are shown below. ______________________________________ .increment.Dmin .increment.Dmax______________________________________Control (0.0 ml) +0.18 -0.160.65 ml BZT +0.13 --0.67 ml I-B + I-C +0.16 -0.141.0 ml I-B + I-C +0.14 -0.21______________________________________ At this concentration of benzotriazole, Dmin post-processing improvements were observed, but significant desensitizatin of the silver halide emulsion had occurred. With the addition of I-B+I-C, BZT was adequately blocked to minimize any desensitization and yet release of BZT occurred at the appropriate time for Dmin post-processing impovements similar to the unblocked BZT stabilizer. EXAMPLE 3 To 10.0 g of a magenta silver halide solution, as described in Example 2, was added 0.95 ml of compound I-D at a concentration of 0.1 g/2.5 ml of methanol and 2.5 ml tetrahydrofuran or 0.65 ml of benzimidazole (BI) at a concentration of 0.1 g/5 ml of methanol. The silver solutions and topcoats were coated, exposed, and processed as described in example 2. The initial sensitometric data are shown below. ______________________________________ Dmin Dmax Speed.sup.1 Contrast.sup.2______________________________________Control (0.0 ml) 0.08 1.92 1.93 2.030.65 ml BI 0.08 1.59 2.64 1.940.95 ml I-D 0.08 1.88 2.01 1.94______________________________________ .sup.1 Log exposure corresponding to density of 0.6 above Dmin. .sup.2 Average contrast measured by the slope of the line joining density points 0.3 and 0.9 above Dmin. The post-processing print stability was measured as described in Example 2, and the results are shown below. ______________________________________ .increment.Dmin .increment.Dmax______________________________________Control (0.0 ml) +0.18 -0.160.65 ml BI +0.14 -0.270.85 ml I-D +0.15 -0.24______________________________________ At this concentration of benzimidazole, Dmin post-processing improvements are observed with significant desensitization of the silver halide emulsion. With the addition of I-D, BI was adequately blocked to minimize any desensitization and yet release of the BI occurred at the appropriate time during processing for Dmin post-processing improvements similar to the unblocked BI stabilizer. EXAMPLE 4 To 9.9 g of the yellow silver halide coating solution as described in Example 1, was added 0.2 ml or 1.0 ml of the isomer mixture, compounds I-E and I-F, at a concentration of 0.2 g/5 ml of methanol. The topcoat was similar to that described in Example 1. The silver solutions and topcoats were coated, exposed and processed as described in Example 1. The initial sensitometric data are shown below. ______________________________________ Dmin Dmax Speed.sup.1 Contrast.sup.2______________________________________Control (0.0 ml) 0.12 2.49 1.90 5.640.2 ml I-E + I-F 0.12 2.45 1.91 5.401.0 ml I-E + I-F 0.11 2.32 1.96 5.28______________________________________ .sup.1 Log exposure corresponding to density of 0.6 above Dmin. .sup.2 Average contrast measured by the slope of the line joining density points 0.3 and 0.9 above Dmin. The post-processing print stability was measured and the results are shown below. ______________________________________ .increment.Dmin .increment.Dmax______________________________________Control (0.0 ml) +0.56 -0.100.2 ml I-E + I-F +0.50 -0.131.0 ml I-E + I-F +0.34 -0.17______________________________________ A 40% improvement in the post-processing Dmin was observed vs. the unstabilized control with little effect on the initial sensitometric response. EXAMPLE 4-A Comparison To 9.9 g of the yellow silver coating solution as described in Example 4, was added 1.0 ml of benzotriazole (BZT) at a concentration of 0.1 g/5 ml of methanol. The topcoat was the same as used in Example 4, and the silver solutions and topcoats were coated, exposed and processed as described in Example 4. The initial sensitometric data are shown below. ______________________________________ Dmin Dmax Speed.sup.1 Contrast.sup.2______________________________________Control (0.0 ml) 0.12 2.22 1.84 4.521.0 ml BZT 0.11 0.30______________________________________ .sup.1 Log exposure corresponding to density of 0.6 above Dmin. .sup.2 Average contrast measured by the slope of the line joining density points 0.3 and 0.9 above Dmin. The post-processing print stability results are shown below. ______________________________________ .increment.Dmin .increment.Dmax______________________________________Control (0.0 ml) +0.47 -0.201.0 ml BZT +0.17 --______________________________________ At this concentration of BZT, significant desensitization of the silver halide emulsion had occurred for post-processing Dmin improvements. In Example 4, BZT was blocked to minimize any desensitization effects but still allowed the release of BZT at the appropriate time during processing for similar post-processing Dmin stabilization at the equivalent molar concentration as the unblocked BZT stabilizer. EXAMPLE 5 To 9.9 g of the yellow silver halide coating solution as described in Example 1, was added 0.5 ml or 1.0 ml of compound I-G at a concentration of 0.44 g/5 ml of methanol, or 0.5 ml or 1.0 ml of 4-methyl-5-trifluoromethyl-4H-1,2,4-triazoline-3(2H)-thione (MFT) at a concentration of 0.2 g/5 ml of methanol. The topcoat was similar to that described in Example 1. The silver solutions and topcoats were coated, exposed, and processed as described in Example 1. The initial sensitometric data are shown below. ______________________________________ Dmin Dmax Speed.sup.1 Contrast.sup.2______________________________________Control (0.0 ml) 0.09 2.42 1.96 5.000.5 ml MFT 0.09 1.90 2.12 4.111.0 ml MFT 0.09 0.10 -- --0.5 ml I-G 0.11 2.44 1.78 5.331.0 ml I-G 0.11 2.29 1.82 5.71______________________________________ .sup.1 Log exposure corresponding to density of 0.6 above Dmin. .sup.2 Average contrast measured by the slope of the line joining density points 0.3 and 0.9 above Dmin. The post-processing print stability was measured and the results are shown below. ______________________________________ .increment.Dmin .increment.Dmax______________________________________Control (0.0 ml) +0.64 -0.060.5 ml MFT +0.36 -0.131.0 ml MFT +0.160.5 ml I-G +0.39 -0.071.0 ml I-G +0.23 -0.12______________________________________ At these concentrations of MFT, significant desensitization of the silver halide occurs with the Dmin post-processing stabilization. The blocking of MFT, as shown in compound I-G, allows significant Dmin post-processing improvements similar to the equivalent molar amounts of the unblocked MFT stabilizer without losses in sensitivity. EXAMPLE 6 To 9.9 g of the yellow silver solution described in Example 5, was added 1.0 ml of comopund I-H or 1.0 ml of compound I-I at a concentration of 0.255 g/3 ml of ethanol and 2 ml tetrahydrofuran and 0.26 g/3 ml of methanol and 2 ml tetrahydrofuran, respectively. The topcoat was the same as described in Example 5, and the silver solutions and topcoats were coated, exposed, and processed as described in Example 1. The initial sensitometric data are shown below. ______________________________________ Dmin Dmax Speed.sup.1 Contrast.sup.2______________________________________Control (0.0 ml) 0.11 2.42 1.85 5.571.0 ml I-H 0.11 2.32 1.74 5.351.0 ml I-I 0.11 2.39 1.77 5.78______________________________________ .sup.1 Log exposure corresponding to density of 0.6 above Dmin. .sup.2 Average contrast measured by the slope of the line joining density points 0.3 and 0.9 above Dmin. The post-processing results are shown below. ______________________________________ .increment.Dmin .increment.Dmax______________________________________Control (0.0 ml) +0.51 -0.061.0 ml I-H +0.33 -0.011.0 ml I-I +0.41 -0.06______________________________________ With little effect on the initial sensitometric responses, compounds I-H and I-I improved the Dmin post-processing stability 35% and 20%, respectively. The α-amidoacetyl derivatives function as post-processing stabilizers and, thus, will contribute to the overall post-processing Dmin improvement as the blocking moiety to post-processing stabilizer precursors.
The post-processing stability of silver halide photothermographic emulsions is enhanced by the presence of stabilizing amounts of certain structurally defined amido compounds.
58,757
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority under 35 U.S.C. §119 to Korean Patent Application No. 10-2016-0089794, filed on Jul. 15, 2016, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety. TECHNICAL FIELD [0002] The following disclosure relates to an end cell heater for a fuel cell. More particularly, the following disclosure relates to an end cell heater for a fuel cell capable of preventing water existing in reaction cells of a fuel cell stack from being frozen to improve initial start ability and initial driving performance of the fuel cell at the time of cold-starting the fuel cell during winter by disposing heaters on end cells disposed at both ends of the fuel cell stack. BACKGROUND [0003] Generally, a fuel cell, which is a power generation device converting chemical energy by oxidation and reduction of hydrogen into electric energy, discharges only water (H 2 O) as a byproduct, does not substantially generate NOx, SOx, and dust, generates a low amount of CO 2 , and does not substantially generate noise unlike existing other chemical energy. Therefore, the fuel cell has been prominent as the next-generation alternative energy. [0004] The fuel cell includes unit cells basically including an electrolyte plate containing an electrolyte, an anode, a cathode, and a separator separating the electrolyte plate containing the electrolyte, the anode, and the cathode from one another. However, since the unit cell generally generates a low voltage of 0.6 to 0.8V, a fuel cell stack 1 in which several tens or several hundreds of unit cells 30 are stacked is configured to obtain a desired electric output, as illustrated in FIG. 1 . In addition, a membrane-electrode assembly (MEA) is configured by forming the electrolyte plate containing the electrolyte, the anode, and the cathode integrally with one another, and patterns are formed in the separator separating the electrolyte plate containing the electrolyte, the anode, and the cathode from one another to allow a fuel and air to flow. [0005] In addition, various fuels such as natural gas, petroleum, coal gas, methanol, and the like, may be used in the fuel cell, and are converted into hydrogen through a fuel reforming device and are used. [0006] However, in the fuel cell configured in a form of the fuel cell stack as described above, water generated by bond between oxygen and hydrogen in unit cells (end cells) positioned at the outermost portions in a stack direction of the unit cells remains, and is frozen in the end cells due to a cold external temperature during winter. Therefore, electricity is not generated in the end cells, such that initial start ability and oscillation ability of the fuel cell are deteriorated. RELATED ART DOCUMENT Patent Document [0007] KR 10-1466507 B1 (Nov. 21, 2014) SUMMARY [0008] An embodiment of the present invention is directed to providing an end cell heater for a fuel cell capable of preventing water existing in reaction cells of a fuel cell stack from being frozen by disposing heaters on end cells disposed at both ends of the fuel cell stack. [0009] An embodiment of the present invention is also directed to providing an end cell heater capable of securing air-tightness and a pressure resistance property of an air passage and a fuel passage formed in an end cell. [0010] In one general aspect, an end cell heater 1000 for a fuel cell includes: an end cell 100 including a body 110 and an upper cover 120 stacked on and in contact with an upper surface of the body 110 , and having air channels 111 formed between the body 110 and the upper cover 120 ; a heating element 200 stacked on and coupled to the end cell 100 ; and an electricity collecting plate 300 stacked on and in contact with the heating element 200 . [0011] Fusing protrusions may be formed to protrude on any one or more of the upper surface of the body 110 and a lower surface of the upper cover 120 , fusing grooves may be concavely formed at both sides of the fusing protrusions so as to be in contact with the fusing protrusions, and the fusing protrusions may be melted, such that the body 110 and the upper cover 120 are bonded to each other. [0012] The fusing protrusions and the fusing grooves may be formed at both sides of the air channels 111 so as to be spaced apart from the air channels 111 . [0013] In the end cell 100 , fusing protrusions may be melted by vibration fusion or laser fusion, such that the body 110 and the upper cover 120 are bonded to and formed integrally with each other. [0014] A seating groove may be concavely formed in a lower surface of the body 110 , and the electricity collecting plate 300 may be stacked on a lower surface of the heating element 200 so as to be in contact with the lower surface of the heating element 200 , such that the heating element 200 and the electricity collecting plate 300 are inserted into and seated in the seating groove. [0015] In another general aspect, an end cell heater 1000 for a fuel cell includes: an end cell 100 including a body 110 , an upper cover 120 stacked on and in contact with an upper surface of the body 110 , and a lower cover 130 stacked on and in contact with a lower surface of the body 110 , having air channels 111 formed between the body 110 and the upper cover 120 , and having fuel channels 112 formed between the body 110 and the lower cover 130 ; a heating element 200 stacked on and coupled to the end cell 100 ; and an electricity collecting plate 300 stacked on and in contact with the heating element 200 . [0016] Fusing protrusions may be formed to protrude on any one or more of the upper surface of the body 110 and a lower surface of the upper cover 120 , fusing grooves may be concavely formed at both sides of the fusing protrusions so as to be in contact with the fusing protrusions, and the fusing protrusions may be melted, such that the body 110 and the upper cover 120 are bonded to each other, and fusing protrusions may be formed to protrude on any one or more of the lower surface of the body 110 and an upper surface of the lower cover 130 , fusing grooves may be concavely formed at both sides of the fusing protrusions so as to be in contact with the fusing protrusions, and the fusing protrusions may be melted, such that the body 110 and the lower cover 130 are bonded to each other. [0017] The fusing protrusions and the fusing grooves may be formed at both sides of each of the air channels 111 and the fuel channels 112 so as to be spaced apart from the air channels 111 and the fuel channels 112 . [0018] In the end cell 100 , fusing protrusions may be melted by vibration fusion or laser fusion, such that the body 110 and the upper cover 120 are bonded to each other and the body 110 and the lower cover 130 are bonded to each other, and the body 110 , the upper cover 120 , and the lower cover 130 are thus formed integrally with one another. [0019] A seating groove may be concavely formed in a lower surface of the lower cover 130 , and the electricity collecting plate 300 may be stacked on a lower surface of the heating element 200 so as to be in contact with the lower surface of the heating element 200 , such that the heating element 200 and the electricity collecting plate 300 are inserted into and seated in the seating groove. [0020] A cross-sectional area of a portion in which a fusing protrusion is melted may be smaller than that of a pair of fusing grooves formed at both sides of each fusing protrusion. [0021] Protruding parts 115 may be formed to protrude on the upper surface of the body 110 , fusing protrusions 113 may be formed to protrude on upper surfaces of the protruding parts 115 , and insertion grooves 121 may be concavely formed at positions corresponding to those of the protruding parts 115 in the upper cover 120 , such that the protruding parts 115 and the fusing protrusions 113 are inserted into the insertion grooves 121 and the fusing protrusions 113 are melted to be fused to the insertion grooves 121 . [0022] A height of the insertion groove 121 may be higher than that of the protruding part 115 , and a cross-sectional area of a space between the protruding part 115 and the insertion groove 121 may be greater than that of a portion in which the fusing protrusion 113 is melted. [0023] A lead terminal 140 in which terminals 141 and injection-molded members 142 are formed integrally with each other by insert-injection-molding the terminals 141 may be again insert-injection-molded, such that the body 110 and the lead terminal 140 are formed integrally with each other. [0024] The end cell heater for a fuel cell may further include: an end plate 600 stacked on the upper cover 120 ; and a gasket 500 interposed between and closely adhering to the upper cover 120 and the end plate 600 . [0025] The gasket 500 may include sealing members 530 formed to protrude on both surfaces of a plate 510 and a plurality of communication holes 520 formed in the plate 510 so as to penetrate through upper and lower surfaces of the plate 510 , and the sealing members 530 formed on the upper and lower surfaces of the plate 510 may be connected to each other through the communication holes 520 . [0026] In the gasket 500 , the plate 510 and the sealing members 530 may be formed integrally with each other by insert-injection-molding. BRIEF DESCRIPTION OF THE DRAWINGS [0027] FIG. 1 is a perspective view illustrating a fuel cell according to the related art. [0028] FIG. 2 is a cross-sectional view illustrating an end cell heater for a fuel cell according to a first exemplary embodiment of the present invention. [0029] FIGS. 3 to 5 are partial cross-sectional views illustrating a fusing process of manufacturing an end cell heater according to the present invention. [0030] FIG. 6 is a cross-sectional view illustrating an end cell heater for a fuel cell according to a second exemplary embodiment of the present invention. [0031] FIGS. 7 to 10 are a cross-sectional view and partial cross-sectional views illustrating various examples of an end cell heater for a fuel cell according to the present invention. [0032] FIG. 11 is a cross-sectional view illustrating a relationship between a cross-sectional area of a portion in which a fusing protrusion is melted at the time of fusion and a cross-sectional area of a space in which a flash formed by melting the fusing protrusion may be filled. [0033] FIG. 12 is a perspective view illustrating a lead terminal according to the present invention. [0034] FIGS. 13 and 14 are, respectively, an exploded perspective view and an assembled perspective view illustrating the end cell heater for a fuel cell according to a second exemplary embodiment of the present invention. [0035] FIG. 15 is a cross-sectional view illustrating an example of a gasket and an end plate according to the present invention. [0036] FIG. 16 is a perspective view illustrating the gasket of FIG. 15 . [0037] FIG. 17 is an exploded perspective view illustrating another example of a gasket according to the present invention. [0038] FIGS. 18 and 19 are, respectively, an assembled perspective view and an exploded perspective view illustrating a fuel cell including the end cell heater for a fuel cell according to the present invention. [0000] [Detailed Description of Main Elements] 1000: end cell heater for fuel cell  100: end cell  110: body  111: air channel  112: fuel channel  113: fusing protrusion  114: fusing groove  115: protruding part  120: upper cover  121: insertion groove  130: lower cover  140: lead terminal  141: terminal  142: injection-molded member  151: air passage  152: fuel passage  200: heating element  300: electricity collecting plate  310: electricity collecting terminal  400: heat insulating sheet  500: gasket  510: plate  520: communication hole  530: sealing member  531: sealing member  540: passage hole  550: electricity collecting terminal hole  600: end plate 2000: fuel cell 1100: fuel cell stack 1100a: reaction cell 1110: air passage  1120: fuel passage 1400: cover  1410: air passage 1420: fuel passage  1500: fastening member DETAILED DESCRIPTION OF EMBODIMENTS [0039] Hereinafter, an end cell heater for a fuel cell according to the present invention having the configuration as described above will be described in detail with reference to the accompanying drawings. First Exemplary Embodiment [0040] FIG. 2 is a cross-sectional view illustrating an end cell heater for a fuel cell according to a first exemplary embodiment of the present invention. [0041] As illustrated, the end cell heater 1000 for a fuel cell according to a first exemplary embodiment of the present invention may be configured to include an end cell 100 including a body 110 and an upper cover 120 stacked on and in contact with an upper surface of the body 110 , and having air channels 111 formed between the body 110 and the upper cover 120 ; a heating element 200 stacked on and coupled to the end cell 100 ; and an electricity collecting plate 300 stacked on and in contact with the heating element 200 . [0042] First, the end cell 100 may mainly consist of the body 110 and the upper cover 120 , and both of the body 110 and the upper cover 120 may be formed of, for example, a plastic plate. In addition, the upper cover 120 is stacked on the upper surface of the body 110 , such that the body 110 and the upper cover 120 may be coupled or bonded to each other so that surfaces thereof facing each other are in contact with each other. In addition, the air channels 111 are formed between the body 110 and the upper cover 120 , such that air may flow along the air channels 111 . In this case, the air channels 111 may be concavely formed in the upper surface of the body 110 or a lower surface of the upper cover 120 . As an example, as illustrated, the air channels 111 may be concavely formed in the upper surface of the body 110 , and opened upper sides of the air channels 111 may be closed by the upper cover 120 coupled or bonded to the upper surface of the body 110 . In addition, the end cell 100 may be formed in various shapes such as a quadrangular shape having a length greater than a width, and the like, and may have air passages formed at both sides thereof in a length direction so as to penetrate through upper and lower surfaces thereof, and the air passages may be connected to the air channels. In addition, the end cell 100 may have a through-hole formed at a central side thereof so as to penetrate through the upper and lower surfaces thereof, and an electricity collecting terminal 310 formed on an electricity collecting plate 300 to be described below may be inserted into the through-hole so as to penetrate through the through-hole. [0043] The heating element 200 , which is a means capable of receiving electricity and generating heat, may be, for example, a film heater formed in a film shape, may be stacked on and coupled to the end cell 100 , be inserted into and seated in a seating groove concavely formed in a lower surface of the body 110 of the end cell 100 as an example, and be coupled and fixed to the end cell 100 . In addition, the heating element 200 may also have a through-hole formed therein so as to penetrate through upper and lower surfaces thereof so that the electricity collecting terminal 310 of the electricity collecting plate 300 may penetrate therethrough and be inserted thereinto. In addition, a heat insulating sheet 400 may be interposed between the end cell 100 and the heating element 200 , may prevent heat generated from the heating element 200 from being transferred to the end cell 100 formed of a plastic material, and may be formed of an electrical insulating material to perform an electrical insulating function. [0044] The electricity collecting plate 300 , which is a part capable of collecting and transferring electricity generated in a fuel cell stack 1100 , may be a metal plate formed of an electrically conductive material to be thus electrically conducted to the fuel cell stack. In addition, the electricity collecting plate 300 may be inserted into and seated in the seating groove formed in the body 110 of the end cell 100 , and may be stacked to closely adhere to and be in contact with the lower surface of the heating element 200 to be thus coupled to the end cell 100 . In addition, the electricity collecting terminal 310 may be formed to protrude on an upper surface of the electricity collecting plate 300 , and may be inserted and coupled into the through-holes of the end cell 100 and the heating element 200 so as to pass through the through-holes. [0045] Therefore, the end cell heater for a fuel cell according to the present invention as described above is stacked on and is coupled to an outer side of the outermost reaction cell of the fuel cell stack so as to closely adhere to the outer side of the outermost reaction cell to thus prevent water in the reaction cell from being frozen, thereby making it possible to improve initial start ability and initial driving performance of the fuel cell. [0046] In addition, fusing protrusions are formed to protrude on any one or more of the upper surface of the body 110 and the lower surface of the upper cover 120 , fusing grooves are concavely formed at both sides of the fusing protrusions so as to be in contact with the fusing protrusions, and the fusing protrusions are melted, such that the body 110 and the upper cover 120 may be bonded to each other. [0047] That is, as an example, as illustrated in FIGS. 3 to 5 , the fusing protrusions 113 may be formed to protrude on the upper surface of the body 110 , and the fusing grooves 114 may be concavely formed at both sides of the fusing protrusions 113 so as to be in contact with the fusing protrusions 113 . A description will be provided on the basis of the fusing protrusions 113 and the fusing grooves 114 formed at an upper side of the body 110 . The fusing protrusions 113 may be formed to protrude to be upwardly convex from the upper surface of the body 110 , and the fusing grooves 114 may be formed adjacently to the fusing protrusions 113 at both sides of the fusing protrusions 113 so as to be downwardly concave from the upper surface of the body 110 . In addition, the lower surface of the upper cover 120 may be a flat surface. Therefore, end portions of the fusing protrusions 113 are melted by fusion, such that the body 110 and the upper cover 120 may be bonded and coupled to each other, and a flash formed by melting and pressing the fusing protrusions 113 may be filled in the fusing grooves 114 . [0048] In addition, the fusing protrusions and the fusing grooves may be formed at both sides of the air channels 111 so as to be spaced apart from the air channels 111 . [0049] That is, the number of air channels 111 may be one or plural, the fusing protrusions 113 and the fusing grooves 114 may be formed along a path in which the air channels 111 are formed, and the fusing protrusions 113 and the fusing grooves 114 may be formed at both sides of the air channels 111 so as to be spaced apart from the air channels 111 . Therefore, as illustrated, a pair of fusing protrusions 113 may be formed per air channel 111 , one fusing protrusion 113 may be formed at each of both sides of one air channel 111 , a pair of fusing grooves 114 may be formed per one fusing protrusion 113 , and one fusing groove 114 may be formed at each of both sides of one fusing protrusion 113 . In other words, protrusions and grooves of which one set is formed by the fusing grooves 114 formed at both sides of one fusing protrusion 113 may be formed at both sides of the channels, and one set of protrusions and grooves may be formed at both sides of each of the channels. Therefore, the fusing protrusions are melted along the channels, such that contact surfaces are bonded to each other, thereby making it possible to secure air-tightness of each of the channels and secure pressure resistance properties of fluids flowing along the channels. [0050] In addition, in the end cell 100 , the fusing protrusions are melted by vibration fusion or laser fusion, such that the body 110 and the upper cover 120 may be bonded to and formed integrally with each other. [0051] That is, in a state in which the body 110 and the upper cover 120 are pressed in a vertical direction so as to closely adhere to each other after the upper cover 120 is disposed on the body 110 in a state in which the end portions of the fusing protrusions 113 are not melted, vibrations such as ultrasonic vibrations, or the like, are applied, such that heat is generated on a surface on which the fusing protrusions 113 and the upper cover 120 are in contact with each other to melt the fusing protrusions 113 , thereby making it possible to bond the body 110 and the upper cover 120 to each other. In this case, the melted flash formed by melting the fusing protrusions 113 may be pushed into the fusing grooves 114 . Therefore, the upper surface of the body 110 and the lower surface of the upper cover 120 may closely adhere and be bonded to each other, and the melted flash may not be introduced between the upper surface of the body 110 and the lower surface of the upper cover 120 . [0052] Alternatively, the body 110 is formed as an absorption layer capable of absorbing a laser beam, and the upper cover 120 is formed as a transmission layer through which the laser beam may transmit, such that the fusing protrusions 113 are melted and fused by the laser fusion, and the body 110 and the upper cover 120 may thus be formed integrally with each other. [0053] That is, in the state in which the body 110 and the upper cover 120 are pressed in the vertical direction so as to closely adhere to each other after the upper cover 120 is disposed on the body 110 in the state in which the end portions of the fusing protrusions 113 are not melted, the laser beam is irradiated to portions of the fusing protrusions 113 , thereby making it possible to bond portions at which the fusing protrusions 113 and the upper cover 120 are in contact with each other to each other while melting the fusing protrusions 113 . Here, the body 110 on which the fusing protrusions 113 are formed is formed to have a black color so that the laser beam may be absorbed therein, such that the body 110 may be formed as a laser absorption layer, and the upper cover 120 is transparently formed so that the laser beam may pass therethrough, such that the upper cover 120 may be formed of a laser transmission layer. Therefore, the laser beam is irradiated from above the upper cover 120 , and may pass through the upper cover 120 to allow the fusing protrusions 113 to be melted and fused. Also in this case, the melted flash formed by melting the fusing protrusions 113 may be pushed into the fusing grooves 114 , and the upper surface of the body 110 and the lower surface of the upper cover 120 may thus closely adhere and be bonded to each other. [0054] In addition, the seating groove is concavely formed in the lower surface of the body 110 , and the electricity collecting plate 300 is stacked on the lower surface of the heating element 200 so as to be in contact with the lower surface of the heating element 200 , such that the heating element 200 and the electricity collecting plate 300 may be inserted into and seated in the seating groove. [0055] That is, as described above, the heating element 200 and the electricity collecting plate 300 may be inserted into and seated in the seating groove concavely formed in the lower surface of the body 110 , and the electricity collecting plate 300 is disposed beneath the heating element 200 so as to be in contact with the heating element 200 . In this case, the heat insulating sheet 400 may be interposed between a lower surface of the seating groove and the heating element 200 , such that the heat insulating sheet 400 may be disposed on the heating element 200 . In addition, a lower surface of the electricity collecting plate 300 may be formed to further protrude as compared with the lower surface of the body 110 of the end cell 100 or coincide with the lower surface of the body 110 of the end cell 100 . Therefore, when the electricity collecting plate of the end cell heater for a fuel cell according to the present invention is coupled to the reaction cell of the fuel cell stack so as to closely adhere to the reaction cell, electrical insulation and air-tightness of the heating element 200 and the electricity collecting plate 300 may be easily maintained. Second Exemplary Embodiment [0056] FIG. 6 is a cross-sectional view illustrating an end cell heater for a fuel cell according to a second exemplary embodiment of the present invention. [0057] As illustrated, the end cell heater 1000 for a fuel cell according to a second exemplary embodiment of the present invention may be configured to include an end cell 100 including a body 110 , an upper cover 120 stacked on and in contact with an upper surface of the body 110 , and a lower cover 130 stacked on and in contact with a lower surface of the body 110 , having air channels 111 formed between the body 110 and the upper cover 120 , and having fuel channels 112 formed between the body 110 and the lower cover 130 ; a heating element 200 stacked on and coupled to the end cell 100 ; and an electricity collecting plate 300 stacked on and in contact with the heating element 200 . [0058] First, the end cell 100 may mainly consist of the body 110 , the upper cover 120 , and lower cover 130 , and all of the body 110 , the upper cover 120 , and the lower cover 130 may be formed of, for example, a plastic plate. In addition, the upper cover 120 is stacked on the upper surface of the body 110 , such that the body 110 and the upper cover 120 may be coupled or bonded to each other so that surfaces thereof facing each other are in contact with each other, and the lower cover 130 is stacked on the lower surface of the body 110 , such that the body 110 and the lower cover 130 may be coupled or bonded to each other so that surfaces thereof facing each other are in contact with each other. In addition, the air channels 111 are formed between the body 110 and the upper cover 120 , such that air may flow along the air channels 111 , and the fuel channels 112 are formed between the body 110 and the lower cover 130 , such that a fuel such as hydrogen, or the like, may flow along the fuel channels 112 . In this case, the air channels 111 may be concavely formed in the upper surface of the body 110 or a lower surface of the upper cover 120 . As an example, as illustrated, the air channels 111 may be concavely formed in the upper surface of the body 110 , and opened upper sides of the air channels 111 may be closed by the upper cover 120 coupled or bonded to the upper surface of the body 110 . In addition, the fuel channels 112 may be concavely formed in the lower surface of the body 110 or an upper surface of the lower cover 130 . As an example, as illustrated, the fuel channels 112 may be concavely formed in the lower surface of the body 110 , and opened lower sides of the fuel channels 112 may be closed by the lower cover 130 coupled or bonded to the lower surface of the body 110 . In addition, the end cell 100 may be formed in various shapes such as a quadrangular shape having a length greater than a width, and the like, and may have air passages and fuel passages formed at both sides thereof in a length direction so as to penetrate through upper and lower surfaces thereof, the air passages may be connected to the air channels, and the fuel passages may be connected to the fuel channels. In addition, the end cell 100 may have a through-hole formed at a central side thereof so as to penetrate through the upper and lower surfaces thereof, and an electricity collecting terminal 310 formed on the electricity collecting plate 300 may be inserted into the through-hole so as to penetrate through the through-hole. [0059] The heating element 200 , which is a means capable of receiving electricity and generating heat, may be, for example, a film heater formed in a film shape, may be stacked on and coupled to the end cell 100 , and be inserted into and seated in a seating groove concavely formed in a lower surface of the lower cover 130 of the end cell 100 as an example to be thus coupled and fixed to the end cell 100 . In addition, the heating element 200 may also have a through-hole formed therein so as to penetrate through upper and lower surfaces thereof so that the electricity collecting terminal 310 of the electricity collecting plate 300 may penetrate therethrough and be inserted thereinto. In addition, a heat insulating sheet 400 may be interposed between the end cell 100 and the heating element 200 , may prevent heat generated from the heating element 200 from being transferred to the end cell 100 formed of a plastic material, and may be formed of an electrical insulating material to perform an electrical insulating function. [0060] The electricity collecting plate 300 , which is a part capable of collecting and transferring electricity generated in a fuel cell stack, may be a metal plate formed of an electrically conductive material to be thus electrically conducted to the fuel cell stack. In addition, the electricity collecting plate 300 may be inserted into and seated in the seating groove formed in the lower cover 130 of the end cell 100 , and may be stacked to closely adhere to and be in contact with the lower surface of the heating element 200 to be thus coupled to the end cell 100 . In addition, the electricity collecting terminal 310 may be formed to protrude on an upper surface of the electricity collecting plate 300 , and may be inserted and coupled into the through-holes of the end cell 100 and the heating element 200 so as to pass through the through-holes. [0061] Therefore, the end cell heater for a fuel cell according to the present invention as described above is stacked on and is coupled to an outer side of the outermost reaction cell of the fuel cell stack so as to closely adhere to the outer side of the outermost reaction cell to thus prevent water in the reaction cell from being frozen, thereby making it possible to improve initial start ability and initial driving performance of the fuel cell. [0062] In addition, fusing protrusions are formed to protrude on any one or more of the upper surface of the body 110 and the lower surface of the upper cover 120 , fusing grooves are concavely formed at both sides of the fusing protrusions so as to be in contact with the fusing protrusions, and the fusing protrusions are melted, such that the body 110 and the upper cover 120 may be bonded to each other, and fusing protrusions are formed to protrude on any one or more of the lower surface of the body 110 and the upper surface of the lower cover 130 , fusing grooves are concavely formed at both sides of the fusing protrusions so as to be in contact with the fusing protrusions, and the fusing protrusions are melted, such that the body 110 and the lower cover 130 may be bonded to each other. [0063] That is, as an example, the fusing protrusions 113 may be formed to protrude on the upper surface and the lower surface of the body 110 , the fusing grooves 114 may be concavely formed at both sides of the fusing protrusions 113 so as to be in contact with the fusing protrusions 113 , and the lower surface of the upper cover 120 and the upper surface of the lower cover 130 may be flat surfaces. Here, a description will be provided on the basis of the fusing protrusions 113 and the fusing grooves 114 formed at an upper side of the body 110 . The fusing protrusions 113 may be formed to protrude to be upwardly convex from the upper surface of the body 110 , and the fusing grooves 114 may be formed adjacently to the fusing protrusions 113 at both sides of the fusing protrusions 113 so as to be downwardly concave from the upper surface of the body 110 . Therefore, end portions of the fusing protrusions 113 are melted by fusion, such that the body 110 and the upper cover 120 may be bonded and coupled to each other, and a flash formed by melting and pressing the fusing protrusions 113 may be filled in the fusing grooves 114 . Likewise, the body 110 and the lower cover 130 may be bonded and coupled to each other by fusion. [0064] In addition, the fusing protrusions and the fusing grooves may be formed at both sides of each of the air channels 111 and the fuel channels 112 so as to be spaced apart from the air channels 111 and the fuel channels 112 . [0065] That is, the number of air channels 111 may be one or plural, the fusing protrusions 113 and the fusing grooves 114 may be formed along a path in which the air channels 111 are formed, and the fusing protrusions 113 and the fusing grooves 114 may be formed at both sides of the air channels 111 so as to be spaced apart from the air channels 111 . Therefore, as illustrated, a pair of fusing protrusions 113 may be formed per air channel 111 , one fusing protrusion 113 may be formed at each of both sides of one air channel 111 , a pair of fusing grooves 114 may be formed per one fusing protrusion 113 , and one fusing groove 114 may be formed at each of both sides of one fusing protrusion 113 . In other words, protrusions and grooves of which one set is formed by the fusing grooves 114 formed at both sides of one fusing protrusion 113 may be formed at both sides of the channels, and one set of protrusions and grooves may be formed at both side of each of the channels. Therefore, the fusing protrusions are melted along the channels, such that contact surfaces are bonded to each other, thereby making it possible to secure air-tightness of each of the channels and secure pressure resistance properties of fluids flowing along the channels. Likewise, the number of fuel channels 112 may also be one or plural, the fusing protrusions 113 and the fusing grooves 114 may be formed along a path in which the fuel channels 112 are formed, and the fusing protrusions 113 and the fusing grooves 114 may be formed at both sides of the fuel channels 112 so as to be spaced apart from the fuel channels 112 . [0066] In addition, in the end cell 100 , the fusing protrusions are melted by vibration fusion or laser fusion, such that the body 110 and the upper cover 120 may be bonded to each other and the body 110 and the lower cover 130 may be bonded to each other. As a result, the body 110 , the upper cover 120 , and the lower cover 130 may be formed integrally with one another. [0067] That is, in a state in which the upper cover 120 , the body 110 , and the lower cover 130 are sequentially stacked and are pressed in a vertical direction so as to closely adhere to one another after the upper cover 120 is disposed on the body 110 and the lower cover 130 is disposed beneath the body 110 in a state in which the end portions of the fusing protrusions 113 are not melted, vibrations such as ultrasonic vibrations, or the like, are applied, such that heat is generated on a surface on which the fusing protrusions 113 formed at the upper side of the body 110 and the upper cover 120 are in contact with each other to melt the fusing protrusions 113 , thereby making it possible to bond the body 110 and the upper cover 120 to each other. In addition, heat is generated on a surface on which the fusing protrusions 113 formed at a lower side of the body 110 and the lower cover 130 are in contact with each other to melt the fusing protrusions 113 , thereby making it possible to bond the body 110 and the lower cover 130 to each other. In this case, the melted flash formed by melting the fusing protrusions 113 may be pushed into the fusing grooves 114 . Therefore, the upper surface of the body 110 and the lower surface of the upper cover 120 may closely adhere and be bonded to each other, and the lower surface of the body 110 and the upper surface of the lower cover 130 may closely adhere and be bonded to each other. In this case, the melted flash may not be introduced between the upper surface of the body 110 and the lower surface of the upper cover 120 by the fusing grooves 114 . [0068] Alternatively, the body 110 is formed as an absorption layer capable of absorbing a laser beam, and the upper cover 120 and the lower cover 130 are formed as transmission layers through which the laser beam may transmit, such that the fusing protrusions 113 are melted and fused by the laser fusion, and the upper cover 120 , the body 110 , and the lower cover 130 may thus be formed integrally with one another. [0069] That is, in a state in which the upper cover 120 , the body 110 , and the lower cover 130 are sequentially stacked and are pressed in a vertical direction so as to closely adhere to one another after the upper cover 120 is disposed on the body 110 and the lower cover 130 is disposed beneath the body 110 in the state in which the end portions of the fusing protrusions 113 are not melted, the laser beam is irradiated from above the upper cover 120 and below the lower cover 130 toward the fusing protrusions 113 , thereby making it possible to bond portions at which the fusing protrusions 113 and the upper cover 120 are in contact with each other to each other and bond portions at which the fusing protrusions 113 and the lower cover 130 are in contact with each other to each other while melting the fusing protrusions 113 . Here, the body 110 on which the fusing protrusions 113 are formed is formed to have a black color so that the laser beam may be absorbed therein, such that the body 110 may be formed as a laser absorption layer, and the upper cover 120 and the lower cover 130 are transparently formed so that the laser beam may pass therethrough, such that the upper cover 120 and the lower cover 130 may be formed of laser transmission layers. Therefore, the laser beam is irradiated from above the upper cover 120 , and may pass through the upper cover 120 to allow the fusing protrusions 113 to be melted and fused and may pass through the lower cover 130 to allow the fusing protrusions 113 to be melted and fused. Also in this case, the melted flash formed by melting the fusing protrusions 113 may be pushed into the fusing grooves 114 . Therefore, the upper surface of the body 110 and the lower surface of the upper cover 120 may closely adhere and be bonded to each other, and the lower surface of the body 110 and the upper surface of the lower cover 130 may closely adhere and be bonded to each other. [0070] In addition, the seating groove is concavely formed in the lower surface of the lower cover 130 , and the electricity collecting plate 300 is stacked on the lower surface of the heating element 200 so as to be in contact with the lower surface of the heating element 200 , such that the heating element 200 and the electricity collecting plate 300 may be inserted into and seated in the seating groove. [0071] That is, as described above, the heating element 200 and the electricity collecting plate 300 may be inserted into and seated in the seating groove concavely formed in the lower surface of the lower cover 130 . In this case, the electricity collecting plate 300 is disposed beneath the heating element 200 so as to be in contact with the heating element 200 , and the heat insulating sheet 400 may be interposed between a lower surface of the seating groove and the heating element 200 , such that the heat insulating sheet 400 may be disposed on the heating element 200 . In addition, a lower surface of the electricity collecting plate 300 may be formed to further protrude as compared with the lower surface of the lower cover 130 or coincide with the lower surface of the lower cover 130 . Therefore, when the electricity collecting plate of the end cell heater for a fuel cell according to the present invention is coupled to the reaction cell of the fuel cell stack so as to closely adhere to the reaction cell, electrical insulation and air-tightness of the heating element 200 and the electricity collecting plate 300 may be easily maintained. [0072] Contents to be described below may be applied to both of the first exemplary embodiment and the second exemplary embodiment of the present invention described above. [0073] First, a cross-sectional area of a portion in which the fusing protrusion 113 is melted may be smaller than that of a pair of fusing grooves 114 formed at both sides of each fusing protrusion 113 . [0074] That is, as described above, the melted flash formed by melting the fusing protrusion 113 at the time of the fusion is pushed into the fusing grooves 114 formed at both sides of the fusing protrusion 113 , and spaces of the pair of fusing grooves 114 are wider than an amount of flash, such that the flash is not pushed into a space between the upper surface of the body 110 and the lower surface of the upper cover 120 and is not pushed into a space between the lower surface of the body 110 and the upper surface of the lower cover 130 . Therefore, the upper surface of the body 110 and the lower surface of the upper cover 120 may closely adhere to each other, and the lower surface of the body 110 and the upper surface of the lower cover 130 may closely adhere to each other. [0075] In addition, protruding parts 115 are formed to protrude on the upper surface of the body 110 , fusing protrusions 113 are formed to protrude on upper surfaces of the protruding parts 115 , and insertion grooves 121 are concavely formed at positions corresponding to those of the protruding parts 115 in the upper cover 120 , such that the protruding parts 115 and the fusing protrusions 113 may be inserted into the insertion grooves 121 and the fusing protrusions 113 may be melted to be fused to the insertion grooves 121 . [0076] That is, as illustrated in FIGS. 7 to 10 , the protruding part 115 formed to protrude upwardly from the upper surface of the body 110 may be inserted and coupled into the insertion groove 121 concavely formed upwardly in the lower surface of the upper cover 120 , such that the body 110 and the upper cover 120 may be bonded to each other in a state in which positions of the body 110 and the upper cover 120 in a horizontal direction are accurately fixed. In this case, the fusing protrusion 113 may be formed to protrude upwardly from the upper surface of the protruding part 115 , have a width narrower than that of the protruding part 115 , and be melted to be bonded to the insertion groove 121 . In addition, the protruding part 115 and the insertion groove 121 may be formed at the outermost portion of the end cell 100 in the horizontal direction, and the protruding part 115 may be formed so that the fusing protrusion 113 and the fusing groove 114 of the body 110 are disposed at an inner side in the horizontal direction. In addition, protruding parts 115 and fusing protrusions 113 , and insertion grooves 121 may also be formed in the body 110 and the lower cover 130 , respectively, as in the coupled and bonded structure between the body 110 and the upper cover 120 described above. [0077] In addition, a height of the insertion groove 121 is higher than that of the protruding part 115 , and a cross-sectional area of a space between the protruding part 115 and the insertion groove 121 may be greater than that of a portion in which the fusing protrusion 113 is melted. [0078] That is, describing the body 110 and the upper cover 120 by way of example, in the case in which the fusing protrusion 113 is formed upwardly from the upper surface of the protruding part 115 of the body 110 as illustrated in FIGS. 7 to 10 , the height of the insertion groove 121 is higher than that of the protruding part 115 , such that the fusing protrusion is in a state in which it is maximally pressed when the upper surface of the body 110 and the lower surface of the upper cover 120 closely adhere to each other while the fusing protrusion is melted. In this case, the flash formed by melting the fusing protrusion is pushed into a space portion formed between the protruding part 115 and the insertion groove 121 . For this reason, the space portion is formed to have a volume greater than an amount of fusing protrusion 113 that may be maximally melted. Here, the volume may be calculated by a cross-sectional area, and in the case in which the protruding part 115 and the insertion groove 121 are formed at the same width, a minimum cross-sectional area of the space portion, which is a value obtained by multiplying a difference between the width of the protruding part 115 and the width of the fusing protrusion 113 by a difference between the height of the insertion groove 121 and the height of the protruding part 115 may be designed to be greater than that of a portion in which the fusing protrusion may be maximally melted and pressed, which is a value obtained by multiplying a value obtained by subtracting the height of the insertion groove from the sum of the height of the protruding part and the height of the insertion groove by the width of the fusing protrusion. That is, as illustrated in FIG. 11 , a cross-sectional area of part A may be smaller than the sum of cross-sectional areas of part B, which is both sides of the fusing protrusion 113 . In addition, although not illustrated, insertion grooves may also be formed in the lower cover 130 , and the protruding parts 115 may be inserted and coupled to the insertion groove. [0079] In addition, a lead terminal 140 in which terminals 141 and injection-molded members 142 are formed integrally with each other by insert-injection-molding the terminals 141 is again insert-injection-molded, such that the body 110 and the lead terminal 140 may be formed integrally with each other. [0080] This is to allow the terminals 141 to be formed integrally with the body 110 when the body 110 is manufactured by injection-molding. Referring to FIGS. 12 and 14 , after two terminals are disposed in parallel with each other so as to be spaced apart from each other and are fixed to an injection mold, primary injection-molding is performed, such that the terminals 141 are insert-injection-molded to be formed integrally with the injection-molded members 142 , thereby making it possible to form an integral lead terminal 140 . After the lead terminal 140 as described above is again fixed to the injection mold, secondary injection-molding is again performed, such that the lead terminal 140 may be insert-injection-molded to be formed integrally with the body 110 . [0081] In addition, the end cell heater 1000 for a fuel cell may be configured to further include an end plate 600 stacked on the upper cover 120 and a gasket 500 interposed between and closely adhering to the upper cover 120 and the end plate 600 . [0082] That is, referring to FIGS. 15 and 16 , since the end cell 100 is formed of a plastic material, the end plate 600 formed of a metal may be coupled to one surface of the end cell 100 in order to increase mechanical rigidity. In this case, the gasket 500 may be interposed between and closely adhere to the end cell 100 and the end plate 600 in order to maintain air-tightness on a contact surface between the end cell 100 and the end plate 600 . [0083] Here, the gasket 500 includes sealing members 530 formed to protrude on both surfaces of a plate 510 and a plurality of communication holes 520 formed in the plate 510 so as to penetrate through upper and lower surfaces of the plate 510 , and the sealing members 530 formed on the upper and lower surfaces of the plate 510 may be connected to each other through the communication holes 520 . [0084] That is, the gasket 500 may include the plate 510 and the sealing members 530 having a plate shape, and the sealing members 530 may be formed to protrude on both surfaces of the plate 510 . In addition, the communication holes 520 penetrating through both surfaces of the plate 510 may be formed in the plate 510 , and the sealing members 530 formed on both surfaces of the plate 510 may be connected to each other through the communication holes 520 . Therefore, the sealing members 530 that are generally formed of a rubber or silicone material to have a difficulty in maintaining shapes are coupled and fixed to the plate 510 , thereby making it possible to easily maintain shapes of the sealing member 530 and prevent moisture, foreign materials, and the like, from being introduced between the end plate 600 and the end cell 100 . [0085] In this case, seating grooves may be concavely formed along portions of both surfaces of the plate 510 on which the sealing members are formed so that portions of the sealing members may be inserted, and separation of the sealing members may thus be prevented. In addition, the end plate 600 may have a through-hole formed therein so that the electricity collecting terminal 310 may pass therethrough, and may have passages formed therein so as to be connected to the passages connected to the channels of the end cell 100 . In addition, the gasket 500 may also have electricity collecting terminal holes 550 therein so that the electricity collecting terminal passes therethrough, and have passage holes 540 formed therein so as to be connected to the passages. In addition, a space between an outer peripheral surface of the electricity collecting terminal 310 penetrating through the end plate 600 and the through-hole of the end plate 600 is sealed by a sealant, or the like, thereby making it possible to prevent moisture, foreign materials, and the like, from being introduced toward the electricity collecting plate 300 . [0086] In addition, in the gasket 500 , the plate 510 and the sealing members 530 may be formed integrally with each other by insert-injection-molding. [0087] That is, after the plate 510 is formed of a metal, insert-injection-molding is performed, such that the gasket 500 may be easily formed in a form in which the sealing members 530 formed on both surfaces of the plate 510 are connected to each other through the communication holes 520 formed in the plate 510 . [0088] In addition, as illustrated in FIG. 17 , the gasket 500 may include only sealing members 530 formed of a rubber or silicone material without including the plate 510 , and sealing members 531 may be disposed at both sides in the length direction to allow air-tightness of the air passages and the fuel passages formed in the end cell 110 to be maintained. [0089] In addition, a thermal pad may be interposed between and closely adhere to the heating element 200 and the electricity collecting plate 300 . That is, although not illustrated, the thermal pad is interposed between and closely adheres to the heating element 200 and the electricity collecting plate 300 so as to improve a thermal conduction function, thereby making it possible to allow the heat generated from the heating element 200 to be well transferred to a reaction cell 1100 a of the fuel cell stack 1100 through the electricity collecting plate 300 . In this case, the thermal pad may also have a through-hole formed therein so that the electricity collecting terminal 310 may penetrate therethrough. [0090] In addition, a fuel cell 2000 including an end cell heater for a fuel cell according to the present invention may be configured to include a fuel cell stack 1100 formed by stacking unit cells and having air passages 1110 and fuel passages 1120 each formed at both sides thereof so as to penetrate through both surfaces thereof in a stack direction; and the end cell heaters 1000 coupled to the fuel cell stack 1100 and stacked on outer sides of unit cells stacked at the outermost portions among the unit cells, such that passages are connected to each other. [0091] That is, the fuel cell 2000 may be formed by stacking the end cell heaters 1000 on the fuel cell stack 1100 formed by stacking the reaction cells 1100 a , as illustrated in FIGS. 1.8 and 19 , and the end cell heaters 1000 may be stacked on and closely adhere to the reaction cells 1100 a stacked at the outermost portions of the fuel cell stack 1100 , in the same direction as the stack direction. In this case, the air passages 1100 and the fuel passages 1120 formed in the fuel cell stack 1100 may be connected to air passages 151 and fuel passages 152 of the end cell heaters 1000 so as to correspond to the air passages 151 and the fuel passages 152 of the end cell heaters 1000 . In this case, cooling passages are formed between the air passages 1110 and the fuel passages 1120 in the fuel cell stack 1100 , such that a heat exchange medium (a refrigerant) may pass through the unit cells to cool the unit cells. [0092] Therefore, the end cell heaters may be installed on the fuel cell stack only by stacking the end cell heaters on outer sides of the outermost reaction cells, like stacking the unit cells constituting the fuel cell stack, and coupling the end cell heaters to the outermost reaction cells so as to closely adhere to the outermost reaction cells, and a structure for connecting the passages to each other is simple, such that the end cell heaters may be very easily installed. In addition, it is possible to prevent water in the end cells of the fuel cell stack from being frozen using the end cell heaters as described above, such that initial start ability and initial driving performance of the fuel cell may be improved. [0093] In addition, the end cell heaters 1000 according to the present invention may be disposed on both sides of the outermost portions of the fuel cell stack 1100 . Here, the end cell heaters 1000 according to the second exemplary embodiment of the present invention in which both of the air channels and the fuel channels are formed may be disposed on both sides of the fuel cell stack 1100 . Alternatively, the end cell heater 1000 according to the first exemplary embodiment of the present invention in which only the air channels are formed may be disposed on one side of the fuel cell stack 1100 , and the end cell heater 1000 according to the second exemplary embodiment of the present invention in which both of the air channels and the fuel channels are formed may be disposed on the other side of the fuel cell stack 1100 . [0094] In addition, the fuel cell 2000 may be configured to further include covers 1400 stacked on outer sides of the end cell heaters 1000 , having air passages 1410 and fuel passages 1420 formed at both sides thereof, respectively, so as to be connected to the air passages 151 and the fuel passages 152 of the end cell heaters 1000 , respectively, formed to expose the electricity collecting terminals 131 of the end cell heaters 1000 to the outside thereof, and formed of an electrical insulating material; and fastening members 1500 having both ends coupled to the covers 1400 so that the fuel cell stack 1100 , the end cell heaters 1000 , and the covers 1400 closely adhere to one another in the stack direction. [0095] That is, the covers 1400 formed of the electrical insulating material may be disposed on outer sides, in a thickness direction, of two end cell heaters 1000 disposed to be stacked, respectively, on both surfaces of the fuel cell stack 1100 in the thickness direction, and the two covers 1400 , the two end cell heaters 1000 , and the fuel cell stack 1100 may be coupled and fixed to one another so as to closely adhere to one another in the stack direction using the fastening members 1500 . In this case, the covers 1400 may have through-holes formed therein so that the electricity collecting terminals 310 may be inserted thereinto and be exposed to the outside thereof. In addition, one of the two covers 1400 may have communication holes formed therein so as to be connected to the fuel passages and the air passages, and the other of the two covers 1400 may have communication holes formed therein so as to be connected to the cooling passages. In addition, the fastening members 1500 may be formed in a plate shape elongated in the thickness direction, and both ends of the fastening members 1500 may be bent in a width direction and be coupled and fixed to the covers 1400 by fastening means such as bolts. [0096] The end cell heater for a fuel cell according to the present invention may prevent water in the reaction cell of the fuel cell stack from being frozen to improve the initial start ability and the initial driving performance of the fuel cell. [0097] In addition, the air-tightness and the pressure resistance properties of the air passages and the fuel passages formed in the end cell may be secured by the vibration fusion and the laser fusion. [0098] The present invention is not limited to the abovementioned exemplary embodiments, but may be variously applied. In addition, the present invention may be variously modified by those skilled in the art to which the present invention pertains without departing from the gist of the present invention claimed in the claims.
Provided is an end cell heater for a fuel cell capable of preventing water existing in reaction cells of a fuel cell stack from being frozen to improve initial start ability and initial driving performance of the fuel cell at the time of cold-starting the fuel cell during winter by disposing heaters on end cells disposed at both ends of the fuel cell stack and capable of securing air-tightness and pressure resistance properties of air passages and fuel passages formed in the end cell.
63,650
CROSS REFERENCE TO RELATED APPLICATION [0001] This application claims the priority of Provisional Application Ser. No. 60/859,591 filed Nov. 17, 2006. TECHNICAL FIELD [0002] The present invention relates to compositions having balanced UVA and UVB protection properties and more particularly to UV protective cosmetic products incorporating titanium dioxide and transparent iron oxide. BACKGROUND OF THE INVENTION [0003] In 2007, there will be more than one million new cases of skin cancer reported of which it is estimated that 90 percent could have been prevented by better protection from the sun. During 2002, 44,582 cases of malignant melanoma were diagnosed in the United States alone. Most Americans do not adequately protect themselves from ultraviolet exposure. [0004] Moreover, individuals receive 50 to 80 percent of their lifetime ultraviolet exposure by the age of eighteen. Thus, children and young people need to be better educated about sun damage. New and cosmetically attractive products would be very helpful in order to realize badly needed changes in behavior. [0005] The situation is compounded by the fact that consumers cannot completely rely on sun protection factor (SPF) ratings, because the same are primarily tied to ultraviolet B light. At one time, it was believed that ultraviolet B light was the primary cause of skin damage. Certainly, reddening and sunburn are largely caused by ultraviolet B exposure. However, while it was not initially recognized, ultraviolet A exposure, in addition to tanning, likely causes long-term damage, including skin cancer and premature aging. Ultraviolet A light is in the range between 400 nm and going down to 320 nm. Ultraviolet B light begins about 320 nm and goes down to about 290 nm. The differences in wavelength are key to providing protection from the sun. [0006] One effective way of reducing exposure to sunlight is the use of titanium dioxide and zinc oxide based sunscreens. The earliest sunscreens involved pigment grade materials and thus appeared like smears of chalk on the skin. Starting in the 1980s, particle manufacturers began to develop very fine particulate sunscreen materials. Typically, today, sun tanning lotions incorporating, for example, 10-150 nm titanium dioxide or zinc oxide are used to achieve a measure of protection from the sun. [0007] References to particle size within this specification refer to the shortest dimension of a pigment particle. For example, if a pigment contains acicular particles which are 20 nm×100 nm, such particles are referred to as having a size of 20 nm. Moreover, references to particle size refer to the primary particle size of the powder ingredient. In various compositions, there may be some measure of conglomeration which would result in conglomeration sizes (i.e. secondary particle sizes) which are larger. Likewise, references to particle size are to the average size of the shortest dimension for an ingredient, as is the custom in the industry. [0008] EP06164522 to Boots relates to 15 nm and 35 nm to about 50 nm titanium dioxide particles which can protect the skin against UVA and UVB light. The sunscreen products that are claimed therein are to some extent transparent to visible light. Similarly, other formulations providing broad spectrum protection are focused on transparency. For example, the prior art attempts to achieve broad spectrum protection by incorporating low refractive index pigment zinc oxide in combination with titanium dioxide. [0009] Advantageously, as particle sizes become smaller, their chalky appearance becomes less and less noticeable, until they become substantially transparent, provided the particles are small enough and/or their concentration in the final product is not too high. Generally, as the particle size becomes much smaller than the wavelength of visible light, particles become invisible. Relatively high SPF products may be prepared using such particulate sunscreens. However, as the particles become substantially invisible, their ability to protect from ultraviolet A light is increasingly compromised. SUMMARY OF THE INVENTION [0010] In accordance with the invention, novel cosmetic products incorporating titanium dioxide and transparent iron oxide are provided. [0011] The invention contemplates sunscreen formulation involving the use of particles of different sizes. For example, particles in the 10 nm range may be very effective in reducing ultraviolet B light. Moreover, because they are very transparent to the eye, they may be incorporated in relatively large quantities into a sunscreen formulation. Thus, a high SPF sunscreen formulation may be achieved with minimal whitening of the skin. In addition, in accordance with the invention, larger particles, for example, 50 nm and 60 nm are also incorporated in the formulation with the object of longer wavelengths of light, for example, light in the ultraviolet A range. In accordance with the invention, it has been discovered that in such formulations, 60 nm particles are particularly effective in providing protection against ultraviolet A light. [0012] However the aesthetics of colorless, for example zinc oxide or titanium dioxide, larger particles if used alone, particularly 60 nm particles, leave something to be desired. They tend to impart a relatively chalky appearance to the skin, and this degree of whitening may not be acceptable to many consumers. For this reason, many products which boast high sun protection factors and high transparency may provide relatively poor protection against ultraviolet A light. [0013] Currently, protection against ultraviolet light is measured using the so-called “PA” (or “PFA”) rating, referring to protection against ultraviolet A light. Current thinking is that the PA rating be at least one third that of the SPF rating. However, in many higher SPF rated products, the PA rating may only be about three, as would be desirable in an SPF 9 product. It is believed that such sunscreen designs are largely implemented for reasons having to do with transparency, as it is believed that consumers will not buy a product which has a chalky appearance, thus reducing the likelihood that consumers will choose to protect themselves against the sun, [0014] In accordance with a preferred embodiment of the invention, chalkiness in the appearance of applied sunscreens is reduced. The same is achieved by using a variety of different materials for the component of a sunscreen formulation which protects against ultraviolet A light. More particularly, in accordance with the invention a blend of white sunscreen material, such as titanium dioxide, is blended with a quantity of colored sunscreen material, such as an iron oxide or iron hydroxide. Because the colored sunscreen material is small enough to be characterized as transparent, it imparts color to the whitish chalky appearance of the other, for example titanium, component. [0015] The result is to reduce the appearance of chalkiness by a tinting effect. At the same time, the amount of, for example, red iron oxide and/or yellow iron oxide, in a formulation is kept at a level which is below that which would provide unacceptable darkening or coloring of the skin. While, the iron oxides do contribute opaque as well as transparent color, the level of the iron oxides is maintained at a low enough value to achieve an acceptable aesthetic appearance. [0016] Generally, it has been discovered that the aesthetic appearance of cosmetic products, such as a sun protecting lotion, sun protecting moisturizer, and sun protecting foundation may be greatly improved while maintaining markedly higher levels of protection to ultraviolet A radiation, by using iron oxides, particularly transparent iron oxides, in the formulation of account of the relatively natural appearance of tinted white sunscreen materials and reflective colored sunscreen materials, provided that the right balance of materials is employed. [0017] The inventive cosmetic products, which may take the form of liquid, crème, stick, compact and other products, are effective products for protecting the skin from sunlight as they contain titanium dioxide and iron oxides of various particle sizes. The inventive products are unlike untinted beach wear sunscreen products, which are expected to be and to varying extents are transparent to visible light in order to avoid undesirable skin whitening. They are also unlike conventional cosmetic products are formulated to provide opacity and cover skin blotches, wrinkles and other imperfections, as well as impart a desirable color and finish to the skin. The inventive products achieve an attractive aesthetic and a large measure of protection by combining what might be regarded as unacceptable amounts of white opacity, colored opacity and colored transparency to provide substantially transparent tinted products having excellent and balanced UV protection. [0018] The cosmetic products contemplated by this invention are color cosmetic products and are typically transparent to modestly opaque products, although they may have lower coverage to make them suitable as make-up primers or cosmetic products for teens. Furthermore, the cosmetic products contemplated by this invention are sunscreen products that provide high amounts of protection against ultraviolet A (UVA) and ultraviolet B (UVB) light. [0019] [TO BE COMPLETED UPON COMPLETION OF CLAIMS] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0020] An essential component of the cosmetic products contemplated by this invention are that they protect the skin against high amounts of UVA light, which is believed responsible for long-term harm to the skin. The present invention also contemplates the design of cosmetic products with a PA (Protection Against UVA) value of 10.0 or greater measured in-vivo using the Japanese method PPD, (Persistent Pigment Darkening) or an equivalent in-vivo method. [0021] The present invention is also aimed at satisfying the requirements of dermatologists, many of whom are requiring sunscreen products that have high amounts of UVA protection. Currently, the American Academy of Dermatology recommends that a product with an SPF of at least 15 be applied daily. There is presently a strong preference by many dermatologist for sunscreen products with a fixed ratio of UVB to UVA protection (SPF to PA protection). This ratio may be described as the UV balance ratio. The cosmetic products contemplated by this invention allow the achievement of an SPF of at least 30 and a PA of 10 and higher for a UV balance ratio of 3.0 to 1.0 and lower. [0022] Titanium dioxide and iron oxides are available at various particle sizes. During the late 1980's titanium dioxide was typically supplied in three sizes 15 nanometers, 35 nanometers, and pigmentary grades larger than 200 nanometers. Presently, many different particle sizes are available ranging from 10 nm to 300 nm, and even several microns. The titanium dioxide and iron oxide particle sizes contemplated by this invention to attenuate ultraviolet light efficiently and provide UV balance range from about 35 nm or lower to about 60 nm, although other grades may be used outside this range to increase SPF or provide greater opacity. [0023] In accordance with the invention, transparent red iron oxide (Fe 2 O 3 ), transparent yellow iron oxide (Fe 2 O(OH)) and transparent black iron oxide (Fe 2 O 4 ) are used in combinations to achieve desired hues and levels of brightness guided by aesthetic considerations moderated by the objective of incorporating a maximum amount of particles with strong UVA attenuation. Particulates are selected keeping in mind UV attenuation. At the same time, the quantities of all particulates are balanced for a pleasant aesthetic effect as noted herein. [0024] An incidental benefit of formulating with iron oxides is UV attenuation, although they are not approved as active sunscreens like titanium dioxide and zinc oxide. Iron oxides provide attenuation against UVA and UVB light, because they scatter and absorb light. Pigmentary iron oxides can contribute more than 0.5 SPF and PA unit per weight percent. The contributions of transparent iron oxides to UV attenuation appear to be greater than for pigmentary grades in cosmetic products. In addition, the aesthetics of the inventive combinations are markedly superior to that achievable with titanium dioxide or zinc oxide based products. [0025] Therefore, the cosmetic products contemplated by this invention seek to provide a PA of at least 10 and a UV balance ratio (UVB:UVA) of 3 to 1 or lower. A likely achievable SPF contemplated by this invention is an SPF of 50 with a PA of 17 and this is believed to be sufficient to protect against sunlight for most commonly encountered circumstances. The cosmetic products contemplated herein attain these high levels of protection using at least 5% of a 35 nm titanium dioxide and roughly about 1.0% or more of a transparent iron oxide, dependent upon the aesthetic result desired. Other particle sizes of titanium dioxides and iron oxides may be added to increase SPF and opacity, similarly, zinc oxide may be added where formulations with less opacity are desired. Larger amounts of UVA attenuating transparent iron oxides will reduce transparency and darken the composition without compromising the acceptability of the aesthetics as appears below. [0026] The following products were formulated using different grades of titanium dioxide to explore the effects of pigment size and pigment content. More particularly, products represent products formulated using dispersions of titanium dioxide containing titanium dioxide particles of different primary particle sizes. A summary of the characteristics of these products is presented below in Table 1. This work is illustrative of potential relationships between titanium dioxide particle size, and the inclusion of iron oxides. [0000] TABLE 1 Exploratory and Inventive Formulations % Primary Particle Iron UV Formula TiO 2 Size SPF PA Oxides Balance SPF/% TiO 2 PA/% TiO 2 KLF- 5.00 60 nm 13.60 5.06 3.00 2.69 2.72 1.01 036 KLF- 5.00 35 nm 16.43 6.00 3.00 2.74 3.29 1.20 036A KSL- 10.00 35 nm 28.40 6.00 0.00 4.73 2.84 0.60 027 KSL- 10.00 50 nm 25.57 7.58 0.00 3.37 2.56 0.76 027A K2005- 19.50 10 nm, 50 nm, 32.00 15.00 3.50 2.13 1.64 0.77 78 60 nm KLF-036 and KLF-036A are aqueous-based products. KSL-027 and KSL-027A are oil-based products. In the above table, PA stands for protection against UVA light. UV balance is the ratio of SPF to PA. Measurements of PA were taken by Consumer Products Testing Co., an independent laboratory. Measurements of SPF were also taken by Consumer Products Testing Co. Example 1 [0027] The ingredients of a first product formulated in accordance with the invention and usable as a moisturizer or sunscreen are shown in Table 2. This product was designated K 2005-76 and was developed with the objective of providing a foundation with high UVA by combining a number of different particle size titanium dioxides and incorporating transparent iron oxides. K 2005-76 was made using a titanium dioxide dispersion sold under catalog number CM3EK25VM by Kobo Products, Inc. This dispersion catalog number CM3EK25VM contains 19.5% active titanium dioxide, by weight that is the weight of the titanium without the weight of surface treatment coatings or the like. K 2005-76 also incorporated a treated titanium dioxide sold under catalog number KQ-MS8 by Kobo Products, Inc. Catalog number KQ-MS8 contains 89.0%, active TiO 2 , by weight. [0028] An emollient light ester base, comprising, principally, isononyl isononanoate, silicones, water, waxes and pigments provides moisturization on account of the humectant characteristics of the esters and butylene glycol. A variety of bases to provide moisturization may be contemplated by the present invention. These bases may include any of the materials typically used as bases in prior art cosmetic formulations. The transparent iron oxides noted in Table 2 synergize with the titanium dioxide ingredients to provide an excellent SPF. At the same time, a high PA is also provided in a formulation which has excellent aesthetic appeal. The surface-treated colors, namely the isopropyl titanium triisostearate treated iron oxides in WE55Y, WE70R, and WE70B dispersions deliver smooth application and slip on skin with excellent wear. [0029] Velvesil 125 is used in the inventive formulation to give the product a velvety, cushion-like texture. Naturally, other additives may be used in place of Velvesil 125. The active ingredients of K 2005-76 are the various titanium dioxides which together compromise approximately 19.77% of the final product by weight together with the iron oxides. [0000] TABLE 2 Ingredients of K 2005-76 SEQ. INGREDIENT/ SUPPLIER Part % TRADE NAME INCI NAME NAME 1 19.00 Salacos 99 isononyl isononanoate Nisshin Oil M 2 2.00 Lucentite SAN-P quaternium-18 hectorite Kobo Products 1.00 Ethyl Alcohol SD39C ethyl alcohol 39C Warner-Graham 1.60 Tarox TRY-100 yellow iron oxide (20 nm × 100 nm Kobo Products size) 0.70 Tarox TRR-100 red iron oxide (20 nm × 100 nm Kobo Products size) 0.05 Black NF Iron oxides, 200 nm, cubic shape Kobo Products 4.50 Abil WE09 polyglyceryl-4 isostearate & cetyl Goldschmidt PEG/PGG-10/1 dimethicone (and) hexyl laurate 3 3.00 Abil WE09 polyglyceryl-4 isostearate & cetyl Goldschmidt PEG PGG-10/1 dimethicone (and) Goldschmidt hexyl laurate 0.50 Abil Wax 9801 cetyl dimethicone Goldschmidt 18.90 TiO 2 KQ-MS8 Titanium dioxide (and) aluminum Kobo Products dydroxide (and) methicone; size is 60 nm alumina coated. 15.12 CM3EK25VM cyclopentasiloxane (and) ethyl Kobo Products trisiloxane (and) titanium dioxide (and) methicone (and) PEG-10 dimethicone; size is 10 nm acicular 2.00 WE55Y yellow iron oxide (C.I. 77491) Kobo Products (and_) polyglyceryl-4 isostearate (and) cetyl PEG/PGG-10/1 dimethicone (and) hexyl laurate (and) isopropyl titanium triisostearate; size is 370-400 nm 0.40 WE70R red iron oxide (C.I. 77492) (and) Kobo Products polyglyceryl-4 isostearate (and) cetyl PEG/PGG-10/1 dimethicone (and) hexyl laurate (and) isopropyl titanium triisostearate; particle size is 70-100 nm 4 0.75 Crill 6 sorbitan isosterate Croda 5 12.50 Water water Symrise 1.00 Symdiol 68 1,2-hexandiol (and) 1,2-octanediol Axo Chemical 2.50 Butylene Glycol butylenes glycol Morton Salt 6 1.00 Sodium Chloride sodium chloride Strahl & Pitsch 1.65 Syncrowax HGL-C C18-36 griglycerides Croda 7 9.98 Velvesil 125 Cyclopentasiloxane (and) C30-45 GES/Kobo alkyl cetearyl dimethicone crosspolymer 8 0.75 Phenonip XB Phenoxyethanol & methylparaben Nipa Products propylparaben & ethylparaben Procedure For Manufacture of K 2005-76 [0030] A first phase is formulated by slowly adding quaternium-18 hectorite to isononyl isononanoate while stirring with a Cowles brand dissolver in a stainless steel beaker at high speed for 20 minutes. The ethyl alcohol 39C is added to the first phase and stirred for an additional 20 minutes. Ethyl alcohol 39C is USP grade of ethyl alcohol. The mixture is then set aside. In time, the same develops into a lucentite gel. [0031] In a separate stainless steel beaker, the 4.50% quantity of Polyglyceryl-4 isostearate and cetyl PEG/PGG-10/1 dimethicone (and) hexyl laurate (Abil WE09) are combined with the transparent iron oxides (product names Tarox TRY-100, Tarox TRR-100, Black NF) to produce phase 2. The mixture is dispersed for 90 minutes using a dispersator, such as a dispersator manufactured by Morehouse, Cowles or Premier Mill Co. [0032] The color particles, namely the transparent iron oxides, are then checked under a microscope. The mixture is looked at to determine if the pigments are fully dispersed. A satisfactory result is indicated by a uniform small appearance of the pigments and the absence of large agglomerates. This indicates that the iron oxide slurry is well dispersed. [0033] When a satisfactory iron oxide slurry has been achieved, the lucentite gel (or, alternatively, any organophilic gel such as versagel, bentones, lucentite or any suitable smectite clay or polymer gel) of phase 1 is combined with the transparent iron oxide slurry of phase 2. The same is stirred at high speed for 30 minutes with a dispersator (such as the Cowles dissolver) until the mixture is homogenous to form a pre-formed color gel phase. [0034] Next, the Polyglyceryl-4 isostearate and cetyl PEG/PGG-10/1 dimethicone and hexyl laurate cetyl dimethicone dispersion; the titanium dioxide, aluminum hydroxide and methicone dispersion; the dispersion of cyclopentasiloxane, ethyl trisiloxane, titanium dioxide, methicone and PEG-10 dimethicone; the dispersion of iron oxide (C.I. 77491) in polyglyceryl-4 isostearate, cetyl PEG/PGG-10/1 dimethicone, hexyl laurate and isopropyl titanium triisostearate; iron oxide (C.I. 77492), polyglyceryl-4 isostearate, cetyl PEG/PGG-10/1 dimethicone, hexyl laurate and isopropyl titanium triisostearate; and Iron Oxide (C.I. 77499) dispersed in polyglyceryl-4 isostearate (and) cetyl PEG/PGG-10/1 dimethicone, hexyl laurate and isopropyl titanium triisostearate of Part 3 are combined in a stainless steel beaker. In the above, C.I. refers to Color Index Number. [0035] Phase 3 is then stirred with a Cowles brand dissolver for 5 minutes. One then slowly adds the pre-formed color gel phase, made by combining phase 1 and phase 2 to phase 3 to form the base. The base is then stirred with a Cowles brand dissolver for 5 minutes. [0036] The sorbitan isosterate of Part 4 is added to the base and mixes for an additional 10 minutes at a high speed with a Cowles brand dissolver. Mixing is then continued for an additional 60 minutes while heating to a temperature in the range of about 60-65 degrees Celsius. [0037] One then adds the waxes, namely the microcrystalline wax and C18-36 triglycerides of Part 6 to the mixture of Part 4, which is maintained at about 65 degrees Celsius. This is stirred for five minutes. The aqueous ingredients of Part 5 are combined and stirred until clear. The mixture is then emulsified with the dispersator while heating to 82 degrees Celsius. During this part of the method, the beaker is kept covered. [0038] After reaching 82 degrees Celsius, the mixture is mixed for an additional five minutes. Such mixing may be done with the Cowles dispersator. The material is removed from the Cowles dissolver and then mixed with a Silverson at 8000 rpm using the largest screen supplied in a steam bath. [0039] Air cooling while mixing is continued for the purpose of homogenizing to form a uniform emulsion. When the mixture reaches 70 degrees Celsius, the mixture of cyclopentasiloxane and C30-45 alkyl cetearyl dimethicone crosspolymer (Velvesil) of Part 7 is added. When the mixture reaches 65 degrees Celsius, the mixture of Part 8, henoxyethanol and methylparaben, and of propylparaben and ethylparaben is added. One then continues homogenizing in the Silverson until the mixture cools down to 25-30 degrees Celsius. It is then introduced into appropriate containers. In vivo tests conducted for SPF using the FDA Monograph, Static Efficacy and for PFA using the JCIA Persistent Pigment Darkening (PPD) yielded the results shown in Tables 3 and 4. [0000] TABLE 3 Results for K 2005-76 Individual SPF Values 8% homosalate (HMS) K2005-76 UV Subject Skin Standard Balance Foundation Number Type Age Sex SPF LMU 1 II 60 F 4.4 32.1 2 III 48 F 6.6 30.0 3 III 55 M 5.0 32.1 Average SPF 5.33 31.40 I - very fair Caucasian II - fair Caucasian III - normal Caucasian IV - Hispanic and Asian skin tone [0000] TABLE 4 Results for K 2005-76 Individual PFA Values Test duration: 180 Minutes K2005-76 UV Subject Skin Balance Foundation Number Type Age Sex Standard Liquid Makeup (LMU) 1 III 43 F 3.75 12.51 2 IV 47 M 4.69 15.61 3 III 47 M 3.75 12.49 Average PFA (n = 3) 4.06 13.54 Example 2 [0040] The ingredients of a second product, K 2005-78, are shown in Table 5. This product was designated K 2005-78 and was developed with the objective of providing a foundation with high UVA by combining a number of different particle size titanium dioxides and incorporating transparent iron oxides. K 2005-78 was made using a titanium dioxide dispersion sold under catalog number CM3EK25VM by Kobo Products, Inc. This dispersion, catalog number CM3EK25VM, contains 19.5% active titanium dioxide, by weight that is the weight of the titanium without the weight of surface treatment coatings or the like. K 2005-78 also incorporated a treated titanium dioxide sold under catalog number KQ-MS8 by Kobo Products, Inc. Catalog number KQ-MS8 contains 89.0%, active titanium dioxide, by weight. K 2005-78 also incorporated a treated titanium dioxide sold under catalog number MT-600B-MS7 by Kobo Products, Inc. Catalog number MT-600B-MS7 contains 93.0%, active titanium dioxide, by weight. [0041] Using the above method steps described with respect to Example 1, the ingredients shown in Table 5 were combined to make a cosmetic foundation. [0000] TABLE 5 Ingredients of K2005-78 SEQ. INGREDIENT/ SUPPLIER Part % TRADE NAME INCI NAME NAME 1 19.00 Salacos 99 isononyl isononanoate Nisshin Oil Mills 2 2.00 Lucentite SAN-P quaternium-18 hectorite Kobo Products 1.00 Ethyl Alcohol ethyl alcohol 39C Warner- SD39C Graham 1.60 Tarox TRY-100 yellow iron oxide, 20 nm × 100 nm Kobo Products size 0.70 Tarox TRR-100 red iron oxide, 20 nm × 100 nm size Kobo Products 0.05 Black NF black iron oxides, 200 nm, cubic Kobo Products shape 4.50 Abil WE09 polyglyceryl-4 isostearate & cetyl Goldschmidt PEG/ PGG-10/1 dimethicone (and) hexyl laurate 3 3.00 Abil WE09 polyglyceryl-4 isostearate & cetyl Goldschmidt PEG/ PGG-10/1 dimethicone (and) hexyl laurate 0.50 Abil Wax 9801 cetyl dimethicone Goldschmidt 12.45 TiO 2 KQ-MS8 titanium dioxide (and) aluminum Kobo Products hydroxide (and) methicone 6.23 MT-600B-MS7 titanium dioxide (and) methicone, 50 nm Kobo Products TiO 2 ; coated with methicone by Kobo 14.94 CM3EK25VM cyclopentasiloxane (and) ethyl Kobo Products trisiloxane (and) titanium dioxide (and) methicone (and) PEG-10 dimethicone 2.00 WE55Y iron oxide (C.I. 77491) (and) Kobo Products polyglyceryl-4 isostearate (and) cetyl PEG/PGG- 10/1 dimethicone (and) hexyl laurate (and) isopropyl titanium triisostearate 0.40 WE70R iron oxide (C.I. 77492) (and) Kobo Products polyglyceryl-4 isostearate (and) cetyl PEG/PGG- 10/1 dimethicone (and) hexyl laurate (and) isopropyl titanium triisostearate 0.10 WE70B Black iron oxide (C.I. 77499) (and) Kobo Products polyglyceryl-4 isostearate (and) cetyl PEG/PGG- 10/1 dimethicone (and) hexyl laurate (and) isopropyl titanium triisostearate; particle size 160-280 nm 4 0.75 Crill 6 sorbitan isostearate Croda 5 12.50 Water Water 1.00 Symdiol 68 1,2-hexandiol (and) 1,2-octanediol Symrise 2.50 Butylene Glycol butylene glycol Axo Chemical 1.00 Sodium Chloride sodium chloride Morton Salt 6 1.00 Microcrystalline microcrystalline wax Strahl & Pitsch SP89 1.65 Syncrowax HGL-C Triglycerides Croda C18-36 7 10.38 Velvesil 125 cyclopentasiloxane (and) C30-45 GES/Kobo alkylCetearyl dimethicone crosspolymer 8 0.75 Phenonip XB phenoxyethanol and methylparaben Nipa Products propylparaben and ethylparaben 100.00 [0042] The mixing method of Example 1 for the various parts was employed to make this product, as well as the other products noted below. SPF and protection from the daylight was measured with the results shown in Tables 6 and 7. [0000] TABLE 6 Results for K 2005-78 Individual SPF Values K2005-78 UV Subject Skin 8% HMS Balance Foundation Number Type Age Sex Standard LMU I II 60 M 5.0 30.0 2 III 45 M 4.4 34.5 3 II 51 F 5.0 30.0 Average SPF 4.80 31.50 [0000] TABLE 7 Individual PFA Values 180 Minutes K2005-78 UV Subject Skin Balance Foundation Number Type Age Sex Standard LMU 4 III 48 F 4.69 15.62 5 IV 48 M 3.75 15.63 6 IV 36 M 4.68 15.62 Average PFA (n = 3) 4.37 15.62 Example 3 [0043] The ingredients of a third product are shown in Table 8. This product was designated K 2005-80 and was developed with the objective of providing a foundation with high UVA by combining a number of different particle size titanium dioxides and incorporating transparent iron oxides. K 2005-80 was made using a titanium dioxide dispersion sold under catalog number CM3EK25VM by Kobo Products, Inc. This dispersion catalog number CM3EK25VM contains 19.5% active titanium dioxide, by weight that is the weight of the titanium without the weight of surface treatment coatings or the like. K 2005-80 also incorporated a treated titanium dioxide sold under catalog number KQ-MS8 by Kobo Products, Inc. Catalog number KQ-MS8 contains 89.0%, active titanium dioxide, by weight. K 2005-80 also incorporated a treated titanium dioxide sold under catalog number MT-600B-MS7 by Kobo Products, Inc. Catalog number MT-600B-MS7 contains 93.0%, active titanium dioxide, by weight. K 2005-80 also incorporated a treated titanium dioxide sold under catalog number MT-500H-11S5 by Kobo Products, Inc. Catalog number MT-500H-11S5 contains 90.0%, active titanium, by weight. [0044] Using the above method steps described with respect to Example 1, the ingredients shown in Table 8 were combined to make a cosmetic foundation. [0000] TABLE 8 Ingredients of K2005-80 SEQ. NAME - INGREDIENT/ Part % TRADE NAME INCI NAME SUPPLIER 1 19.00 Salacos 99 isononyl isononanoate Nisshin Oil Mills 2 2.00 Lucentite SAN-P quaternium-18 hectorite Kobo Products 1.00 Ethyl Alcohol SD39C ethyl alcohol 39C Warner- Graham 1.60 Tarox Try-100 yellow iron oxide, 20 nm × 100 nm Kobo Products size 0.70 Tarox TRR-100 red iron oxide, 20 nm × 100 nm size Kobo Products 0.05 Black NF black iron oxides, 200 nm, cubic Kobo Products shape 4.50 Abil WE09 polyglyceryl-4 isostearate & cetyl Goldschmidt PEG/PGG-10/1 dimethicone (and) hexyl laurate 3 3.00 Abil WE09 polyglyceryl-4 isostearate & cetyl Goldschmidt PEG/PGG-10/1 dimethicone (and) hexyl laurate 0.50 Abil Wax 9801 cetyl dimethicone Goldschmidt 6.20 TiO 2 KQ-MS8 titanium dioxide (and) aluminum Kobo Products hydroxide (and) methicone 6.20 MT-600B-MS7 titanium dioxide (and) methicone, Kobo Products 50 nm TiO 2 , coated with methicone by Kobo 6.20 MT-500H-11S5 titanium dioxide (and) alumina (and) Kobo Products triethoxycaprylylsilane; 35 nm TiO 2 , coated with alumina by supplier and coated with methicone by Kobo 14.88 CM3EK25VM cyclopentasiloxane (and) ethyl Kobo Products trisiloxane (and) titanium dioxide (and) methicone (and) PEG-10 dimethicone 2.00 WE55Y iron oxide (C.I. 77491) (and) Kobo Products polyglyceryl-4 isostearate (and) cetyl PEG/PGG-10/1 dimethicone (and) hexyl laurate (and) isopropyl titanium triisostearate 0.40 WE70R iron oxide (C.I. 77492) (and) Kobo Products polyglyceryl-4 isostearate (and) cetyl PEG/PGG-10/1 dimethicone (and) hexyl laurate (and) isopropyl titanium triisostearate 0.10 WE70B iron oxide (C.I. 77499) (and) Kobo Products polyglyceryl-4 isostearate (and) cetyl PEG/PGG-10/1 dimethicone (and) hexyl laurate (and) isopropyl titanium triisostearate 4 0.75 Crill 6 sorbitan isostearate Croda 5 12.50 Water Water 1.00 Symdiol 68 1,2-hexandiol (and) 1,2-octanediol Symrise 2.50 Butylene Glycol butylene glycol Axo Chemical 1.00 Sodium Chloride sodium chloride Morton Salt 6 1.00 Microcrystalline microcrystalline wax Strahl & Pitsch SP89 1.65 Syncrowax HGL-C C18-36 triglycerides Croda 7 10.52 Velvesil 125 cyclopentasiloxane (and) C30-45 GES/Kobo alkyl cetearyl dimethicone crosspolymer 8 0.75 Phenonip XB phenoxyethanol & methylparaben Nipa Products propylparaben & pthylparaben 100.00 [0045] SPF and protection from the daylight was measured with the results shown in Tables 9 and 10. [0000] TABLE 9 Results for K 2005-80 Individual SPF Values K2005-80 Subject Skin 8% HMS Balance Foundation Number Type Age Sex Standard LMU 1 II 44 M 5.0 34.5 2 III 43 M 5.0 32.1 3 II 43 F 4.4 34.5 Average SPF 4.80 33.71 [0000] TABLE 10 Individual PFA Values 180 Minutes K2005-80 UV Subject Skin Balance Foundation Number Type Age Sex Standard LMU 1 III 21 M 3.00 12.50 2 IV 30 F 4.69 15.62 3 III 36 F 3.75 12.49 Average PFA 3.81 13.54 Example 4 [0046] The ingredients of a forth product are shown in Table 11. This product was designated K 2005-82 and was developed with the objective of providing a foundation with high UVA protection by combining a number of different particle size titanium dioxides and incorporating transparent iron oxides. K 2005-82 was made using a titanium dioxide dispersion sold under catalog number CM3EK25VM by Kobo Products, Inc. This dispersion catalog number CM3EK25VM contains 19.5% active titanium dioxide, by weight that is the weight of the titanium without the weight of surface treatment coatings or the like. K 2005-82 also incorporated a treated titanium dioxide sold under catalog number KQ-MS8 by Kobo Products, Inc. Catalog number KQ-MS8 contains 89.0%, active TiO 2 , by weight. K 2005-82 also incorporated a treated titanium dioxide sold under catalog number MT-600B-MS7 by Kobo Products, Inc. Catalog number MT-600B-MS7 contains 93.0%, active TiO 2 , by weight. K 2005-82 also incorporated a treated titanium dioxide sold under catalog number MT-500B-11S5 by Kobo Products, Inc. Catalog number MT-500B-11S5 contains 95.0%, active TiO 2 , by weight. [0047] Using the above method steps described with respect to Example 1, the ingredients shown in Table 11 were combined to make a cosmetic foundation. [0000] TABLE 11 Ingredients of K2005-82 SEQ. NAME INGREDIENT/ Part % TRADE NAME INCI NAME SUPPLIER 1 19.00 Salacos 99 isononyl isononanoate Nisshin Oil Mills 2 2.00 Lucentite SAN-P Quaternium-18 hectorite Kobo Products 1.00 Ethyl Alcohol SD39C Ethyl alcohol 39C Warner- Graham 1.60 Tarox TRY-100 yellow iron oxide, 20 nm × 100 nm Kobo Products size 0.70 Tarox TRR-100 red iron oxide, 20 nm × 100 nm size Kobo Products 0.05 Black NF black iron oxide, 200 nm, cubic Kobo Products shape 4.50 Abil WE09 polyglyceryl-4 isostearate & cetyl Goldschmidt PEG/PGG-10/1 dimethicone (and) hexyl laurate 3 3.00 Abil WE09 polyglyceryl-4 isostearate & cetyl Goldschmidt PEG/PGG-10/1 dimethicone (and) hexyl laurate 0.50 Abil Wax 9801 cetyl dimethicone Goldschmidt 6.26 TiO 2 KQ-MS8 titanium dioxide (and) aluminum Kobo Products hydroxide (and) methicone 6.26 MT-600B-MS7 titanium dioxide (and) methicone; Kobo Products 50 nm TiO 2 , coated with methicone by Kobo 6.26 MT-500B-11S5 titanium dioxide (and) Kobo Products triethoxycaprylylsilane; 35 nm TiO 2 ; coated with alumina by supplier and coated with methicone by Kobo; and 35 nm TiO 2 coated with silane by Kobo 12.53 CM3EK25VM cyclopentasiloxane (and) ethyl Kobo Products trisiloxane (and) titanium dioxide (and) methicone (and) PEG-10 dimethicone 2.00 WE55Y iron oxide (C.I. 77491) (and) Kobo Products polyglyceryl-4 isostearate (and) cetyl PEG/PGG-10/1 dimethicone (and) hexyl laurate (and) isopropyl titanium triisostearate 0.40 WE70R iron oxide (C.I. 77492) (and) Kobo Products polyglyceryl-4 isostearate (and) cetyl PEG/PGG-10/1 dimethicone (and) hexyl laurate (and) isopropyl titanium triisostearate 0.10 WE70B iron oxide (C.I. 77499) (and) Kobo Products polyglyceryl-4 isostearate (and) cetyl PEG/PGG-10/1 dimethicone (and) hexyl laurate (and) Isopropyl titanium triisostearate 4 0.75 Crill 6 sorbitan isostearate Croda 5 12.50 Water Water 1.00 Symdiol 68 1,2-hexandiol (and) 1,2-octanediol Symrise 2.50 Butylene Glycol butylene glycol Axo Chemical 1.00 Sodium Chloride sodium chloride Morton Salt 6 1.00 Microcrystalline microcrystalline wax Strahl & Pitsch SP89 1.65 Syncrowax HGL-C C18-36 triglycerides Croda 7 12.69 Velvesil 125 cyclopentasiloxane (and) C30-45 GES/Kobo alkyl cetearyl dimethicone crosspolymer 8 0.75 Phenonip XB phenoxyethanol and methylparaben Nipa Products propylparaben and ethylparaben 100.00 [0048] SPF and protection from the day light was measured with the results shown in Tables 12 and 13. [0000] TABLE 12 Results for K 2005-82 Individual SPF Values K2005-82 UV Subject Skin 8% HMS Balance Foundation Number Type Age Sex Standard LMU 1 II 43 M 4.4 34.5 2 II 61 M 4.4 30.0 3 III 57 F 4.4 32.1 Average SPF 4.40 32.20 [0000] TABLE 13 Individual PFA Values 180 Minutes K2005-82 UV Subject Skin Balance Foundation Number Type Age Sex Standard LMU 1 * * * * * 2 III 27 F 3.75 12.50 3 III 41 F 3.75 15.63 4 III 31 F 3.75 12.51 Average PFA (n = 3) 3.75 13.55 * Data not included in calculations - Panelist noncompliant - Data rejected. [0049] The constituents of the ingredients in the examples are detailed below in Table 14. [0000] TABLE 14 Compositional Breakdown for Inventive Composition (Weight Percent) INGREDIENT MT- MT- MT- TiO2 CM3EK- BLACK 600B- 500H- 500B- KQ- 25VM NF MS7 11S5 11S5 MS8 WE55Y WE70R WE70B Constituents of — — — — — — — — Ingredients Cyclopenta- 35-39 — — — — — — — — siloxane Ethyl Trisiloxane 24-28 — — — — — — — — Titanium 17-22 — 91-95 88.4-92   94-96 85-90 — — — Dioxide PEG-10 10-14 — — — — — — — — Dimethicone Alumina 2-5 — —   3-6.6 — — — — — Methicone 0.5-2.5 — 6-8 — — 6-9 — — — Iron Oxides — — — — — —   52-54.5 67-69 — (C.I. 77491) Iron Oxides — — — — — — — — 67-69 (C.I. 77492) Iron Oxides — 95-100 — — — — — — — (C.I. 77499) Triethoxycaprylylsilane — — — 4-6 4-6 — — — — Aluminum — — — — — 1-4 — — — Hydroxide Hexyl — — — — — — 13-17  8-12  8-12 Laurate Cetyl — — — — — — 13-17  8-12  8-12 PEG/PPG-10/1 Dimethicone Polyglyceryl-4 — — — — — — 13-17  8-12  8-12 Isostearate Isopropyl — — — — — — .90-1.3 1.2-1.6 1.2-1.6 Titanium Triisostearate [0050] In accordance with the present invention, a dispersion for achieving cosmetic products of the type of the present invention may also be provided. Such dispersion may be used in place of conventional dispersions in otherwise conventional product recipes. It is contemplated in accordance with the invention that conventional dispersion manufacturing techniques may be used to incorporate particulates into a dispersion. A typical formulation for such a dispersion is given in Table 15. The particulates used may be hydrophobic or hydrophilic and may be incorporated in water or oil vehicles as is known in the prior art for such materials. [0051] For example, such a formulation may be achieved by putting solvents (in an amount of approximately equal in weight to the weight of the particulates) such as cyclopentasiloxane and ethyl trisoloxane in a mixing tank. Next, a surfactant is dissolved in the solvents. Lastly, the particulates as detailed in Table 15 are headed. The particulates are then mixed with the surfactant and solvent at approximately 500 rpm with the disburse or blade. The mixture is then transferred to a mixing tank and subsequently milled using a bead mill to the desired particle size. [0052] If desired, a dispersant such as polyhydroxystearic acid may be used without the need for using hydrophobized particulates, despite the use of a nonaqueous vehicle. Alternatively, hydrophobized particulates may be used in an oil, or other nonaqueous vehicle. The incorporation of the particulates may also be made into an aqueous base, or a silicone based carrier vehicle. [0000] TABLE 15 Particulate Ingredients for Dispersion INGREDIENT/ SUPPLIER Parts TRADE NAME INCI NAME NAME 16 Tarox TRY-100 yellow iron oxide, 20 nm × Kobo 100 nm size Products 7 Tarox TRR-100 red iron oxide, 20 nm × 100 nm Kobo size Products .5 Black NF black iron oxides, 200 nm, cubic Kobo shape Products 110 60 nm titanium dioxide 55 50 nm titanium dioxide 30 10 nm titanium 10 370-400 nm yelow iron oxide (C.I. 77491) 2.8 70-100 iron oxide (C.I. 77492) .7 black iron oxide (C.I. 77499); particle size 160-280 nm
A cosmetic composition comprises a transparent substantially colorless pigment. The substantially colorless pigment comprises a first group of particles sufficiently small to be substantially transparent to visible light and substantially opaque to ultraviolet B light. The substantially colorless pigment further comprises a second group of particles sufficiently small to be minimally reflective to visible light and substantially opaque to ultraviolet A light. A second group of particles results in minimal visible reflection by the cosmetic composition. A substantially transparent coloring pigment substantially transmits visible light and reflects a substantial portion of incident ultraviolet A light to impart color to tint visible light reflected by the cosmetic composition when they cosmetic composition is disposed over the skin. These materials are maintained in a carrier vehicle.
96,251
RELATED APPLICATIONS This application is a continuation application of copending U.S. patent application Ser. No. 15/004,783 filed on Jan. 22, 2016, which is a continuation application of U.S. patent application Ser. No. 14/821,599 filed on Aug. 7, 2015 and issued as U.S. Pat. No. 9,244,189 on Jan. 26, 2016, which is a continuation application of U.S. patent application Ser. No. 14/163,374 filed on Jan. 24, 2014 and issued as U.S. Pat. No. 9,133,703 on Sep. 15, 2015, which is a divisional application of U.S. patent application Ser. No. 12/816,250 filed on Jun. 15, 2010 and issued as U.S. Pat. No. 8,659,298 on Feb. 25, 2014, which is a continuation application of U.S. patent application Ser. No. 11/835,154 filed on Aug. 7, 2007 and issued as U.S. Pat. No. 7,775,301 on Aug. 17, 2010, the disclosures of which are incorporated herein by reference. BACKGROUND OF THE INVENTION The present application is generally related to steering tools for horizontal directional drilling and, more particularly, to a system and method using supplemental magnetic information in a steering tool type arrangement. A boring tool is well-known as a steerable drill head that can carry sensors, transmitters and associated electronics. The boring tool is usually controlled through a drill string that is extendable from a drill rig. The drill string is most often formed of drill pipe sections, which may be referred to hereinafter as drill rods, that are selectively attachable with one another for purposes of advancing and retracting the drill string. Steering is often accomplished using a beveled face on the drill head. Advancing the drill string while rotating should result in the drill head traveling straight forward, whereas advancing the drill string with the bevel oriented at some fixed angle will result in deflecting the drill head in some direction. One approach that has been taken by the prior art for purposes of monitoring the progress of a boring tool in the field of horizontal directional drilling, resides in what is commonly referred to as a “steering tool”. This term has come to describe an overall system which essentially predicts the position of the boring tool, as it is advanced through the ground using a drill string, such that the boring tool can be steered toward a desired target or along a planned drill path within the ground. Steering tool systems are considered as being distinct from other types of locating systems used in horizontal directional drilling at least for the reason that the position of the boring tool is monitored in a step-wise fashion as it progresses through the ground. For this reason, positional error can accumulate with increasing progress through the ground up to unacceptable levels. Generally, in a steering tool system, pitch and yaw angles of the drill-head are measured in coordination with extension of the drill string. From this, the drill-head position coordinates are obtained by numerical integration. Nominal or measured drill rod lengths can serve as a step size during integration. While this method appears to be sound and might enable an experienced driller to use the steering tool successfully, there are a number of concerns with respect to its operation, as will be discussed immediately hereinafter. With respect to the aforementioned positional error, it is noted that this error can be attributed, at least in part, to pitch and yaw measurement errors that accumulate during integration. This can often result in large position errors after only a few hundred feet of drilling. Another concern arises with respect to underground disturbances of the earth's magnetic field, which can cause significant yaw measurement bias errors, potentially leading to very inaccurate position estimates. Still another concern arises to the extent that steering effectiveness of a typical HDD drill bit depends on many factors including drill bit design, mud flow rate and soil conditions. For example, attempting to steer in wet and sandy soil with the tool in the 12 o'clock roll position might become so ineffective that measured pitch does not provide correct vertical position changes. That is, the orientation of drill head, under such drilling conditions, does not necessarily reflect the direction of its travel. One approach in dealing with the potential inaccuracy of the steering tool system is to confirm the position of the drill head independently. For example, the drill head can be fitted with a dipole transmitter. A walk over locator can then be used to receive the dipole field and independently locate the drill head. This approach is not always practical, for example, when drilling under a river, lake or freeway. In these situations, the operator might notice position errors too late during drilling and consequently might not have an opportunity to implement a drill-path correction. The foregoing examples of the related art and limitations related therewith are intended to be illustrative and not exclusive. Other limitations of the related art will become apparent to those of skill in the art upon a reading of the specification and a study of the drawings. SUMMARY The following embodiments and aspects thereof are described and illustrated in conjunction with systems, tools and methods which are meant to be exemplary and illustrative, not limiting in scope. In various embodiments, one or more of the above-described problems have been reduced or eliminated, while other embodiments are directed to other improvements. In general, a system and associated method are described in which a steering tool is movable by a drill string and steerable in a way that is intended to form an underground bore along an intended path, beginning from a starting position. In one aspect, a sensing arrangement, forming one part of the steering tool, detects a pitch orientation and a yaw orientation of the steering tool at a series of spaced apart positions of the steering tool along the underground bore, each of which spaced apart positions is characterized by a measured extension of the drill string. At least one marker is positioned proximate to the intended path, for transmitting a rotating dipole field such that at least a portion of the intended path is exposed to the rotating dipole field. A receiver, forming another part of the steering tool, receives the rotating dipole field with the steering tool at a current one of the spaced apart positions to produce magnetic information. A processor is configured for using the detected pitch orientation, the detected yaw orientation and the measured extension of the drill string in conjunction with the magnetic information, corresponding to the current one of the positions of the steering tool, to determine a current location of the steering tool, relative to the starting position, with a given accuracy such that using only the detected pitch orientation, the detected yaw orientation and the measured extension of the drill string to determine the current position, without the magnetic information, would result in a reduced accuracy in the determination of the current location, as compared to the given accuracy. In another aspect, a sensing arrangement is provided, forming one part of the steering tool, for detecting a pitch orientation and a yaw orientation of the steering tool. The steering tool is moved sequentially through a series of spaced apart positions along the underground bore. Each of the spaced apart positions is characterized by a measured extension of the drill string. At least one marker is arranged, proximate to the intended path, for transmitting a rotating dipole field such that at least a portion of the intended path is exposed to the rotating magnetic dipole. The dipole field is received using a receiver that forms another part of the steering tool, with the steering tool at a current one of the spaced apart positions on the portion of the intended path, to produce magnetic information. A processor is configured for using the detected pitch orientation, the detected yaw orientation and the measured extension of the drill string in conjunction with the magnetic information, corresponding to the current one of the positions of the steering tool, to determine a current location of the steering tool relative to the starting position with a given accuracy such that using only the detected pitch orientation, the detected yaw orientation and the measured extension of the drill string to determine the current location, without the magnetic information, results in a reduced accuracy in the determination of the current location, as compared to the given accuracy. In still another aspect, a sensing arrangement is provided, forming one part of the steering tool, for detecting a pitch orientation and a yaw orientation of the steering tool. The steering tool is moved sequentially through a series of spaced apart positions to form the underground bore. Each of the spaced apart positions is characterized by a measured extension of the drill string, a detected pitch orientation and a detected yaw orientation. At least one portion of the intended path is identified along which an enhanced accuracy of a determination of the current location of the steering tool is desired. One or more markers is arranged proximate to the portion of the intended path, each of which transmits a rotating dipole field such that at least the portion of the intended path is exposed to one or more rotating dipole fields. A receiver is provided, as part of the steering tool, for generating magnetic information responsive to the rotating dipole fields. A processor is configured for operating in a first mode using the detected pitch orientation, the detected yaw orientation and the measured extension of the drill string to determine a current location of the steering tool corresponding to any given one of the spaced apart positions with at least a given accuracy and for defaulting to a second mode using the detected pitch orientation, the detected yaw orientation, the measured extension of the drill string and the magnetic information, when the magnetic information is received, to determine the current location of the steering tool with an enhanced accuracy that is greater than the given accuracy. In yet another aspect, a method for establishing a customized accuracy in determination of a position of the steering tool with respect to the intended path is described. A sensing arrangement, forming one part of the steering tool, detects a pitch orientation and a yaw orientation of the steering tool. The steering tool is moved sequentially through a series of spaced apart positions to form the underground bore. Each of the spaced apart positions is characterized by a measured extension of the drill string, a detected pitch orientation and a detected yaw orientation. One or more portions of the intended path are identified along which an enhanced accuracy of the determination of the current location of the steering tool is desired. One or more markers are arranged proximate to each one of the portions of the intended path where each of the markers transmits a rotating dipole field such that each one of the identified portions of the intended path is exposed to one or more rotating dipole fields. As a result of the transmission range of the rotating dipole field, more than just those portions of the intended path may be exposed to the rotating dipole field(s). A receiver is provided, as part of the steering tool, for generating magnetic information responsive to the rotating dipole fields. A processor is configured for operating in a first mode using the detected pitch orientation, the detected yaw orientation and the measured extension of the drill string to determine a current location of the steering tool corresponding to any given one of the spaced apart positions with at least a given accuracy and for operating in a second mode using the detected pitch orientation, the detected yaw orientation, the measured extension of the drill string and the magnetic information to determine the current location of the steering tool with an enhanced accuracy that is greater than the given accuracy, at least for the one or more portions of the intended path, to customize an overall position determination accuracy along the intended path. In addition to the exemplary aspects and embodiments described above, further aspects and embodiments will become apparent by reference to the drawings and by study of the following descriptions. BRIEF DESCRIPTION OF THE DRAWINGS Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be illustrative rather than limiting. FIG. 1 is a diagrammatic view, in elevation, of a system according to the present disclosure operating in a region. FIG. 2 is a diagrammatic plan view of the system of FIG. 1 in the region. FIG. 3 a is a block diagram which illustrates one embodiment of a steering tool that is useful in the system of FIGS. 1 and 2 . FIG. 3 b is a diagrammatic view, in perspective, of a marker that is useful in the system of FIGS. 1 and 2 . FIG. 3 c shows a coordinate system in which pitch and yaw are illustrated. FIGS. 4 and 5 illustrate one embodiment of a setup technique that can be used in conjunction with the system of FIGS. 1 and 2 . FIG. 6 is a diagrammatic view, in elevation, of a drill path along which the steering tool is disposed, shown here to illustrate one embodiment of a technique for providing an initial solution estimate for the position of the steering tool. FIG. 7 a is a diagrammatic, further enlarged view, of a portion of FIG. 6 , shown here to illustrate further details of the initial solution estimate technique. FIG. 7 b is a flow diagram which illustrates one possible embodiment of a technique for determining the position of the steering tool using a Kalman filter. FIG. 8 is a plot of random distance error versus distance. FIGS. 9 a and 9 b are plots of pitch angle and yaw angle, respectively, versus drill string length for use in a detailed simulation. FIG. 10 a is a plot in a simulation of estimated Y (lateral) steering tool position with respect to X position, employing a basic steering tool without the use of markers. FIG. 10 b is a plot in the simulation of estimated Z (elevational) steering tool position with respect to X position, employing a basic steering tool without the use of markers. FIG. 10 c is a plot, for the simulation of FIGS. 10 a and 10 b , of steering tool coordinate position error versus X position, which illustrates positional errors for the X, Y and Z axes without the use of markers. FIG. 11 a is a plot in a simulation of estimated Y (lateral) steering tool position with respect to X position, employing a steering tool in conjunction with one marker. FIG. 11 b is a plot in the simulation of estimated Z (elevational) steering tool position with respect to X position, employing the steering tool in conjunction with one marker. FIG. 11 c is a plot, for the simulation of FIGS. 11 a and 11 b , of steering tool coordinate position error versus X position, which illustrates positional errors for the X, Y and Z axes with the use of one marker. FIG. 12 a is a plot in a simulation of estimated Y (lateral) steering tool position with respect to X position, employing a steering tool in conjunction with two markers. FIG. 12 b is a plot in the simulation of estimated Z (elevational) steering tool position with respect to X position, employing the steering tool in conjunction with two markers. FIG. 12 c is a plot, for the simulation of FIGS. 12 a and 12 b , of steering tool coordinate position error versus X position, which illustrates positional errors for the X, Y and Z axes with the use of two markers. FIG. 13 a is a plot in a simulation of estimated Y (lateral) steering tool position with respect to X position, employing a steering tool in conjunction with three markers. FIG. 13 b is a plot in the simulation of estimated Z (elevational) steering tool position with respect to X position, employing the steering tool in conjunction with three markers. FIG. 13 c is a plot, for the simulation of FIGS. 13 a and 13 b , of steering tool coordinate position error versus X position, which illustrates positional errors for the X, Y and Z axes with the use of three markers. FIGS. 14 a - c are plots of position error estimates, available through the Kalman filter analysis, versus the X axis and directly compared with position error plots show in FIG. 13 c for the drill path of FIGS. 13 a and 13 b FIG. 15 is a diagrammatic plan view of a drilling region for a concluding portion of an intended drill path, shown here to illustrate various aspects of arranging and moving markers along the drill path. FIG. 16 is a diagrammatic plan view of the drilling region and drill path of FIG. 16 , shown her to illustrate further aspects with respect to arranging and moving markers along the drill path. DETAILED DESCRIPTION The following description is presented to enable one of ordinary skill in the art to make and use the invention and is provided in the context of a patent application and its requirements. Various modifications to the described embodiments will be readily apparent to those skilled in the art and the generic principles taught herein may be applied to other embodiments. Thus, the present invention is not intended to be limited to the embodiment shown, but is to be accorded the widest scope consistent with the principles and features described herein, including modifications and equivalents, as defined within the scope of the appended claims. It is noted that the drawings are not to scale and are diagrammatic in nature in a way that is thought to best illustrate features of interest. Descriptive terminology such as, for example, upper/lower, right/left, front/rear top/bottom, underside and the like has been adopted for purposes of enhancing the reader's understanding, with respect to the various views provided in the figures, and is in no way intended as being limiting. Turning now to the figures, wherein like components are designated by like reference numbers whenever practical, attention is immediately directed to FIGS. 1 and 2 , which illustrate an advanced steering tool system that is generally indicated by the reference number 10 and produced according to the present disclosure. FIG. 1 is a diagrammatic elevation view of the system, whereas FIG. 2 is a diagrammatic plan view of the system. System 10 includes a drill rig 18 having a carriage 20 received for movement along the length of an opposing pair of rails 22 which are, in turn, mounted on a frame 24 . A conventional arrangement (not shown) is provided for moving carriage 20 along rails 22 . A steering tool 26 includes an asymmetric face 28 and is attached to a drill string 30 which is composed of a plurality of drill pipe sections 32 . An intended path 40 of the steering tool includes positions that are designated as k and k+1. The steering tool is advanced from position k to k+1 by either a full or a fraction rod length. If very short drill pipe sections are used, the distance between positions k and k+1 could be greater than a rod length. By way of example, drill pipe sections have a rod length of two feet would be considered as very short. The steering tool is shown as having already passed through points 1 and 2 , where point 1 is the location at which the steering tool enters the ground at 42 , serving as the origin of the master coordinate system. While a Cartesian coordinate system is used as the basis for the master coordinate systems employed by the various embodiments disclosed herein, it is to be understood that this terminology is used in the specification and claims for descriptive purposes and that any suitable coordinate system may be used. An x axis 44 extends from entry point 42 to a target location T that is on the intended path of the steering tool, as seen in FIG. 1 and illustrated as a rectangle, while a y axis 46 extends to the left when facing in the forward direction along the x axis, as seen in FIG. 2 . A z axis 48 extends upward, as seen in FIG. 1 . Further descriptions will be provided at an appropriate point below with respect to establishing this coordinate system. As the drilling operation proceeds, respective drill pipe sections, which may be referred to interchangeably as drill rods, are added to the drill string at the drill rig. For example, a most recently added drill rod 32 a is shown on the drill rig in FIG. 2 . An upper end 50 of drill rod 32 a is held by a locking arrangement (not shown) which forms part of carriage 20 such that movement of the carriage in the direction indicated by an arrow 52 causes section 32 a to move therewith, which pushes the drill string into the ground thereby advancing the boring operation. A clamping arrangement 54 is used to facilitate the addition of drill pipe sections to the drill string. The drilling operation is controlled by an operator (not shown) at a control console 60 which itself can include a telemetry section 62 connected with a telemetry antenna 64 , a display screen 66 , an input device such as a keyboard 68 , a processor 70 , and a plurality of control levers 72 which, for example, control movement of carriage 20 . Turning now to FIG. 3 a , an electromechanical block diagram is shown, illustrating one embodiment of steering tool 26 that is configured in accordance with the present disclosure. Steering tool 26 includes a slotted non-magnetic drill tool housing 100 . A triaxial magnetic field sensing arrangement 102 is positioned in housing 100 . For this purpose, a triaxial magnetometer or coil arrangement may be used depending on considerations such as, for example, space and accuracy. A triaxial accelerometer 104 is also located in the housing. Outputs from magnetic field sensing arrangement 102 and accelerometer 104 are provided to a processing section 106 having a microprocessor at least for use in determining a pitch orientation and a yaw heading of the steering tool. A dipole antenna and associated transmitter 108 are optionally located in the steering tool which can be used, responsive to the processing section, for telemetry purposes, for transferring encoded data such as roll, pitch, magnetometer readings and accelerometer readings to above ground locations such as, for example, telemetry receiver 62 ( FIG. 1 ) of console 60 via a dipole electromagnetic field 110 and for locating determinations such as, for example, determining a distance to the steering tool. For such locating determinations, dipole electromagnetic field 110 can be used in conjunction with a walkover locator, although this is not a requirement and is not practical in some cases, as discussed above. Generally, the dipole axis of the dipole antenna is oriented coaxially with an elongation axis of the steering tool in a manner which is well-known in the art. Of course, all of these functions are readily supported by processing section 106 , which reads appropriate inputs from the magnetometer and accelerometer, performs any necessary processing and then performs the actual encoding of information that is to be transmitted. In another embodiment, processing section 106 is configured for communication with processor 70 ( FIG. 1 ) of console 60 using a wire-in-pipe approach wherein a conductor is provided in drill string 30 for transferring information above ground as described, for example, in commonly owned U.S. Pat. No. 6,223,826 entitled AUTO-EXTENDING/RETRACTING ELECTRICALLY ISOLATED CONDUCTORS IN A SEGMENTED DRILL STRING, which is incorporated by reference in its entirety. The conductor in the drill string is in electrical communication with a line 112 that is in electrical communication with processing section 106 . It is noted that this approach may also be used to provide power to a power supply 114 from above ground, as an alternative or supplemental to the use of batteries. Still referring to FIG. 3 a , regulated power supply 114 , which may be powered using batteries or through the aforedescribed wire-in-pipe arrangement, provides appropriate power to all of the components in the steering tool, as shown. It is noted that magnetic field sensor 102 can be used to measure the field generated by a rotating magnet as well as measuring the Earth's magnetic field. The later may be thought of as a constant, much like a DC component of an electrical signal. In this instance, the Earth's magnetic field may be used advantageously to determine a yaw heading. Referring again to FIGS. 1 and 2 , system 10 is illustrated having three markers 140 a - c , each of which includes a rotating magnet for generating a rotating dipole field. Markers 140 a and 140 b are arranged along a line that is generally orthogonal to the X axis, while marker 140 c is offset toward drill rig 18 . A rotating dipole field can be generated either by a rotating magnet or by electromagnetic coils. Throughout this disclosure, the discussion may be framed in terms of a rotating magnet, but the described applications of magnets carry over to coils and wire loops with only minor modifications. As will be described in further detail, markers can be placed along the drill-path so that they are at least generally close to the target or other points of interest where high positioning accuracy is required, although one or two markers may provide sufficient accuracy for many drilling applications. That is, the marker signal should be receivable by the steering tool along a portion of the intended path including the target or other point(s) of interest. Aside from this consideration, the position of each marker can be arbitrary. Markers can be placed on the ground, on an elevated structure or even lowered within the ground. In each case, the marker can be at an arbitrary angular orientation. The rotation frequency (revolutions per second) of each magnet can be on the order of 1 Hz, but dipole field frequencies should be distinguishable if more than one marker/magnet is in use. A frequency difference of at least 0.5 Hz is considered to be acceptable for this purpose. Each magnet emits a rotating magnetic dipole field whose total flux is recorded by the steering tool magnetometer and subsequently converted to distance between magnet and tool. During rotation, the magnet of each marker emits a time dependent magnetic dipole field that is measured by the tri-axial magnetometer of the steering tool. As will be seen, a minimum value of the recorded total flux provides a distance between each marker and the steering tool. Turning now to FIG. 3 b , one embodiment of marker 140 is diagrammatically illustrated. It is noted that aforedescribed markers 140 a - c may be of this design as well as any additional markers used hereinafter. In this embodiment, each marker 140 can include a drive motor 142 having an output shaft 144 which directly spins a magnet 146 having a north pole, which is visible. Motor 142 is electrically driven by a motor controller 148 to provide stable rotation of the magnet. The motor can rotate the magnet slowly, for example, at about 1 revolution per second (1 Hz), as indicated by arrow 150 , thereby emitting a rotating magnetic dipole field 152 (only partially shown). It should be appreciated that a relatively wide range of rotational speeds may be employed, for example, from approximately 0.5 Hz to 600 Hz. In one embodiment, a proportional-integral-derivative (PID) controller can be used to drive motor 142 with user selectable rotational velocity. It is noted that such PIDs are commercially available. A benefit associated with using lower rotational velocity resides in a decreased influence by local magnetic objects such as, for example, rebar. If a higher rotational velocity is desired loop antennas can be used to create the rotational field. Further, the rotational velocity can be varied so that the fields from various markers are distinguishable when simultaneously rotating. A suitable power supply can be used, as will be recognized by one having ordinary skill in the art, such as for example a battery and voltage regulator, which have not been shown. It should be appreciated that there is no need for an encoder, since the specific angle of the magnet, corresponding to a particular measurement position, is not involved in making the determinations that are described below. Further, orientation sensors and a telemetry section in marker 140 are not needed. As will be seen, variation in rotation rate of magnet 146 will introduce associated positional error. Hence, a desire to increase measurement accuracy is associated with increasing the rotational stability of magnet 146 . Still referring to FIG. 3 b , while the axis of rotation of magnet 146 is illustrated as being vertical, this is not a requirement. The axis of rotation can be horizontal or at some arbitrary tilted orientation. Moreover, positioning of the marker for field use does not require orienting the marker in any particular way. This remarkable degree of flexibility and ease of positioning these markers is one of the benefits of the system and method taught herein. Most conventional applications of the steering tool function rely on a nominal value for drill rod length when integrating pitch and yaw to determine position. In accordance with the present disclosure, however, pitch and yaw can be measured more than once along each drill rod such that the distance between successive steering tool measurement positions can be less than the nominal length of one drill rod. This is particularly the case when the length of the drill rod is exceptionally long such as, for example, thirty feet. For this purpose, a laser distance meter, a potentiometer, an ultrasonic arrangement or some other standard distance measurement device can be mounted on the drill rig. An ultrasonic arrangement will be described immediately hereinafter. Referring again to FIGS. 1 and 2 , a drill string measuring arrangement includes a stationary ultrasonic transmitter 202 positioned on drill frame 18 and an ultrasonic receiver 204 with an air temperature sensor 206 ( FIG. 2 ) positioned on carriage 20 . It should be noted that the positions of the ultrasonic transmitter and receiver may be interchanged with no effect on measurement capabilities. Transmitter 202 and receiver 204 are each coupled to processor 70 or a separate dedicated processor (not shown). In a manner well known in the art, transmitter 202 emits an ultrasonic wave 208 that is picked up at receiver 204 such that the distance between the receiver and the transmitter may be determined to within a fraction of an inch by processor 70 using time delay and temperature measurements. By monitoring movements of carriage 20 , in which drill string 30 is either pushed into or pulled out of the ground, and clamping arrangement 54 , processor 70 can accurately track the length of drill string 30 throughout a drilling operation. While it is convenient to perform measurements in the context of the length of the drill rods, with measurement positions corresponding to the ends of the drill rods, it should be appreciated that this is not a requirement and the ultrasonic arrangement can provide the total length of the drill string at any given moment in time. Further, the length according to the number of drill rods multiplied by nominal rod length can be correlated to the length that is determined by ultrasonic measurement. Referring to FIG. 1 , control console 60 , in this embodiment, serves as a base station to communicate with steering tool 26 , to monitor its power supply, to receive and process steering tool data and to send commands to the steering tool, if so desired. Determined drill-path positions and estimated position errors can be displayed on display screen 66 for monitoring by the system operator. This functionality may also be extended to a remote base station configuration, for example, by using telemetry section 64 to transmit information 210 to a remote base station 212 for display on a screen 214 . Measured Quantities The steering method requires measurement of the following variables: Tool pitch and yaw angles φ,β Distances D i between N M magnets and the steering tool (i=1, . . . N M ) Magnet positions (X M i ,Y M i ,Z M i ), (i=1, . . . N M ) Initial tool position (X 1 ,Y 1 ,Z 1 ) Rod length increments Δs k+1 (k=1,2,3, . . . ) Referring to FIGS. 1 and 2 , pitch and yaw are measured and magnet-to-tool distances are determined at a series of tool positions including the initial tool position. Point 1 , which is additionally denoted by the reference number 42 , designates the position of drill begin. The steering tool is currently located at a measurement position k and is intended to proceed to position k+1. These positions can correspond to the end points of a drill rod or to intermediate points along the length of each drill rod. As discussed above, intermediate points may be needed, for example, when an exceptionally long drill rod is used such as, for example, 30 feet. Higher accuracy will generally be provided through the use of relatively more measurement positions. In some cases, the drill rod length may be sufficiently short that the number of drill rods may provide a sufficiently accurate value as to the length of the drill string. The latter situation may also be characterized by drill rods having a tolerance in their average length that is reasonably close to a nominal value. In some embodiments, there may be no correspondence between the drill rod length and the measurement positions, for example, where a measurement system, such as is employed by system 10 , is capable of measuring and monitoring an overall length of the drill string. For purposes of simplicity of description, it will be assumed that the drill rod length is used in the remainder of this description to establish the measurement positions. It is noted that measurements at each measurement position may be performed on-the-fly while pushing and/or rotating the drill string; however, enhanced accuracy can be achieved by stopping movement of the steering tool at each of the measurement positions during the measurements. A rod length increment Δs k+1 is defined as the arc-length between tool measurement positions (X k ,Y k ,Z k ) and (X k+1 ,Y k+1 ,Z k+1 ). The setup of this coordinate system is described immediately hereinafter. Set-up of Steering System Referring to FIG. 3 c , in conjunction with FIGS. 1 and 2 , the origin and directions of the X,Y,Z—coordinate system can be specified in relation to drill begin point 1 and target T. The location where drilling begins is a convenient choice for the origin and the direction from this position to the projection of the target onto a level plane through the origin defines the X-coordinate axis. The Z-coordinate axis is positive upward and the Y-coordinate axis completes a right-handed system. If desired, a different right-handed Cartesian coordinate system or any suitable coordinate system may be used. In the present example, the formulation constrains the X-axis to be level. As noted above, yaw orientation is designated as β measured from the X axis in a level X, Y plane, whereas pitch orientation is designated as φ measured vertically from the yawed tool position in the X, Y plane as represented by a dashed line in the X, Y plane. FIG. 3 c defines pitch and yaw as Euler angles that require a particular sequence of yaw and pitch rotations in order to rotate the steering tool from a hypothetical position along the X axis into its illustrated position. Magnet Position Measurements The use of an Electronic Distance Measurement device (EDM) is currently the quickest and most accurate method of defining the X-coordinate axis and measuring magnet position coordinates. However, using an EDM for this purpose requires the presence of a surveyor at the HDD job site, which may sometimes be difficult to arrange. Accordingly, any suitable method may be used. As an alternative to an EDM, a laser distance measurement device can be used. Devices of this kind are commercially available with a maximum range of about 650 feet and a distance measurement accuracy of ⅛ of an inch; the Leica Disto™ laser distance meter is an example of such a device. The device is placed at the position of drill-begin and pointed at the target to obtain the distance between these two positions. For short range measurements, the device can be handheld, but for larger distances it should be fixedly mounted to focus reliably. When an EDM, laser distance measurement device or similar device is used to determine the magnet positions, the accuracy of the device itself can be used as the magnet position error in the context of the discussions below. Referring to FIGS. 4 and 5 , one embodiment of a setup technique is illustrated. FIG. 4 illustrates a diagrammatic plan view of steering tool 26 positioned ahead of drill begin point 1 with target T arranged along the X axis and a marker M 1 that is offset from the X axis. The target is located at coordinates X t ,Y t ,Z t . FIG. 5 illustrates a diagrammatic elevational view of steering tool 26 positioned ahead of drill begin point 1 on a surface 230 of the ground. In one embodiment, a laser distance meter (LDM) can be used having a tilt sensor so that horizontal and vertical distances X t ,Z t to the target can either be calculated or are directly provided by the LDM. The relative position (ΔX, ΔY, ΔZ) between the target and a marker, M 1 , located near the target can also be measured using the LDM, with a measuring tape or in any other suitable manner. Marker position coordinates can be obtained by adding position increments to target coordinates, as follows: X M1 =X t ×ΔX   (1) Y M1 =ΔY   (2) Z M1 =Z t +ΔZ   (3) The foregoing procedure can be repeated for any number of markers that are arranged proximate to the target. In another embodiment, the position of each marker can be measured directly, for example using an EDM, with no need to measure the location of the target, so long as some other position has been provided that establishes the X axis from point 1 of drill begin. For example, a marker M 2 may be arranged along the X axis. As will be further described, location accuracy along the X axis can be customized based on the arrangement of markers therealong. The need for enhanced accuracy for some portion of the path of the steering tool can be established, for example, based on the presence of a known inground obstacle 232 . Reference Yaw Angle Continuing to refer to FIGS. 4 and 5 , a reference yaw angle β ref is defined as the yaw angle of the steering tool, measured by the steering tool, with its elongation axis aligned with the X-direction. In the present example, the reference yaw angle is measured as a compass orientation from magnetic north, based on the Earth's magnetic field. Since steering tool yaw has previously been defined as positive for a counterclockwise rotation the particular reference yaw angle β ref shown in FIG. 4 is negative. Accordingly, in order to measure yaw accurately without interference from the magnetic influence of the drill rig, the steering tool can be placed on a level ground a sufficient distance ahead of the drill; 30 feet is usually adequate. The elongation axis of the steering tool is at least approximately on or at least parallel to the X-axis. Yaw angle β m , measured as a compass heading during steering, is subsequently replaced by β=β m −β ref . Steering Procedure Formulation Nomenclature c A =pitch and yaw error covariance matrix C e =empirical coefficient C M =magnet position error covariance matrix D=distance between marker and steering tool F=continuous state equations matrix H=observation coefficient vector N M =number of markers P=error covariance matrix Q=continuous process noise covariance parameter matrix Q k =discrete process noise covariance matrix R=observation covariance scalar {right arrow over (r)}=vector of magnet position measurement error s=arc-length along drill-rod axis v D =distance measurement noise v M =magnet position measurement noise {right arrow over (x)}=state variables vector X,Y,Z=global coordinates X k ,Y k ,Z k =steering tool position coordinates z=measurement scalar β=yaw angle δX,δY,δZ=position state variables δX M ,δY M ,δZ M =magnet position increments δβ,δφ=yaw and pitch angle increments Δs=rod length increment φ=pitch angle Φ k =discrete state equation transition matrix σ=standard deviation σ 2 =variance, square of standard deviation Subscripts bias=bias error D=distance ex=exact value i=i-th magnet k=k-th position on drill path M=magnet m=measured ref=reference 1=initial tool position (drill begin at k=1) Superscripts ( ) . = d d ⁢ ⁢ s ( ) − =indicates last available estimate ( )′=transpose ( )*=nominal drill path {circle around ({right arrow over (x)})}=state variables vector estimate Tracking Equations The method is based on two types of equations, referred to as steering tool process equations and distance measurement equations. The former are a set of ordinary differential equations describing how tool position (X,Y,Z) changes along the drill-path as a function of measured pitch φ and yaw β and shown as equations 4. { X . Y . Z . } = { cos ⁢ ⁢ ϕ ⁢ ⁢ cos ⁢ ⁢ β cos ⁢ ⁢ ϕ ⁢ ⁢ sin ⁢ ⁢ β sin ⁢ ⁢ ϕ } ( 4 ) The over-dot indicates that derivatives of position coordinates are to be taken with respect to arc-length s along the axis of the drill rod. Pitch and yaw angles are illustrated in FIG. 3 c . Accordingly, the premise of a conventional steering tool resides in a numerical integration of equations 4 with respect to arc length s of the drill string. Unfortunately, as discussed above, this technique readily produces potentially serious positional errors in and by itself. The aforementioned distance measurement equations are of the form: D 2 =( X M −X ) 2 +( Y M −Y ) 2 +( Z M −Z ) 2   (5) The distance measurement equations express distance D between the center of a rotating magnet of a marker and the center of tri-axial steering tool magnetometer 102 (see FIG. 1 ) in terms of tool position (X,Y,Z) and magnet position (X M ,Y M ,Z M ). Accordingly, N M of such equations can be written for a system, corresponding to the total number of markers. The origin of the global X,Y,Z-coordinate system in which tool position will be tracked can be chosen to coincide with the location of drill begin (point 1 in FIGS. 1 and 2 ). X 1 =0 Y 1 =0 Z 1 =0   (6) Equations (4), (5) and (6) represent an initial value problem that can be solved for steering tool position coordinates. Nonlinear Solution Procedures The foregoing initial value problem can be solved using either a nonlinear solution procedure, such as the method of nonlinear least squares, the SIMPLEX method, or can be based on Kalman filtering. The latter will be discussed in detail beginning at an appropriate point below. Initially, however, an application of the SIMPLEX method will be described where the description is limited to the derivation of the nonlinear algebraic equations that are to be solved at each drill-path position. Details of the solver itself are well-known and considered as within the skill of one having ordinary skill in the art in view of this overall disclosure. The present technique and other solution methods can replace the derivatives {dot over (X)},{dot over (Y)},Ż in equations (4) with finite differences that are here written as: X . = X k + 1 - X k Δ ⁢ ⁢ s k + 1 ( 7 ) Y . = Y k + 1 - Y k Δ ⁢ ⁢ s k + 1 ( 8 ) Z . = Z k + 1 - Z k Δ ⁢ ⁢ s k + 1 ( 9 ) Resulting algebraic equations read: f 1 =X k+1 −X k −Δs k+1 cos φ k cos β k =0   (10) f 2 =Y k+1 −Y k −Δs k+1 cos φ k sin β k =0   (11) f 3 =Z k+1 −Z k −Δs k+1 sin φ k =0   (12) The distance measurement equations (5) provide additional N M equations written as: f 4 i =D k−1, i 2 −( X k+1 −X M i ) 2 −( Y k−1 −Y M i ) 2 −( Z k+1 −Z M i ) 2 =0   (13) Starting with the known initial values (Equations 6) at drill begin, the coordinates of subsequent positions along the drill path can be obtained by solving the above set of nonlinear algebraic equations (10-13) for each new tool position. The coordinates of position k+1 are calculated iteratively beginning with some assumed initial solution estimate that is sufficiently close to the actual location to assure convergence to the correct position. One suitable estimate will be described immediately hereinafter. Referring to FIGS. 6 and 7 a , the X,Z plane is illustrated with a drill path 240 formed therein and in a direction 242 using a plurality of drill rods 32 , at least some of which have been designated by reference numbers. FIG. 7 a is an enlarged view within a dashed circle 244 of FIG. 6 . An initial solution estimate is given by a point on what may be referred to as a nominal drill-path 246 that can be found by linear extrapolation of the previously predicted/last determined position to a predicted position 248 . The linear extrapolation is based on equations 4 and a given incremental movement Δs k+1 of the steering tool from a k th position where: { X k + 1 * Y k + 1 * Z k + 1 * } = { X k Y k Z k } + Δ ⁢ ⁢ s k + 1 ⁢ { cos ⁢ ⁢ ϕ k ⁢ cos ⁢ ⁢ β k cos ⁢ ⁢ ϕ k ⁢ sin ⁢ ⁢ β k sin ⁢ ⁢ ϕ k } ( 14 ) Where predicted positions are indicated in equations 14 using an asterisk ( )*. It should be appreciated that the position of the steering tool is characterized as predicted or estimated since the location is not identified in an affirmative manner such as is the case, for example, when a walk-over locater is used. The use of a steering tool differs at least for the reason that the position of the steering tool is estimated or predicted based on its previous positions. Thus, the actual position of the steering tool, for a sufficiently long drill path, can be significantly different than the position that is determined by a steering tool technique, as a result of accumulating error, if this error is not managed appropriately. Application of the SIMPLEX method requires definition of a function that is to be minimized during the solution procedure. An example of such a function that is suitable in the present application reads: F = ∑ p = 1 3 + N M ⁢ ⁢ f p 2 ( 15 ) As noted above, it is considered that one having ordinary skill can conclude the solution procedure under SIMPLEX in view of the foregoing. Kalman Filter Solution In another embodiment, a method is described for solving the tracking equations employing Kalman filtering. The filter minimizes the position error caused by measurement uncertainties in a least square sense. The filter determines position coordinates as well as position error estimates. The three tool position coordinates (X,Y,Z) are chosen as the main system parameters. Increments (δX,δY,δZ) of these parameters are referred to as state variables. The solution method can be characterized as a predictor-corrector technique. Assuming all drill-path variables are known at a last determined position and a drill string increment is known, the current or next-determined position on the drill path can be approximated by linear extrapolation, as described above with respect to FIGS. 6 and 7 a . This is the predictor step that gives a point on nominal drill path 246 . The Kalman filter, in turn, performs a corrector step in which state variables are calculated and added to the nominal drill path. Initial tool position coordinates (X 1 ,Y 1 ,Z 1 ) are assumed and corresponding error variances (σ X 1 2 ,σ Y 1 2 ,σ Z 1 2 ) are known. For example, at (X 1 ,Y 1 ,Z 1 ), which is the origin of the coordinate system, the error variances are zero. If (X 1 ,Y 1 ,Z 1 ) is not the origin, the error variances are based on the accuracy of measurement from the origin. The tracking procedure starts from this initial position and proceeds along the drill path, as follows: As is illustrated in FIGS. 6 and 7 a , the last known drill path position (X k ,Y k ,Z k ) is extrapolated linearly to obtain an approximate or estimated tool position, previously introduced as nominal drill path position (X k+1 *, Y k+1 *, Z k+1 *). The filter determines state variables (δX k+1 ,δY k+1 ,δZ k+1 ) and standard deviations of position error (σ X k+1 ,σ Y k+1 ,σ Z k+1 ). State variables are added to the nominal drill path position to find the new tool position (X k+1 ,Y k+1 ,Z k+1 ). { X k + 1 Y k + 1 Z k + 1 } = { X k + 1 * Y k + 1 * Z k + 1 * } + { δ ⁢ ⁢ X k + 1 δ ⁢ ⁢ Y k + 1 δ ⁢ ⁢ Z k + 1 } ( 16 ) Measurement Errors The Kalman filter takes the following random measurement errors into account which must therefore be known before tracking begins. Tool pitch and yaw angle errors σ φ , σ β Distance error σ β Magnet position errors (σ X M ,σ Y M ,σ Z M ) Initial tool position errors (σ X 1 ,σ Y 1 ,σ Z 1 ) Error values are empirical and depend on the type of instrumentation used. Note that the effect of drill rod length measuring error is not part of the analysis since arc-length along the axis of the drill rod is used as an independent variable. Knowing initial tool position errors (σ X 1 ,σ Y 1 ,σ Z 1 ), the corresponding error covariance matrix P 1 is given as: P 1 = [ σ X 1 2 0 0 0 σ Y 1 2 0 0 0 σ Z 1 2 ] ( 17 ) Adding the latter to equations (4) to (6) completes the formulation of the initial value problem to be solved by Kalman filtering. Linearized Tracking Equations In addition to various measured quantities that are summarized above, the Kalman filter solution uses input of the following parameters. Φ k discrete state equation transition matrix Q k discrete process noise covariance matrix z measurement scalar H observation coefficient vector R observation error covariance scalar The above parameters are derived by linearizing the steering tool process equations and distance measurement equations about the nominal drill path position. The resulting two sets of linear equations are the so-called state equations and the observation equations. They are summarized below. The state variables are defined as position increments. {right arrow over (x)} =(δ X,δY,δZ )′  (18a) {right arrow over ({dot over (x)})} =(δ {dot over (X)},δ{dot over (Y)},δŻ )′  (18b) The state equations governing state variables read {right arrow over (x)} k+1 =Φ k {right arrow over (x)} k +Δs k+1 G k {right arrow over (u)} k   (19) Where Δs k+1 G k {right arrow over (u)} k represents pitch and yaw measurement noise. It is noted that, hereinafter, subscripts may be dropped for purposes of clarity. Accordingly: Φ=I   (20) Q =cov((Δ s )( G{right arrow over (u)} )   (21) and {right arrow over (u)} =(δΦ,δβ)′  (22) G = [ - sin ⁢ ⁢ ϕ ⁢ ⁢ cos ⁢ ⁢ β - cos ⁢ ⁢ ϕ ⁢ ⁢ sin ⁢ ⁢ β - sin ⁢ ⁢ ϕ ⁢ ⁢ sin ⁢ ⁢ β cos ⁢ ⁢ ϕ ⁢ ⁢ cos ⁢ ⁢ β cos ⁢ ⁢ ϕ 0 ] ( 23 ) The discrete noise covariance matrix Q k becomes: c A = [ σ ϕ 2 0 0 σ β 2 ] ( 24 ) Q=c e (Δ s ) 2 Gc A G′   (25) Note that the empirical coefficient c e has been added to equation (25) in order to account for pitch and yaw bias errors. It has unit value if pitch and yaw measurement errors are entirely random. The observation equation of a rotating magnet reads: z=H{right arrow over (x)}+v D +v M   (27) R =cov( v D +v M )   (28) Where the term v D represents distance measurement noise and the term v M represents magnet position measurement noise. The term H will be described at an appropriate point below. The symbol z, seen in equation (27) is a difference between measured distance D and calculated distance D* from a marker to the nominal drill path position, given as: z=D−D*   (29) D* 2 =( X*−X M ) 2 +( Y*−Y M ) 2 +( Z*−Z M ) 2   (30) The first term H on the right hand side of equation (27) is the observation coefficient vector, written as: H = ( X * - X M D * , Y * - Y M D * , Z * - Z M D * ) ( 31 ) The following form of the observation covariance scalar R is used in the steering tool method: R=σ 2 D +Hc M H′   (32) c M = [ σ X M 2 0 0 0 σ Y M 2 0 0 0 σ Z M 2 ] ( 33 ) Projection of State Variables and Estimation Errors An estimate of the state vector at the next steering tool position k+1 is denoted by {circumflex over ({right arrow over (x)})} and its error covariance matrix is P − where the superscript ( ) − indicates the last available estimate. Before the filter is applied at the new tool position, set {circumflex over ({right arrow over (x)})}={0}  (34) The error covariance matrix P k is projected to the new position using P k+1 − =Φ k P k Φ k ′+Q k   (35) Kalman Filter Loop The filter loop is executed once for each marker, resulting in a flexible arrangement that is able to process any number of markers in use by the steering tool system. The classical, well documented version of the filter loop is chosen as a basis for the current steering tool embodiment. It consists of three steps: Kalman gain: K=P − H ′( HP − H′+R ) −1   (36) State variables: {circumflex over ({right arrow over (x)})}={circumflex over ({right arrow over (x)})} − +K ( z−H{circumflex over ({right arrow over (x)})} − )   (37) Error covariance matrix: P =( I−KH ) P −   (38) Position Coordinate Errors Having completed the filter analysis at a new position, its coordinates are given by equation (16). Corresponding one-sigma position errors follow from: σ X =√{square root over ( P 11 )}  (39) σ Y =√{square root over ( P 22 )}  (40) σ Z =√{square root over ( P 33 )}  (41) FIG. 7 b is a flow diagram, generally indicated by the reference number 260 , which illustrates one embodiment of a Kalman filter implementation according to the descriptions above. At 262 , the nominal position of the steering tool at k+1 is determined using equation 14. At 264 , the error covariance matrix is projected to position k+1 using equation 35. The state vector is initialized at 266 . Beginning with step 270 , a loop is entered using magnetic measurements associated with one marker. The distance D* between a point on the nominal drill path and the marker is determined per equation 30. The observation coefficient vector H in turn is calculated using equation 31. Equation 32 provides the observation covariance scalar R. At 272 , the Kalman filter is executed using equations 36-38. At 274 , a determination is made as to whether magnetic information is available that is associated with another marker. If so, execution returns to step 270 . If magnetic information from all markers has been processed, step 276 establishes the final coordinates of the current position of the steering tool based on equation 16 and can associate a position error estimate with these coordinates, based on equations 39-41. Numerical Simulations Several numerical simulations were performed to estimate positions of the steering tool assisted by up to three rotating magnets. In all cases the steering tool was tracked, moving along a drill-path defined by: 0≦X ex ≦300 ft   (42) Y ex = 15 ⁢ ⁢ sin ( π 300 ⁢ X ex ) ( 43 ) Z ex =−2 Y ex   (44) Note that drilling starts at the origin of the global coordinate system. The steering tool reaches a maximum depth of 30 feet and yaws to the side with a maximum lateral displacement of 15 feet before it reaches the target 300 feet out. The above coordinates are exactly known coordinates from which values for pitch, yaw and tool to magnet distances were derived. Table 1 summarizes random and bias errors that were added to these exact values to generate “measured” data. TABLE 1 Errors for Generating “Measured” Simulation Data Pitch Error σ ø = 0.25 deg φ bias = 0.25 deg Yaw Error σ β = 0.50 deg β bias = 0.50 deg Drill Rod Length Error σ Δs = 0.01 ft Distance Error D bias = 0.02 ft (See also, FIG. 8) FIG. 8 sets forth random distance error σ D in feet, plotted against distance D in feet. It is noted that errors were chosen based on empirical measurements with specific pitch and yaw sensors as well as with rotating magnets. Table 2 summarizes the random errors used as input for the filter. Note that the rod length increment error is used only for generating measured data; it is not used by the filter. TABLE 2 Random Errors Used in Kalman Filter Pitch Error σ φ = 0.5 deg Yaw Error σ β = 1 deg Distance Error σ D (see FIG. 8) Magnet Position Errors σ X M = σ Y M = σ Z M = 0.02 ft Initial Position Error σ X 1 = σ Y 1 = σ Z 1 = 0 FIGS. 9 a and 9 b are plots against drill string length, in feet, which compare exact with “measured” pitch and yaw angles, respectively, used in all the simulations described below. Exact pitch and yaw values are shown by dotted lines, while measured pitch and yaw values are shown by solid lines. Increments between adjacent measurement positions along the drill-path were approximately three feet. Estimated steering tool positions and position errors are illustrated by FIGS. 10 a - c , as an application of the basic steering tool function without the use of markers. It is noted that, in subsequent figures, an increasing number of magnets is added to the system to demonstrate the improvements that are provided through the use of markers. Illustrated position errors are shown as the differences between estimated and exact values. Since “measured” values for pitch and yaw contain bias as well as random components, lateral and vertical position errors are also biased. FIG. 10 a is a diagrammatic plan view of the estimated drill path, designated by the reference number 300 , whereas FIG. 10 b is an elevational view of the estimated drill path, designated by the reference number 302 . FIG. 10 c illustrates the X coordinate positional error as a solid line 310 , the Y coordinate positional error as a dashed line 312 and the Z coordinate positional error as a dotted line 314 . In the present example, without the use of magnets, it can be seen that there is a continuously accumulating Y coordinate error, which increases to about three feet upon reaching X=300 feet, the X axis coordinate of target T. The Z coordinate error is over one foot. Referring collectively to FIGS. 11 a - c , simulations are now presented including the use of markers. One marker 320 is used at a location of X=300 ft, Y=−5 ft, and Z=5 ft. FIG. 11 a is a diagrammatic plan view of the estimated drill path, designated by the reference number 322 , whereas FIG. 11 b is an elevational view of the estimated drill path, designated by the reference number 324 . FIG. 11 c illustrates the X coordinate positional error as a solid line 326 , the Y coordinate positional error as a dashed line 328 , and the Z coordinate positional error as a dotted line 330 . In the present example, with the use of only one magnet near target T, it can be seen that the Y coordinate error is dramatically reduced to just over one foot upon reaching the target X coordinate at 300 feet. Referring collectively to FIGS. 12 a - c , a second marker 340 is added at a location of X=305 ft, Y=0 ft and Z=5 ft. FIG. 12 a is a diagrammatic plan view of the estimated drill path, designated by the reference number 342 , whereas FIG. 12 b is an elevational view of the estimated drill path, designated by the reference number 344 . FIG. 12 c illustrates the X coordinate positional error as a solid line 346 , the Y coordinate positional error as a dashed line 348 , and the Z coordinate positional error as a dotted line 350 . In the present example, with the use of two magnets near target T, it can be seen that the Y coordinate error is still further reduced to a relatively small fraction of one foot upon reaching the target X coordinate at 300 feet. Moreover, the X and Z coordinate errors are likewise reduced to a small fraction of one foot upon reaching the target X coordinate at 300 feet. Referring collectively to FIGS. 13 a - c , a third marker 360 is added at a location of X=300 ft, Y=5 ft and Z=5 ft. FIG. 13 a is a diagrammatic plan view of the estimated drill path, designated by the reference number 362 , whereas FIG. 13 b is an elevational view of the estimated drill path, designated by the reference number 364 . FIG. 12 c illustrates the X coordinate positional error as a solid line 366 , the Y coordinate positional error as a dashed line 368 , and the Z coordinate positional error as a dotted line 370 . In the present example, with the use of three magnets near target T, it can be seen that the X, Y and Z coordinate errors are reduced to a very small fraction of one foot upon reaching the target X coordinate at 300 feet. In view of the foregoing, the use of two or three markers proximate to a point of interest on the drill path (such as the target) enables a high precision guidance of the steering tool to a target at least 300 feet out from the point of drill begin, or enables high precision steering relative to some point of interest along the drill path at least 300 feet out. It should be appreciated that, in the aforedescribed numerical simulations, errors defined as the difference between estimated and exact positions can be calculated, since exact drill-path coordinates are known. This type of error can not be calculated during actual drill-head tracking. Accordingly, a different type of error estimate is used for actual drilling. The Kalman filter analysis provides such an error estimate in the form of standard deviations of position coordinates. In this regard, FIGS. 14 a - c illustrate the two types of position errors for the drill-path of FIGS. 13 a - b with three markers placed near the target. The solid lines denote the +1 sigma position error provided by the Kalman filter analysis, whereas the dashed lines represent the corresponding −1 sigma errors. For comparison, the position errors of FIG. 13 c , defined as the difference between estimated and exact positions, are also shown in FIGS. 14 a - c . As seen, position errors expressed in terms of standard deviations vary smoothly along the drill-path since they are based on a statistical measure. In contrast, estimated positions and, hence, the errors shown as dotted lines in FIGS. 14 a - c are based on one set of partly random measurements resulting in an irregular distribution of position errors. Repeating the Kalman filter analysis with a different set of random measurements would produce different error distributions of this type. Numerical simulations were performed with c e =16. Attention is now directed to FIGS. 15 and 16 for purposes of describing additional aspects of the present disclosure. FIG. 15 illustrates a plan view of a drilling region 400 having a concluding section of an intended drill path 402 defined therein. Further, a first inground obstacle 404 and a second inground obstacle 406 are shown in relation to intended path 402 . As can be seen, intended path 402 has been specifically designed to avoid inground obstacles 404 and 406 . Such path design can be based on any knowledge of inground features that should be avoided and can include a reliance on any suitable resource including but not limited to utility surveys, available design drawings and exploratory excavations. Moreover, inground obstacles 404 and 406 are intended to represent any type of feature within the ground that should be avoided. Still referring to FIGS. 14 and 15 , an exemplary plurality of markers 140 a - e is distributed along intended path 402 such that markers 140 a and 140 b are in the vicinity of obstacle 404 , marker 104 c is in the vicinity of obstacle 406 , and markers 140 d and 140 e are in the vicinity of target T. It should be appreciated that orientation of the markers is arbitrary so long as the steering tool, on the intended path and proximate to some inground feature of interest, is capable of receiving at least the magnetic field that is emanated by the markers in its general vicinity. As seen above, with each marker that is added proximate to target T, there is a corresponding increase in steering tool accuracy. That is, the steering tool tracks the intended path with proportionally increasing accuracy. Placement of markers proximate to points of interest, as illustrated, likewise produces a corresponding increase in accuracy along any portion of the intended path that is exposed to the magnetic field that is emanated by that marker. In this way, an enhanced steering accuracy, of a selective degree, can be provided at any desired point or points along the intended path. Accordingly, a highly advantageous customized steering accuracy is provided along the intended path. In this regard, as discussed above, the described technique readily accommodates receiving signals from any number of markers at any given point along the intended path or receiving no marker signals for some portions of the path, such as might be the case at a point 410 midway between markers 140 c and 140 d of the present example. Even though the present example illustrates the use of five markers, fewer markers may actually be necessary since the markers can be moved along the intended drill path responsive to the progression of the steering tool. For example, after the steering tool passes obstacle 404 , marker 140 a can be moved to the position of marker 140 c . At a suitable time, marker 140 b can be moved to the position of marker 140 d . Once the steering tool passes obstacle 406 , marker 140 a can then be moved to the illustrated position of marker 140 e . Accordingly, long drill runs can be made with as few as one or two markers. Applicants consider that sweeping advantages are provided over the state-of-the-art with respect to steering tool systems and methods. While there are systems in the prior art that use rotating magnet signals, it should be apparent from the detailed descriptions above that providing the capability to use rotating magnet signals in the context of a steering tool system is neither trivial nor obvious. In this regard, Applicants are unaware of any prior art use of a rotating magnet signal in the context of a steering tool system and, particularly, with such flexibility and ease of use where the rotating magnet field markers can not only be arbitrarily placed, but arbitrarily oriented. While a number of exemplary aspects and embodiments have been discussed above, those of skill in the art will recognize certain modifications, permutations, additions and sub-combinations thereof. It is therefore intended that the following appended claims and claims hereafter introduced are interpreted to include all such modifications, permutations, additions and sub-combinations as are within their true spirit and scope.
A steering tool is movable by a drill string to form an underground bore along an intended path. A sensing arrangement of the steering tool detects its pitch and yaw orientations at a series of spaced apart positions along the bore, each position is characterized by a measured extension of the drill string. The steering tool further includes a receiver. At least one marker is positioned proximate to the intended path, for transmitting a rotating dipole field to expose a portion of the intended path to the field for reception by the receiver. The detected pitch orientation, the detected yaw orientation and the measured extension of the drill string are used in conjunction with magnetic information from the receiver to locate the steering tool. The steering tool may automatically use the magnetic information when it is available. A customized overall position determination accuracy can be provided along the intended path.
93,488
GENERAL FIELD [0001] The invention relates to the field of rotatably movable blades. [0002] The invention relates more particularly to the field of characterization of vibrations which such blades sustain when set in rotation. PRIOR ART [0003] An impeller is a hub comprising a plurality of blades, or vanes. During design and certification of turbine engines, it is necessary to verify whether such a rotatably movable impeller in a casing has suitable frequencies likely to be excited in the field of operation of the motor of such turbine engines. [0004] It is also necessary to quantify the levels of associated vibratory restrictions for suitable modes identified in this field of operation. [0005] A first known technique for characterizing vibrations sustained by blades in operation consists of the use of deformation gauges stuck to the impeller. It is possible to characterize the blades in the frequency domain and calculate the constraints within the material from measuring micro-deformations at the surface of the material. [0006] However, this first technique comprises many disadvantages. [0007] First, the gauges stuck to the vanes are subjected to huge centrifugal forces (of the order of 100,000 g) potentially associated with very high temperatures, especially when the instrumentation is done on a high-pressure turbine. The shelf life of gauges is consequently limited. [0008] Second, placing the gauge requires substantial knowhow, minutiae and time (especially for the firing of cements in which the gauges are set). [0009] Third, it is necessary to have the signal coming from the gauges embedded in the movable impeller transit to a fixed marker. For this, connecting wires on the motor shaft must lead to a turning collector. Apart from the length of the wires and the turning connection of the collector, generating noise measurements, preliminary studies for integration of a turning collector on a motor are long and costly. [0010] A second technique based on the use of probes positioned facing the rotating vanes, and therefore in a fixed marker, has been proposed to eliminate these disadvantages. [0011] This second technique makes a measurement of the time passage spreads before the optical probes for two vibratory states of a vane (in the presence or not of vibrations). Such a measuring method, called “tip timing”, recalculates amplitudes of alternated shifts at the vane tip. The knowledge of mode shapes puts the levels of shift at the tip of vane in relation to the levels of constraints in the vane. [0012] This method of “tip timing” described in documents U.S. Pat. No. 3,208,269 and U.S. Pat. No. 4,757,717 especially uses conductors having a zigzag shape and arranged around the axis of rotation of the vane. [0013] This second technique however does not produce frequency information on the vibrations measured. Because of the zigzag shape of the conductors used, only overall levels of shifts at the vane tip are in fact identifiable by this second technique without knowing which vane mode is excited. For vibratory monitoring purposes, this limitation can be widely penalizing. [0014] Also, the “tip timing” process sometimes has ambiguities disallowing identification of the order of excitation responsible for the levels of recorded shifts. PRESENTATION OF THE INVENTION [0015] The invention therefore aims to allow characterization of vibrations sustained by a vane when set in rotation, especially measuring information representing vibration frequencies of the vane. [0016] According to a first aspect, an assembly for turbine engine is therefore proposed, the assembly comprising a casing and an impeller rotatably movable in the casing, the impeller comprising at least one vane having a tip facing the casing, the assembly being characterized in that the tip comprises a magnet and in that the casing comprises an electrical conductor adapted to generate between its terminals an electrical voltage induced by the magnet of the facing tip and representative of vibrations sustained by the tip of the vane when the impeller is set in rotation. [0017] According to a second aspect, a method of characterizing vibrations of a vane of an assembly for turbine engine according to the first aspect is also proposed, the method comprising the steps of: setting in rotation of the impeller in the casing, measuring at the terminals of the electrical conductor of an electrical voltage induced by the magnet contained in the tip of the vane facing the casing, determining information representative of the vibrations sustained by the tip of the vane from the measured electrical voltage. [0021] The magnet generates a magnetic field. When the rotatably movable impeller is set in rotation relative to the casing, the relative movement of the magnetic field relative to the electrical conductor (movement due to rotation of the impeller and its vibrations) induces electric current in the electrical conductor in the casing located facing the tip of the vane which comprises the magnet. This electric current spreads as far as the terminals of the electrical conductor. The voltage at these terminals characterizes the vibrations sustained by the vane, especially identifies frequencies of suitable modes of the vane. [0022] The assembly for turbine engine according to the first aspect, and the method according to the second aspect overcome direct measurements of constraints on the impeller, and avoid heavy instrumentation in the movable marker linked to the vane, to characterize the vibrations of the vane fitted with the magnet. The instrumentation is minimum in this movable marker (just one magnet is integrated into the vane) and also minimum in the fixed marker linked to the casing (insertion of an electrical conductor on the casing) to get information equivalent to that obtained by way of the devices of the prior art described in the introduction. [0023] The voltage measured at the terminals of the electrical conductor is representative of the vibrations of the magnet made outside the path plane, but this voltage is independent of the rotary movement of the vane around its axis of rotation (so, in a perfect situation in which the vane would not be subject to any vibration, the voltage at the terminals of the electrical conductors when the magnet is facing a portion of the central part would be zero). [0024] Also, the fact that the central part of the conductor is over its entire length in the path plane of the magnet produces continuous signal voltage over time usable for analysis in the frequency domain. On the contrary, the zigzag conductors used in the methods of the prior art produce only fragmented and segmented signals, unsuitable for spectral analysis. [0025] The assembly according to the first aspect can be completed by the following characteristics, taken singly or in any of their technically possible combinations. [0026] The central part extending around the axis of rotation of the impeller can comprise two ends located at different angular positions around the axis of rotation of the impeller. Such an embodiment acquires vibration information for different angular positions of the vane around the axis of rotation of the impeller; also, the different angular positions of the two ends of the central part create discontinuity to produce “turn peaks” which can act as time reference during continuous measuring made at the terminals of the electrical conductor. [0027] The central part can also extend over fewer than 360 degrees around the axis of rotation especially to simplify mounting of the electrical conductor on or in the casing. In such an embodiment, in which the length of the central part is shortened, a space not covered by the electrical conductor is left around the axis of rotation of the impeller between the ends of its central part. This space, also called “turn opening”. [0028] The central part and the two branches can be coplanar, each branch extending from a respective end radially to the outside relative to the axis of rotation of the impeller. [0029] The magnet can further be adapted to emit a magnetic field radially oriented relative to the axis of rotation of the impeller. [0030] The voltages at the terminals of the electrical conductors are generally low. Also, a voltage amplifier can be connected to the terminals of the electrical conductor, with measurements being made at the output of this amplifier. [0031] The electrical conductor can be embedded at least partially in an abradable deposit located on an internal surface of the casing facing the impeller, the abradable deposit being made of paramagnetic or diamagnetic material. In this way, the magnetic flow of the magnet is barely modified, and the entire magnetic flow generated by the magnet can be exploited in the measurements taken. [0032] The assembly can further comprise a measuring device adapted to apply a Fourier transform to the signal of electrical voltage so as to produce a spectrum representative of frequencies of vibrations of the vane. DESCRIPTION OF FIGURES [0033] Other characteristics, aims and advantages of the invention will emerge from the following description which is purely illustrative and non-limiting and which must be considered with respect to the appended drawings, in which: [0034] FIG. 1 is a first view in partial section of an assembly for turbine engine according to an embodiment of the invention. [0035] FIG. 2 is a second view in partial section of the assembly of FIG. 1 . [0036] FIG. 3 is a flowchart of steps of a method of characterizing vibrations sustained by a vane, according to an embodiment of the invention. [0037] FIG. 4 shows markers associated with different elements of the assembly E shown in FIGS. 1 and 2 . [0038] FIG. 5 schematically illustrates electromagnetic interactions between elements of the assembly for turbine engine illustrated in FIGS. 1 and 2 . [0039] FIGS. 6 a to 6 c each illustrate a voltage time signal obtained during execution of the method of FIG. 3 . [0040] FIG. 7 shows a spectrum corresponding to the signal shown in FIG. 6 c. [0041] In all figures similar elements bear identical reference numerals. DETAILED DESCRIPTION OF THE INVENTION [0042] In reference to FIG. 1 , an assembly E for turbine engine comprises a casing 1 and an impeller 2 rotatably movable relative to the casing 1 . The impeller 1 is here defined by a set of vanes (or blading) distributed over the circumference of a wheel. [0043] The casing 1 has an internal surface 10 defining a space which houses the impeller 2 . This internal surface 10 is for example cylindrical. [0044] The impeller 2 is mounted on a motor shaft 24 extending along an axis of rotation (perpendicular to the plane of FIG. 1 ). The impeller 2 comprises a disc 22 around the shaft 24 , and a plurality of vanes. Each vane extends substantially radially from the disc 22 until it terminates by a respective tip. In this way, the tip of each vane is facing a surface portion of the casing 1 , irrespective of the angular position occupied by the impeller 2 movable relative to the casing 1 . [0045] At least one of the vanes of the impeller, referenced 20 , comprises a magnet 3 at its tip 21 . The magnet can for example brush the maximal radius of the tip of the vane, relative to the axis of rotation. [0046] The magnet 3 is attached to the vane 20 , in turn attached to the disc 22 ; it is assumed hereinbelow that the movement of the magnet 3 is representative of the movement of the tip 21 of the vane 20 . [0047] The topology of the magnetic field created by the magnet 3 is similar to that of a solenoid with several turns: it forms a torus enclosing the magnet 3 and oriented from its north pole to its south pole. The magnet 3 is adapted to generate a magnetic field of radial orientation relative to the axis of rotation of the impeller 2 . [0048] In reference to FIG. 2 , the casing 1 comprises an electrical conductor 4 . [0049] The electrical conductor 4 comprises a so-called “central” part forming a turn or a portion of turn around the axis of rotation of the impeller 2 . This central part 40 is for example fixed to the internal surface 10 of the casing 1 facing the impeller 2 . [0050] The central part 40 comprises two ends 42 , 42 ′ located at different angular positions around the axis of rotation of the impeller 2 . [0051] The electrical conductor 4 also comprises two branches 44 , 44 ′ each prolonging a respective end of the central part 40 . [0052] The central part 40 preferably does not extend over the entire circumference of the casing 1 around the axis of rotation of the impeller 2 , but forms an arc of a circle formed by an angular sector of fewer than 360 degrees around the axis of rotation of the impeller. The two ends 42 , 42 ′ delimit a portion of circumference of the casing 1 not covered by the central part 40 ; this non-covered potion is qualified below as “turn opening”, referenced 46 . [0053] In a variant not illustrated, the central part extends over more than one complete revolution around the axis of rotation of the impeller. [0054] The branches 44 , 44 ′ extend in a direction substantially radial to the outside relative to the axis of rotation of the impeller 2 in the casing 1 . At the end 42 (respectively 42 ′) which it prolongs, each branch 44 (respectively 44 ′) forms for example with the central part 40 , an angle of between 80 degrees and 100 degrees, preferably 90 degrees. [0055] The central part 40 extends over its entire length between the ends 42 , 42 ′ in a plane which coincides with a path plane of the magnet 3 during a revolution of the vane 20 around the axis of rotation of the impeller 2 . [0056] The branches 44 , 44 ′ which prolong this central part 40 can also extend in this same path plane. [0057] When the impeller 2 occupies an angular position such that the magnet 3 is facing a point of the central part 40 , the relative vibratory movement of the magnetic field generated by the magnet 3 relative to the central part 40 induces an electric current in a portion of the central part 40 of length L in the vicinity of this point, a current which spreads to the terminals formed by the branches 44 , 44 ′. Voltage U 1 is generated between the two terminals of the electrical conductor 4 . [0058] In the embodiment illustrated in FIG. 2 , the central part 40 of the first electrical conductor 4 defines a portion of a circle centered on a point of the axis of rotation; in this way the airgap between the magnet 3 and any point of the central part 40 is a constant distance. As a variant, the central part can also have other forms than a circular shape or as a portion of a circle. [0059] The terminals of the electrical conductor 4 are connected to the input of a voltage amplifier 5 . [0060] The output of the voltage amplifier 5 is connected to a voltage measuring device 6 comprising means for performing spectral analysis of a voltage time signal amplified by the amplifier 5 . General Principle of a Method of Characterizing Vane Vibrations [0061] FIG. 3 shows the steps of a method of characterizing vibrations sustained by the vane 20 comprising the magnet 3 . [0062] In a preliminary step 101 , the impeller 2 is set in rotation around its axis of rotation. This setting in rotation is likely to generate vibrations of the vane 20 . [0063] One period of revolution of the vane 20 around the axis of rotation of the impeller 2 comprises two different phases, each corresponding to a respective range of angular positions of the impeller 2 movable relative to the casing 1 : a phase during which the magnet 3 is facing a portion of the central part 40 , and a phase during which the magnet 3 is facing the turn opening 46 left between its two ends 42 , 42 ′. [0064] When the magnet 3 is facing a portion of the central part 40 , vibratory movement relative to the magnetic field B generated by the magnet 3 relative to the central part 40 causes an electric current in the central part 40 , which spreads as far as the terminals formed by the branches 44 , 44 ′. Voltage U 1 is generated between the two terminals of the electrical conductor 4 . [0065] This voltage U 1 , generally very low, is amplified by the amplifier 5 during a step 102 . [0066] In a step 103 , the measuring device 6 acquires from the voltage amplified by the amplifier 5 a voltage time signal of duration greater than the period of revolution of the vane 20 around the axis of rotation. [0067] In a step 104 , the device calculates the Fourier transform of the voltage time signal acquired. The result of this transform constitutes a spectrum representative of the vibratory frequencies of the vane 20 in which the magnet 3 is embedded. [0068] As the central part 40 of the conductor extends continuously in the path plane of the magnet, the time signal obtained as the magnet passes along the central part 40 is also continuous. Such a continuous signal is rich in exploitable frequency information after calculation of the Fourier transform. [0069] By comparison, a conductor having a zigzag shape, as per the “tip-timing” method, is not constantly in the path plane of the magnet. A signal acquired by such a zigzag conductor is discontinuous, and accordingly is insufficiently sampled to authorize a Fourier transform of this signal, in light of exploiting the information supplied by the spectrum resulting from this Fourier transform. [0070] The electromagnetic actions of the magnet 3 during these two phases will now be described in more detail. [0000] Electromagnetic Action of the Magnet when it is Facing the Central Part [0071] In reference to FIG. 4 , a fixed frame R is associated with the casing 1 , and a movable frame R′ is associated with the magnet 3 . [0072] The fixed frame R is defined by a center O, the axis of rotation of the impeller 2 , referenced z, and axes x and y defining a plane perpendicular to the motor axis and containing the movement of the magnet 3 . [0073] The movable frame R′ is defined by a center O′ representative of the position of the magnet 3 , an axis z′ parallel to the axis z, an axis x′ supported by the straight OO′, and an axis such as the marker R′ is a direct trihedral. The movable frame R′ forms an angle θ relative to the fixed marker R. [0074] In general, the laws of change of frame from R to R′ of a point M in the marker R′ impose the following relation: [0000] {right arrow over ( V M/R )}={right arrow over ( V O′/R )}+{right arrow over ( V M/R′ )} [0075] In reference to FIG. 5 , a point of the central part 40 is considered as a point M. This can be shown as: [0000] {right arrow over ( V O′/M )}=−{right arrow over ( V M/R′ )} [0076] This relation shows that, equivalently, the magnet 3 at the tip of vane 20 moves relative to the central part 40 fixed in the fixed marker, or that the central part 40 moves relative to the magnet 3 fixed in the movable marker. [0077] Given an electron belonging to the central part 40 , immobile in the fixed frame R, its apparent speed in the turning frame R′ will be the vector {right arrow over (V M/R′ )}, i.e, the speed which a point of the turning marker in the fixed marker at the distance r+e would have, where e designates the airgap between the magnet 3 and the central part 40 and r the distance OO′. [0078] Given that this point M is completely in the axis of the magnet 3 O′x′, the resulting Fl of the Lorentz force to be applied to the electron will be oriented as shown in FIG. 5 . [0079] The device in the plane O′x′z can be considered and the components of the field B can be considered only on the components x′ and z. The speed of advancement of the electron in the turning frame is that which a fixed point in the turning marker at the distance r+e would have, given the radius r of the blade and the airgap e between the magnet 3 and the abscissa in the turning marker of the point M. The electromotor field can be expressed as follows: [0000] E → M = v → M / R × B → =  0 ( r + e )  θ . × 0   B x ′ B y ′ B z ′ =  ( r + e )  θ .  B z ′ 0 - ( r + e )  θ .  B x ′ =   E x ′ E y ′ E z ′ [0080] When the magnet 3 is subjected to vibrations of the vane 20 , the electromotor field generated in this way by the vibratory movement of the vane 20 becomes: [0000] E → M = V ′ → × B → =  v VIBx ( r + e )  θ . + v VIBy × v VIBz   B x ′ B y ′ B z ′ =  ( r + e )  θ .  B z ′ + v VIBy  B z ′ - v VIBz  B y ′ v VIBz  B x ′ - v VIBx  B z ′ v VIBx  B y ′ - ( r + e )  θ .  B x ′ - v VIBy  B x ′ =   E M   x ′ E My ′ E Mz ′  where  :   V M / R ′ → + V M / R ′ → = V ′ → [0081] A current induced in the central part 40 is measurable when the electromotor field will be oriented according to the component y, i.e., in the axis of the conductor. A measurable component will therefore be: [0000] {right arrow over ( E Mutile )}=( Vvibz. B x , −Vvibx.B z′ ){right arrow over ( e′ y )} [0082] Besides, if the hypothesis is made that the magnet 3 is contained in the plane of the central part 40 , this component is rewritten as: [0000] {right arrow over (E Mutile )}=( Vvibz. B x′ ){right arrow over ( e′ y )} [0083] As a consequence, in the event where the magnet 3 is in the plane of the central part 40 , only vibratory behavior along the axis z (axis of rotation) will result in measurable induced currents. In the absence of vibratory activity there will therefore not be a measurable signal. [0084] The instantaneous voltage U 1 measured at the terminals of the electrical conductor 4 while a segment AB is present in the field of influence of the magnet 3 is expressed in the following form: [0000] U 1 =∫ A B {right arrow over (E)} m′ {right arrow over (dl)}=∫ A B V VIBz B x′ {right arrow over (e)} 0′ {right arrow over (dl)}=V VIBz B x′ l AB [0000] where l AB designates the length of the segment AB subject to the influence of the magnet 3 , B x′ is the radial component of the magnetic field generated by the magnet 3 , and Vvibz is the vibratory speed component of the magnet 3 along the axis x. Electromagnetic Action of the Magnet when it is Facing the Turn Opening [0085] When the magnet 3 is facing the turn opening 46 the electrical conductor 4 escapes the influence of the magnetic field B of the magnet 3 , a phenomenon which naturally generates induced currents. [0086] As this turn opening 46 is made along the axis x′, only the component x′ of the electromotor field generates voltage in the output branches 44 , 44 ′ of the central part 40 . [0087] The electromotor field generated in the output branches 44 , 44 ′ of the central part 40 is proportional both to the rotation speed of the rotor and also to the component of the magnetic field. [0088] The passing of the instrumented vane 20 in front of this turn opening 46 causes what is called a “turn peak” in the voltage time signal measured by the measuring device 6 such as that shown in FIG. 6 . The turn opening 46 therefore enables formation of such turn peaks. [0089] The turn peaks consist of information of interest in the time signal voltage measured by the measuring device 6 . In fact, they can serve as time reference for measuring the rotation speed of the impeller 2 around its axis. They are also representative of the sensitivity of measurements taken. [0090] But these turn peaks introduce harmonics which can impair interpretation of the voltage time signal or the corresponding spectrum prepared by the measuring device 6 . [0091] It can therefore prove interesting to minimize the presence of these peaks in the voltage time signal. [0092] The temporal extent of the turn peaks can be minimized by reducing the size of the turn opening 46 : for example, distant ends 42 , 42 ′ of an arc formed by an angular sector around the axis of rotation of the impeller of fewer than 20 degrees, or even fewer than 10 degrees can be provided. Minimizing the turn opening maximizes the time during which the central part 40 will be sensitive to the vibrations of the impeller 20 . [0093] The turn peaks can further be minimized by orienting each branch of the electrical conductor 4 at an angle between 80 and 100 degrees, preferably 90 degrees, relative to the end of the central part 40 which this branch prolongs. This orientation of angle further makes for easy integration of the branches in the casing 1 . Time Analysis [0094] The time signal in voltage s(t) recorded at the terminals of the central part 40 is the direct image of the vibratory speed component of the vane 20 parallel to the axis of rotation z′ of the impeller 2 . [0095] In an ideal situation in which the vane 20 sustains no vibration, the resulting signal s(t) can be seen as the repetition of a pattern m(t) depending on the speed motor. This signal can be seen as the convolution of this pattern m(t) with a Dirac comb ε Tr (t) having as period Tr the period of revolution of the magnet 3 around the axis of rotation of the impeller 2 . [0000] s ( t )= m ( t )*δ Tr ( t ) [0096] FIG. 6 a shows a signal s(t) corresponding to such an ideal situation and comprising two turn peaks of duration dT. [0097] In a real situation during which the magnet 3 is subjected to vibratory movement of the tip 21 of the vane 20 , the voltage time signal becomes: [0000] s ( t )= m ( t )*δ Tr ( t )+ s v ( t ) [0000] where s v (t) is a vibratory component. An example of such a signal is shown in FIG. 6 b. During rotation, if the blade is animated by vibratory movement comprising an axial component at the magnet 3 , the movement vibratory induces voltage (for minor shifts) proportional to its axial speed. [0098] FIG. 6 c also shows a voltage time signal over a period longer than the period of revolution of the vane; a plurality of turn peaks is accordingly present in this signal. Spectral Analysis [0099] A spectrum S(f) corresponding to the signal s(t), obtained during step 104 and also shown in FIG. 7 , is expressed in the form: [0000] S ( f )= M ( f )δ Fr ( f )+ Sv ( f ) [0000] where M(f) is the spectrum of the pattern m(t) and Sv(f) the spectrum of the vibratory signal sv(t) and Fr is the frequency of rotation of the impeller 2 corresponding to the period Tr. [0100] It is therefore clear that the frequency representation of the signal measured at the terminals of the electrical conductor 4 will be composed of the spectrum of the vibratory component, an additive term corresponding to the set of patterns. This latter term will be a Dirac comb at the frequency Fr, modulated by the spectrum of the pattern m(t). [0101] Signature analysis of turbines is generally done as a function of the speeds of the different mobile generators (NG) or free turbines. In fact these mobiles constitute the main sources of excitations in a turbine engine, which is why the evolution of the spectral content is shown as a function of the excitation speed. An excitation frequency fexc such as fexc=speed/60 is associated with a speed of a mobile. [0102] The variation of the spectral content of the signal S(f) can therefore be represented as a function of the speed of the impeller 2 . For this, the measuring step 103 is repeated, each measurement starting when a triggering condition is predetermined. The different time signals acquired each correspond to a respective observation window of the same duration or time width. [0103] The acquisition of each time window is achieved for example as a function of a condition of variation of the speed. Each time the condition will be respected the acquisition of an observation window will be made, as will the calculation of a corresponding spectrum (step 104 ). [0104] The start of acquisition can typically be initiated each time the speed rises by a pitch of predetermined speed, for example 60 rpm, or else periodically. [0105] The time windows can be temporally contiguous or else non-contiguous. In practice observation windows are advantageously contiguous so as to be sure of temporally following the evolution of the spectrum. The width of each window is controlled at the same time as a function of a preferred frequency resolution and a “refreshment” rate of the spectrum. [0106] Each spectrum can be determined from a respective time signal, as seen previously, or else as a variant, from an average of N time signals acquisition of which is triggered successively. [0107] In any case, repetition of steps 103 and 104 produces a plurality of spectra which can be combined so as to work out different types of diagrams of interest known to those skilled in the art such as a time-frequency diagram or a Campbell diagram. [0108] A time-frequency diagram for displaying the evolution of the spectrum associated with the vibrations of the tip 21 as a function of time (the Fourier transform performed is a short-time Fourier transform). In this case, partially covering observation windows are advantageous as they improve the time and frequency resolution of such a time-frequency diagram. [0109] A Campbell diagram displays the evolution of the spectrum associated with the vibrations of the tip 21 as a function of the motor speed. [0110] The consequences of frequency analysis of the signal of the spectrum worked out in this way are of several orders: The whole motor orders is clearly materialized on the spectrum by the Dirac comb whereof the frequency is synchronous to the speed. The amplitude of the different motor orders will be modulated in frequency by the spectrum of the turn pattern, which will decrease the amplitudes of the peaks near the limits of the analysis band. The terms corresponding to the motor orders and the useful signal are additive, which better reveals the resonance phenomena of any vanes, whereas each resonance identified between a vane mode 2 and a motor order will be the sum of these two contributions (and therefore not representative of the vibratory amplitude of the vane). [0114] The formulated spectra can form the object of other processing in the frequency domain. For carrying out such processing, those skilled in the art could refer to the work by M. Kay called “Modern Spectral Estimation”. Materials [0115] The electrical conductor 4 can be positioned directly on the internal surface 10 of the casing 1 , facing the impeller 2 . [0116] As a variant, the conductor can be positioned inside the casing 1 , but ensuring that any portion of material of the casing 1 located between the electrical conductor 4 and the magnet 3 promotes good transmission of the magnetic field generated by the magnet 3 to a portion of the electrical conductor 4 . It could be ensured that said portion of material is made of paramagnetic and diamagnetic material, as these materials in fact have magnetic permeability values close to 1. So since the magnetic flow of the magnet 3 would be slightly modified, the whole magnetic flow generated by the magnet 3 could therefore be exploited in the measurements taken. [0117] The electrical conductor 4 is for example embedded all or part in an abradable deposit located on the internal surface 10 of the casing 1 facing the impeller 2 , the abradable deposit being made of such paramagnetic or diamagnetic material. [0118] The magnet 3 can further comprise aluminium-nickel-cobalt (AlNiCo) with a Curie point between 800° C. and 850° C. (the Curie point being the temperature at which the material loses its spontaneous magnetization). [0119] The amplifier 5 can be an amplifier of constant current type, advantageously applying gains of up to 3000. It is possible to boost the voltage at the terminals of the electrical conductor 4 to produce measurable voltage of the order of a millivolt. [0120] The assembly E for turbine engine described can be applied to any type of impeller rotatably movable in a fixed structure similar to a casing: axial wheels, centrifugal impellers, high-pressure turbines, free turbines, etc. [0121] A turbine engine comprising such an assembly E can also be embedded in any type of vehicle, especially an aircraft.
An assembly for a turbine engine, the assembly including a casing and an impeller rotatably movable inside the casing, the impeller including at least one blade having a tip edge opposite the casing, wherein the tip edge includes a magnet and wherein the casing includes an electrical conductor suitable for generating between the terminals thereof an electric voltage induced by the magnet of the tip edge opposite same and representing vibrations sustained by the tip edge of the blade when the impeller is rotated.
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FIELD OF THE INVENTION [0001] The present invention relates to a cosmetic formulation comprising an amphiphilic urethane resin carrying a polysiloxane compound. BACKGROUND OF THE INVENTION [0002] There are a variety of cosmetic formulations in which coating characteristics are utilized, including hair cosmetic formulations, nail formulations, facial pack formulations, eye formulations and the like. For example, a hair formulation contains, as an essential component, a hair-styling component which has been selected from anionic, nonionic or amphiphilic acrylic polymers, vinyl pyrrolidone-based polymers, cationic vinyl pyrrolidone-based or cellulose-based polymers and the like. A nail formulation contains nitrocellulose, an acrylic polymer and the like as a film-forming agent or film-forming aid and a facial pack formulation contains a polyvinyl alcohol, polyvinyl acetate and the like as a film forming agent, while an eye formulation such as a mascara and eyeliner contains an acrylic polymer, polyvinyl acetate and the like as a film-forming agent. [0003] However, any of the materials described above is not a film-forming agent which is satisfactory for providing a product which meets a consumer's demand. [0004] JP-A-11-228363 discloses a cosmetic resin composition containing an amphiphilic urethane resin. JP-A-2000-191476 discloses an amphiphilic urethane resin obtained by introducing a polysiloxane chain into the backbone of the amphiphilic urethane resin using a polysiloxane compound having an active hydrogen-containing functional group on the both or either one of the terminals of the siloxane chain. JP-A-2001-48735 discloses a cosmetic formulation into which an amphiphilic urethane resin and a silicone polymer are incorporated each as a formulation component. However, any of these cosmetic formulations and resin-containing formulations is not satisfactory in terms of the handling performance and the stability. [0005] Under such circumstances, the present invention is intended to develop a coating agent consisting of a novel amphiphilic urethane resin obtained by improving a conventional urethane resin and to apply such a formulation to a cosmetic product. SUMMARY OF THE INVENTION [0006] Now we discovered that the problems discussed above can be solved by developing a novel coating agent in which a polysiloxane compound is carried on an amphiphilic urethane resin, whereby establishing the invention. [0007] Thus, the invention is a cosmetic formulation comprising an amphiphilic urethane resin carrying a polysiloxane compound. [0008] A novel amphiphilic urethane resin employed in the invention is characterized structurally by a polysiloxane compound carried thereon. [0009] The phrase “carrying” a polysiloxane here means “restricting” a polysiloxane compound by an amphiphilic urethane resin backbone, or “tangling” a polysiloxane compound with an amphiphilic urethane resin backbone, rather than binding a polysiloxane compound chemically with an amphiphilic urethane resin backbone. Accordingly, the term “carried” used herein means that a polysiloxane compound is “restricted” by an amphiphilic urethane resin backbone or that a polysiloxane compound is “tangled” with an amphiphilic urethane resin backbone. Nevertheless, it is acceptable that a part of the polysiloxane compound eventually forms a part of the backbone of an amphiphilic urethane resin, and such a partial chemical binding is not excluded as long as an intended amphiphilic urethane resin is obtained. The carrying of a polysiloxane compound on an amphiphilic urethane resin can be identified for example by IR spectroscopy. [0010] The amphiphilic urethane resin as a constituent of the amphiphilic urethane resin carrying a polysiloxane compound employed in a cosmetic formulation of the invention is preferably an amphiphilic urethane resin formed by reacting at least compounds (A) to (D): [0011] (A) a polyol compound; [0012] (B) a polyisocyanate compound; [0013] (C) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a carboxyl group; and, [0014] (D) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a tertiary amino group. [0015] To exist means here that a polysiloxane compound just exists in the reaction system rather than that the polysiloxane compound is reacted intentionally, while it is acceptable that a irreversible and partial reaction may eventually be caused. The term “exist” in conjunction with the production of an inventive amphiphilic urethane resin carrying a polysiloxane compound is employed here to have the meaning described above. [0016] The amphiphilic urethane resin carrying a polysiloxane compound described above which is employed preferably can be obtained using at least compounds (A) to (D) and (S): [0017] (A) a polyol compound; [0018] (B) a polyisocyanate compound; [0019] (C) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a carboxyl group; [0020] (D) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a tertiary amino group; and, [0021] (S) a polysiloxane compound; [0022] by a method comprising a first step for producing an isocyanate group-containing prepolymer by reacting the compounds (A), (B) and (C) under an isocyanate group-excess condition and a second step for reacting said isocyanate group-containing prepolymer with the compound (D), [0023] wherein the compound (S) is allowed to exist in at least one of the first step and second step. [0024] The amphiphilic urethane resin carrying a polysiloxane compound described above which is employed preferably can be obtained using at least compounds (A) to (D) and (S): [0025] (A) a polyol compound; [0026] (B) a polyisocyanate compound; [0027] (C) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a carboxyl group; [0028] (D) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a tertiary amino group; and, [0029] (S) a polysiloxane compound; [0030] by a method comprising a first step for producing an isocyanate group-containing prepolymer by reacting the compounds (A), (B) and (D) under an isocyanate group-excess condition and a second step for reacting said isocyanate group-containing prepolymer with the compound (C), [0031] wherein the compound (S) is allowed to exist in at least one of the first step and second step. [0032] In the production of an inventive amphiphilic urethane resin carrying a polysiloxane compound, a polysiloxane compound is allowed to exist in either of the first step and the second step. [0033] In producing an inventive amphiphilic urethane resin carrying a polysiloxane compound using at least the compounds (A) to (D) and (S) described above, it is preferable that after the second step a step for mixing the reaction product from the second step with water to perform a chain elongation reaction is further provided. [0034] It is further preferred in producing an inventive amphiphilic urethane resin carrying a polysiloxane compound using at least the compounds (A) to (D) and (S) described above that after the second step a step for mixing the reaction product from the second step with basic water to perform a chain elongation reaction or a step for adding a basic compound to the reaction product from the second step followed by mixing with water to perform a chain elongation reaction is further provided. [0035] The amphiphilic urethane resin carrying a polysiloxane compound employed in the invention may be an amphiphilic urethane resin formed by reacting in the presence of a polysiloxane compound at least compounds (A) to (E): [0036] (A) a polyol compound; [0037] (B) a polyisocyanate compound; [0038] (C) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a carboxyl group; [0039] (D) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a tertiary amino group; and, [0040] (E) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a structural unit represented by Formula (1): —(C 2 H 4 O) p (C 3 H 6 O) q —  (1) [0041] wherein p is an integer of 1 to 500 and q is an integer of 0 to 400. [0042] The amphiphilic urethane resin carrying a polysiloxane compound described above which is employed preferably can be obtained using at least compounds (A) to (E) and (S): [0043] (A) a polyol compound; [0044] (B) a polyisocyanate compound; [0045] (C) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a carboxyl group; [0046] (D) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a tertiary amino group; [0047] (E) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a structural unit represented by Formula (1): —(C 2 H 4 O) p (C 3 H 6 O) q —  (1) [0048] wherein p is an integer of 1 to 500 and q is an integer of 0 to 400; and, [0049] (S) a polysiloxane compound; [0050] by a method comprising a first step for producing an isocyanate group-containing prepolymer by reacting the compounds (A), (B), (C) and (E) under an isocyanate group-excess excess condition and a second step for reacting said isocyanate group-containing prepolymer with the compound (D), [0051] wherein the compound (S) is allowed to exist in at least one of the first step and second step. [0052] Furthermore, the amphiphilic urethane resin carrying a polysiloxane compound described above which is employed preferably can be obtained using at least compounds (A) to (E) and (S): [0053] (A) a polyol compound; [0054] (B) a polyisocyanate compound; [0055] (C) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a carboxyl group; [0056] (D) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a tertiary amino group; [0057] (E) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a structural unit represented by Formula (1): —(C 2 H 4 O) p (C 3 H 6 O) q —  (1) [0058] wherein p is an integer of 1 to 500 and q is an integer of 0 to 400; and, [0059] (S) a polysiloxane compound; [0060] by a method comprising a first step for producing an isocyanate group-containing prepolymer by reacting the compounds (A), (B), (D) and (E) under an isocyanate group-excess condition and a second step for reacting said isocyanate group-containing prepolymer with the compound (C), [0061] wherein the compound (S) is allowed to exist in at least one of the first step and second step. [0062] In producing an inventive amphiphilic urethane resin carrying a polysiloxane compound using at least the compounds (A) to (E) and (S) described above, it is preferable that after the second step a step for mixing the reaction product from the second step with water is performed to effect a chain elongation reaction. [0063] Moreover, in producing an inventive amphiphilic urethane resin carrying a polysiloxane compound using at least the compounds (A) to (E) and (S) described above, it is preferable that after the second step a step for mixing the reaction product from the second step with basic water is performed to effect a chain elongation reaction or a step for adding a basic compound to the reaction product from the second step followed by mixing with water is performed to effect a chain elongation reaction. [0064] In producing an inventive amphiphilic urethane resin carrying a polysiloxane compound, a polysiloxane compound is allowed to exist in at least one of the first step and the second step. The polysiloxane compound employed here may exist at any time during the first step and the second step, and the polysiloxane compound is not necessary to exist at an early stage of the reaction. It is sufficient that the polysiloxane compound exists not later than the mixing of the reaction product from the second step with water. Accordingly, in the invention, “the first step” covers the duration from the initiation of the first step through the initiation of the second step, while “the second step” covers the duration from the initiation of the second step through the initiation of the subsequent step (more typically, the step for mixing the reaction product from the second step with water as described below). [0065] A polysiloxane compound employed in the production of an inventive amphiphilic urethane resin carrying a polysiloxane compound is preferably a polysiloxane compound which does not have, on both or either one of the terminals of the siloxane, at least one group selected from a hydroxyl group, primary amino group and secondary amino group. [0066] A polysiloxane compound employed in the production of an inventive amphiphilic urethane resin carrying a polysiloxane compound is one or more selected from a dimethylpolysiloxane, polyether-modified silicone, cyclic silicone, phenyl-modified silicone, alkyl-modified silicone and alkoxy-modified silicone. [0067] An inventive amphiphilic urethane resin carrying a polysiloxane compound is incorporated preferable as an aqueous liquid of said amphiphilic urethane. [0068] An inventive amphiphilic urethane resin is preferably an amphiphilic urethane resin having a carboxyl group and a tertiary amino group in one molecule. [0069] A cosmetic formulation to which the invention is applied preferably is a hair formulation and a dermal external formulation. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0070] The embodiments of the invention are described below. [0071] A cosmetic formulation of the invention contains an amphiphilic urethane resin carrying a polysiloxane compound. The amphiphilic urethane resin described above which is employed preferably in the invention is an amphiphilic urethane resin having a carboxyl group and a tertiary amino group in one molecule. [0072] An amphiphilic urethane resin as a constituent of an inventive amphiphilic urethane resin carrying a polysiloxane compound having a carboxyl group and a tertiary amino group in one molecule (hereinafter sometimes referred to as a polysiloxane-carrying amphiphilic urethane resin) is preferably an amphiphilic urethane resin formed by reacting at least compounds (A) to (D): [0073] (A) a polyol compound; [0074] (B) a polyisocyanate compound; [0075] (C) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a carboxyl group; and, [0076] (D) a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a tertiary amino group. [0077] A polyol compound employed in the invention (hereinafter referred to as a compound (A)) is not limited particularly provided that it is a polyol compound employed ordinarily in producing an urethane resin. The compound (A) may for example be a polyester polyol, polyether polyol, low molecular weight polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, polyolefin polyol, polyacrylate-based polyol and the like, any of which can be employed alone or in combination. Among those listed above, a polyester polyol, polyether polyol and low molecular weight polyol are employed preferably. [0078] Such a polyester polyol may for example be a polyester polyol obtained by condensation polymerization of at least one dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid and terephthalic acid with at least one polyhydric acid such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, spiroglycol and trimethylol propane, as well as a polyester polyol obtained by ring-opening polymerization of a lacton. [0079] A polyether polyol mentioned above may for example be a polyether polyol obtained by ring-opening addition polymerization of water and a polyhydric alcohol employed in the synthesis of a polyester polyol described above as well as a phenol such as bisphenol A and a hydride thereof, a primary amine or secondary amine, with a cyclic ether such as ethylene oxide, propylene oxide, oxethane and tetrahydrofuran. Those also exemplified include a polyoxypropylene polyol, polyoxytetramethylene polyol, as well as a polyether polyol obtained by ring-opening addition polymerization of bisphenol A with at least one of propylene oxide and ethylene oxide (when a copolymer results, it may be a block copolymer or random copolymer). [0080] A low molecular weight polyol mentioned above may for example be 1,4-cyclohexanedimethanol, ethylene glycol, propylene glycol, isopropylene glycol, 1,4-butanediol, 1,3-butanediol, butylene glycol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, dipropylene glycol, spiroglycol, trimethylol propane, glycerin, diglycerin, triglycerin and the like. [0081] A compound (A) may be employed alone or in combination. A preferred compound (A) is 1,4-cyclohexane dimethanol. [0082] In the invention, a compound (A), which overlaps with a compound (E) described below, is included in a compound (E) rather than in a compound (A). Also in the invention, a compound (A), which overlaps with a compound (C) described below, is included in a compound (C) rather than in a compound (A). Furthermore in the invention, a compound (A), which overlaps with a compound (D) described below, is included in a compound (D) rather than in a compound (A). [0083] A polyisocyanate compound employed in the invention (hereinafter sometimes referred to as a compound (B)) is not limited particularly provided that it is a polyisocyanate compound employed ordinarily in producing an urethane resin. The compound (B) may for example be an organic diisocyanate compound such as an aliphatic diisocyanate compound, alicyclic diisocyanate compound and aromatic diisocyanate compound, which can be employed alone or in combination with each other. [0084] An aliphatic diisocyanate mentioned above may for example be ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 1,6-hexamethylene diisocyanate. [0085] An alicyclic diisocyanate mentioned above may for example be hydrogenated 4,4′-diphenylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate and norbornane diisocyanate. [0086] An aromatic diisocyanate mentioned above may for example be 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, toluene diisocyanate and naphthalene diisocyanate. [0087] Among the compounds (B) listed above, 1,6-hexamethylene diisocyanate, isophorone diisocyanate and norbornane diisocyanate and the like are preferred because of excellent weatherability and less expense. Any of compounds (b) may be employed alone or in combination. [0088] A compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a carboxyl group (hereinafter sometimes referred to as a compound (C)) employed in the invention is not limited particularly provided that it is a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having at least one carboxyl group and can give an intended amphiphilic urethane resin. The compound (C) may preferably be a carboxylic acid of 3 to 26, preferably 3 to 12 carbon atoms having a dialkylol group such as dimethylol, diethanol and dipropanol. Those exemplified typically include dimethylol propanoic acid (DMPA) and dimethylol butanoic acid. A carboxyl group-containing polycaprolactonediol can also be employed. Those listed above may be employed alone or in combination. [0089] A compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having a tertiary amino group (hereinafter sometimes referred to as a compound (D)) employed in the invention is not limited particularly provided that it is a compound having at least one group selected from a hydroxyl group, primary amino group and secondary amino group and also having at least one tertiary amino group and can give an intended amphiphilic urethane resin. The compound (D) may for example be an N-alkyldialkanolamine compound one having a dialkylol group similar to a compound (C) such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine and N-methyldipropanolamine. The number of carbon atoms in the alkyl group of an N-alkyl in an N-alkyldialkanolamine is preferably 1 to 24, especially 1 to 8. Those also exemplified are an N,N-dialkylalkanolamine compound such as N,N-dimethylethanolamine, N,N-diethylethanolamine and N,N-dibutylethanolamine as well as triethanolamine. Those listed above may be employed alone or in combination. [0090] A polysiloxane compound employed in the invention (hereinafter sometimes referred to as a compound (S)) is not limited particularly provided that it is a polysiloxane compound which is capable of being incorporated into a cosmetic formulation and which does not have, on both or either one of the siloxane chain terminals, at least one group selected from a hydroxyl group, primary amino group and secondary amino group and can give an intended amphiphilic urethane resin. Such a polysiloxane compound may for example be a dimethylpolysiloxane, polyether-modified silicone, cyclic silicone, phenyl-modified silicone, alkyl-modified silicone and alkoxy-modified silicone. These polysiloxane compounds may be employed alone or in combination. [0091] A dimethylpolysiloxane may for example be a compound represented by Formula (2): [0092] wherein n is an integer of 1 or more. [0093] In the formula, n is preferably an integer of 1 to 100, more preferably 1 to 50, especially 3 to 30. [0094] A dimethylpolysiloxane in the invention may be any commercially available one, such as SH 200 series (trade name) produced by Dow Corning Toray Silicone Co. Ltd., and as well as KF 96 series produced by Shin-Etsu Chemical Co. Ltd. [0095] A polyether-modified silicone may for example be a compound represented by Formula (3): [0096] wherein m is an integer of 0 or more, n is an integer of 1 or more, and R 1 is a group represented by Formula (4): —(CH 2 ) a —(OC 2 H 4 ) b (OC 3 H 6 ) c —OR 2   (4) [0097] wherein R 2 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, a is an integer of 1 to 10, b is an integer of 1 to 300 and c is an integer of 0 to 300. [0098] In Formula (3), m is preferably an integer of 1 to 300, more preferably 1 to 100, particularly 1 to 50. n is preferably an integer of 1 to 300, more preferably 1 to 100, particularly 1 to 50. Also in Formula (4), a is preferably an integer of 1 to 5, particularly 2 to 4. b is preferably an integer of 2 to 50, more preferably 2 to 40, particularly 2 to 30. c is preferably an integer of 0 to 50, more preferably 0 to 40, particularly 0 to 30. [0099] A compound (S) represented by Formula (3) which is preferred is a compound represented by Formula (3) wherein m is an integer of 1 to 300, n is an integer of 1 to 300, R 1 is a group represented by Formula (4), a is an integer of 1 to 5, b is an integer of 2 to 50 and c is an integer of 0 to 50. [0100] A compound (S) represented by Formula (3) which is more preferred is a compound represented by Formula (3) wherein m is an integer of 1 to 100, n is an integer of 1 to 100, R 1 is a group represented by Formula (4), a is an integer of 2 to 4, b is an integer of 2 to 40 and c is an integer of 0 to 40. [0101] A compound (S) represented by Formula (3) which is especially preferred is a compound represented by Formula (3) wherein m is an integer of 1 to 50, n is an integer of 1 to 50, R 1 is a group represented by Formula (4), a is an integer of 2 to 4, b is an integer of 2 to 30 and c is an integer of 0 to 30. [0102] A polyether-modified silicone represented by Formula (3) may for example be SH3746, SH3771C, SH3772C, SH3773C, SH3775C, SH3748, SH3749, SH3771M, SH3772M, SH3773M and SH3775M (trade name) produced by Dow Corning Toray Silicone Co. Ltd., as well as KF351A, KF353A, KF945A, KF352A, KF615A, KF6011, KF6012, KF6013, KF6015, KF6016 and KF6017 (trade name) produced by Shin-Etsu Chemical Co. Ltd. [0103] A phenyl-modified silicone may for example be a compound represented by Formula (5): [0104] wherein each of R 3 and R 4 , which may be same or different, is a hydrocarbon group having 1 to 12 carbon atoms (for example, a straight or branched saturated hydrocarbon group having 1 to 12 carbon atoms), —OSi(CH 3 ) 3 or phenyl group, provided that at least one of R 3 and R 4 is a phenyl group, m is an integer of 0 or more and n is an integer of 1 or more. [0105] In Formula (5), m is preferably an integer of 1 to 300, more preferably 1 to 100, particularly 1 to 50. n is preferably an integer of 1 to 500, more preferably 1 to 100, particularly 1 to 50. A phenyl-modified silicone which is preferred especially is a methylphenylpolysiloxane represented by Formula (5) wherein R 3 ═CH 3 or —OSi(CH 3 ) 3 , R 4 ═C 6 H 5 , m=0 and n=1 to 100. [0106] A phenyl-modified silicone represented by Formula (5) may for example be SH556, SF557, SF558 and SH559 (trade name) produced by Dow Corning Toray Silicone Co. Ltd., and KF50-100cs, KF50-1000cs, KF53, KF54 and KF56 (trade name) produced by Shin-Etsu Chemical Co. Ltd. [0107] An alkyl-modified silicone may for example be a compound represented by Formula (6): [0108] wherein each of R 5 to R 7 , which may be same or different, is a hydrocarbon group having 1 to 50 carbon atoms, provided that at least one of R 5 to R 7 is a hydrocarbon group having 5 to 30 carbon atoms, m is an integer of 1 or more and n is an integer of 1 or more. [0109] In Formula (6), each of R 5 to R 7 may for example be a straight or branched saturated hydrocarbon group having 1 to 50 carbon atoms. The number of carbon atoms in the hydrocarbon group is preferably 5 to 30, more preferably 5 to 20, particularly 1 to 20. m is preferably an integer of 10 to 300, more preferably 1 to 100, particularly 1 to 50. n is preferably an integer of 1 to 300, more preferably 1 to 100, particularly 1 to 50. [0110] An alkyl-modified silicone represented by Formula (6) may for example be SF8416 (trade name) produced by Dow Corning Toray Silicone Co. Ltd., and KF-412, KF-413 and KF-414 (trade name) produced by Shin-Etsu Chemical Co. Ltd. [0111] An alkoxy-modified silicone may for example be a compound represented by Formula (7): [0112] wherein each of R 8 to R 10 , which may be same or different, is a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 50 carbon atoms, provided that at least one of R 8 to R 10 is an alkoxy group having 1 to 50 carbon atoms, m is an integer of 0 or more, and n is an integer of 1 or more. [0113] While each of R 8 to R 10 in Formula (7) is a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 50 carbon atoms, such a hydrocarbon group having 1 to 12 carbon atoms may for example be a straight or branched saturated hydrocarbon group and an alkoxy group having 1 to 50 carbon atoms may for example be a straight or branched alkoxy group. The number of carbon atoms in the hydrocarbon group having 1 to 50 carbon atoms is preferably 1 to 30, more preferably 1 to 25, particularly 1 to 20. m is preferably an integer of 1 to 500, more preferably 1 to 100, particularly 1 to 50. n is preferably an integer of 1 to 100, more preferably 1 to 80, particularly 1 to 50. [0114] An alkoxy-modified silicone represented by Formula (7) may for example be KF-851 and X-22-801B (trade name) produced by Shin-Etsu Chemical Co. Ltd. [0115] A cyclic silicone may for example be a compound represented by Formula (8): [0116] wherein R 11 is a hydrocarbon group having 2 to 12 carbon atoms which may be same or different among repeating units, m is an integer of 1 or more, n is an integer of 0 or more, and m+n=3 to 10. [0117] In Formula (8), R 11 may for example be a straight or branched saturated hydrocarbon group having 1 to 12 carbon atoms. The number of the carbon atoms in R 11 is preferably 2 to 10, more preferably 2 to 8, particularly 2 to 5. m is preferably an integer of 3 to 8, more preferably 4 to 8, particularly 4 to 6. n is preferably an integer of 0 to 7, more preferably 0 to 5, particularly 0 to 3. m+n is preferably 3 to 8, more preferably 4 to 8, particularly 4 to 6. [0118] A cyclic silicone represented by Formula (8) may for example be SH244, SH344, SH245, DC345 and DC246 (trade name) produced by Dow Corning Toray Silicone Co. Ltd., as well as KF994, KF995 and KF9937 (trade name) produced by Shin-Etsu Chemical Co. Ltd. [0119] The repeating units of the compounds represented by Formulae (3) and (5) to (8) may be of any type of the polymerization such as random polymerization and block polymerization. [0120] The viscosity (dynamic viscosity) of a compound (S) at 25° C. is preferably 1 to 5000 mm 2 /s, more preferably 1 to 2000 mm 2 /s, particularly 1 to 1000 mm 2 /S. A preferred compound (S) is a dimethylpolysiloxane or polyether-modified silicone. The compound (S) can be employed alone or in combination. [0121] A preferred polysiloxane-carrying amphiphilic urethane resin of the invention is an amphiphilic urethane resin produced by reacting at least compounds (A) to (D) described above in the presence of a compound (S) described above. Such a polysiloxane-carrying amphiphilic urethane resin according to the invention can be produced using at least compounds (A) to (D) and (S) described above, by a method comprising a first step for producing an isocyanate group-containing prepolymer by reacting the compounds (A), (B) and (C) under an isocyanate group-excess condition and a second step for reacting said isocyanate group-containing prepolymer with the compound (D), wherein the compound (S) is allowed to exist in at least one of the first step and second step. In the production, the order of the reactions of the compounds (C) and (D) may be exchanged. [0122] The weight ratio between a compound (S) and compounds (A), (B), (C) and (D), thus, (S)/((A)+(B)+(C)+(D)) is preferably 0.1/100 to 30/100, more preferably, 0.5/100 to 25/100, particularly 1/100 to 20/100. [0123] The molar ratio between a compound (B) and compounds (A), (C) and (D), thus, (B)/((A)+(C)+(D)) is preferably 2.0/1.8 to 2.0/0.8, more preferably, 2.0/1.8 to 2.0/1.0, particularly 2.0/1.8 to 2.0/1.2. [0124] The reactions in the first step and second step described above are conducted under the conditions employed ordinarily for producing a polyurethane in the presence of polymerization catalysts as appropriate. Such a polymerization catalyst may be one employed ordinarily for producing an urethane resin. The polymerization catalyst may for example be a tertiary amine catalyst, organometal catalyst and the like. The tertiary amine catalyst may for example be [2.2.2]diazabicyclooctane (DABCO), tetramethylenediamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like. The organometal catalyst may for example be dibutyltin dilaurate and the like. [0125] For producing an amphiphilic urethane resin described above, the reactions in the first step and the second step may employ organic solvents as desired, and it is preferred for example to use an organic solvent capable of dissolving the both of compounds (A) to (D) and a resultant amphiphilic urethane resin. Such an organic solvent may for example be an amide such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide, a ketone such as acetone and methylethylketone, an ester such as ethyl acetate, as well as cellosolve acetate and cellosolve ether. [0126] After a second step, the reaction product from the second step is preferably mixed with water to perform a chain elongation reaction. After the second step, the reaction product from the step is mixed with basic water to perform the chain elongation reaction. Alternatively, the reaction product from the second step is preferably admixed with a basic compound and then combined with water to perform the chain elongation reaction. Among such procedures, the procedure in which after the second step the reaction product from the step is mixed with basic water to perform the chain elongation reaction is especially preferred. In the invention, it is preferred that the reactions in the first step and second step are performed in an organic solvent and then the reaction product from the second step is mixed with basic water to perform the chain elongation reaction consecutively in water. Such an embodiment involving the mixing of the reaction product from the second step with the basic water to perform the chain elongation reaction consecutively in water is preferred because it allows an amphiphilic urethane resin whose molecular weight is increased to be obtained readily. In the production method in this embodiment, it is preferable to select a production condition capable of yielding a reaction product from the second step which is a prepolymer containing an isocyanate group on its terminal. [0127] The basic water described above means water containing a basic substance dissolved therein and exhibiting a basic nature, such as water containing triethylamine, triethanolamine, ammonia, potassium hydroxide, sodium hydroxide, 2-amino-2-methyl-1-propanol and the like dissolved therein. [0128] A chain elongation reaction in the process for producing a polysiloxane-carrying amphiphilic urethane resin according to the invention may employ a chain elongation agent, and such a chain elongation agent serves to control the characteristics of the polysiloxane-carrying amphiphilic urethane resin as a final product. The chain elongation agent is a compound employed in a chain elongation reaction such as a low molecular weight polyol, amine, water and the like. Such a low molecular weight polyol may for example be a glycol such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, spiroglycol, bis(β-hydroxyethoxy)benzene, xylylene glycol and the like, as well as a triol such as trimethylol propane, glycerin and the like. An amine mentioned above may for example be methylene (bis-o-chloroaniline) and the like. [0129] In the invention, it is preferable to use as a polysiloxane-carrying amphiphilic urethane resin one having a structural unit derived from an alkylene oxide (hereinafter sometimes referred to as RO) in the resin structure for the purpose of improving the stability and the characteristics of a cosmetic formulation. The structural unit derived from RO may for example be an ethylene oxide (hereinafter sometimes referred to as EO) unit or a propylene oxide (hereinafter sometimes referred to as PO) unit, with the EO unit being preferred. [0130] A compound having a structural unit derived from RO in its structure is not limited particularly provided that it is capable of introducing the structural unit derived from RO into the structure of a polysiloxane-carrying amphiphilic urethane resin. [0131] A compound having a structural unit derived from RO in its structure is preferably a compound having at least one selected from a hydroxyl group, primary amino group and secondary amino group and a structural unit represented by Formula (1): —(C 2 H 4 O) p (C 3 H 6 O) q —  (1) [0132] wherein p is an integer of 1 to 500 and q is an integer of 0 to 400. [0133] Formula (1) wherein q is 0 gives a polymer of C 2 H 4 O (polyoxyethylene), while that wherein q is not 0 gives a copolymer of C 2 H 4 O with C 3 H 6 O. Such a copolymer may be a random copolymer or block copolymer. [0134] In Formula (1), p is an integer of 1 to 500. Whether q is not 0 or q is 0, p is preferably 3 to 250, more preferably 3 to 120, particularly 3 to 50. q less than 1 leads to a too small amount of the EO units introduced into an amphiphilic urethane resin, resulting in a poor hydrophilicity, which makes a hair conditioner, for example, to which the amphiphilic urethane resin is applied poorly hydrophilic and poorly hair-washable. On the other hand, n exceeding 500 leads to a too high hydrophilicity of an amphiphilic urethane resin itself, resulting in an adverse effect on the moisture resistance and the like. [0135] Also, the repeating number q of the PO units in Formula (1) is an integer of 0 to 400, preferably q=0. When q is not 0, it is preferred to select as q a number within the range of 3 to 200, more preferably 3 to 100. A particularly preferred number is 3 to 40. Whether q is not 0 or q is 0, p+q is preferably within the range from 3 to 300, more preferably 10 to 120, particularly 3 to 50. [0136] Whether q is 0 or not, the weight ratio between the EO units and the PO units as EO units/PO units is within the range preferably from 10/0 to 2/8, more preferably from 10/0 to 3/7, particularly 10/0 to 4/6. [0137] A compound (E) is preferably of both-terminal OH introduction type, both-terminal NH 2 introduction type, one-terminal OH introduction type and one-terminal NH 2 introduction type. When using a both-terminal OH introduction type or both-terminal NH 2 introduction type compound, an amphiphilic urethane resin having a structural unit represented by Formula (1) in its backbone is obtained. Also, when using a one-terminal OH introduction type or one-terminal NH 2 introduction type compound, an amphiphilic urethane resin having a structural unit represented by Formula (1) on its side chain or on its terminal is obtained. [0138] The weight mean molecular weight of a compound (E) described above is preferably 200 to 20000, more preferably 200 to 5000, particularly 500 to 2000. [0139] A compound (E) may for example be a polyethylene glycol (PEG), polyethylene polypropylene glycol, polyethylene polypropylene block copolymer and the like. Among those listed above, a polyethylene glycol is employed preferably. The compound (E) can be employed alone or in combination. [0140] A polysiloxane-carrying amphiphilic urethane resin when a compound (E) is added is preferably an amphiphilic urethane resin produced by reacting at least compounds (A) to (E) described above in the presence of a compound (S) described above. [0141] Such a resin can be produced by a method similar to that employed when a compound (E) is not added. Thus, it can be produced using at least compounds (A) to (E) and (S) described above, by a method comprising a first step for producing an isocyanate group-containing prepolymer by reacting the compounds (A), (B), (C) and (E) under an isocyanate group-excess condition and a second step for reacting said isocyanate group-containing prepolymer with the compound (D), wherein the compound (S) is allowed to exist in at least one of the first step and second step. It is also possible that the order of the reactions of the compounds (C) and (D) may be exchanged. [0142] The weight ratio between a compound (S) and compounds (A), (B), (C), (D) and (E), thus, (S)/((A)+(B)+(C)+(D)+(E)) is preferably 0.1/100 to 30/100, more preferably, 0.5/100 to 25/100, particularly 1/100 to 20/100. [0143] The molar ratio between a compound (B) and compounds (A), (C), (D) and (E), thus, (B)/((A)+(C)+(D)+(E)) is preferably 2.0/1.8 to 2.0/0.8, more preferably, 2.0/1.8 to 2.0/1.0, particularly 2.0/1.8 to 2.0/1.2. [0144] The reactions in the first step and second step described above are conducted under the conditions employed ordinarily for producing a urethane in the presence of polymerization catalysts as appropriate similarly to the procedure employing no compound (E). The polymerization catalyst, organic solvent and chain elongation reaction are as discussed above. Also when adding a compound (E), the first step and the second step are conducted preferably in an organic solvent, with the chain elongation reaction performed in water being more preferred. [0145] A polysiloxane-carrying amphiphilic urethane resin of the invention has a carboxyl group and a tertiary amino group in one molecule. The ratio of the carboxyl group and the tertiary amino group (number ratio between both functional groups) when represented as carboxyl group/tertiary amino group is preferably 1/50 to 50/1, more preferably 1/1 to 50/1, particularly 1/1 to 25/1. A ratio of the carboxyl group and the tertiary amino group in a polysiloxane-carrying amphiphilic urethane resin within the range from 1/50 to 50/1 gives a hair conditioner containing such a polysiloxane-carrying amphiphilic urethane resin capability to impart a further improved touch to the hair. When effecting a reaction, the molar ratio of a compound (C) and a compound (D), i.e., compound (C)/compound (D) is preferably 1/50 to 50/1, more preferably 1/1 to 50/1, particularly 1/1 to 25/1. [0146] A polysiloxane-carrying amphiphilic urethane resin according to the invention is not necessarily one containing the polysiloxane chain of a polysiloxane compound in its backbone via a covalent bond but is one containing the polysiloxane chain as a result of restricting the polysiloxane compound by the backbone of the amphiphilic urethane resin or as a result of tangling the polysiloxane chain of the polysiloxane compound mechanically with the backbone of the amphiphilic urethane resin. Such a restricting or tangling structure is believed to become further complicated as the polymerization reaction of an amphiphilic urethane is further advanced, resulting in a difficulty in allowing the polysiloxane compound to be released from the resultant amphiphilic urethane resin. [0147] Such a restricting or tangling state between the backbone of an amphiphilic urethane resin and a polysiloxane compound is referred here to as a state in which the backbone of the amphiphilic urethane resin is “carrying” the polysiloxane compound. The “carrying” has a meaning here which may vary depending on whether the amphiphilic urethane resin is in the form of an aqueous solution or aqueous dispersion. While the backbone of the amphiphilic urethane resin is usually in a straight chain structure, it may be in a branched chain structure or crosslinked structure, and it is understood that the polysiloxane chain is intercalated in the backbone of the amphiphilic urethane resin when the amphiphilic urethane resin is in the form of an “aqueous solution”. [0148] On the other hand, the amphiphilic urethane resin in the form of an “aqueous dispersion” is understood to be in a state where the amphiphilic urethane resin is present as a particle dispersed in water, the particle being restricted by the polysiloxane chain in various morphologies. In the first morphology, the polysiloxane chain is enclosed entirely or partially in the particle. In the second morphology, a terminal of the polysiloxane chain is enclosed in the particle. In the third morphology, the polysiloxane chain is deposited on the surface of the particle. Any of the first to third morphologies represents the “restricting” state, and mixture of the first to third morphologies also represents the “restricting” state. [0149] As discussed above, the backbone of an amphiphilic urethane resin according to the invention carries a polysiloxane compound. As a result, the polysiloxane chain is considered to be difficult to be released from the amphiphilic urethane resin while it maintains relatively higher mobility. [0150] The Production Examples of polysiloxane-carrying amphiphilic urethane resins according to the invention and other urethane resins for comparison are described below. PRODUCTION EXAMPLE 1 Polysiloxane-Carrying Amphiphilic Urethane Resin (A) [0151] A four-necked flask fitted with a stirrer, thermometer, nitrogen inlet and condenser was filled with 70 g of isophorone diisocyanate (IPDI), 63 g of a polypropylene glycol (PPG, weight mean molecular weight: 1000), 7 g of 1,4-cyclohexane dimethanol (CHDM), 8 g of a dimethylpolysiloxane (viscosity at 25° C.: 10 mm 2 /s, SH200C-10cs (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) and 20 g of dimethylol butanoic acid (DMBA) together with 50 g of ethyl acetate as a solvent, which were heated to 80° C. using an oil bath and reacted for 3 hours. Subsequently, 2 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were further added and reacted at 80° C. for further 3 hours to obtain a prepolymer in which the isocyanate group was still remaining. After this prepolymer in which the isocyanate group was still remaining was cooled to 50° C., it was dispersed in 700 g of water containing 10 g of potassium hydroxide by a high speed agitation, and then subjected to a chain elongation reaction at 50° C. for 3 hours to increase the molecular weight. From the resultant aqueous liquid, ethyl acetate was recovered to obtain an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (A) containing substantially no solvent. PRODUCTION EXAMPLE 2 Polysiloxane-Carrying Amphiphilic Urethane Resin (B) [0152] Using the method similar to that in Production Example 1 except for using 8 g of a polyether-modified silicone (viscosity at 25° C.: 1600 mm 2 /s, SH3775C (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Production Example 1, an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (B) was obtained. [0153] PRODUCTION EXAMPLE 3 Polysiloxane-Carrying Amphiphilic Urethane Resin (C) [0154] Using the method similar to that in Production Example 1 except for using 8 g of a cyclic silicone (viscosity at 25° C.: 4 mm 2 /S, SH245 (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Production Example 1, an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (C) was obtained. PRODUCTION EXAMPLE 4 Polysiloxane-Carrying Amphiphilic Urethane Resin (D) [0155] Using the method similar to that in Production Example 1 except for using 8 g of a phenyl-modified silicone (viscosity at 25° C.: 22 mm 2 /s, SH556 (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Production Example 1, an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (D) was obtained. PRODUCTION EXAMPLE 5 Polysiloxane-Carrying Amphiphilic Urethane Resin (E) [0156] Using the method similar to that in Production Example 1 except for using 8 g of an alkyl-modified silicone (viscosity at 25° C.: 500 mm 2 /S, KF-412 (trade name) produced by Shin-Etsu Chemical Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Production Example 1, an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (E) was obtained. PRODUCTION EXAMPLE 6 Polysiloxane-Carrying Amphiphilic Urethane Resin (F) [0157] Using the method similar to that in Production Example 1 except for using 8 g of an alkoxy-modified silicone (viscosity at 25° C.: 80 mm 2 /S, KF-851 (trade name) produced by Shin-Etsu Chemical Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Production Example 1, an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (F) was obtained. PRODUCTION EXAMPLE 7 Polysiloxane-Carrying Amphiphilic Urethane Resin (G) [0158] Using the method similar to that in Production Example 1 except for using 8 g of a dimethylpolysiloxane (viscosity at 25° C.: 10 mm 2 /S, SH200C-10cs (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Production Example 1, an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (G) was obtained. PRODUCTION EXAMPLE 8 Polysiloxane-Carrying Amphiphilic Urethane Resin (H) [0159] Using the method similar to that in Production Example 1 except for using 20 g of a polyether-modified silicone (viscosity at 25° C.: 1600 mm 2 /s, SH3775C (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Production Example 1, an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (H) was obtained. PRODUCTION EXAMPLE 9 Polysiloxane-Carrying Amphiphilic Urethane Resin (I) [0160] A four-necked flask fitted with a stirrer, thermometer, nitrogen inlet and condenser was filled with 70 g of isophorone diisocyanate (IPDI), 55 g of a polypropylene glycol (PPG, weight mean molecular weight: 1000), 8 g of a polyethylene glycol (PEG, weight mean molecular weight: 1000), 7 g of 1,4-cyclohexane dimethanol (CHDM), 8 g of a dimethylpolysiloxane (viscosity at 25° C.: 10 mm 2 /S, SH200C-10cs (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) and 20 g of dimethylol butanoic acid (DMBA) together with 50 g of ethyl acetate as a solvent, which were heated to 80° C. using an oil bath and reacted for 3 hours. Subsequently, 2 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were further added and reacted at 80° C. for further 3 hours to obtain a prepolymer in which the isocyanate group was still remaining. After this prepolymer in which the isocyanate group was still remaining was cooled to 50° C., it was dispersed in 700 g of water containing 10 g of potassium hydroxide by a high speed agitation, and then subjected to a chain elongation reaction at 50° C. for 3 hours to increase the molecular weight. From the resultant aqueous liquid, ethyl acetate was recovered to obtain an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (I) containing substantially no solvent. PRODUCTION EXAMPLE 10 Polysiloxane-Carrying Amphiphilic Urethane Resin (J) [0161] Using the method similar to that in Production Example 9 except for using 8 g of a polyether-modified silicone (viscosity at 25° C.: 1600 mm 2 /S, SH3775C (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Production Example 9, an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (J) was obtained. PRODUCTION EXAMPLE 11 Polysiloxane-Carrying Amphiphilic Urethane Resin (K) [0162] Using the method similar to that in Production Example 9 except for using 20 g of a dimethylpolysiloxane (viscosity at 25° C.: 10 mm 2 /S, SH200C-10cs (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Production Example 9, an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (K) was obtained. PRODUCTION EXAMPLE 12 Polysiloxane-Carrying Amphiphilic Urethane Resin (L) [0163] Using the method similar to that in Production Example 9 except for using 20 g of a polyether-modified silicone (viscosity at 25° C.: 1600 mm 2 /S, SH3775C (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Production Example 9, an aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin (L) was obtained. COMPARATIVE PRODUCTION EXAMPLE 1 Amphiphilic Urethane Resin (M) [0164] Using the method similar to that in Production Example 1 without using dimethylpolysiloxane used in Production Example 1, an aqueous liquid of an amphiphilic urethane resin (M) was obtained. COMPARATIVE PRODUCTION EXAMPLE 2 Amphiphilic Urethane Resin (N) [0165] A four-necked flask fitted with a stirrer, thermometer, nitrogen inlet and condenser was filled with 70 g of isophorone diisocyanate (IPDI), 63 g of a polypropylene glycol (PPG, weight mean molecular weight: 1000), 7 g of 1,4-cyclohexane dimethanol (CHDM) and 20 g of dimethylol butanoic acid (DMBA) together with 50 g of ethyl acetate as a solvent, which were heated to 80° C. using an oil bath and reacted for 3 hours. Subsequently, 2 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were further added and reacted at 80° C. for further 3 hours to obtain a prepolymer in which the isocyanate group was still remaining. After this prepolymer in which the isocyanate group was still remaining was cooled to 50° C., it was dispersed in 700 g of water containing 10 g of potassium hydroxide by a high speed agitation, and then subjected to a chain elongation reaction at 50° C. for 3 hours to increase the molecular weight. From the resultant aqueous liquid, ethyl acetate was recovered to obtain an aqueous liquid of an amphiphilic urethane resin containing substantially no solvent, and then 8 g of a dimethylpolysiloxane (viscosity at 25° C.: 10 mm 2 /S , SH200C-10cs (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) was added to obtain an aqueous liquid of an amphiphilic urethane resin (N). COMPARATIVE PRODUCTION EXAMPLE 3 Amphiphilic Urethane Resin (O) [0166] Using the method similar to that in Comparative Production Example 2 except for using 8 g of a polyether-modified silicone (viscosity at 25° C.: 1600 mm 2 /s, SH3775C (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Comparative Production Example 2, an aqueous liquid of an amphiphilic urethane resin (O) was obtained. [0167] COMPARATIVE PRODUCTION EXAMPLE 4 Amphiphilic Urethane Resin (P) [0168] Using the method similar to that in Comparative Production Example 2 except for using 8 g of a cyclic silicone (viscosity at 25° C.: 4 MM2/S, SH245 (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Comparative Production Example 2, an aqueous liquid of an amphiphilic urethane resin (P) was obtained. COMPARATIVE PRODUCTION EXAMPLE 5 Amphiphilic Urethane Resin (Q) [0169] Using the method similar to that in Comparative Production Example 2 except for using 8 g of a phenyl-modified silicone (viscosity at 25° C.: 22 mm 2/S SH556 (trade name) produced by Dow Corning Toray Silicone Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Comparative Production Example 2, an aqueous liquid of an amphiphilic urethane resin (O) was obtained. COMPARATIVE PRODUCTION EXAMPLE 6 Amphiphilic Urethane Resin (R) [0170] Using the method similar to that in Comparative Production Example 2 except for using 8 g of a alkyl-modified silicone (viscosity at 25° C.: 500 MM2/S, KF-412 (trade name) produced by Shin-Etsu Chemical Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Comparative Production Example 2, an aqueous liquid of an amphiphilic urethane resin (R) was obtained. COMPARATIVE PRODUCTION EXAMPLE 7 Amphiphilic Urethane Resin (S) [0171] Using the method similar to that in Comparative Production Example 2 except for using 8 g of a alkoxy-modified silicone (viscosity at 25° C.: 80 mm 2 /s, KF-851 (trade name) produced by Shin-Etsu Chemical Co. Ltd.) instead of 8 g of the dimethylpolysiloxane employed in Comparative Production Example 2, an aqueous liquid of an amphiphilic urethane resin (S) was obtained. COMPARATIVE PRODUCTION EXAMPLE 8 Amphiphilic Urethane Resin (T) [0172] Using the method similar to that in Production Example 1 except for using 8 g of a dimethylpolysiloxanediol (both-terminal OH introduction type, viscosity at 25° C.: 62 mm 2 /s, KF-6002 (trade name) produced by Shin-Etsu Chemical Co. Ltd.) and 55 g of a polypropylene glycol (PPG, weight mean molecular weight: 1000) instead of 8 g of the dimethylpolysiloxane and 63 g of the polypropylene glycol (PPG, weight mean molecular weight: 1000), respectively, employed in Production Example 1, an aqueous liquid of an amphiphilic urethane resin (T) was obtained. COMPARATIVE PRODUCTION EXAMPLE 9 Amphiphilic Urethane Resin (U) [0173] Using the method similar to that in Production Example 1 except for using 8 g of a dimethylpolysiloxanediol (both-terminal OH introduction type, viscosity at 25° C.: 88 mm 2 /s, X-22-176B (trade name) produced by Shin-Etsu Chemical Co. Ltd.) and 55 g of a polypropylene glycol (PPG, weight mean molecular weight: 1000) instead of 8 g of the dimethylpolysiloxane and 63 g of the polypropylene glycol (PPG, weight mean molecular weight: 1000), respectively, employed in Production Example 1, an aqueous liquid of an amphiphilic urethane resin (U) was obtained. [0174] Cosmetic formulations containing polysiloxane-carrying amphiphilic urethane resins are discussed below. [0175] In a cosmetic formulation of the invention, it is preferred to use a polysiloxane-carrying amphiphilic urethane resin as an aqueous liquid, and a polysiloxane-carrying amphiphilic urethane resin according to the invention preferably forms an aqueous liquid when being mixed with water. In the invention, such an aqueous liquid means an aqueous solution state in which a polysiloxane-carrying amphiphilic urethane resin is dissolved completely in water as well as an aqueous dispersion state and/or aqueous suspension state in which a polysiloxane-carrying amphiphilic urethane resin is dispersed and/or suspended in water. Nevertheless, it is also acceptable to use a resin component of a polysiloxane-carrying amphiphilic urethane resin obtained by substantially removing solvents such as water. An aqueous liquid of a polysiloxane-carrying amphiphilic urethane resin described above may be imparted with a crosslinking ability by adding a crosslinking agent such as a silane coupling agent. Various additives can also be added for obtaining the storage stability, and protective colloidal agents, antibacterial agents and antifungal agents may be mentioned. [0176] A cosmetic formulation of the invention can be obtained in a standard manner by incorporating a polysiloxane-carrying amphiphilic urethane resin described above as a component of the cosmetic formulation. The invention is advantageous especially in obtaining an excellent cosmetic formulation capable of exerting the functional coating characteristics of a polysiloxane-carrying amphiphilic urethane resin. Such a cosmetic formulation is not limited particularly, and the invention can be applied widely to hair formulations such as hair dressing formulations including hair dressing foams, hair dressing gels, hair dressing aerosol sprays, hair dressing pump sprays as well as hair conditioners, makeup formulations such as mascaras, eyeliners, nail polishes, foundations and lip colors, dermal external formulations such as facial packs and masks, shaving aids, creams, milky lotions, lotions, essences (beauty essences) and the like, fragrances, body formulations and the like. [0177] The form of a cosmetic formulation may also vary widely, including solution systems, solubilized systems, emulsion systems, foams, powder systems, powder dispersion systems, oil systems, gel systems, ointment systems, aerosol systems, spray systems, pump spray systems, water-oil two-layer systems, water-oil-powder three-layer systems and the like. [0178] While the amount of a polysiloxane-carrying amphiphilic urethane resin described above in the invention may vary depending on the types of the cosmetic formulations, it is preferably 0.1 to 25.0% by weight based on the total amount of the cosmetic formulation. For example, the amount when used as a film-forming agent in a hair formulation is preferably 0.1 to 10.0% by weight based on the total amount of the cosmetic formulation, more preferably 0.5 to 0.8% by weight. The amount when used in a makeup formulation such as mascara, eyeliner, nail polish, foundation, lip color and the like is preferably 0.1 to 25.0% by weight based on the total amount of the cosmetic formulation. The amount in a facial pack or mask is preferably 0.1 to 25.0% by weight based on the total amount of the cosmetic formulation. The amount in a dermal external formulation such as a shaving formulation, cream, milky lotion, lotion, essence (beauty essence) and the like is preferably 0.1 to 15.0% by weight based on the total amount of the cosmetic formulation. [0179] In addition to the components described above, other auxiliary components employed usually in cosmetic and pharmaceutical formulations may also be added to an inventive cosmetic formulation as long as they do not affect the invention adversely. For example, oil components, powder components, surfactants, humectants, water-soluble polymers, thickening agent, coatings, UV absorbers, metal ion sequestering agents, saccharides, amino acids, organic amines, pH modifiers, skin nutrients, vitamins, antioxidants, fragrances and water can be mentioned. [0180] The invention is further detailed in Examples shown below. An amount indicated is a % by weight. A % is a % by weight unless otherwise specified. Prior to the description of Examples, the tests for evaluating the effects of the invention are described below. [0181] (Elasticity: Curl Memory Method) [0182] A black virgin hair (20 cm in length, 4 g in weight) was coated with 0.5 g of a prepared styling moose, and 5 curls were produced per sample and dried at 50° C. for 1 hour. The length of each curled hair strand was measured and recorded as an initial value (c). Then a 60 g load was applied to the tip of the hair over a period of 15 minutes, after which the load was removed and the scale was read at the hair tip point (d). According to the following equation, the curl memory value was calculated. Curl memory value (%)={(20 −d )/(20 −c )}×100 [0183] A curl memory value closer to 100% indicates a higher % curl maintenance and higher elasticity. The evaluation criteria are shown below. [0184] ⊚: 90% or higher [0185] ◯: 70 to less than 90% [0186] Δ: 50 to less than 70% [0187] x: Less than 50% [0188] (Flaking) [0189] A black virgin hair (20 cm in length, 4 g in weight) was coated with 0.5 g of a prepared styling moose, dried at 50° C. for 1 hour, and then allowed to stand in a thermostat chamber at 25° C. and 60% relative humidity over a period of 30 minutes. This hair strand was subjected to a 5-time combing and the resultant flaking was examined visually. [0190] The evaluation criteria are shown below. [0191] ⊚: Absolutely no flaking [0192] ◯: No flaking [0193] Δ: Slight flaking [0194] x: Flaking [0195] (Stability) [0196] 30 samples of a styling moose were prepared in transparent containers, subjected to a thermal cycle test (50° C., to −10° C., 2 cycle/day, 1 month), examined visually by a trained expert engineer for any separation, creaming or aggregation, and evaluated in accordance with the following criteria. [0197] ⊚: Zero samples exhibited separation, creaming, aggregation and the like. [0198] ◯: One sample exhibited separation, creaming, aggregation and the like. [0199] Δ: Two samples exhibited separation, creaming, aggregation and the like. [0200] x: Three of more samples exhibited separation, creaming, aggregation and the like. EXAMPLES 1 to 6 [0201] First, the characteristics of an inventive cosmetic formulation were demonstrated by conducting an evaluation test using a styling moose as a hair formulation. Styling mousses of Examples 1 to 6 were produced using the formulations shown in Table 1 and examined for the elasticity, flaking and emulsion stability. The results are also indicated in Table 1. The polysiloxane-carrying amphiphilic urethane was added as an aqueous liquid. [0202] (Production Method) [0203] For obtaining an emulsion part, the component (1) was added to the components (2), (3), (4) and a part of the component (16) and the mixture was emulsified using a homomixer. Then a part of the component (15) was added to form the emulsion part. An ethanol part was obtained by dissolving the components (5), (12) to (14) by stirring. For obtaining an aqueous part, the remainder of the component (16), components (6) to (11) and the remainder of the component (15) were admixed and stirred until uniform. These three parts were mixed appropriately to obtain a moose stock solution. 92 Parts of the resultant moose stock solution was filled in an aerosol canister, to which a valve was fitted and 8 parts of liquefied petroleum gas (LPG) was charged, whereby obtaining each styling moose. TABLE 1 Example 1 2 3 4 5 6 1 Dimethylpolysiloxane (6mPa · s) 5.0 5.0 5.0 5.0 5.0 5.0 2 1,3-Butylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 3 Glycerin 5.0 5.0 5.0 5.0 5.0 5.0 4 Polyoxyetylene hardened 2.0 2.0 2.0 2.0 2.0 2.0 caster oil (40EO) 5 Ethanol 10.0 10.0 10.0 10.0 10.0 10.0 6 Polysiloxane-carrying 15.0 — — — — — amphiphilic urethane resin (A) (resin content 20%) 7 Polysiloxane-carrying — 15.0 — — — — amphiphilic urethane resin (B) (resin content 20%) 8 Polysiloxane-carrying — — 15.0 — — — amphiphilic urethane resin (C) (resin content 20%) 9 Polysiloxane-carrying — — — 15.0 — — amphiphilic urethane resin (D) (resin content 20%) 10 Polysiloxane-carrying — — — — 15.0 — amphiphilic urethane resin (E) (resin content 20%) 11 Polysiloxane-carrying — — — — — 15.0 amphiphilic urethane resin (F) (resin content 20%) 12 Special grade lauric 0.2 0.2 0.2 0.2 0.2 0.2 acid diethanol amide (1:1 type) 13 Alkyltrimethylammonium 0.1 0.1 0.1 0.1 0.1 0.1 chloride 14 Paraben 0.1 0.1 0.1 0.1 0.1 0.1 15 Polyoxyethylene lauryl ether 0.4 0.4 0.4 0.4 0.4 0.4 16 Ion exchange water bal. bal. bal. bal. bal. bal. Elasticity ⊚ ⊚ ⊚ ◯ ⊚ ◯ Flaking ⊚ ⊚ ◯ ⊚ ◯ ◯ Stability ◯ ⊚ ◯ ◯ ◯ ◯ [0204] As evident from Examples 1 to 6 shown in Table 1, each of the styling mousses of Examples 1 to 6 which contained each of the polysiloxane-carrying amphiphilic urethane resins (A) to (F) according to the invention exhibited excellent results with regard to all of the elasticity, flaking and stability. EXAMPLES 7 TO 12 [0205] Using the formulations shown in Table 2, styling mousses of Examples 7 to 12 were produced by the method similar to that in Table 1 and examined for the elasticity, flaking and emulsion stability. The results are included in Table 2. Each polysiloxane-carrying amphiphilic urethane resin was added in the form of an aqueous liquid similarly to Table 1. TABLE 2 Example 7 8 9 10 11 12 1 Dimethylpolysiloxane (6mPa · s) 5.0 5.0 5.0 5.0 5.0 5.0 2 1,3-Butylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 3 Glycerin 5.0 5.0 5.0 5.0 5.0 5.0 4 Polyoxyetylene hardened 2.0 2.0 2.0 2.0 2.0 2.0 caster oil (40EO) 5 Ethanol 10.0 10.0 10.0 10.0 10.0 10.0 6 Polysiloxane-carrying 15.0 — — — — — amphiphilic urethane resin (G) (resin content 20%) 7 Polysiloxane-carrying — 15.0 — — — — amphiphilic urethane resin (H) (resin content 20%) 8 Polysiloxane-carrying — — 15.0 — — — amphiphilic urethane resin (I) (resin content 20%) 9 Polysiloxane-carrying — — — 15.0 — — amphiphilic urethane resin (J) (resin content 20%) 10 Polysiloxane-carrying — — — — 15.0 — amphiphilic urethane resin (K) (resin content 20%) 11 Polysiloxane-carrying — — — — — 15.0 amphiphilic urethane resin (L) (resin content 20%) 12 Special grade lauric 0.2 0.2 0.2 0.2 0.2 0.2 acid diethanol amide (1:1 type) 13 Alkyltrimethylammonium 0.1 0.1 0.1 0.1 0.1 0.1 chloride 14 Paraben 0.1 0.1 0.1 0.1 0.1 0.1 15 Polyoxyethylene lauryl ether 0.4 0.4 0.4 0.4 0.4 0.4 (12EO) 16 Ion exchange water Bal. Bal. Bal. Bal. Bal. Bal. Elasticity ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Flaking ◯ ⊚ ⊚ ⊚ ◯ ⊚ Stability ◯ ⊚ ◯ ⊚ ◯ ⊚ [0206] As evident from Examples 7 to 12 shown in Table 2, each of the styling mousses of Examples 7 to 12 which contained each of the polysiloxane-carrying amphiphilic urethane resins (G) to (L) according to the invention exhibited excellent results with regard to all of the elasticity, flaking and stability. [0207] (Comparatives 1 to 5) [0208] Using the formulations shown in Table 3, styling mousses of Comparative 1 to 5 were produced and examined for the elasticity, flaking and emulsion stability. The results are included in Table 3. Each amphiphilic urethane resin was added in the form of an aqueous liquid. [0209] (Production Method) [0210] For obtaining an emulsion part, the component (1) was added to the components (2), (3), (4), a part of the component (15) and the mixture was emulsifying using a homomixer. Then a part of the component (14) was added to form the emulsion part. An ethanol part was obtained by dissolving the components (5), (11) to (13) by stirring. For obtaining an aqueous part, the remainder of the component (15), components (6) to (10) and the remainder of the component (14) were admixed and stirred until uniform. These three parts were mixed appropriately to obtain a moose stock solution. 92 Parts of the resultant moose stock solution was filled in an aerosol canister, to which a valve was fitted and 8 parts of liquefied petroleum gas (LPG) was charged, whereby obtaining each styling moose. TABLE 3 Comparative 1 2 3 4 5 1 Dimethylpolysiloxane (6mPa · s) 5.0 5.0 5.0 5.0 5.0 2 1,3-Butylene glycol 5.0 5.0 5.0 5.0 5.0 3 Glycerin 5.0 5.0 5.0 5.0 5.0 4 Polyoxyetylene hardened 2.0 2.0 2.0 2.0 2.0 caster oil (40EO) 5 Ethanol 10.0 10.0 10.0 10.0 10.0 6 Amphiphilic urethane 15.0 — — — — resin (H) (resin content 20%) 7 Amphiphilic urethane — 15.0 — — — resin (N) (resin content 20%) 8 Amphiphilic urethane — — 15.0 — — resin (O) (resin content 20%) 9 Amphiphilic urethane — — — 15.0 — resin (P) (resin content 20%) 10 Amphiphilic urethane — — — — 15.0 resin (Q) (resin content 20%) 11 Special grade lauric 0.2 0.2 0.2 0.2 0.2 acid diethanol amide (1:1 type) 12 Alkyltrimethylammonium 0.1 0.1 0.1 0.1 0.1 chloride 13 Paraben 0.1 0.1 0.1 0.1 0.1 14 Polyoxyethylene lauryl ether 0.4 0.4 0.4 0.4 0.4 (12EO) 15 Ion exchange water Bal. Bal. Bal. Bal. Bal. Elasticity Δ Δ Δ ◯ Δ Flaking ◯ ◯ Δ X X Stability X X X X X [0211] As evident from Comparatives 1 to 5 in Table 3, each of the styling mousses of Comparatives 1 to 5 which contained each of the amphiphilic urethane resins (M) to (Q) departing from the scope of the invention was not satisfactory with regard to all of the elasticity, flaking and stability. [0212] (Comparative 6 to 10) [0213] Using the formulations shown in Table 4, styling mousses of Comparatives 6 to 10 were produced by the method similar to that in Table 3 and examined for the elasticity, flaking and emulsion stability. The results are included in Table 4. Each amphiphilic urethane resin added was in the form of an aqueous liquid similarly to Table 3. TABLE 4 Comparative 6 7 8 9 10 1 Dimethylpolysiloxane (6mPa · s) 5.0 5.0 5.0 5.0 5.0 2 1,3-Butylene glycol 5.0 5.0 5.0 5.0 5.0 3 Glycerin 5.0 5.0 5.0 5.0 5.0 4 Polyoxyetylene hardened caster 2.0 2.0 2.0 2.0 2.0 oil (40EO) 5 Ethanol 10.0 10.0 10.0 10.0 10.0 6 Amphiphilic urethane resin 15.0 — — — — (R) (resin content 20%) 7 Amphiphilic urethane resin — 15.0 — — — (S) (resin content 20%) 8 Amphiphilic urethane resin — — 15.0 — — (T) (resin content 20%) 9 Amphiphilic urethane resin — — — 15.0 — (U) (resin content 20%) 10 Amphiphilic polymer (resin — — — — 15.0 content 30%) (Note) 11 Special grade lauric acid 0.2 0.2 0.2 0.2 0.2 diethanol amide (1:1 type) 12 Alkyltrimethylammonium 0.1 0.1 0.1 0.1 0.1 chloride 13 Paraben 0.1 0.1 0.1 0.1 0.1 14 Polyoxyethylene lauryl ether 0.4 0.4 0.4 0.4 0.4 (12EO) 15 Ion exchange water Bal. Bal. Bal. Bal. Bal. Elasticity Δ Δ ◯ ◯ X Flaking X X X X ◯ Stability X X X X Δ [0214] As evident from Comparatives 6 to 10 in Table 4, each of the styling mousses of Comparatives 6 to 9 which contained each of the amphiphilic urethane resins (R) to (U) departing from the scope of the invention was not satisfactory with regard to all of the elasticity, flaking and stability. Similarly, Comparative 10 containing an amphiphilic polymer which was not an amphiphilic urethane resin was not satisfactory with regard to all of the elasticity, flaking and stability. [0215] Examples of the invention are further described below. Each polysiloxane-carrying amphiphilic urethane resin incorporated was an aqueous liquid. While the evaluation tests in the following descriptions were not detailed individually, they allowed the characteristics of each polysiloxane-carrying amphiphilic urethane resin of the invention to be exerted sufficiently. Example 13 Facial Pack (Jelly Peel-Off Type) [0216] [0216] Ingredient Amount (% by wt) (1) Polyvinyl alcohol 10.0 (2) Polysiloxane-carrying 2.5 amphiphilic urethane resin (A) (0.5% as resin) (20% aqueous liquid) (3) Polysiloxane-carrying 2.5 amphiphilic urethane resin (J) (0.5% as resin) (20% aqueous liquid) (4) Carboxymethyl cellullose 5.0 (5) 1,3-Butylene glycol 5.0 (6) Ethanol 12.0 (7) Fragrance Appropriate (8) Methylparaben 0.2 (9) Buffer (citric acid, Na citrate) Appropriate (10) Polyoxyethylene oleyl alcohol 0.5 (11) Ion exchange water Balance [0217] (Production Method) [0218] The components (9), (5), (2) and (3) were added to the component (11) and the mixture was heated at 70 to 80° C. Then the components (4) and (1) were added and dissolved by stirring. The components (7), (8) and (10) were added to the component (6) and dissolved, and then the mixture was deaerated, filtered and cooled. The resultant product imparted a watery and smooth touch to the skin together with desirable suppleness. EXAMPLE 14 O/W Emulsion Foundation [0219] [0219] Ingredient Amount (% by wt) (1) Talc 3.0 (2) Titanium dioxide 5.0 (3) Red ocher 0.5 (4) Iron oxide yellow 1.4 (5) Iron oxide black 0.1 (6) Bentonite 0.5 (7) Polyoxyethylene sorbitan monostearate 0.9 (8) Triethanolamine 1.0 (9) Propylene glycol 10.0 (10) Polysiloxane-carrying 10.0 amphiphilic urethane resin (B) (0.5% as resin) (20% aqueous liquid) (11) Ion exchange water Balance (12) Stearic acid 2.2 (13) Isohexadecyl alcohol 7.0 (14) Glycerin monostearate 2.0 (15) Liquid lanolin 2.0 (16) Liquid paraffin 8.0 (17) Ethylparaben 0.1 (18) Fragrance Appropriate [0220] (Production Method) [0221] The component (6) dispersed in the component (9) was added to the component (11), treated using a homomixer at 70° C., combined with the remaining aqueous phase components (7), (8) and (10), and stirred thoroughly. To this, the powder part which had been mixed and pulverized thoroughly was added, and treated using a homomixer at 70° C. Then the liquid phase components (12) to (16) and the component (17) which had been heated and dissolved at 70 to 80° C. were added in portions, and treated using a homomixer at 70° C. The mixture was cooled by stirring to 45° C., at which the component (18) was added, and then the mixture was cooled to room temperature. Finally, the mixture was deaerated and filled in a container. The resultant emulsion foundation was watery and smooth, and gave a long-lasting makeup. Example 15 Eyeliner [0222] [0222] Ingredient Amount (% by wt) (1) Iron oxide black 14.0 (2) Polysiloxane-carrying 45.0 amphiphilic urethane resin (C) (0.9% as resin) (20% aqueous liquid) (3) Glycerin 5.0 (4) Polyoxyethylene sorbitan monooleate 1.0 (5) Carboxymethyl cellulose 1.5 (6) Acetyltributyl citrate 1.0 (7) Ion exchange water Balance (8) Methylparaben 0.1 (9) Fragrance Appropriate [0223] (Production Method) [0224] The components (2), (3) and (4) were added to the component (7), heated and dissolved, and then combined with the component (1), and treated using a colloid mill (pigment part). The remaining components were added and the mixture was heated at 70° C. To this mixture, the pigment part was added and dispersed uniformly using a homomixer. The resultant eyeliner exhibited suitable elasticity, and could be used satisfactorily. Example 16 Skin Lotion [0225] [0225] Ingredient Amount (% by wt) (1) 1,3-Butylene glycol 6.0 (2) Glycerin 5.0 (3) Polyethylene glycol 400 3.0 (4) Olive oil 0.5 (5) Polyoxyethylene(20)sorbitan monostearate 1.5 (6) Polyoxyethylene(5)oleyl alcohol ether 0.3 (7) Ethanol 10.0 (8) Fragrance Appropriate (9) Colorant Appropriate (10) Phenoxyethanol Appropriate (11) Citric acid Appropriate (12) Sodium citrate Appropriate (13) Anti-yellowing agent Appropriate (14) Ion exchange water Balance (15) Polysiloxane-carrying 0.5 amphiphilic urethane resin (D) (0.1% as resin) (20% aqueous liquid) (16) Polysiloxane-carrying 0.5 amphiphilic urethane resin (L) (0.1% as resin) (20% aqueous liquid) [0226] (Production Method) [0227] The components (1), (2), (3), (11), (12), (15) and (16) were added to the component (14) and dissolved at room temperature. On the other hand, the components (4), (5), (6), (10) and (8) were added to the component (7), and dissolved at room temperature. This alcohol phase was added to the aqueous phase described above, to which the components (9) and (13) were added to prepare a microemulsion. The resultant skin lotion was watery and smooth and imparted suppleness to the skin. Example 17 Milky Lotion [0228] [0228] Ingredient Amount (% by wt) (1) Cetyl alcohol 1.0 (2) Beeswax 0.5 (3) Petrolatum 2.0 (4) Squalane 6.0 (5) Dimethylpolysiloxane (viscosity 20 MPa · S) 2.0 (6) Ethanol 4.0 (7) Glycerin 4.0 (8) 1,3-Buthylene glycol 4.0 (9) Polyoxyethylene(10) monooleate 1.0 (10) Glycerol monostearate 1.0 (11) Quince seed extract (5% aqueous solution) 10.0 (12) Polysiloxane-carrying 10.0 amphiphilic urethane resin (E) (2% as resin) (20% aqueous liquid) (13) Methylparaben Appropriate (14) Colorant (dye) Appropriate (15) Fragrance Appropriate (16) Ion exchange water Balance [0229] (Production Method) [0230] The components (7), (8), (12) and (14) were added to the component (16), and heated at 70° C. The components (1) to (5) were combined with the components (9) and (10), and heated at 70° C. This was added to an aqueous phase and pre-emulsified. To this, the components (11) and (13) dissolved in the component (6) were added, and the emulsion particle was made uniform using a homomixer, and then the mixture was deaerated, filtered, combined with the component (15) and then cooled. The resultant milky lotion was watery and smooth, and imparted elasticity to the skin. Example 18 Cream [0231] [0231] Ingredient Amount (% by wt) (1) Stearyl alcohol 6.0 (2) Stearic acid 2.0 (3) Hydrogenated lanolin 4.0 (4) Squalane 9.0 (5) Octyl dodecanol 10.0 (6) 1,3-Butylene glycol 6.0 (7) Polyethylene glycol 1500 4.0 (8) Polysiloxane-carrying 3.0 amphiphilic urethane resin (F) (0.6% as resin) (20% aqueous liquid) (9) Polyoxyethylene(25) cetyl alcohol ether 3.0 (10) Glycerin monostearate 2.0 (11) Methylparaben Appropriate (12) Vitamin E Appropriate (13) Fragrance Appropriate (14) Ion exchange water Balance [0232] (Production Method) [0233] The components (6), (7) and (8) were added to the component (14), and heated at 70° C. The components (1) to (5) were heated and dissolved, and then combined with the components (9), (10), (11), (12) and (13), and adjusted at 70° C. This was combined with the aqueous phase described above, and the emulsion particle was made uniform using a homomixer, and then the mixture was deaerated, filtered and cooled. The resultant cream was watery and smooth, and imparted elasticity to the skin. Example 19 Whitening Essence [0234] [0234] Ingredient Amount (% by wt) (1) Dipropylene glycol 5.0 (2) Ethanol 10.0 (3) Hydrogenated lanolin 4.0 (4) Carboxyvinyl polymer 0.3 (5) Sodium alginate 0.3 (6) Potassium hydroxide 0.15 (7) Polyoxyethylene sorbitan monostearate 1.0 (8) Sorbitan monooleate 0.5 (9) Polysiloxane-carrying 0.5 amphiphilic urethane resin (G) (0.1% as resin) (20% aqueous liquid) (10) Oleyl alcohol 0.5 (11) Placenta extract 0.2 (12) Vitamin E acetate 0.2 (13) Fragrance Appropriate (14) Methylparaben Appropriate (15) Trisodium edetate Appropriate (16) Ion exchange water Balance [0235] (Production Method) [0236] The components (4) and (5) were dissolved in a part of the component (16), in which then the components (1), (2) and (15) were dissolved successively. In the component (3), the components (7), (8), (10), (11), (12), (13) and (14) were dissolved successively, and then combined with the aqueous phase described above, and the mixture was microemulsified. Finally, the component (6) was dissolved in a part of the component (16) and added to the mixture, to which then the component (9) was added, and the mixture was stirred, deaerated and filtered. The resultant whitening essence was watery and smooth, and imparted elasticity to the skin. Example 20 Anti-UV Essence [0237] [0237] Ingredient Amount (% by wt) (1) Stearic acid 3.0 (2) Cetanol 1.0 (3) Lanolin derivative 3.0 (4) Liquid paraffin 5.0 (5) 2-Ethylhexyl stearate 3.0 (6) 1,3-Butylene glycol 6.0 (7) Polysiloxane-carrying 4.0 amphiphilic urethane resin (H) (0.8% as resin) (20% aqueous liquid) (8) Polyoxyethylene cetyl alcohol 2.0 ether (9) Glycerin monostearate 2.0 (10) Triethanolamine 1.0 (11) 2-Hydroxy-4- 4.0 methoxybenzophenone (12) Dibenzoylmethane derivative 4.0 (13) Sorbic acid 0.2 (14) Fragrance Appropriate (15) Ion exchange water Balance [0238] (Production Method) [0239] The components (6), (7) and (10) were dissolved in the component (15) and kept at 70° C. by heating. The components (1) to (5) were dissolved by heating at 70 to 80° C., and then the components (8), (9), (11), (12), (13) and (14) were added successively and the mixture was kept at 70° C. The oil phase was added by stirring the aqueous phase described above to effect emulsification. The emulsion particle was made uniform using a homomixer, and then the mixture was deaerated, filtered and cooled. The resultant anti-UV essence was watery and smooth, and imparted suitable elasticity to the skin. Example 21 Hair Styling Gel [0240] [0240] Ingredient Amount (% by wt) (1) Carboxyvinyl polymer 0.7 (2) Polysiloxane-carrying 5.0 amphiphilic urethane resin (I) (1.0% as resin) (20% aqueous liquid) (3) Polysiloxane-carrying 5.0 amphiphilic urethane resin (K) (1.0% as resin) (20% aqueous liquid) (4) Glycerin 2.5 (5) 1,3-Butylene glycol 2.5 (6) Polyoxyethylene hardened castor oil (40EO) 0.5 (7) Dimethylpolysiloxane 100cs 5.0 (8) Polyether-modified silicone 1.0 (trade name: KF6011, produced by Shin-Etsu Chemical Co. Ltd.) (9) Sodium hydroxide Appropriate (for adjusting at pH7.5) (10) Ethanol 20.0 (11) Polyoxyethylene octyldodecyl ether 0.1 (12) Fragrance 0.1 (13) Trisodium edetate 0.03 (14) Ion exchange water Balance [0241] (Production Method) [0242] To the components (4), (5), (6), (8) and a part of (14), the component (7) was added and the mixture was emulsified. Then a part of the component (14) was added to form an emulsion part. On the other hand, the components (1), (2), (3), (9), (10), (11), (12) and (13) were dissolved uniformly in the remainder of the component (14), to which the emulsion part described above was added to obtain an emulsion type hair styling gel. EXAMPLE 22 Nail Polish [0243] [0243] Ingredient Amount (% by wt) (1) Ethyl carbitol 2.5 (2) 1,3-Butylene glycol 1.0 (3) Polysiloxane-carrying 45.0 amphiphilic urethane resin (B) (9.0% as resin) (20% aqueous liquid) (4) Polysiloxane-carrying 40.0 amphiphilic urethane resin (A) (8.0% as resin) (20% aqueous liquid) (5) Clay mineral 0.2 (6) Polyoxyethylene hardened castor oil (40EO) 0.3 (7) Colorant Appropriate (8) Ion exchange water Balance [0244] (Production Method) [0245] The component (6) was dissolved in the component (8), with which the component (7) was then mixed and dispersed thoroughly. Then the components (1) to (5) were mixed uniformly by stirring to obtain a nail polish. EXAMPLE 23 Mascara [0246] [0246] Ingredient Amount (% by wt) (1) Iron oxide (black) 10.0 (2) Polysiloxane-carrying 20.0 amphiphilic urethane resin (C) (6.0% as resin) (30% aqueous liquid) (3) Polysiloxane-carrying 10.0 amphiphilic urethane resin (G) (3.0% as resin) (30% aqueous liquid) (4) Solid paraffin 8.0 (5) Lanolin wax 8.0 (6) Light isoparaffin 30.0 (7) Sesqui-oleic acid sorbitan 4.0 (8) Ion exchange water Balance (9) Preservative Appropriate (10) Fragrance Appropriate [0247] (Production Method) [0248] The component (8) was combined with the component (1), dispersed using a homomixer, admixed with the components (2) and (3), and kept at 70° C. by heating (aqueous phase). Other components were mixed and kept at 70° C. by heating (oil phase). The aqueous phase was dispersed uniformly in the oil phase using a homomixer. EXAMPLE 24 Lip Color [0249] [0249] Ingredient Amount (% by wt) (1) Titanium oxide 4.5 (2) Red No. 201 2.5 (3) Ceresin 4.0 (4) Candelilla wax 8.0 (5) Carnauba wax 2.0 (6) Castor oil 30.0 (7) Isostearic acid diglyceride 40.0 (8) Polyoxyethylene hardened castor oil (20EO) 1.0 (9) Ion exchange water Balance (10) Polysiloxane-carrying 2.0 amphiphilic urethane resin (D) (0.6% as resin) (30% aqueous liquid) (11) Polysiloxane-carrying 3.0 amphiphilic urethane resin (E) (0.9% as resin) (30% aqueous liquid) (12) Glycerin 2.0 (13) Fragrance Appropriate (14) Antioxidant Appropriate [0250] (Production Method) [0251] The components (1) and (2) were added to a part of the component (6), and treated using a roller (pigment part). The components (9) to (12) were mixed (aqueous phase). The components (3) to (5), a part of the component (6) and the components (7), (8) and (14) were mixed, melted by heating, combined with the pigment part at 80° C., and mixed uniformly using a homomixer. Subsequently, water was added, and the mixture was emulsified and dispersed using a homomixer, combined with the component (13) and then poured into a mold. INDUSTRIAL APPLICABILITY [0252] According to the invention, an excellent cosmetic formulation capable of allowing the coating characteristics of a novel polysiloxane-carrying amphiphilic urethane resin to be exerted sufficiently can be obtained. For example, a hair cosmetic formulation in particular can give an improved hair elasticity without undergoing any flaking upon combing, and exhibits an excellent emulsion stability of the product. A makeup cosmetic formulation exhibits a watery touch and a long-lasting performance for example to its wearing resistance. A dermal cosmetic formulation is also watery and smooth and imparts suitable elasticity to the skin.
It is intended to develop a film agent made of a novel amphoteric urethane resin and apply to cosmetics, in particular, hair cosmetics and external preparations for the skin. Namely, cosmetics characterized by containing an amphoteric urethane resin carrying a polysiloxane compound. Thus excellent cosmetics which can fully exert the film properties of the novel polysiloxane-carrying amphoteric urethane resin can be obtained. In case of hair cosmetics, for example, a favorable elasticity of the hair and excellent brushing properties without causing flaking can be established. In case of skin cosmetics, a moist and smooth feel and an appropriate elasticity can be imparted to the skin.
97,099
FIELD OF THE INVENTION This invention relates to a radiotelephone unit, and more particularly to, a radiotelephone unit including a receiving circuit for TDMA (time division multiple access), such as PHS (personal handy-phone system). BACKGROUND OF THE INVENTION A conventional receiver circuit to conduct TDMA receiving (herein, also referred to as `time division multiplex receiving`) comprises a receive mixer circuit, an IR (intermediate-frequency) filter, an IF amplifier, a demodulator, and a controller to which a field strength output from the IF amplifier is input. This is a typical receiving circuit in which one IF filter is provided for one intermediate frequency. For example, TDMA transmitting and receiving are conducted by using four transmit slots, T1, T2, T3 and T4 followed by four receive slots, R1, R2, R3 and R4. The four transmit slots and four receive slots compose one frame length. The TDMA transmitting and receiving are conducted by repeating such frames. With regard to the four receive slots, in typical cases, one slot is assigned to a control channel and the other three slots are assigned to call channels. Thus, three calls at maximum can be simultaneously used. Also, whether a receive slot is vacant and can be used as a call channel is judged as follows. In general, the field strength output from the IF amplifier is compared with a predetermined threshold value in the controller. When the former is higher than the latter, it is judged that an electric field exists and the receive slot is occupied. On the other hand, when the former is lower than the latter, it is judged that no electric field exists and the receive slot is vacant. Thus, call channels can be in turn assigned to vacant slots, thereby allowing three calls at maximum to be used. However, in the conventional TDMA receiver circuit, there is the problem that a receive slot to be duly judged as having no received field is erroneously judged as having a received field due to a delay in fall time of the field strength output for the previous receive slot. Therefore, the receive slot is not available for a call channel, thereby the three calls at maximum cannot be obtained and the connection rate must be reduced. The problem is frequently caused by the performance of a SAW filter typically used as the IF filter. Thus, it may happen that a receive slot duly available for a call channel cannot be used. This causes a reduction in the connection rate. Especially when a received field to be input is high, the erroneous judgment as having a received field may frequently happen because the delay in field detection up to the next slot becomes significant with an increase in field strength level. SUMMARY OF THE INVENTION Accordingly, it is an object of the invention to provide a radiotelephone unit that all receive slots can be effectively used. It is a further object of the invention to provide a method for conducting time division multiplex receiving that all receive slots can be effectively used. According to the invention, a radiotelephone unit for conducting time division multiplex receiving, comprises: two intermediate-frequency filters provided with a same performance; and means for switching alternately the two intermediate-frequency filters every time when a receive slot is changed. According to another aspect of the invention, a method for conducting time division multiplex receiving, comprises the step of: providing two intermediate-frequency filters with a same performance; and switching alternately the two intermediate-frequency filters every time when a receive slot is changed; wherein a propagation response delay in the output of either of the two intermediate-frequency filters for a receive slot is cancelled by switching into the other of the two intermediate-frequency filters for the next receive slot. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be explained in more detail in conjunction with the appended drawings, wherein: FIG. 1 is a block diagram showing a conventional TDMA receiver circuit, FIGS. 2A to 2D are timing charts illustrating the operation of the circuit in FIG. 1, FIG. 3 is a block diagram showing a radiotelephone unit in a preferred embodiment according to the invention, and FIGS. 4A to 4F are timing charts illustrating the operation of the radiotelephone unit in FIG. 3. DESCRIPTION OF THE PREFERRED EMBODIMENTS Before explaining a radiotelephone unit in the preferred embodiment, the aforementioned conventional receiver circuit to conduct TDMA receiving will be explained in FIGS. 1 to 2D. FIG. 1 shows the conventional receiver circuit to conduct TDMA receiving. The receiver circuit comprises a receive mixer circuit 1, an IF (intermediate-frequency) filter 2, an IF amplifier 6, a demodulator 9, and a controller 10 to which a field strength output 7 from the IF amplifier 6 is input. This is a typical receiving circuit where one IF filter is provided for one intermediate frequency. The TDMA receiving operation of the receiver circuit, which is taken as an example of a radiotelephone device for PHS base station, will be explained in FIGS. 2A to 2D. FIG. 2A shows transmit and receive slots used for TDMA transmitting and receiving. One slot length is 625 μ,sec, and four transmit slots, T1, T2, T3 and T4 are followed by four receive slots, R1, R2, R3 and R4. The four transmit slots and four receive slots compose one frame length of 5 msec. The TDMA transmitting and receiving are conducted by repeating such frames. With regard to the four receive slots, in typical cases, one slot is assigned to a control channel and the other three slots are assigned to call channels. Thus, three calls at maximum can be simultaneously used. Also, whether a receive slot is vacant and can be used as a call channel is judged as follows. In general, the field strength output 7 from the IF amplifier 6 is compared with a predetermined threshold value in the controller 10. When the former is higher than the latter, it is judged that an electric field exists and the receive slot is occupied. On the other hand, when the former is lower than the latter, it is judged that no electric field exists and the receive slot is vacant. Thus, call channels can be in turn assigned to vacant slots, thereby allowing three calls at maximum to be used. However, in the conventional TDMA receiver circuit, there is the problem that a receive slot to be duly judged as having no received field is erroneously judged as having a received field due to a delay in fall time of the field strength output 7 for the previous receive slot. For example, even when the third receive slot R3 receives an electric field and the fourth receive slot R4 receives no electric field (FIG. 2B), the output of the IF filter 2 may be not instantly returned to zero due to the propagation response delay that can have a fall time of tens of microseconds (FIG. 2C). If some field strength output 7 remains in the fourth receive slot R4 so that it can be judged as having a received field (FIG. 2D), the fourth receive slot R4 is not available. Next, a radiotelephone unit in the preferred embodiment will be explained in FIG. 3, wherein like parts are indicated by like reference numerals as used in FIG. 1. The radiotelephone unit in the embodiment, adding to the conventional unit composition in FIG. 3, comprises a receive mixer circuit 1, two IF (intermediate-frequency) filters 2, 3 inserted between the receive mixer circuit 1 and the IF amplifier 6, and filter switches 4, 5 to switch alternately the two IF filters 2, 3. The filter switches 4, 5 are controlled by a slot change point signal 8 from the controller 10. The operation of the radiotelephone unit will be explained in FIGS. 4A to 4F. When the slot change point signal 8 from the controller 10 is at high level., the filter switches 4, 5 switch into the direction of the IF filter 2 for the first receive slot R1 and third receive slot R3. The output of the IF filter 2 is input to the IF amplifier 6, then applied as a field strength output 7 to the controller 10, where it is used to judge the existence of electric field. On the other hand, when the slot change point signal 8 from the controller 10 is at low level, the filter switches 4, 5 switch into the direction of the IF filter 3 for the second receive slot R2 and fourth receive slot R4. The output of the IF filter 3 is input to the IF amplifier 6, then applied as a field strength output 7 to the controller 10, where it is used to judge the existence of electric field. Now, taken is an example that only the third receive slot R3 is receiving (FIG. 4C). When the above-mentioned propagation response delay occurs at the IF filter 2 (FIG. 4D), an IF filter available is already switched into the IF filter 3 for the fourth receive slot R4 to follow R3. Thereby, the output of the IF filter 3 (FIG. 4E) is applied as a field strength output 7 (FIG. 4F) to the controller 10 to be used to judge the existence of electric field. Therefore, the propagation response delay occurring at the IF filter 2 does not affect the judgment of the existence of electric field in the controller 10. Although the invention has been described with respect to specific embodiment for complete and clear disclosure, the appended claims are not to be thus limited but are to be construed as embodying all modification and alternative constructions that may be occurred to one skilled in the art which fairly fall within the basic teaching here is set forth
A radiotelephone unit for conducting time division mutiplex receiving includes a two intermediate-frequency filters provided with the same performance, and switches for switching alternately the two intermediate-frequency filters every time when a receive slot is changed. First and third receive slots are associated with one IF filter and second and fourth receive slots are associated with the other IF filter.
9,809
INTRODUCTION [0001] This invention relates generally to electropositive metals for repelling elasmobranchs and methods of using electropositive metals to repel elasmobranchs. BACKGROUND OF THE INVENTION [0002] Elasmobranchs represent a significant problem in the commercial fishing industry. Elasmobranchs are often inadvertently caught on fishing tackle directed at other more commercially valuable kinds of fish. This inadvertent catching of elasmobranchs (or other non-valued fish) is called “by-catch.” As many as 100 million elasmobranchs are killed each year as by-catch. This loss of life has resulted in a real threat to several shark species. Currently, as many as 80 species of shark are considered threatened with extinction. [0003] Further, when elasmobranchs are caught as by-catch, fishing operations receive no return on their investment since the shark is caught on a hook that might have otherwise brought in a marketable fish. Additionally, the fishing tackle on which a shark is caught often must be cut loose for the safety of those working on the fishing vessel causing a loss of both equipment and time. [0004] Longlining is a commercial fishing method that suffers significant losses from shark by-catch. Longlining uses multiple baited individual fish hooks with leaders strung at intervals along an often very long (2-3 miles) main fishing line. Longline fishing operations routinely target swordfish and tuna. The longline hooks, however, are not selective and elasmobranchs are sometimes caught in greater numbers than the intended catch. The result is great loss of life in elasmobranchs and significant financial losses in the longline industry. Elasmobranchs cause additional losses in the longline fishing industry by scavenging marketable fish caught on longlines before the fish may be retrieved for processing. [0005] Elasmobranchs also represent a problem in the commercial trawling industry. Trawling is a commercial fishing method that catches fish in nets. Elasmobranchs cause significant losses for trawlers because they scavenging fish caught in trawl nets before they are retrieved for processing. As such, valuable fish are often lost to shark predation. Also, sharks often tear holes in the nets, resulting in partial or complete loss of catch and significant repair costs. [0006] There has been a long-felt need for methods and devices to deter elasmobranchs from commercial fishing lines and nets. Attempts in the middle of the twentieth century were made to protect trawl nets with electric discharge devices (Nelson, “Shark Attack and Repellency Research: An Overview,” Shark Repellents from the Sea ed. Bernhard Zahuranec (1983) at pg. 20). Nevertheless, no commercially effective repellent has yet to be made available for reducing shark by-catch in the commercial fishing industry or for reducing loss of valuable fish or fishing tackle to shark predation. Further, Applicant is unaware of any consideration in the art of the use of electropositive metals to repel elasmobranchs to limit by-catch and other losses from elasmobranchs. [0007] An effective shark repellent would not only be valuable to the fishing industry but also would be valuable for protecting humans from shark attacks. No effective repellent has yet to be marketed for limiting the risk of shark attacks faced by humans exposed to elasmobranchs. Over the last 50 years antishark measures employed to protect humans from shark have included electrical repellent devices (Gilbert & Springer 1963, Gilbert & Gilbert 1973), acoustical playbacks (Myrberg et al. 1978, Klimley & Myrberg 1979), visual devices (Doak 1974) and chemical repellents (Tuve 1963, Clark 1974, Gruber & Zlotkin 1982). None of these procedures proved satisfactory in preventing shark attacks. (Sisneros (2001)). As such, the long felt need for an effective repellent had not been satisfied. [0008] Researchers have historically used several bio-assays to determine if a repellent evokes a flight response in shark. One such bio-assay measures the effect of a repellent on a shark that is immobilized in “tonic immobility.” Tonic immobility is a state of paralysis that typically occurs when a shark is subject to inversion of its body along the longitudinal axis. This state is called “tonic,” and the shark can remain in this state for up to 15 minutes thereby allowing researchers to observe effects of repellents. After behavioral controls are established, an object or substance that has a repelling effect will awaken a shark from a tonic state. Researchers can quantify the strength of a repellent effect from these studies. BRIEF SUMMARY OF THE INVENTION [0009] The applicant has discovered that an electropositive metal is an effective elasmobranch repellent useful in limiting by-catch as well as protecting humans. Electropositive metals, particularly the Lanthanide metals, known or hereinafter developed, that are of sufficient electropositivity to repel elasmobranchs are acceptable in aspects of the present invention. [0010] According to a non-limiting embodiment of the present invention, an apparatus for repelling elasmobranchs is provided comprising an electropositive metal. Preferably, the electropositive metal is a Lanthanide metal. More preferably, the electropositive metal is a Mischmetal. Electropositive metals may have a shape of a cylinder, a cone, a circle, a cube, a disk, a bar, a sphere, a plate, a rod, a ring, a tube, a stick or a block. [0011] Electropositive metals of the present invention preferably have a revised Pauling electronegativity of less then 1.32. In a non-limiting embodiment, an electropositive metal has a cathode half-cell standard electrode potential greater then 1.9 volts in aqueous solution. In a non-limiting embodiment, the electropositive metal is a Lanthanide metal, a Mischmetal, an Alkaline Earth metal, an Alkali metal, or a Group 3 metal on the periodic table. [0012] According to a first non-limiting aspect of the present invention, an apparatus is provided comprising an electropositive metal and a buoy, a barge, a net, fishing tackle or any combination thereof. Fishing tackle may comprise a longline, a main line, a gangion, a branchline, a weight, a buoy, a net, or any combination thereof. [0013] According to a second non-limiting aspect of the present invention, an apparatus is provided comprising an electropositive metal and a fish hook. Such fish hook may be individual or attached to longline or mainline and such fish hook may have a single or multiple hooks. [0014] According to a third non-limiting aspect of the present invention, an apparatus is provided comprising a surfboard and an electropositive metal. [0015] In fourth non-limiting aspect of the present invention, a method is provided for repelling elasmobranchs comprising attaching an electropositive metal to a human body or to clothing or accessories associated with a human body. In an aspect of the invention, an electropositive metal may be attached to a human ankle or wrist. In a further aspect an electropositive metal may be attached to a bracelet. In yet a further aspect an electropositive metal may be attached to a belt, a weight belt for diving or flippers. In yet a further aspect, an electropositive metal may be housed within a surfboard or attached to a surfboard. In yet another aspect, an electropositive metal may be trailed along with a human in water. BRIEF DESCRIPTION OF THE DRAWINGS [0016] The invention will now be described by way of example with reference to the accompanying drawings wherein: [0017] FIG. 1 illustrates a traditional circle hook ( 40 ) attached to a line ( 30 ) and preferred zone (I) for locating an electropositive metal in accordance with the present invention. [0018] FIGS. 2A-C illustrate non-limiting positions within the zone (I) for locating an electropositive metal in accordance with the present invention. FIG. 2A illustrates an electropositive metal attached to the line above the hook. FIG. 2B illustrates an electropositive metal attached to the hook. FIG. 2C illustrates an electropositive metal attached to the hook shank and clear of the hook eye. [0019] FIG. 3A-C illustrate non-limiting positions within the zone (I) for locating an electropositive metal on a J-hook in accordance with the present invention. FIG. 3A illustrates an electropositive metal attached to the line above the hook. FIG. 3B illustrates an electropositive metal attached to the hook. FIG. 3C illustrates an electropositive metal attached to the hook shank and clear of the hook eye. [0020] FIG. 4A-B illustrate non-limiting positions within the zone (I) for locating an electropositive metal on a treble hook in accordance with the present invention. FIG. 4A illustrates an electropositive metal attached to the line above the hook. FIG. 4B illustrates an electropositive metal attached to the hook. [0021] FIG. 5 illustrates a demersal longline with an electropositive metal in accordance with the present invention. [0022] FIGS. 6A-B illustrate non-limiting apparatuses and methods of repelling elasmobranchs in accordance with the present invention. FIG. 6A illustrates a buoy and electropositive metal and a net with a plurality of electropositive metals in accordance with the invention. FIG. 6B illustrates a barge and an electropositive metal. [0023] FIGS. 7A-B illustrate non-limiting surfboards with an electropositive metal in accordance with the invention. FIG. 7A illustrates a surfboard with an electropositive metal that is capable of spinning in accordance with the invention. FIG. 7A illustrates a surfboard with an electropositive metal embedded in or attached to the surfboard in accordance with the invention. FIG. 7B illustrates exemplary surfboards in accordance with an aspect of the invention. FIG. 7C illustrates electropositive metal or plurality of electropositive metals in association with one another wherein the electropositive metal or metals are capable of spinning when placed in water. [0024] FIGS. 8A-C illustrate accessories for attaching an electropositive metal to a human or other subject or object. FIG. 8A illustrates a belt or weight belt with an electropositive metal in accordance with the invention. FIG. 8B illustrates a bracelet or wristband with an electropositive metal in accordance with the invention. FIG. 8C illustrates flippers for snorkeling or diving with an electropositive metal in accordance with the present invention. DETAILED DESCRIPTION OF THE INVENTION [0025] “By-catch” is any kind of fish that is caught in a fishing operation wherein the catching of the fish is not the object of the fishing operation. For example, if the target fish of a longline fishing operation is tuna, an elasmobranch caught on a hook of the longline is by-catch. [0026] “Elasmobranchs” in this specification means one or more elasmobranchii in the super-orders Galeomorphii, Squalomorphii, and Batoidea and orders Squaliformes (dogfish), Carcharhiniformes (requiem sharks), Lamniformes (mackerel sharks), Rajiformes (true rays), Pristiformes (sawfishes), Torpediniformes (electric rays) and certain Orectolobiformes (carpet sharks). Elasmobranchs in this specification includes nurse sharks, an Orectolobiform, but this specification does not include the other carpet sharks, such as wobbegongs. [0027] An “Electropositive metal” is a metal which readily donates electrons to form positive ions. Electropositive metals are strong reducing agents and all react with water to some degree, typically liberating hydrogen gas or forming a hydroxide. The most electropositive metals tends to be found on the left-hand side of the Periodic Table of the elements, particularly in Groups I, II, III, and the Lanthanides. In general, electropositivity decreases and electronegativity increases as one moves to the right hand side of the Periodic Table of the elements. The most electropositive metal known is Francium, which is radioactive. The most stable electropositive metal is Cesium which is highly reactive in water and air. Electropositive metals typically do not exhibit any permanent magnetism (ferromagnetism) at room temperature. [0028] “Revised Pauling Electronegativity” is is a chemical property which describes the power of an atom to attract electrons towards itself. First proposed by Linus Pauling in 1932 as a development of valence bond theory it has been shown to correlate with a number of other chemical properties. Electronegativity cannot be directly measured and must be calculated from other atomic or molecular properties The Pauling electronegativity for an element is calculated using the dissociation energies of at least two types of covalent bonds formed by that element. Linus Pauling's original values were updated in 1961 to take account of the greater availablity of thermodynamic data, and it is these “Revised Pauling” values of the electronegativity which are most usually used. [0029] “Standard Electrode Potential” is the measure of the individual potential of any electrode at standard ambient conditions, which is at a temperature of 298K, solutes at a concentration of 1 M, and gases at a pressure of 1 bar. The basis for an electrochemical cell such as the galvanic cell is always a reduction-oxidiation reaction which can be broken down into two half-reactions: oxidation at anode (loss of electron) and reduction at cathode (gain of electron). Electricity is generated due to electric potential difference between two electrodes. This potential difference is created as a result of the difference between individual potentials of the two metal electrodes with respect to the electrolyte (In practice, seawater serves as the conductive electrolyte). In an electrochemical cell, an electropositive metal acts as the cathode, and the standard electrode potential represents the voltage of the reduction half-cell reaction. [0030] A “Lanthanide metal” belongs to the series comprising the 15 elements with atomic numbers 57 through 71, from Lanthanum to Lutetium. All lanthanides are f-block elements, corresponding to the filling of the 4f electron shell, except for lutetium which is a d-block Lanthanide. The Lanthanide series is named after Lanthanum. The Lanthanide series is also commonly referred to as the “rare earths” or “rare earth elements”. [0031] “Mischmetal” is an alloy of Lanthanide elements in various naturally-occurring proportions. The term “Mischmetal” is aerived from the German “Mischmetall” meaning mixed metals. Mischmetals are also called Cerium mischmetal, rare earth mischmetal or misch metal. A typical composition includes approximately 50% Cerium and 45% Lanthanum, with small amounts of Neodymium and Praseodymium. Other Mischmetal alloy mixtures include Lanthanum-rich Mischmetal, Ferrocerium, and Neodymium-Praseodymium Mischmetal. [0032] An “Alkaline Earth” metal belongs to the series of elements comprising Group 2 of the Periodic Table of elements: Beryllium, Magnesium, Calcium, Strontium, Barium, and Radium. The alkaline earth metals are silvery colored, soft, low-density metals, which react readily with halogens to form ionic salts, and with water to form strongly alkaline hydroxides. [0033] An “Alkali Earth” metal belongs to the series of elements comprising Group I of the Periodic Table of elements: Lithium, Sodium, Potassium, Rubidium, Cesium, and Francium. The alkali metals are all highly reactive and are rarely found in elemental form in nature. As a result, in the laboratory they are stored under mineral oil. They also tarnish easily and have low melting points and densities. [0034] A “Group 3 metal” belongs to the third vertical column of the Periodic Table of elements. While Lanthanides are usually considered part of Group 3, the metallic elements Yttrium and Scandium all always considered Group 3 metals. The physical properties of Yttrium and Scandium resemble Lanthanides and these two metals are commonly considered part of the “rare earths”. [0035] “Longline” refers to a fishing line that may extend up to many miles wherein a mainline extends the full length of the longline and individual shorter gangion lines attached to the mainline are spaced at set intervals (perhaps several feet or meters or perhaps 1000 feet or greater apart). Hooks are attached to the individual gangion lines. Hooks may be baited and used to catch target fish. The addition of an electropositive metal repels elasmobranchs from the baited hooks as well as from the region of the longline generally. [0036] “Target fish” is any kind of fish, the catching of which is the object of a fishing operation. For example, the target fish of a longline fishing operation may be tuna. A fish that is caught on the longline that is not tuna would not be a target fish. [0037] “Tonic immobility” is the state of paralysis that typically occurs when an elasmobranch is subject to inversion of its body along the longitudinal axis of the body, i.e., is belly up. An elasmobranch can remain in this state for up to 15 minutes. While in tonic immobility, the shark is comatase and unresponsive to many external stimuli. Biologists often perform surgery on sharks using tonic immobility, precluding anesthesia. An effective shark repellent terminates tonic immobility, often violently, thus, tonic immobility is useful as a bioassay for testing the effectiveness of electropositive metals. I. ELECTROPOSITIVE METALS AS REPELLENTS OF ELASMOBRANCHS [0038] The applicant first observed the unusual repellent effects of electropositive Lanthanide metals on sharks when tonically-immobilized juvenile lemon sharks ( N. brevirostris ) exhibited violent rousing behavior in the presence of a 153 gram 99.95% Samarium metal ingot. As the Samarium metal was moved towards the immobilized shark's head, the shark terminated tonic immobility, in the direction away from the approaching metal. For experimental controls, pure Chromium, an antiferromagnetic metal, and pyrolytic graphite, a highly diamagnetic substance, failed to produce any behavioral responses in juvenile lemon sharks. [0039] A polystyrene white plastic blinder was used to remove any visual and motion cues from an approaching electropositive metal. This blinder was placed close to the shark's eye, sufficiently shielding its nares, eyes, gills, and head up to its pectoral fin. Again, Samarium metal terminated tonic immobility in all test subjects at a range of 2 to 50 cm from the blinder. Chromium metal and pyrolytic graphite did not produce any notable behavioral shifts. In order to confirm that pressure waves were not affecting the test subjects, the tester's hand was moved underwater towards the shark's head both with and without blinders at varying speeds. This motion also did not disrupt the immobilized state. The same series of experiments were repeated with juvenile nurse sharks ( G. cirratum ) and yielded the same behavioral results. [0040] The same experimental protocol was repeated with a 73 gram ingot of 99.5% Gadolinium metal, an electropositive Lanthanide metal, and yielded the same behavioral results in both juvenile lemon sharks and nurse sharks. It is noted that the rousing behavior was most violent when Samarium metal was used. Additionally, the Gadolinium metal corroded quickly after seawater exposure, and therefore would be appropriate for a one-time use application. [0041] In order to eliminate the possibility of galvanic cell effects, juvenile sharks were removed from their pens and brought at least 15 meters away from any submerged metal objects. All testers and witnesses removed watches, rings, and jewelry so that only the lanthanide metal was exposed to seawater. The same experimental method was repeated in lemon sharks and we report that tonic immobility was terminated with electropositive Samarium metal in all tests. [0042] The application has discovered that waving Samarium or Gadolinium in air above immobilized or resting sharks does not effect behavior, even when the metal is very close to the water's surface. The electropositive metal must be in contact with seawater in order to produce the repellent effect. This is notably different from the effects of a rare-earth magnet, which will often terminate tonic immobility at close range in air. [0043] The effects of an electropositive Lanthanide metal on free-swimming sharks were also evaluated. Two juvenile nurse sharks (less than 150 cm total length) were allowed to rest in an open-water captive pen. The tester approached the nurse sharks and moved his hand near the pen wall. His hand contained no metal. Both nurse sharks remained at rest. Next, the tester presented the 153 gram ingot of electropositive Samarium metal underwater to the pen wall and we note that both nurse sharks awakened and rapidly swam away from the tester's locale. Next, a highly-stimulated competitively-feeding population of six blacknose sharks ( C. acronotus ) (total length up to 120 cm) and six Caribbean reef sharks ( C. perezii ) (total length up to 210 cm) was established using chum and fish meat. A diver entered the water near the population of sharks with the 153 gram of Samarium metal secured to one end of a 1.5 meter-long polyvinyl chloride pole. As free-swimming sharks swam close to the diver, the control end of the pole (without metal) was presented in a left-right waving motion. Approaching sharks would swim past, bump, or briefly bite the pole. The diver then turned the Samarium metal-end of the pole towards the approaching sharks. All blacknose sharks exhibited a “twitching” or “jerking” behavior as they came near the metal ingot and quickly swam away. Caribbean reef sharks generally avoided the metal, but did not exhibit the twitching behavior. [0044] Following the aforementioned initial experiments, many electropositive metals were procured and presented to tonic-immobilized juvenile sharks. The violence of the shark's response to each metal was scored on a scale of 0 to 4, with 0 equating to no response and 4 equating to a violent rousing reaction. All testing was performed in the Bahamas using open-water captive pens. Arc-melted 100 gram Lanthanide metal ingots, Calcium, and Strontium were obtained from Metallium Inc., USA. Lanthanum, Cerium, Neodymium, Yttrium, Praseodymium and Mischmetal samples were obtained from HEFA Rare Earth Metals, Canada. Magnesium, Beryllium, transition metals and nonmetals were procured as surplus items online from EBay. [0045] In juvenile N. brevirostris and G. cirratum, the applicant has found that the following Lanthanide metals all terminated the tonic state at distances less than 0.1 meters: 100 grams of 99% purity Lanthanum metal, 90 grams of 99% purity Cerium metal, 100 grams of 99% purity Praseodymium metal, 100 grams of 99% purity Neodymium metal, 73 grams of 99.95% purity Samarium met al, 145 g of arc-melted 99% purity Terbium metal, 89 g of arc-melted 99% purity Erbium metal, 100 grams of arc-melted 99% purity Holmium metal, 100 grams of arc-melted 99% Gadolinium metal, 100 grams of arc-melted 99% Dysprosium metal, and 100 grams of arc-melted 99% purity Ytterbium metal. [0046] In the same experiment, 75 grams of 99% purity Yttrium metal, a Group 3 metal, also terminated tonic immobility in juvenile N. brevirostris. [0047] In the same experiment, a 30 gram 99% purity ingot of Strontium and separately, a 40 gram 99% purity ingot of Calcium terminated tonic immobility in juvenile G. cirratum. These metals were highly reactive in seawater and dissolved before a second series of tests could be performed. [0048] In the same experiment, the following Misch.metals terminated tonic immobility in N. brevirostris: An 80 gram slice of Cerium Misch.metal, and a 100 gram slice of Neodymium-Praseodymium Mischmetal. [0049] In the same experimental, the following Alkaline Earth metals terminated tonic immobility in N. brevirostris: A 70 gram block of 99% Magnesium, and a 10 gram pellet of 99% purity Barium. The Barium pellet reacted violently with seawater and a subsequent test could not be performed. [0050] Transition metals and nonmetals, which are much less electropositive than the Lanthanides, Alkali, Alkaline Earth, and Group 3 metals, were also screened using the tonic immobility bioassay. The following transition metals and metalloids failed to illicit a rousing response in immobilized juvenile N. brevirostris: A 20 gram disc of 99.95% purity Tellurium, a 20 gram cylinder of 99.5% purity Tungsten, a 20 gram cylinder of 99.5% purity Cobalt, a 20 gram cylinder of 99.5% purity Iron, a 20 gram cylinder of 99.5% purity Niobium, a 20 gram cylinder of 99.5% purity Zirconium, a 20 gram square of 99.95% Rhenium, a 100 gram pillow of Aluminum, and a 15 gram square of pyrolytic graphite (Carbon). [0051] Based on the aforementioned experimental results, a close correlation was found between the revised Pauling electronegativity values for the electropositive metals, and behavioral response. As the revised Pauling electronegativity decreased, the violence of the shark's response seemed to increase. A significant repellency threshold was found at a revised Pauling electronegativity of 1.32 or less—Metals with electronegativities greater than 1.32 did not produce the response. Highly reactive metals, such as Strontium and Calcium (electronegativities of 0.89 and 1.00 respectively) produced a violent rousing reaction as expected. [0052] An electropositive metal for repelling elasmobranchs may comprise the shape of a cylinder, a cone, a circle, a cube, a disk, a bar, a sphere, a plate, a rod, a ring, a tube, a stick, a block, a tapered cone, or any other shape. [0053] The mode of action of electropositive metals on elasmobranchs is not fully understood. While not wishing to be bound by any particular theory, one plausible theoretical explanation for this surprising finding of repellent activity of electropositive metals is the possibility that relatively high voltages, ranging from 0.8 VDC to 2.7 VDC with currents up to 0.1 milliamperes, are created between the metal and the shark's skin. This electromotive force may over-stimulate the ampullae of Lorenzini (known to be used by elasmobranchs for navigation and orientation), which saturate below 100 nanovolts, causing a highly unnatural stimulus to the shark. [0054] Electropositive metals exhibit no measurable permanent magnetism (ferromagnetism). The applicant hypothesized that a magnetic or electrical field was being induced by the metal's movement through seawater. The applicant attempted to measure minute magnetic fields being produced by the movement of Samarium metal through seawater in a closed system. A submersible calibrated milliGauss meter probe was secured in a plastic tank containing seawater with the same salinity, pH, and temperature of the water used in previous shark testing. After zeroing out the Earth's magnetic field, the applicant did not detect any magnetic fields being produced by the movement of Samarium metal through the tank, within tenths of a milliGauss [0055] Electromotive forces generated by electropositive metals are effective repellents for elasmobranchs, excluding certain carpet sharks in the family Orectolobidae. It is believed that electropositive metals are not effective repellents against carpet sharks because carpet sharks, particularly spotted wobbegongs ( Orectolobus maculatus ), are ambush predators and rely more on visual, olfaction, and lateral line clues than this electromagnetic sense. This species of shark is found chiefly in Australia and Indonesia, and does not represent significant by-catch species or species that are known to be aggressive against humans. Electropositive metals, however, are effective against nurse sharks, another Orectolobiform. [0056] Electropositive metals have been demonstrated to act as acceptable repellents of elasmobranchs. The repellent activity of electropositive has been shown to be better than existing shark-repellent technology with the exception of certain chemical repellents and magnetic repellents being developed by SHARK DEFENSE LLC that have a greater range of action. [0057] A. Electromotive Forces [0058] The repellency of an electropositive metal may be measured in a variety of ways. The applicant has found that the standard electrode potential of the cathode half-cell reaction of an electropositive metal in aqueous medium can be measured in a closed system using an electropositive metal at the anode (the site of oxidation), a piece of shark skin at the cathode (the site of reduction), and seawater as an electrolyte. Electromotive forces were measured using a calibrated direct current voltmeter. Electromotive forces greater than 0.8 volts were recorded for all electropositive metals, with Lithium metal, an Alkali earth metal, producing the highest measurable voltage at 2.71 volts. This demonstrated that cations and anions were exchanged through the electrolyte. These measured electromotive forces closely correlated to published standard electrode potentials for electropositive metals. A closed system using an electropositive metal at the external cathode (−) and a piece of shark skin at the external anode (+) with seawater electrolyte represents a simple and effective means of measuring electromotive forces and predicting repellency. [0059] The strength of an electropositive metal's electromotive force field is inversely related to the distance an object is from the metal. As such, metals with a low standard electrode potential may repel elasmobranchs if the elasmobranch moves close enough to sense the electromotive force field of the metal. A highly electropositive metal having sufficient strength to repel an elasmobranch at sufficient distance such that the elasmobranch is deterred from striking a baited hook or coming near a person or other subject is preferred. It is more preferred that an electropositive metal have a standard electrode potential of at least 2.00 volts in seawater to provide sufficient electromotive force to repel an elasmobranch away from a baited hook or a person before the elasmobranch may bight the hook or harm the person. Because an elasmobranch may act to strike a hook or person at a distance from the target, the higher the standard electrode potential or the lower the revised Pauling electronegativity of the metal, the more effective it will be. II. METHODS AND DEVICES FOR ELECTROPOSITIVE METALS [0060] A. Electropositive Metals [0061] Exemplary and non-limiting electropositive metals in accordance with the invention may be constructed of any metal that is capable of generating an electromotive force in seawater relative to the shark's skin. [0062] Electromotive forces may be generated in any manner known to the skilled artisan who is practicing aspects of the invention or electrochemistry. [0063] There are many varieties of electropositive metals including the Lanthanide metals, the Alkaline Earth metals, the Alkali metals, Mischmetals, and the Group 3 metals on the periodic table of elements. Any electropositive metal having sufficient standard electrode potential or a low revised Pauling electronegativity may be used as a repellent of elasmobranchs. [0064] Exemplary electropositive metals include Lanthanum, Cerium, Neodymium, Praseodymium, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Ytterbium, Lutetium, Yttrium, Scandium, Lithium, Magnesium, Calcium, Strontium, Barium, Cerium Mischmetal, Neodymium-Praseodymium Mischmetal, and Lanthanum-rich Mischmetal. Electropositive metals may be flexible or inflexible. [0065] A preferred electropositive metal contemplated within an aspect of the invention is Neodymium-Praseodymium Mischmetal. Neodymium-Praseodymium Mischmetal is a more preferred material than pure forms of Lanthanide or Alkaline earth metals due to cost and low corrosion reactivity in seawater. Pure Lanthanide metals, particularly the “late Lanthanides” comprising elements 63 through 71, are prohibitively expensive in pure form. Pure Alkali metals are extremely reactive in seawater and present fire hazards in storage. Certain Alkaline earth metals are also highly reactive in seawater, such as Barium and are too short-lived for commercial fishing applications. Highly electropositive metallic elements such as Promethium, Radium, and Francium are highly radioactive and are not feasible for any elasmobranch repelling application. [0066] In selecting an electropositive metal, a revised Pauling electronegativity of less than 1.32 is preferred. A revised Pauling electronegativity of about 1.14 or less is more preferred since the impact of the electromotive force field will be felt at a slightly greater distance from the metal. [0067] Early Lanthanide metals, particularly elements•57 through 62, commonly called the “early Lanthanides”, possess revised Pauling Electronegativities less than 1.2, which is preferred. Similarly, Mischmetals containing combinations of Lanthanum, Cerium, Neodymium, and Praseodymium exhibit calculated revised Pauling electronegativities of less than 1.2, which is preferred. [0068] In order to maximize electromotive forces, the surface area of an electropositive metal may be maximized. For example, a 6″ diameter by 2″ thick cylindrical Cerium Mischmetal block (revised Pauling electronegativity of 1.15) may be effective in repelling elasmobranchs at a range of 8 inches. [0069] A plurality of electropositive metals may be employed to repel elasmobranchs. For example, 1″ cube metals may be arranged in a 12″ long bar and used to repel elasmobranchs. The cube metals may be of any electropositive metal material capable of producing sufficient electromotive force at any distance of interest from the metal to repel elasmobranchs. Alternatively, a plurality of 1″ cube electropositive metals may be arranged linearly with a distance between each piece of metal. [0070] B. Electropositive Metals in Combination with Hooks [0071] A non-limiting aspect of the present invention is the use of electropositive metals to repel elasmobranchs from baited hooks. Exemplary and non-limiting combinations of an electropositive metal and a hook are illustrated in FIGS. 1-4 . For example, in FIG. 1 , an exemplary and non-limiting circle hook ( 140 ) is illustrated attached to a line ( 150 ) along with exemplary and non-limiting zone (I) in the circle hook and line where an electropositive metals may be placed or affixed. The preferred region (zone I) for metal placement is any region wherein the affixed or placed magnet does not obstruct the hook gap distance (zone II). Not more than 20% of the hook gap distance (zone II) is preferably obstructed by the metal such that the hook is not prevented from setting in the corner of the mouth of a target fish. Nevertheless, any arrangement wherein the hook is not prevented from catching target fish is acceptable. Tapered conical designs (not illustrated) are contemplated such that the diameter of the electropositive metal at the hook end is smaller than the diameter of the electropositive metal at the line end of zone I. [0072] Exemplary and non-limiting combinations of an electropositive metal on a hook and line are illustrated in FIG. 2 . An electropositive metal ( 210 ) may be placed in proximity to a circle or offset circle hook ( 240 ) such that it rests on the hook eye ( 241 ) providing an exemplary embodiment such as the hook-metal combination embodied at 260. An electropositive metal ( 210 ) may be placed in proximity to a circle or off-set circle hook ( 240 ) such that it rests on the shank ( 242 ) of the hook providing an exemplary embodiment such as the hook-metal combination embodied at 270 . A metal ( 210 ) may be placed on a circle or offset circle hook ( 240 ) such that it is secured to the outside of the shank ( 242 ) and the hook eye ( 241 ) providing an exemplary embodiment such as the hook-metal combination embodied at 280 . Vinyl electric tape (not illustrated) may be used to secure the metal. Black vinyl tape is preferred to reduce reflections of light. [0073] Electropositive metals may be provided in any shape. It is preferred that a metal's shape not significantly obstruct the hook gap distance (zone II). The metal may comprise a hole through which a lead, or gangion, or mainline ( 250 ) or other filamentous object may pass. Exemplary non-limiting shapes may include a cube or block of any size or other object having at least one plane comprising four right angles and a hole passing through the object such that fishing line or other filament may be passed through to affix the magnet in place on fishing tackle or other object. Alternative, non-limiting shapes may also include cylindrical or other circular, oval or oblong three-dimensional shapes having a hole passing through some portion of the shape ( 210 ). Alternative, non-limiting shapes may also include a hollow pyramid or a hollow trapezoid. [0074] Alternative, non-limiting shapes may also include a solid cube or similar shape, a solid rectangle or similar shape, a solid bar or similar shape, a solid pyramid or similar shape, a solid trapezoid or similar shape or any other shape. Metals may be shaped as a ring, a trapezoid, a series of trapezoids, a series of trapezoids arranged in a larger ring pattern, a cone, a tapered cone, a narrow or wide cylinder or in the shape of a Billy club. Preferably, the shape when combined with a hook provides a hook in proximity to an electropositive metal comprising sufficient electromotive force field strength to repel elasmobranchs. [0075] Exemplary and non-limiting combinations of electropositive metal and hook are also illustrated in FIG. 3 . An electropositive metal ( 310 ) may be placed in proximity to a j-hook ( 340 ) such that it rests on the hook eye ( 341 ) providing an exemplary embodiment such as the hook-metal combination embodied at 360 . An electropositive metal ( 310 ) may be placed in proximity to a j-hook ( 340 ) such that it rests on the shank ( 342 ) of the hook providing an exemplary embodiment such as the hook-metal combination embodied at 370 . An electropositive metal ( 310 ) may be placed on a j-hook ( 340 ) such that it is secured to the outside of the shank ( 342 ) and the hook eye ( 341 ) providing an exemplary embodiment such as the hook-metal combination embodied at 380 . As described above in the illustration of FIG. 2 , electropositive metal may be provided in any shape. [0076] Exemplary and non-limiting combinations of an electropositive metal and hook are also illustrated in FIG. 4 . An electropositive metal ( 410 ) may be placed in proximity to a treble hook ( 440 ) such that it rests on the hook eye ( 441 ) providing an exemplary embodiment such as the hook-metal combination embodied at 460 . An electropositive metal ( 410 ) may be placed in proximity to a treble hook ( 440 ) such that it contacts the shank ( 442 ) of the hook providing an exemplary embodiment such as the hook-metal combination embodied at 470 . [0077] A hook in accordance with the invention may be any hook that is capable of catching target fish. The hook may comprise stainless steel, steel, galvanized metals, ferromagnetic metals or any other material, metallic or plastic or any other composite. [0078] C. Electropositive Metals on Longlines [0079] An exemplary and non-limiting method of repelling elasmobranchs involving repelling elasmobranchs from longlines in accordance with the invention is illustrated in FIG. 5 . A longline ( 500 ) may be deployed from a boat ( 561 ) to fish for a target fish of interest. The main line ( 550 ) of the longline may be attached to a buoy ( 520 ) and at a set distance from the buoy may be attached to an anchor ( 562 ). A set of gangions ( 530 ) with hooks ( 540 ) may be attached to the mainline beginning at the anchor ( 562 ) and may be spaced sufficiently to limit interaction between individual gangion lines ( 530 ). Each hook may have an electropositive metal mounted resting on the hook eye ( 541 ). Alternatively, the electropositive metal may be mounted on a hook shank ( 542 ) or may be secured to the outside of the hook ( 540 ). The hooks may be baited. The longline may be a demersal longline such that the main line is proximal to the ocean or otherwise water's floor. The longline may be a pelagic long line, such that the main line is nearer to the surface of the water, suspending in the water column, typically at 100-500 feet below the surface. In the aspect of the invention where the longline is a pelagic longline, anchors ( 562 ) may have less weight or may be absent from the longline apparatus. The longline may also be a semipelagic longline wherein the mainline is further down the water column from the surface as compared to a pelagic line but is not proximal to the water's floor or is not proximal to the water's floor on at least one end of the longline. Use of electropositive metals with longlines reduces by-catch of elasmobranchs. [0080] Longlines comprising electropositive metals may be handled in the commercial environment in a manner similar to those practices known in the art of longline commercial fishing. Because hooks must be carefully managed to control tangling and hooking of objects on a longlining boat, including other portions of the tackle of the longline, commercial fishing operations and those of skill in the art will recognize how to handle longlines with hooks. Electropositive metals on longlines likewise may be handled in the same manners as one would consider appropriate in the art to avoid entanglements. [0081] As described above, electropositive metals of any size may be used in combination with a longline hook so long as the target fish may be caught on the hook. An exemplary electropositive metal on a longline hook may be 2″×0.25″×2″. Smaller electropositive metals are also acceptable. Electropositive metals of less than 0.5″ cubed may be appropriate for smaller hook settings. [0082] D. Electropositive Metal Repellents on Buoys, Nets and Barges [0083] An exemplary and non-limiting method of repelling elasmobranchs with an electropositive metal or a plurality of electropositive metals placed on a buoy or barge or net is illustrated in FIG. 6 . Buoys with electropositive metals as their weighted bases are shown as element 660 and 661 in FIG. 6A . The floating portion of the buoy ( 620 ) allows the buoy to float while the electropositive metal portion of the buoy ( 610 ) remains in the water because of its weight. A series of buoys comprising electropositive metals may be placed in a region to repel elasmobranchs or may be placed around a swimming area or rescue area to repel elasmobranchs. A series of buoys with electropositive metals may be accompanied by a series of electropositive metals submerged ( 611 ) in an area of interest, such as a swimming area. As illustrated in FIG. 6B , very large electropositive metals may be placed on a large floating barge ( 670 ) comprising an electropositive metal ( 610 ). [0084] An exemplary and non-limiting method of repelling elasmobranchs with a plurality of electropositive metals is illustrated in FIG. 6A as element 600 , an elasmobranch repelling net apparatus. Buoys ( 660 and 661 ) may be employed to float a net ( 650 ) comprising a series of electropositive metals ( 640 ) held within the net and electropositive metal rings ( 630 ) holding the ropes of the net together. The net may be strung to the bottom of the water column using weighted electropositive metals ( 611 ). The net may be anchored to a specific location to provide a physical barrier. The net may provide a curtain of electromotive field forces to repel elasmobranchs from an area or to keep elasmobranchs from entering an area of interest, such as a swimming or working area. A net ( 650 ) comprising electropositive metals such as those illustrated as elements 610 , 611 , 630 and 640 may also be used to trawl for fish, shrimp or other aquatic species. In another non-limiting aspect of the invention, electropositive metals may be placed in aquaculture cages to repel sharks from predation or scavenging of cultured stock. Electropositive metals are useful to prevent damage by elasmobranchs to aquaculture cages, nets or other equipment. [0085] E. Surfboard Fitted with Electropositive Metal [0086] A non-limiting repelling device in accordance with the invention may comprise a surfboard comprising an electropositive metal device. FIG. 7B illustrates exemplary surfboards in accordance with an aspect of the invention. A surfboard ( 720 ) may comprise an electropositive metal device such as Mischmetal ( 710 ) imbedded, affixed, attached or otherwise associated in any manner contemplated by one of skill in the art with the surfboard An electropositive metal may be pressed into a space drilled into the surfboard ( 730 ). It may also be affixed with glue, waterproof tape, Velcro or any other mechanism known in the art now and hereafter. [0087] In an alternative non-limiting example in Figure A, a surfboard ( 750 ) may comprise an electropositive metal or plurality of electropositive metals in association with one another wherein the electropositive metal or metals are capable of spinning when placed in water ( 740 ). Such a spinning electropositive metal ( 740 ) may comprise individual metal pieces attached to a hub ( 770 ) that is attached to an axle ( 760 ) to allow free spinning of the electropositive metal or metals attached to the surfboard ( 720 ) when water current is present. [0088] An electropositive metal may be enclosed in the body of a surfboard or other watercraft or may be trailed behind a surfboard, other watercraft or swimmer. [0089] F. Electropositive Metal Repellents on Swimming and Diving Clothing and Accessories [0090] One exemplary non-limiting aspect of the present invention comprises an electropositive metal material for producing an electromotive force field near a swimmer or diver or other person or object in an elasmobranch environment. [0091] Electropositive metals, such as for example, Mischmetal, or other electropositive metals may be worn as a bracelet or a band or otherwise placed in proximity of a person or object. An increase in the number of electropositive metals and an increase in the standard electrode potential of the metals that may be worn increases the electromotive force field around the wearer and increases the repelling activity of the bracelet, band or other metal article. [0092] In a non-limiting example, an omnidirectional electromotive force field may be affixed or arranged near a subject or object exposed to an elasmobranch environment. The electromotive force field may be generated from, for example, an electropositive metal. An electropositive metal may be affixed, for example, to any portion of a swimmer's or diver's body such as the head, the leg, the arm, the torso, the ankle, the wrist, or any other portions of the body. [0093] FIG. 8 illustrates a non-limiting example of electropositive metals ( 810 ) attached to a belt ( 801 ) ( FIG. 8A ) or bracelet ( 802 ) ( FIG. 88 ) or flippers ( 803 ) ( FIG. 8C ). [0094] Electropositive metals may likewise be attached to clothing or water accessories such as swim trunks, wet suits, headbands, flippers, goggles or other piece of clothing or accessory. Electropositive metals may be sewn into such clothing or may be affixed with tape, glue, Velcro or any other mechanism for affixing to clothing or accessories for swimming, diving or otherwise working or playing in water. [0095] Many human-shark interactions in shallow water, especially around the State of Florida in the United States, are hypothesized to be “mistaken identity” by the shark in water with poor visibility. The blacktip shark ( C. limbatus ) and nurse shark ( G. cirratum ) are often implicated in these encounters. The sharks do not have an olfactory clue in most of these “mistaken identity” cases. A series of electropositive metals, such as Mischmetal or other electropositive metal, may be used as means to repel the shark as it approaches within a few inches of the metal. With an electropositive metal, such as Cerium, or an increased number of electropositive metals, to increase electromotive force field strength, repellent activity increases and the chance that a shark will be repelled prior to an investigatory bump or bite is greatly increased. [0096] The invention is further described with the following non-limiting examples, which are provided to further illuminate aspects of the invention. III. EXAMPLES Example 1 Tonic Immobility Responses to Electropositive Metals [0097] In order to screen the repellency potential of various metals, 193 individual trials were conducted on juvenile sharks at South Bimini, Bahamas in open ocean pens. All sharks were placed into tonic immobility, and the behavioral response of the shark towards a test metal was scored using a scale of 0 to 4. A score of zero represented no response, with the shark remaining immobilized. A score of one represented a slight fin flinch or eye blink A score of two represented a slight bend (less than 15 degrees) away from the metal, without rousing. A score of three represented a strong bend away from the metal (more than 15 degrees), without rousing. A score of four represents the termination of tonic immobility, with a rousing response, indicating adequate repellency. No more than three consecutive trials were performed on any one given shark. A minimum of 4 hours of rest was allotted before a shark was retested. Classifying the behavioral scores with a specific group on the Periodic Table of the element demonstrates that the electropositive metals found in Group 2 and Group 3 of the periodic table of elements produced a stronger repellent response than transition metals (Groups3 through 12), a poor metal (Group 13), a metalloid (Group 16), and a nonmetal (Group 14). See Table 1. [0000] TABLE 1 Group Tests (Periodic table) Performed Average Score Group 1 1 4 Group 2 13 3.23 Group 2 Alloy 34 2.79 Group 3 84 2.28 Group 8 6 1.17 Group 13 4 0.75 Group 5 5 0.20 Group 14 21 0.10 Group 9 5 0 Group 7 6 0 Group 6 4 0 Group 4 5 0 Group 16 6 0 [0098] The aforementioned tests can also be analyzed in terms of the type of metal tested on the immobilized sharks. As expected, Alkali metals, Alkaline earths, Mischmetals, early Lanthanides, and late Lanthanides produced the highest repellency behavioral scores. These types of metals are electropositive and have revised Pauling electronegativities less then 1.32. See Table 2. [0000] TABLE 2 Tests Type of metal Performed Average Score Alkali metal 1 4 Alkaline earth 13 3.23 Mischmetal 34 2.79 Early Lanthanide 49 2.66 Late Lanthanide 29 1.83 Rare Earth 6 1.333 Poor metal 4 0.75 Transition metal 31 0.26 Nonmetal 21 0.10 Metalloid 6 0 Example 2 Published Standard Electrode Potentials of Electropositive Metals [0099] The published standard electrode potentials (SEP) for the cathode half-cell reaction of electropositive metals is a practical means of determining the repellency of the metal without performing a bioassay. As the cathode half-cell reaction voltage increases, the repellent effect is also expected to increase. The published voltage represents the electromotive force between the electropositive metal and the reference electrode. Published standard electrode potentials typically use a standard hydrogen electrode as the reference electrode. In practice, shark skin is the reference electrode and produces measurable voltages at about 88% of the published standard electrode potentials. The safe handling of highly electropositive metals must be considered, as well as the longevity of the metal in seawater. See Table 3. [0000] TABLE 3 Cathode SEP Terminates Tonic metal (Volts) Immobility? Safety Comments Lithium 3.05 YES Short-lived in water Rubidium 2.98 PROBABLE Explosive in water Potassium 2.93 PROBABLE Fire hazard in water Cesium 2.92 PROBABLE Explosive in water Barium 2.91 PROBABLE Short-lived in water Strontium 2.89 YES Short-lived in water Calcium 2.76 YES Short-lived in water Sodium 2.71 PROBABLE Fire hazard in water Lanthanum 2.52 YES Safe for repellent use Cerium 2.48 YES Safe for repellent use Praseodymium 2.47 YES Safe for repellent use Neodymium 2.44 YES Safe for repellent use Samarium 2.41 YES Safe for repellent use Europium 2.41 PROBABLE Corrodes quickly in air Gadolinium 2.40 YES Safe for repellent use Terbium 2.39 YES Safe for repellent use Magnesium 2.38 YES Safe for repellent use Yttrium 2.37 YES Safe for repellent use Dysprosium 2.35 YES Safe for repellent use Holmium 2.32 YES Safe for repellent use Erbium 2.31 YES Safe for repellent use Thulium 2.31 PROBABLE Safe for repellent use Lutetium 2.30 PROBABLE Safe for repellent use Ytterbium 2.22 YES Safe for repellent use Beryllium 1.847 NOT PROBABLE Weakly repellent, toxic oxides Aluminum 1.662 NO Not a repellent Zirconium 1.45 NO Not a repellent Niobium 1.099 NO Not a repellent Chromium 0.744 NO Not a repellent Rhenium 0.3 NO Not a repellent Tungsten 0.1 NO Not a repellent [0100] Beryllium and Magnesium metals are Alkaline earths in Group 2 of the periodic table of elements. These metals exhibit larger revised Pauling electro-negativities (1.56 and 1.31 respectively) than the Lanthanide metals. Magnesium, however, has a higher standard electrode potential (see Table 3) than beryllium and therefore is expected to be a better shark repellent than beryllium. Tonic immobility testing has confirmed that magnesium indeed produces aversive behavior in immobilized juvenile sharks. It is anticipated the beryllium would be weakly repellent based on the published standard electrode potentials. Additionally, the highly toxic nature of beryllium compounds preclude its use as a safe shark repellent. Example 3 Target Fish not Repelled by Electropositive Metals [0101] Preliminary research conducted on the effects of electropositive metals on adult cobia, Rachycentron canadum, suggests that electromotive forces produced by electropositive metals had little effect on captive cobia. Digital video of cobia striking at electropositive metals was recorded. Cobia were observed directly biting electropositive metals as well as transition metals. It is hypothesized that the shiny nature of the metals acted as a visual attractant to the fish. Since bony fish lack the ampullae of Lorenzini organ found in sharks, the fish were unable to detect the electromotive forces produced by the electropositive metals.
Devices and methods are disclosed for repelling elasmobranchs with electropositive metals, including apparatuses and methods for reducing by-catch in commercial fisheries and protecting humans from attacks by elasmobranchs.
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CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation-in-part of International Patent Application No. PCT/CN2012/084998, filed on Nov. 22, 2012, which in turn claims the benefit and priority of Chinese Patent Application No. 201210099615.5, filed on Apr. 6, 2012. The entire contents of all applications are incorporated herein by reference in their entireties. FIELD OF THE INVENTION [0002] The present invention relates to use of 7-alkoxy fangchinoline compounds in preventing, alleviating and/or treating depression. TECHNICAL FIELD [0003] Chinese Patent Publication No. CN102274227A disclosed the use of tetrandrine (TET in the preparation of a medicament for preventing, alleviating and/or treating depression. Depression is a clinically common mood disorder and the incidence rate thereof is increasing. Abnormal enhancement of GSK-3β activity is believed to be highly relevant to the pathogenesis of depression or schizophrenia and to the therapeutic mechanism of anti-depression or anti-schizophrenic drugs. There is an urgent need to develop a novel anti-depression drug suitable for clinical treatment. SUMMARY OF THE INVENTION [0004] In one aspect, the present invention provides a method of preventing, alleviating and/or treating depression, comprising the step of administering to a subject in need thereof a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable derivative thereof, [0000] [0005] wherein, R 1 is an alkyl of general formula —C n H 2n+1 , and n is an integer greater than or equal to 1; R 2 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and acyl; X 1 , X 2 , X 3 and X 4 may be the same or different, and each independently represent hydrogen, fluorine, chlorine, bromine, iodine, nitro, hydroxyl or methoxy; and when n is 1, X 1 , X 2 , X 3 and X 4 may not all be hydrogen. [0006] The present invention also provides a method of alleviating and/or treating schizophrenia, comprising the step of administering to a subject in need thereof a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable derivative thereof as defined above. [0007] The term “pharmaceutically acceptable derivative” as used herein includes a pharmaceutically acceptable salt, ester, ether, solvate, hydrate, stereoisomer or prodrug of a compound of formula (I). In the meantime, stereoisomers in which C(1) and C(1′) are RR, SS, 1S1′R and 1R1′S configurations are included. [0008] The term “therapeutically effective amount” as used herein refers to an amount of the therapeutic agent sufficient to result in a desired biological or medical response in a subject as expected by a clinical physician. The “therapeutically effective amount” of a compound of the present invention may be determined by a skilled artisan in consideration of factors such as administration route, weight and age of the subject, and disease condition. For example, a typical daily dose may range from 0.01 mg/kg to 100 mg/kg of the therapeutic agent. In other embodiments, the daily dose may range from about 0.01 mg/kg to about 1.0 mg/kg, from about 0.8 mg/kg to about 10 mg/kg, from about 8.0 mg/kg to about 30 mg/kg, from about 25 mg/kg to about 50 mg/kg, from 45 mg/kg to about 70 mg/kg, or from 65 mg/kg to about 100 mg/kg. [0009] In clinical practice, the compound of the present invention may be administered by any conventional route, e.g. orally or parenterally. The compound of the present invention may be formulated into any suitable dosage form, e.g. tablet, powder, capsule, or injection. [0010] In some embodiments of the present invention, R 1 is methyl, and at least one of X 1 , X 2 , X 3 and X 4 represents fluorine, chlorine, bromine, iodine or nitro. In some embodiments, R 1 is methyl, and X 1 and X 3 each independently represent chlorine or bromine In some embodiments, R 1 is methyl, and X 1 and X 3 are the same and represent chlorine or bromine [0011] Preferably, R 2 is methyl. [0012] In some embodiments of the present invention, n is 2, 3 or 4 (R 1 may be ethyl, propyl, isopropyl, butyl, or isobutyl). Preferably, R 2 is methyl. [0013] In some preferred embodiments of the present invention, compound of formula (I) is selected from the group consisting of 5-chloro-7-methoxy fangchinoline (Compound 1), 5,14-dibromo-7-methoxy fangchinoline (Compound 2), 7-ethoxy fangchinoline (Compound 3, also referred to as YH-200), 5-bromo-7-ethoxy fangchinoline (Compound 4), 5,14-dibromo-7-ethoxy fangchinoline (Compound 5), 7-propoxy fangchinoline (Compound 6), 7-butyl fangchinoline (Compound 7), 7-isopropoxy fangchinoline (Compound 8), and any combinations thereof. [0014] In another aspect, the present invention provides a compound of formula (I) or a pharmaceutically acceptable derivative thereof, [0000] [0015] wherein, R 1 is ethyl; R 2 is methyl; X 1 , X 2 , X 3 and X 4 may be the same or different, and each independently represent hydrogen, fluorine, chlorine, bromine, iodine, nitro, hydroxyl or methoxy. [0016] In some embodiments of the present invention, X 1 and X 3 each independently represent fluorine, chlorine, bromine, iodine or nitro. In some embodiments, X 1 and X 3 each independently represent chlorine or bromine In some embodiments, X 1 and X 3 are the same and represent chlorine or bromine. [0017] In some preferred embodiments of the present invention, compound of formula (I) is selected from the group consisting of 5-bromo-7-ethoxy fangchinoline (Compound 4) and 5,14-dibromo-7-ethoxy fangchinoline (Compound 5). [0018] The 7-alkoxy fangchinoline compound of formula (I) or a pharmaceutically acceptable derivative thereof may be used alone or in combination with other anti-mental disorder medicament or adjuvant therapeutic medicament for treating and/or alleviating depressive symptoms. BRIEF DESCRIPTION OF THE DRAWINGS [0019] FIG. 1 illustrates the influence of YH-200 (Compound 3) on GSK-3β phosphorylation level in prefrontal lobe cortex, hipocampus, corpus striatum and hypothalamus in mice (Mean±SE, n=4); *P<0.05, **P<0.01 as compared with control group (Student's t-test). [0020] FIG. 2 illustrates that the anti-depression effect of YH-200 (Compound 3) may be inhibited by a 5-HT 1A receptor antagonist, pMPPI (Mean±SE, n=12-15). [0021] FIG. 3 illustrates that the 5-HT 1A receptor antagonist pMPPI may significantly inhibit the YH-200 (Compound 3)-induced enhancement of GSK-3β phosphorylation level in prefrontal lobe cortex, hipocampus, corpus striatum and hypothalamus in mice (Mean±SE, n=6). [0022] FIG. 4 illustrates that the YH-200 (Compound 3)-induced reduction of immobility time and extension of immobility latency period in mice forced swimming test may be inhibited by a 5-HT 2A receptor agonist, DOI (Mean±SE, n=12-15). [0023] FIG. 5 illustrates that the 5-HT 2A receptor agonist, DOI, may inhibit the YH-200 (Compound 3)-induced enhancement of GSK-3β phosphorylation level in prefrontal lobe cortex, hipocampus, corpus striatum and hypothalamus in mice (Mean±SE, n=6). DETAILED DESCRIPTION OF EMBODIMENTS [0024] Compounds 1-8 of the present invention are as follows. [0025] Compound 1. 5-chloro-7-methoxy fangchinoline (Berbaman, 5-chloro-6,6′,7,12-tetramethoxy-2,2′-dimethyl-). ESI-MS(m/z): 658.25 (M+1). C 38 H 41 N 2 O 6 C1. 1 H NMR (300 MHz, CDCl 3 ) δ: 2.31(s, 3H, NCH 3 ), 2.70(s, 3H, NCH 3 ), 3.23(s, 3H, OCH 3 ), 3.38(s, 3H, OCH 3 ), 3.76(s, 3H, OCH 3 ), 3.92(s, 3H, OCH 3 ), 6.05˜7.34(m, 9H, aromatic hydrocarbon H). [0026] Compound 2. 5,14-dibromo-7-methoxy fangchinoline (Berbaman, 5,14-dibromo-6,6′,7,12-tetramethoxy-2,2′-dimethyl-). An acicular crystal (Methanol), mp: 187-189° C. ESI-MS(m/z): 781.2(M+1), C 38 H 40 N 2 O 6 Br 2 . 1 H NMR (300 MHz, CDCl 3 ) δ: 2.27(s, 3H, NCH 3 ), 2.65(s, 3H, NCH 3 ), 3.24(s, 3H, OCH 3 ), 3.38(s, 3H, OCH 3 ), 3.74(s, 3H, OCH 3 ), 3.89(s, 3H, OCH 3 ), 2.44-3.96(m, 14H, alkane H), 6.02 (s, 1H, aromatic hydrocarbon H), 6.34(dd, J=9.0, 2.3 Hz, 1H, aromatic hydrocarbon H), 6.53(s, 1H, aromatic hydrocarbon H), 6.60(s, 1H, aromatic hydrocarbon H), 6.84(dd, J=10.0, 2.7 Hz, 1H, aromatic hydrocarbon H), 7.05(dd, J=10.0, 2.7 Hz, 1H, aromatic hydrocarbon H), 7.07(s, 1H, aromatic hydrocarbon H), 7.34(dd, J=9.0, 2.3 Hz, 1H, aromatic hydrocarbon H). [0027] Compound 3. 7-ethoxy fangchinoline (Berbaman, 6,6′,12-trimethoxy-7-ethoxy-2,2′-dimethyl) (also referred to as YH-200). A colorless acicular crystal (Ethanol), mp: 109.5-111.° C. ESI-MS (m/z): 637.33 (M+1), C 39 H 44 N 2 O 6 . 1 H NMR(300 MHz, CDCl 3 ) δ: 0.80 (t, 3H, OCH 2 CH 3 ), 2.32 (s, 3H, NCH 3 ), 2.58 (s, 3H, NCH3), 2.40˜3.80(m, 16H, alkane H), 3.37 (s, 3H, OCH3), 3.74 (s, 3H, OCH3), 3.93(s, 3H, OCH 3 ), 5.95 (s, 1H, aromatic hydrocarbon H), 6.30(s, 1H, aromatic hydrocarbon H), 6.32(dd, J=9.2, 2.1 Hz, 1H, aromatic hydrocarbon H), 6.50(s, 1H, aromatic hydrocarbon H), 6.52 (dd, J=10.2, 2.2 Hz, 1H, aromatic hydrocarbon H), 6.81(dd, J=9.2, 2.1 Hz, 1H, aromatic hydrocarbon H), 6.83(s, 1H, aromatic hydrocarbon H), 6.87(dd, J=10.2, 2.2 Hz, 1H, aromatic hydrocarbon H), 7.14(s, (dd, J=9.0, 1.0 Hz, 1H, aromatic hydrocarbon H), 7.36(dd, J=9.0, 1.0 Hz, 1H, aromatic hydrocarbon H). [0028] Compound 4. 5-bromo-7-ethoxy fangchinoline (Berbaman, 5-bromo-6,6′,12-tetramethoxy-7-ethoxy-2,2′-dimethyl-). An acicular crystal (Methanol-Diethyl ether), mp: 146-148° C. ESI-MS (m/z): 716.24(M+1), C 39 H 43 N 2 O 6 Br. 1 H NMR (300 MHz,CDCl 3 ) δ: 0.81(t, 3H, OCH 2 C H 3 ), 2.32(s, 3H, NCH 3 ), 2.60(s, 3H, NCH 3 ), 2.40˜3.80(m, 16H, alkane H), 3.39(s, 3H, OCH 3 ), 3.72(s, 3H, OCH 3 ), 3.92(s, 3H, OCH 3 ), 6.03˜7.35(m, 9H, aromatic hydrocarbon H). [0029] Compound 5. 5,14-dibromo-7-ethoxy fangchinoline (Berbaman, 5,14-dibromo-6,6′,7,12-tetramethoxy-2,2′-dimethyl-). An acicular crystal (Methanol), mp: 186-188° C. ESI-MS (m/z): 795.26 (M+1), C 39 H 42 N 2 O 6 Br 2 . 1 H NMR (300 MHz, CDCl 3 ) δ: 0.80(t, 3H, OCH 2 CH 3 ), 2.28(s, 3H, NCH 3 ), 2.69(s, 3H, NCH 3 ), 3.38(s, 3H, OCH 3 ), 3.73(s, 3H, OCH 3 ), 3.89(s, 3H, OCH 3 ), 2.44-3.96(m, 16H, alkane H), 6.02 (s, 1H, aromatic hydrocarbon H), 6.33(dd, J=9.0, 2.3 Hz, 1H, aromatic hydrocarbon H), 6.54(s, 1H, aromatic hydrocarbon H), 6.60(s, 1H, aromatic hydrocarbon H), 6.83(dd, J=10.0, 2.7 Hz, 1H, aromatic hydrocarbon H), 7.04(dd, J=10.0, 2.7 Hz, 1H, aromatic hydrocarbon H), 7.06(s, 1H, aromatic hydrocarbon H), 7.34(dd, J=9.0, 2.3 Hz, 1H, aromatic hydrocarbon H). [0030] Compound 6. 7-propoxy fangchinoline (Berbaman, 6, 6′,12-trimethoxy-7-propoxy-2,2′-dimethyl-). An acicular crystal (MeOH), mp: 174.8-176.3; ESI-MS (m/z): 651.35 (M+1), C 40 H 46 N 2 O 6 . 1 H NMR (300 MHz,CDCl 3 ) δ: 0.79 (t, 3H, OCH 2 CH 2 C H 3 ), 2.32 (s, 3H, NCH 3 ), 2.58 (s, 3H, NCH3), 2.40˜3.81(m, 18H,alkane H), 3.37 (s, 3H, OCH3), 3.73 (s, 3H, OCH3), 3.92 (s, 3H, OCH 3 ), 5.94˜7.36(m, 10H, aromatic hydrocarbon H). [0031] Compound 7. 7-butyl fangchinoline (Berbaman, 6,6′,12-trimethoxy-7-butoxy-2,2′-dimethyl-). A columnar crystal (MeOH); mp: 155-156° C.; ESI-MS (m/z): 665.38 (M+1), C 41 H 48 N 2 O 6 . 1 H NMR (300 MHz,CDCl 3 ) δ: 0.78(t, 3H, OCH 2 CH 2 CH 2 C H 3 ), 1.13˜3.60(m, 20H, alkane H), 2.32(s, 3H, NCH 3 ), 2.59(s, 3H, NCH 3 ), 3.36(s, 3H, OCH 3 ), 3.73(s, 3H 2 OCH 3 ), 3.92(s, 3H, OCH 3 ), 5.94˜7.36(m, 10H, aromatic hydrocarbon H). [0032] Compound 8. 7-isopropoxy fangchinoline (Berbaman, 6,6′,12-trimethoxy-7-isopropoxy-2,2′-dimethyl-). ESI-MS (m/z): 651.34(M+1); C 40 H 46 N 2 O 6 . 1 H NMR (300 MHz,CDCl 3 ) δ: 0.76[d, 6H, OCH(C H 3 ) 2 ], 2.34(s, 3H, NCH 3 ), 2.62(s, 3H, NCH 3 ), 2.40˜3.60(m, 15H, alkane H), 3.34(s, 3H, OCH 3 ), 3.71(s, 3H, OCH 3 ), 3.92(s, 3H, OCH 3 ), 5.86˜7.38(m, 10H, aromatic hydrocarbon H). EXAMPLES [0033] The present invention will be further illustrated with reference to the following experiments, taking compounds 1-8 as examples. The invention, however, should not be limited to any of the details in these examples. Example 1 GSK-3β Activity Assay [0034] The GSK-3β phosphorylation level was determined by using a Z′-LYTE assay (Life Technologies). The assay was performed in a 384-well plate. The wells of the testing plate were divided into blank control wells (without the enzyme), enzyme control wells (without the testing substance), and testing wells (with the enzyme and the testing substance at various concentrations). The inhibition rate of the testing substance is expressed as: inhibition %=(E−S)/(E−B)×100, wherein E is the average emission ratio of enzyme control wells; B is the average emission ratio of blank control wells; S is the emission ratio of the testing sample wells. The median effective concentration of each compound (EC 50 μM) was calculated by using the resultant inhibition rate of each sample at various concentrations. [0000] TABLE 1 EC 50 in the inhibition of GSK-3β activity (n = 3) Compounds Mean EC 50 (μM) Compound 1 (5-chloro-7-methoxy fangchinoline) 3.21 Compound 2 (5,14-dibromo-7-methoxy fangchinoline) 2.01 Compound 3 (7-ethoxy fangchinoline, YH-200) 0.86 Compound 4 (5-bromo-7-ethoxy fangchinoline) 1.22 Compound 5 (5,14-dibromo-7-ethoxy fangchinoline) 1.26 Compound 6 (7-propoxy fangchinoline) 1.68 Compound 7 (7-butyl fangchinoline) 2.33 Compound 8 (7-isopropoxy fangchinoline) 1.35 tetrandrine (7-methyl fangchinoline) 9.02 5,7-dimethoxy-fangchinoline >10 berbamine (12-desmethyltetrandrine) >10 12-acetoxyberbamine >10 12-(4-ethoxy)-butoxyberbamine >10 [0035] It was demonstrated by the study that compounds 1-8 of the present invention all exhibited a high inhibition effect against GSK-3β activity (EC 50 <3.5 μM) (see, Table 1). As compared with tetrandrine (TET), 5,7-dimethoxy-fangchinoline, berbamine (12-desmethyltetrandrine) and 12-acetoxy berbamine, compounds 1-8 had a 3-10 times lower median effective concentration (EC 50 ), indicating an evident potency advantage. [0036] The results suggested that compounds 1-8 all had potency for treating schizophrenia and depression disorders that are associated with abnormally elevated GSK-3β activity. Example 2 [0037] The ameliorating/therapeutic effect of compounds 1-8 on depression behaviors in a chronic unpredictable stress (CUS) model in rats, in comparison with tetrandrine, 5,7-dimethoxy-fangchinoline, berbamine, 12-acetoxyberbamine and 12-(4-ethoxy)-butoxyberbamine. [0038] The chronic unpredictable stress model is usually used as a depression model. [0039] The experimental method is as follows. Stimulation includes forced swimming (10° C., 6 min), tail clamping (1 cm from the tail tip, 1 min), water deprivation (24 h), fasting (24 h), isolated housing (24 h), tail suspension (1 h), immobility (2 h), high-speed horizontal oscillation (120 times/min, 1 h), foot shock for 45 minutess (mean 1 mA, time course 1 s, once/min). These stressors were randomly scheduled over a one-week period and repeated throughout the 23-day experiment. The non-stress control group was housed under normal conditions. Time: between 9:00 a.m. and 2:00 p.m. Since Day 15, the animals in each group were daily intragastrically administered with the subject medicament and double distilled water based on body weight (blank group and CUS model group) respectively, 60 minutes before the stress. Imipramine (intraperitoneally, IP) was adopted as a positive control. Behavior and sleep electroencephalogram analyses were carried out on Day 22-23 of the stress. On Day 21, 60 minutes after the final administration, a sucrose solution intake test was carried out and sleep electroencephalogram was recorded simultaneously. On Day 22, EPM and forced swimming tests were carried out. [0000] TABLE 2 The influence of the compounds of formula (I) on forced swimming, sucrose solution preference and autonomous mobility in a chronic unpredictable stress model in rats (means ± SEM, n = 10) Forced swimming Sucrose Immobility solution time preference Autonomous movement Groups (seconds) (%) Distance (mm) Speed (mm/second) Blank control group  57.4 ± 4.5 100 14870.12 ± 1187.70 49.57 ± 3.96 CUS model group 180.8 ± 6.3**  51.6 ± 3.1**  1097.52 ± 716.52**  3.66 ± 2.39** Model group + compound 1 7.50 mg/kg 157.4 ± 5.6 ##,$$  69.6 ± 4.6 ##  7581.17 ± 845.04 ##,$$ 25.27 ± 2.38 ##,$$ 15.0 mg/kg  99.2 ± 2.9 ##,$$  78.8 ± 4.0 ##,$$  9518.08 ± 704.12 ##,$$ 31.73 ± 3.44 ##,$$ 30.0 mg/kg  76.6 ± 4.7 ##,$$  81.6 ± 3.7 ##,$$ 10347.64 ± 923.01 ##,$$ 34.49 ± 3.75 ##,$$ Model group + compound 2 7.50 mg/kg 136.2 ± 4.6 ##,$$  72.5 ± 3.0 ##  9031.41 ± 639.33 ##,$$ 30.10 ± 3.88 ##,$$ 15.0 mg/kg  96.7 ± 4.5 ##,$$  89.0 ± 4.6 ##,$$ 10116.74 ± 746.48 ##,$$ 33.72 ± 4.02 ##,$$ 30.0 mg/kg  76.8 ± 3.4 ##,$$  88.5 ± 3.1 ##,$$ 12062.32 ± 903.42 ##,$$ 40.21 ± 5.36 ##,$$ Model group + compound 3 7.50 mg/kg 120.6 ± 6.4 ##,$$  82.3 ± 3.3 ##,$$ 13612.65 ± 792.22 ##,$$ 45.38 ± 2.64 ##,$$ 15.0 mg/kg  88.5 ± 4.3 ##,$$  93.6 ± 4.6 ##,$$ 14409.83 ± 664.54 ##,$$ 48.03 ± 4.02 ##,$$ 30.0 mg/kg  58.7 ± 5.2 ##,$$  98.1 ± 3.7 ##,$$ 14636.14 ± 812.31 ##,$$ 48.78 ± 5.36 ##,$$ Model group + compound 4 7.50 mg/kg 134.3 ± 4.4 ##,$$  79.2 ± 3.4 ##,$$ 13257.21 ± 756.36 ##,$$ 44.19 ± 2.64 ##,$$ 15.0 mg/kg  96.1 ± 3.74 ##,$$  81.5 ± 4.7 ##,$$ 13615.71 ± 743.43 ##,$$ 45.39 ± 4.02 ##,$$ 30.0 mg/kg  60.5 ± 5.3 ##,$$  93.6 ± 3.2 ##,$$ 14362.26 ± 771.52 ##,$$ 47.87 ± 5.36 ##,$$ Model group + compound 5 7.50 mg/kg 144.4 ± 4.0 ##,$$  84.1 ± 3.3 ## 13732.42 ± 732.45 ##,$$ 45.77 ± 2.64 ##,$$ 15.0 mg/kg  99.6 ± 3.7 ##,$$  86.0 ± 3.5 ##,$$ 14003.63 ± 737.47 ##,$$ 46.68 ± 4.02 ##,$$ 30.0 mg/kg  69.7 ± 4.8 ##,$$  91.5 ± 4.2 ##,$$ 14561.84 ± 807.52 ##,$$ 48.54 ± 5.36 ##,$$ Model group + compound 6  7.5 mg/kg 134.6 ± 5.2 ##,$$ 79.45 ± 3.3 ##  8940.78 ± 714.35 ##,$$ 29.80 ± 2.64 ##,$$   15 mg/kg  98.8 ± 4.7 ##,$$  85.5 ± 3.6 ##,$$ 11574.92 ± 732.36 ##,$$ 38.58 ± 3.02 ##,$$   30 mg/kg  78.5 ± 3.9 ##,$$  90.4 ± 4.3 ##,$$ 12566.27 ± 764.42 ##,$$ 41.89 ± 4.36 ##,$$ Model group + compound 7  7.5 mg/kg 142.2 ± 6.0 ##,$$  70.7 ± 4.1 ##  8823.36 ± 673.14 ##,$$ 29.41 ± 2.64 ##,$$   15 mg/kg  94.4 ± 5.3 ##,$$  87.1 ± 3.5 ##  9586.43 ± 756.75 ##,$$ 31.95 ± 4.02 ##,$$   30 mg/kg  81.3 ± 4.3 ##,$$  86.3 ± 3.4 ##,$$ 11768.25 ± 903.41 ##,$$ 39.23 ± 5.36 ##,$$ Model group + compound 8  7.5 mg/kg 136.5 ± 5.8 ##,$$  80.5 ± 3.6 ##  9968.41 ± 965.52 ##,$$ 33.22 ± 2.64 ##,$$   15 mg/kg 102.3 ± 6.2 ##,$$  84.7 ± 3.2 ##,$ 12194.23 ± 887.65 ##,$$ 40.64 ± 4.02 ##,$$   30 mg/kg  72.4 ± 5.5 ##,$$  90.1 ± 3.8 ##,$$ 13053.78 ± 1005.46 ##,$$ 43.51 ± 5.36 ##,$$ Model group + tetrandrine  7.5 mg/kg 179.5 ± 8.3  55.4 ± 3.2  1369.54 ± 532.47  4.57 ± 1.85   15 mg/kg 175.3 ± 8.8  52.9 ± 3.7  1124.37 ± 504.85  3.75 ± 1.98   30 mg/kg 162.7 ± 8.5 #  67.7 ± 3.3 #  1027.36 ± 456.76  3.42 ± 1.33   60 mg/kg 160.8 ± 7.6 ##  70.2 ± 4.6 ##  1285.41 ± 401.24  4.28 ± 1.56 Model group + 5,7-dimethoxyfangchinoline   30 mg/kg 179.1 ± 6.8  53.7 ± 4.8  1189.64 ± 315.84  3.97 ± 1.48   60 mg/kg 168.3 ± 5.2  55.3 ± 4.2  936.47 ± 366.32  3.12 ± 1.42 Model group + berbamine   30 mg/kg 179.2 ± 6.2 55.05 ± 3.06  1387.56 ± 584.24  4.63 ± 1.49   60 mg/kg 175.8 ± 7.5 49.56 ± 4.27  1053.45 ± 476.33  3.51 ± 1.65 Model group + 2-acetoxyberbamine   30 mg/kg 179.2 ± 6.6 54.29 ± 3.74  984.41 ± 542.67  3.28 ± 1.35   60 mg/kg 169.9 ± 7.4 53.34 ± 3.04  1135.49 ± 575.54  3.78 ± 1.46 Model group + 12-(4-ethoxy)-butoxy-berbamine   30 mg/kg 179.5 ± 6.3 54.19 ± 4.45  1367.52 ± 683.88  4.56 ± 1.74   60 mg/kg 175.3 ± 8.4 53.27 ± 3.55  935.73 ± 586.51  3.12 ± 1.31 Imipramine 40 mg/kg  58.3 ± 3.8 ##,$$  68.4 ± 5.3 # 12483.88 ± 1142.77 ##,$$ 41.62 ± 3.81 ##,$$ **P < 0.01 as compared with control group; # P < 0.05, ## P < 0.01 as compared with CUS group; $ P < 0.05, $$ P < 0.01 as compared with tetrandrine 60 mg/kg group. The data were analyzed by one-way analysis of variance (ANOVA) followed by post hoc Student-Newman-Keuls test for multiple comparisons, and the sucrose preference test was analyzed by two-way repeated measures ANOVA (one factor repetition). [0040] Result 1: As shown in Table 2, compounds 1-8, intragastrically administered for consecutive 7 days at doses of 7.5, 15 and 30 mg/kg, could all evidently ameliorate depression-like behaviors in a CUS model in rats, such as a desperate behavior (immobility time in forced swimming, p<0.01), interest lost (sucrose solution preference, p<0.01), activity reduction (autonomous mobility, p<0.01) etc. Meanwhile, tetrandrine (TET) exhibited merely certain amelioration effect on the immobility time in forced swimming (p<0.05) and sucrose solution preference (p<0.05) at a higher dose (60 mg/kg). Furthermore, 5,7-dimethoxy fangchinoline, berbamine, 12-acetoxy berbamine and 12-(4-ethoxy)-butoxy berbamine exhibited no amelioration effect at doses of 30 and 60 mg/kg. In this experiment, as compared with tetrandrine, compounds 1-8 had an evidently suporior amelioration/treatment effect with respect to various indices of CUS model in rats (p<0.01). By comparison of the range of minimal effective dose, it was shown that compounds 1-8 had an efficacy 8 times higher than that of tetrandrine. It was found that, as compared with tetrandrine, 5,7-dimethoxy fangchinoline, berbamine, 12-acetoxyberbamine and 12-(4-ethoxy)-butoxyberbamine, compounds 1-8 not only had a stronger inhibition effect on GSK-3β activity, but also had a better amelioration effect on depression symptoms such as pleasure lost (anhedonia), despair, mobility reduction and anxiety etc. It was suggested that compounds 1-8 had an unexpected superior anti-depression effect. [0041] Result 2: The influence of the compounds of formula (I) on anxiety behaviors in a CUS depression model in rats was examined by using a well-established elevated plus-maze (EPM) anxiety test procedure. [0042] As shown in the experimental results, the CUS model in rats had obviously decreased percentage of residence time in open arm area and percentage of entry into open arms, as compared with blank control group (p<0.01, see, Table 3). It was suggested that the CUS model rats developed an anxiety behavior. Compounds 1-8 in various dose groups (7.5, 15 and 30 mg/kg) all remarkably increased residence time in open arm area and entries into open arms. Whereas 5,7-dimethoxyfangchinoline, berbamine, 12-acetoxyberbamine and 12-(4-ethoxy)-butoxyberbamine exhibited no anti-anxiety-like effect at doses of 30 and 60 mg/kg. Although tetrandrine (TET) could increase entries into open arms in a CUS depression model in rats at a higher dose (60 mg/kg), it had no amelioration effect on the residence time in open arms, indicating that tetrandrine could ameliorate an exploratory behavior in a CUS depression model in rats, without amelioration effect on anxiety-like behaviors at a higher dose (60 mg/kg). In this experiment, compounds 1-8 exhibited an anti-anxiety-like effect even at a dose of 7.5 mg/kg, whereas tetrandrine exhibited an amelioration effect on the exploratory behavior in a CUS model in rats merely at a dose of 60 mg/kg. It was suggested that compounds 1-8 had an evidently superior amelioration/treatment effect on anxiety-like behaviors in a CUS model in rats, as compared with tetrandrine, 5,7-dimethoxyfangchinoline, berbamine, 12-acetoxyberbamine and 12-(4-ethoxy)-butoxyberbamine (p<0.01). By comparison of the minimal effective dose, it was shown that compounds 1-8 had a valence which was approximately 8 times higher than that of tetrandrine. It was suggested that compounds 1-8, as represented by the compound YH-200, had an unexpected superior amelioration effect on anxiety symptoms in a patient suffered from depression. [0000] TABLE 3 Influence of the compound of formula (I) on anxiety-like behaviors in a chronic unpredictable stress (CUS) model in rats (Means ± SEM, n = 10). Percentage of entries into open arms relative Percentage of residence to total entries into Groups time in open arms (%) arms (%) Blank control group 70.2 ± 4.9 62.0 ± 2.5 CUS model group 41.9 ± 3.8** 37.0 ± 1.6** Model group + Compound 1 7.50 mg/kg 53.6 ± 4.6 ##,$$ 41.2 ± 2.3 ## 15.0 mg/kg 60.8 ± 4.0 ##,$$ 46.7 ± 3.4 ## 30.0 mg/kg 60.6 ± 3.7 ##,$$ 53.9 ± 3.5 ##,$$ Model group + Compound 2 7.50 mg/kg 56.5 ± 3.0 ##,$$ 45.1 ± 3.8 ## 15.0 mg/kg 63.6 ± 4.1 ##,$$ 49.7 ± 4.0 ## 30.0 mg/kg 64.5 ± 3.6 ##,$$ 56.2 ± 5.3 ##,$$ Model group + Compound 3 7.50 mg/kg 69.1 ± 2.4 ##,$$ 57.2 ± 1.8 ##,$$ 15.0 mg/kg 72.3 ± 3.6 ##,$$ 59.7 ± 2.2 ##,$$ 30.0 mg/kg 71.8 ± 3.2 ##,$$ 60.2 ± 2.0 ##,$$ Model group + Compound 4 7.50 mg/kg 66.2 ± 3.4 ##,$$ 54.2 ± 2.6 ##,$ 15.0 mg/kg 69.5 ± 4.2 ##,$$ 55.3 ± 4.0 ##,$ 30.0 mg/kg 68.6 ± 3.2 ##,$$ 59.7 ± 5.3 ##,$$ Model group + Compound 5 7.50 mg/kg 64.1 ± 3.0 ##,$$ 52.7 ± 2.6 ## 15.0 mg/kg 67.2 ± 3.1 ##,$$ 54.6 ± 3.2 ##,$ 30.0 mg/kg 68.4 ± 4.2 ##,$$ 60.4 ± 4.6 ##,$$ Model group + Compound 6  7.5 mg/kg 59.4 ± 3.3 ##,$$ 47.0 ± 2.6 ##   15 mg/kg 64.1 ± 3.6 ##,$$ 50.5 ± 3.2 ##   30 mg/kg 66.0 ± 4.2 ##,$$ 57.3 ± 4.6 ##,$$ Model group + Compound 7  7.5 mg/kg 54.7 ± 4.1 ##,$$ 43.4 ± 2.6 ##   15 mg/kg 62.1 ± 3.4 ##,$$ 47.9 ± 4.0 ##   30 mg/kg 61.5 ± 3.0 ##,$$ 54.3 ± 5.6 ##,$ Model group + Compound 8  7.5 mg/kg 60.5 ± 3.2 ##,$$ 49.2 ± 2.6 ##   15 mg/kg 66.1 ± 3.4 ##,$$ 51.6 ± 3.1 ##,$   30 mg/kg 67.5 ± 3.8 ##,$$ 58.5 ± 4.3 ##,$$ Model group + tetrandrine  7.5 mg/kg 42.1 ± 3.7 38.0 ± 2.3   15 mg/kg 40.6 ± 4.8 39.5 ± 3.0   30 mg/kg 41.3 ± 3.0 43.8 ± 3.2   60 mg/kg 42.8 ± 3.5 46.2 ± 2.9 # Model group + 5,7-dimethoxyfangchinoline   30 mg/kg 43.2 ± 4.1 38.9 ± 1.8   60 mg/kg 42.8 ± 4.8 37.2 ± 1.4 Model group + berbamine   30 mg/kg 41.0 ± 3.0 38.3 ± 1.9   60 mg/kg 39.6 ± 4.2 37.5 ± 1.6 Model group + 12-acetoxyberbamine   30 mg/kg 41.9 ± 3.7 38.2 ± 1.8   60 mg/kg 43.3 ± 3.4 36.8 ± 1.6 Model group + 12-(4-ethoxy)-butoxyberbamine   30 mg/kg 40.1 ± 4.5 36.6 ± 1.7   60 mg/kg 39.2 ± 3.5 37.2 ± 1.3 Imipramine 40 mg/kg 76.1 ± 1.9 ##,$$ 57.1 ± 1.8 ##,$ **P < 0.01 as compared with control group; # P < 0.05, ## P < 0.01 as compared with CUS group; $ P < 0.05, $$ P < 0.01 as compared with tetrandrine 60 mg/kg group. The data were analyzed by one-way ANOVA test followed by post hoc Student-Newman-Keuls test for multiple comparisons. [0043] Result 3: Sleep disturbance is one of the most common symptoms of neuropsychiatry. From a view of therapeutics, sleep disturbance is one of the most distressful events in patients suffered from nervous diseases and mental illness, especially in depression, and also one of major adverse events that may exacerbate the conditions of nervous disease and mental illness and impede the recovery in patients. For example, patients who are suffering from depression associated with insomnia may have an apparently higher incidence of a suicidal behavior, as compared with a non-insomnia group. Sleep disturbance in nervous and mental diseases can be simulated by using a CUS model in rats. As shown in Table 4, the CUS model in rats exhibited sleep disturbance, which was characterized by indices such as decreased total sleep (TS) and slow wave sleep (SWS) duration, and increased awakening times and rapid eye movements (REM) sleep times, etc.. YH-200 (Compound 3) had an evident amelioration effect on the sleep disturbance in the CUS model in rats. Therefore, YH-200 could be useful for treating and ameliorating sleep disturbance in a patient suffering from depression (see, Table 4). [0000] TABLE 4 The amelioration effect of YH-200 (30 mg/kg, p.o.) on sleep in a CUS depression model in rats (Means ± SEM, n = 8). Time (min) Rapid eye movement NREM sleep Deep sleep (SWS) (REM) sleep Total sleep Day 0 Normal group 177.89 ± 16.05 40.14 ± 15.17 30.20 ± 9.62 208.09 ± 23.41 CUS 172.99 ± 13.63 38.36 ± 13.36 37.22 ± 4.10 210.21 ± 14.44 CUS + YH-200 174.44 ± 8.35 39.31 ± 10.22 37.95 ± 6.28 212.40 ± 12.65 Day 21 Normal group 170.32 ± 20.86 40.46 ± 20.25 31.12 ± 3.39 201.44 ± 22.24 CUS 138.50 ± 5.88** 24.62 ± 3.49** 22.29 ± 9.14* 160.79 ± 9.10* CUS + YH-200 165.27 ± 7.97 # 48.18 ± 13.77 # 34.06 ± 1.75 # 199.33 ± 9.11 # REM: rapid eye movement sleep; NREM: non-REM sleep; SWS: slow-wave sleep; TS: total sleep. *P < 0.05, **P < 0.01 as compared with blank group; # P < 0.05 as compared with model group (SNK-test). Example 3 [0044] The influence of YH-200 (Compound 3) on GSK-3β phosphorylation level in prefrontal lobe cortex, hipocampus, corpus striatum and hypothalamus in mice (Mean±SE, n=4); *P<0.05, **P<0.01 as compared with control group (Student's t-test) [0045] ICR mice were intragastrically administered of subject medicaments and vehicle. One hour later, brains of those treated mice were obtained after decapitation. Prefrontal lobe cortex, hipocampus, corpus striatum and hypothalamus were isolated and collected respectively. Then protein electrophoresis (Western blot) was carried out with each sample. The results were shown in FIG. 1 . Intragastric administration of YH-200 at 30 mg/kg had no evident influence on phosphorylated GSK-3β (p-GSK-3β) and total-GSK-3β in prefrontal lobe cortex, hipocampus and corpus striatum in mice, but resulting in an evidently increased p-GSK-3β level in hypothalamus, as compared with blank control group. However, YH-200, at a dose of 60 mg/kg, resulted in a significantly increased p-GSK-3β level in said four brain sections, but had no influence on the total GSK-3β level. Example 4 [0046] The relevance of the anti-depression mechanism of YH-200 to the GSK-3β phosphorylation level, 5-HT 1A and 5-HT 2A receptor [0047] A desperate behavior status of human beings may be simulated by an immobility status in a forced swimming model in mice. The mice were put into a cylindrical glass jar (height 20 cm, diameter 10 cm) with a water depth of 15 cm and water temperature of 25±1° C. The mice were allowed to pre-swim for 15 minutes before the experiment, and then were taken out, wiped dry at a warm place, and sent back into cages. In 24 hours, the mice received an intragastric administration; and 60 minutes after the administration, the mice were put into the above-mentioned environment. The accumulative immobility time of the mice in the jar during the 5-minute period of time after six minutes of swimming was measured. A decrease in immobility time was taken as evaluation index. [0048] As shown in the experimental results, compounds 1-8 all exhibited a strong amelioration effect on the immobility latency period and immobility time in swimming, which were representative for desperate behaviors. It was suggested that compounds 1-8 had an amelioration effect on desperate behaviors. As shown in FIG. 2 , the anti-depression effect of YH-200 could be inhibited by a 5-HT 1A receptor antagonist, pMPPI (Mean±SE, n=12-15). As shown in FIG. 3 , an intraperitoneal administration of the 5-HT 1A receptor antagonist pMPPI 15 minutes before the intragastric administration of YH-200 could evidently inhibit the YH-200-induced enhancement of GSK-3β phosphorylation level in prefrontal lobe cortex, hipocampus, corpus striatum and hypothalamus in mice (Mean±SE, n=6). As shown in FIG. 4 , the YH-200-induced reduction of immobility time and extension of immobility latency period in forced swimming model could be inhibited by a 5-HT 2A receptor agonist, DOI (Mean±SE, n=12-15). As shown in FIG. 5 , the 5-HT 2A receptor agonist DOI inhibited the YH-200 induced enhancement of GSK-3β phosphorylation level in prefrontal lobe cortex, hipocampus, corpus striatum and hypothalamus in mice (Mean±SE, n=6). It was thus deduced that the anti-depression effect of YH-200 might be relevant to the enhancement of 5-HT 1A receptor function, the inhibition of 5-HT 2A receptor activity, and the enhancement of GSK-3β phosphorylation level of YH-200. In the figures: *P<0.05, **P<0.01 as compared with control group; # P<0.05, ## P<0.05 as compared with YH-200 (60 mg/kg) group. The data were analyzed by one-way ANOVA test followed by post hoc Student-Newman-Keuls test for multiple comparisons. Example 5 [0049] The influence of compounds 1-8 and tetrandrine by intragastric administration for consecutive 14 days on aspartate transaminase (also called aspartate aminotransferase, AST) and alanine transaminase (also called alanine aminotransferase, ALT) in mice. [0050] The mice were administered with compounds 1-8 and tetrandrine for consecutive 14 days. Blood was collected from epicanthal, stood at room temperature for about 2 hours, and centrifuged for 12 minutes at 3000 r/min after coagulation. The serum was removed and centrifuged again. Alanine transaminase (ALT) and aspartate transaminase (AST) levels were determined [0000] TABLE 5 The influence of intragastric administration for consecutive 14 days on AST, ALT and AST/ALT in serum of mice (Means ± SEM, n = 10) Dose Compound (mg/kg/day) AST (U/L) ALT (U/L) AST/ALT Blank control —  91.8 ± 12.9 77.8 ± 18.1 1.18 ± 0.24 Compound 1 60 117.7 ± 16.1 80.9 ± 21.4 1.45 ± 0.21 Compound 2 60 108.4 ± 17.4 87.2 ± 24.7 1.24 ± 0.26 Compound 3 60 102.3 ± 14.5 82.1 ± 16.4 1.25 ± 0.18 Compound 4 60  88.6 ± 20.3 79.5 ± 19.1 1.11 ± 0.25 Compound 5 60 101.5 ± 18.7 91.7 ± 15.5 1.11 ± 0.19 Compound 6 60  99.4 ± 21.1 92.3 ± 21.2 1.08 ± 0.27 Compound 7 60  93.6 ± 17.8 82.4 ± 17.9 1.14 ± 0.20 Compound 8 60  89.2 ± 16.7 80.1 ± 21.3 1.11 ± 0.21 tetrandrine 30  204.8 ± 21.8** 83.8 ± 15.9  2.44 ± 0.21** 60  205.6 ± 22.8** 113.2 ± 20.6*  1.82 ± 0.26* *P < 0.05 and **P < 0.01 as compared with control group (Student's t-test). [0051] Usually, aspartate transaminase (AST) and alanine transaminase (ALT) are present in hepatocytes. They enter into blood when the hepatocytes are impaired, thus enhancing the level thereof in blood serum. Therefore, the activities of aspartate transaminase (AST) and alanine transaminase (ALT) and the ratio thereof could reflect the extent of hepatic impairment. The inventors found that (see, Table 5), there was no evident change in aspartate transaminase (AST) activity, alanine transaminase (ALT) activity and the ratio thereof (AST/ALT) in blood serum after an intragastric administration of compounds 1-8 (60 mg/kg) for consecutive 14 days; meanwhile, as a result from an intragastric administration of tetrandrine for consecutive 14 days, the aspartate aminotransferase (AST) activity, the alanine transaminase (ALT) activity and the ratio thereof (AST/ALT) were all evidently enhanced by tetrandrine at a dose of 60 mg/kg, as compared with control group (P<0.01). Moreover, the aspartate transaminase (AST) activity (P<0.01) and the AST/ALT ratio (P<0.05) were evidently enhanced by tetrandrine at a dose of 30 mg/kg. It proved that, with respect to liver, compounds 1-8 were safer than tetrandrine. Example 6 Preparation of Compounds 4 and 5 [0052] 1 eq. of Compound 3 (YH-200) was dissolved in CF 3 COOH and added with H 2 O (q.s.). The reaction was boiled under reflux at 100° C. , added with Br 2 -containing CH 3 COOH solution dropwise (done within 20 minutes), and then carried on for 1 h at 100° C. . The reaction solution was poured into ice water, neutralized with saturated concentrated aqueous ammonia, and extracted by CHCl 3 . The phase of CHCl 3 was dried under anhydrous sodium sulfate, condensed and separated via column chromatography (CH 2 Cl 2 /MeOH 10/1), giving a light yellow solid. Compound 4 was obtained if Br 2 was added at the same equivalent concentration as the YH-200; and Compound 5 was obtained if Br 2 was added at a double-equivalent concentration.
The present invention provides a method of preventing, alleviating and/or treating depression, comprising the step of administering to a subject in need thereof a therapeutically effective amount of a 7-alkoxy fangchinoline compound or a pharmaceutically acceptable derivative thereof.
55,361
BACKGROUND OF THE INVENTION Semiconductor transducers have become miniaturized, due to the use of monocrystalline silicon formed as a thin diaphragm which may be deflected. This monocrystalline silicon, on the one hand, is advantageous due to essentially zero hysteresis or nearly perfect elasticity, but, on the other hand, if the elastic limit is exceeded, rupture of the diaphragm ensues and it no longer maintains fluid media isolation or an operative structure. Such silicon diaphragm transducers may be used in pressure transducers, strain gauge transducers, and accelerometers, especially where a mass acts on the diaphragm. However, in all such cases of silicon diaphragm transducers, they are at times subjected to pressures or excursions of the diaphragm in excess of their designed value, which at best may cause a shift in the output, and at worst may permanently deform or rupture the transducer diaphragm. Often, this overpressure is transitory in nature, as a common example, caused by a hammer effect. In particular, differential pressure transducers used to measure fluid flow are susceptible to a one-sided overpressure due to the removal of line pressure from either side of the diaphragm. Pressure transducers have historically used a variety of methods to restrain the excursions of the movable parts to non-catastrophic bounds that will then allow recovery, albeit in many cases with an accuracy shift. Methods in common use or suggested include capsular techniques, e.g., U.S. Pat. No. 4,333,350; isolation diaphragms, e.g., U.S. Pat. No. 4,199,991; and stops or overtravel limits of mechanical, hydrostatic, and pneumatic type, e.g., U.S. Pat. Nos. 4,080,830; 4,295,115; 4,454,771; 4,519,255; 4,520,675; and 4,649,363. Regardless of the overexcursion protection method used, it was necessary to apply it on a unit basis, increasing per-unit cost. It is the objective of this invention to present a method of providing single, on either side, or double-sided mechanical stops for integrated circuit diaphragm transducers that may be economically incorporated at the wafer level of fabrication of hundreds or thousands of individual transducers. SUMMARY OF THE INVENTION The problem is solved by a semiconductor transducer comprising, in combination, a semiconductor base having first and second planar parallel faces, a cavity formed in said base from said first face to form a deformable diaphragm unitary with said base, a substrate having a planar surface bonded to said first face of said base, a physical stop integral with and carried by said substrate and positioned in said cavity, and said physical stop having a stop face substantially parallel to and positioned closely adjacent to said diaphragm to be contactable by said diaphragm upon excessive excursion to prevent rupture thereof. The problem is further solved by the method of forming a semiconductor transducer with a diaphragm, comprising the steps of providing a substrate having a first face, establishing stop and locator means including first etching a portion of said first face of said substrate to a substantially planar level to achieve a second portion as a physical stop on said substrate, said physical stop having a substantially planar stop face and an enlarged base at said planar level, providing a semiconductor base having parallel first and second planar faces, etching a sloping sided cavity into said semiconductor base from said first face thereof to form a deformable diaphragm in said semiconductor base, and bonding said semiconductor base first face to said substrate planar level with said physical stop located in said cavity and with said stop face acting to prohibit excess movement of said diaphragm. The present invention uses suitably formed physical stops of either glass or silicon placed plane parallel to the diaphragm at a predetermined distance from the diaphragm. The clearance necessary between the diaphragm and the stop can be approximated by calculating the rupture deflection and applying a safety factor. The rupture deflection may be approximated by reference to the classic Timoshenko's plate formulas, as set forth in the volume Theory of Plates and Shells. A diameter-to-deflection ratio of 200:1 is typical of a safe clearance for a monocrystalline silicon diaphragm. When the diaphragm has been deflected sufficiently to engage the physical stop, the stop is subjected almost entirely to compressive forces, which greatly enhances its utility. Due to the nature of susceptibility of a pressure transducer to applied stresses normal to the active portion, or, for piezoresistive types, also including stresses, parallel or angular to the active portion, it is necessary to form the stop substrate from a material that is closely matched to silicon in thermal expansion. Either silicon or certain borosilicate glasses, e.g., Corning Glass Code No. 7740 or No. 7070, satisfies this requirement. It is further necessary to provide a bond between the stop substrate and the active monocrystalline silicon that is rigid, to avoid creepage that induces system errors. Therefore, any polymer or metallic bonding has been found to be not adequate. Anodic field-assisted or electrostatic bonding of silicon to glass or silicon to silicon provides a sufficiently stiff bonding method. This type of bonding is disclosed in the Pomerantz U.S. Pat. No. 3,397.278. The double-sided stop method will be described, since a single-sided stop is just the application of either half of the double-sided stop. The diaphragmatic cavity side stop is preformed on a substrate material by etching as a current practice example, and may be made from either glass or silicon. As examples, if a glass substrate is used, the glass may be etched to form the stop. A superior method is to bond a silicon wafer to glass material to form a composite substrate, pattern a plurality of resists on the silicon wafer, and etch this silicon wafer using the glass as the etch stop. This provides a plurality of raised physical stops in those locations not etched. This exposes the original glass surface for subsequent bonding to the silicon transducer structure. The active surface side stop may be formed by a glass etch into a glass substrate, which is subsequently bonded to the opposite or upper side of the silicon wafer and is the preferred method for a piezoresistive pressure transducer. A silicon preetch into the silicon wafer, in order to establish the diaphragm slightly below the plane of the upper surface of the silicon wafer, is practically necessary for a capacitive pressure transducer for top plate clearance. Since this side uses a shallow etch, it is possible to maintain adequate tolerance and surface quality when etching either the glass or the silicon, due to superior control of dimensions required in capacitance type transducers. Since this upper surface of the silicon wafer is usually metallized and contains the bonding pads for external connection, it would normally preclude bonding. However, the conductors may be diffused or implanted into the silicon as isolated feed-throughs in the area used for bonding. The bonding pad area may be left uncovered, and this may be accomplished by etching the glass area over the bonding pads so that bonding at these locations does not occur. Next, a depth-controlled slice is made just through the glass before dicing. After dicing, the glass over the bonding pads, now without any support, will fall away. Alternatively, the bonding pads may be formed as V-grooves in the silicon or U-channels in the glass that expose the bonding pads but are sealed in the inter-pad spaces. Another method involves using a U-shaped, three-edged bonding area if surface isolation is not required. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional view through a composite substrate of silicon and glass; FIG. 2 is a sectional view after the silicon has been etched down to the glass; FIG. 3 is a sectional view after a cavity has been etched into a silicon wafer to form a diaphragm at a cavity and the wafer bonded to the glass substrate; FIG. 4 is a cross-sectional view of the transducer with a second glass substrate bonded at the top; FIG. 5 is a cross-sectional view of a glass substrate; FIG. 6 is a similar sectional view after the glass has been patterned and etched; FIG. 7 is a similar cross-sectional view after a silicon wafer has been patterned and etched to form a diaphragm at a cavity and the wafer bonded to the glass substrate; FIG. 8 is a similar cross-sectional view of the unit after an upper glass substrate has been bonded on the silicon wafer; FIG. 9 is a plan view of a U-shaped bonding method; FIG. 10 is a sectional view on line 10--10 of FIG. 9; FIG. 11 is a sectional view on line 11--11 of FIG. 9; FIG. 12 is a plan view of a capacitive integrated circuit differential pressure transducer; FIG. 13 is a sectional view generally along line 13--13 of FIG. 12 after the pressure transducer is mounted in a housing; FIG. 14 is a sectional view on line 14--14 of FIG. 12, showing the electronics section; and FIG. 15 is a sectional view on line 15--15 of FIG. 12, showing the bonding pad area. DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 illustrates a composite substrate 15 which is a silicon wafer 16, typically two inches to six inches in diameter, bonded to a glass material substrate of approximately the same size. The silicon wafer is a monocrystalline silicon and the glass material substrate 17 is one having a substantially equal coefficient of expansion, e.g., Corning Glass Code 7740 or 7070. A stiff bond between the wafer and the substrate 17 is required, and anodic or electrostatic bonding has been found to be satisfactory. Hundreds, or even thousands, of individual resists 18 are patterned onto the upper surface of the silicon wafer 16 according to the desired size of the eventual silicon diaphragm transducers desired, and in accordance with the diameter of the wafer 16. FIG. 2 illustrates that the silicon wafer 16 has been etched away to a planar level 22 of the glass 17 at those locations not covered by the resist 18 in accordance with normal integrated circuit manufacturing processes. The resist has been removed in this figure to illustrate a stop face 19 on the physical stop 20, which is secured to the glass substrate 17 at a base 21. FIG. 3 illustrates the glass substrate 17 and physical stop 20, now with a silicon wafer 24 having first and second faces 25 and 26, respectively. The first face 25 of the wafer 24 is bonded to the planar level face 22 of the glass substrated 17 by anodic bonding. Previously, the silicon wafer would have been patterned with a resist on the first face 25, and then etched to form a plurality of cavities, one such cavity 28 being shown. FIG. 4 illustrates a shallow depression 33 etched in the usual anisotropic manner into the second face 26 to establish a thin diaphragm 29, unitary with the silicon wafer 24, and which diaphragm has an upper face 31 and a lower face 30. At the edges of the diaphragm, at both faces, isotropic etching is used to form a filet for stress relief. A metal capacitor plate 34, less than a micron thick, has been formed on the upper face 31. A second capacitor plate 35 has been formed in a similar manner on a face 36 of a glass substrate 37, which has been anodically bonded to the second face 26 of the silicon wafer 24. Conduits 39 and 40, formed in any suitable manner, lead from the exterior into the cavity 28 and the shallow depression 33, respectively. The silicon wafer 24, as well as the silicon wafer 16, are preferably from bulk <100> silicon, and hence the anisotropic etching angle will be 54 degrees for a truncated cone of each physical stop 20. This etching angle is preserved on both the physical stop and the cavity 28, and this yields minimum cavity volume for prompt response and increases the strength of the physical stop 20. This makes the structure shown in FIG. 4 self-aligning within the tolerance of the gap between the cavity 28 and the physical stop 20. FIGS. 5 through 8 show another embodiment of the invention with a unitary substrate 45 shown in FIG. 5 with a resist 18 applied in a desired pattern to obtain the individual physical stops. This unitary substrate is preferably of a glass, such as Corning Glass Code 7740 or 7070, which has a thermal expansion similar to that of silicon. FIG. 6 shows the substrate 45 after etching to a controlled depth, and with the resist removed. The etching is to a controlled depth to obtain a substantially planar level or face 46 and a physical stop 47 with a planar stop face 19. FIG. 7 shows a silicon wafer 24A having the first and second faces 25 and 26, with the first face 25 bonded to this planar face 46 of the glass substrate 45. Before bonding, the silicon wafer 24A has been patterned and etched to a controlled depth--in this case, a slightly deeper etch than the silicon wafer 24 of FIG. 3. The reason for this is shown in FIG. 8, wherein electrical components 48 are on the diaphragm 29. The electrical components may be a part of a capacitor plate or, as shown, may be implanted piezoresistors. In the usual piezoresistive configuration, these may be four such resistors connected in a Wheatstone bridge. FIG. 8 also shows a second glass substrate 37A, with a shallow depression 50 immediately over the diaphragm 29. The back wall of this depression will act as a physical stop for upward movement of the diaphragm 29. The glass substrate 37A is bonded at face 36 to the second face 26 of the silicon wafer 24A. Again, this may be by anodic bonding. The conduits 39 and 40 lead to the cavity 28 and the shallow depression 50, respectively, so that differential pressure may be applied to the diaphragm 29 and measured. This method of fabricating the physical stop 47 of FIGS. 5-8 achieves a physical stop face 19 which is the same size as that in the method of FIGS. 1 to 4, and the physical stop 47 is unitary with the glass substrate 45. FIGS. 9, 10, and 11 illustrate the bonding of the second substrate 37 to the silicon wafer 24A. The diaphragm 29 is shown in FIG. 11, but is not shown in FIG. 9, which is a plan view looking through the glass substrate 37A to view a U-shaped bonding area 52 which ends at a controlled depth slice 53. This controlled depth slice is shown in FIG. 11 which ends at a shallow depression 54 in the glass substrate 37A. After dicing, the portion 57 of the glass substrate over bonding pads 55 will fall away, since it has no support. The bonding pads 55 may be made by the usual surface metallization and connected in any usual manner to the electrical components on the diaphragm (not shown in FIGS. 9, 10, and 11 but within the area inside the U-shaped bonding area 52). External connection to the bonding pads 55 may be made by individual wire conductors, and where the piezolectric resistors are used as the electrical components, the internal connections may be formed by surface metallization on the silicon wafer 24A. The wall 56 provides the physical stop on the active surface side, which wall defines the shallow depression 54. FIG. 11 shows an exaggerated stop clearance to the wall 56 for clarity in the drawings. FIG. 12 refers to another embodiment of a full cover stop on the active surface side. This method is most applicable to capacitive integrated circuit differential pressure transducers, since, by definition, they need an additional layer of some type attached to the active surface onto which is placed the second plate. This FIG. 12 illustrates a fully differential floating twin capacitor integrated circuit such as that disclosed in U.S. Pat. No. 4,625,560. FIG. 12 is a plan view looking through the upper glass substrate 37 and showing a bonding area by a dotted line, double cross-hatch. What is viewed in FIG. 12 is primarily one die of the silicon wafer 24. Sloping walls 61 and 62 define the shallow depressions at which the diaphragm 63 and the reference capacitor plate are located, and in the center of each is a capacitor plate 65 and 66, respectively. This is similar to the shallow depression 33 with diaphragm 29 and capacitor plate 34 shown in FIG. 4. The capacitor plates 65 and 66 may be the usual metallized plates with unitary conductors 67 and isolated, heavy doping, e.g., emitter-doped, conductive paths 68 to an integrated circuit 69 which is isoplanar and formed in an area beneath a shallow depression in the glass substrate 37 caused by sloping walls 70. The conductive paths 68 typically may be emitter diffusion in an isolation well or tub. Bonding pads 71 are provided on the wafer 24 adjacent the respective upper capacitor plates 72 and 73, so that a metallic pressure weld with a metallization tail on the upper glass substrate 37 makes electrical connection from the upper capacitor plate 72 or 73, respectively, on this glass substrate to the bonding pads 71. Conductive paths 78, similar in construction to paths 68, lead from the bonding pads 71 to the integrated circuit 69. Because of the pre-etch establishing the sloping walls 61, 62 and 70, most of the metallization may be applied normally. The pre-etch to establish the sloping walls may be in either the silicon wafer 24 for better control or the glass plate 37 with isoplanar processing and still the normal metallization may be achieved. The integrated circuit 69 has output terminals 74 which are connected through conductive paths 75 achieved by isolated, heavy doping, e.g., emitter doping, to form these conductive paths 75. These lead to output bonding pads 76, which again may be metallized bonding pads. Such bonding pads may be metallizing V-grooves in the silicon wafer 24, or may be on the flat surface of the silicon wafer and isolated by U-shaped grooves 77 etched into the glass substrate 37. In such case, the external connection may be made by placing an individual wire conductor into each U-shaped groove 77 plus a ball of Indium solder, which will melt at a low temperature and will wet both the metal conductor and the metallized bonding pads 76. The silicon wafer 24 may have an optically visible aligning mark, which usually is a physical feature of an integrated circuit, such as a transistor, or may alternatively be a mark 79, such as that shown in FIG. 12, in order to help the optical alignment of the wafer 24 with the glass substrate 37 and with the glass substrate 17. This aligning or orienting of the parts is aided by the physical stops 20 which are aligned with and fit within the various cavities 28 (see FIGS. 3 and 4). The processing of the pressure transducer preferably includes the steps of: (a) completing all of the masking, etching, doping, metallization, etc. necessary on the upper face 26 of the silicon wafer 24; (b) completing all processing on glass substrates 17 and 37; (c) electrostatically bonding the upper glass substrate 37 to the upper face 26 of the silicon wafer aligned by the orienting means so there is alignment of metallization, etc.; (d) mask-to-mask aligning, e.g., using a double-sided aligner, for the diaphragmatic cavity etch into the lower face 25 of the silicon wafer 24; and (e) electrostatically bonding the lower face 25 onto the substrate 17 with self-alignment of the stops 20 or 47 in the cavities 28, or, more elegantly, optical alignment through the transparent substrate 17 to observable features on the lower face 25. A semiconductor wafer 24 may be considered a semiconductor base, and the physical stops 20 combined with the alignment mark 79 may be considered stop and locator means for limiting the movement of the diaphragm and for locating the silicon wafer 24 relative to the glass substrate 17. FIG. 13 shows a cross section through the completed capacitive integrated circuit differential pressure transducer when the substrate 17 is sealed to a base 81, such as a metal base, and then a metal can housing 82 is sealed to this base 81. The base has a fluid inlet port 83 and the housing 82 has a fluid inlet port 84. A conduit 85 leads through the glass substrate 37 to the capacitor plate 66 so that this capacitor is subjected to the same temperature, pressure, and dielectric material, e.g., dry or wet gas, as is the capacitor incorporating the plate 65. The design of the physical stops both above and below the diaphragm is such that the distance between the plates zeroes well before the rupture deflection is reached. The subsequent shorting of the plates when the diaphragm is overstressed upwardly may be sensed and an output as an overpressure signal achieved. Overstressing of the diaphragm in the downward direction is resisted by the flat stop face 19 on the physical stop 20, so the diaphragms are protected in both directions. The plurality of dice on the entire wafer may be processed at the same time so that hundreds, and even thousands, of the pressure transducers may be produced at one time without requiring individual attention to achieve the physical stops both upwardly and downwardly. Since the bonding area 60 surrounds and isolates each section, maintenance of isolated pressure chambers is achieved and essentially hermetic protection for the active electronics 69 exists. The pressure porting is via the apertures 39, 40 and 85 in the glass substrates which, due to their small size, aids in protecting the capacitor plates from particulate contamination. Volumetric displacement from zero to stop is measured in subpicoliters, minimizing the physical time constant and overshooting. The bonding between the silicon wafer 24 and the glass substrates 17 and 37 is accomplished as a three-layer sandwich, with the outer glass plates being somewhat smaller in diameter than the silicon wafer, which allows the establishment of the necessary electrical fields for the anodic bonding. The present disclosure includes that contained in the appended claims, as well as that of the foregoing description. Although this invention has been described in its preferred form with a certain degree of particularity, it is understood that the present disclosure of the preferred form has been made only by way of example and that numerous changes in the details of the circuit and the combination and arrangement of circuit elements may be resorted to without departing from the spirit and the scope of the invention as hereinafter claimed.
A semiconductor transducer with a diaphragm is constructed utilizing a substrate wherein a first portion of that first face is etched to a planar level to achieve a second portion as a physical stop on this substrate, the physical stop having a planar stop face, a sloping sided cavity is etched into a semiconductor wafer from a first face thereof to form a deformable diaphragm in this semiconductor wafer. The semiconductor wafer is anodically bonded to the substrate planar level, with the physical stop located in the cavity and with the stop face acting to prohibit excess movement of the diaphragm. The foregoing abstract is merely a resume of one general application, is not a complete discussion of all principles of operation or applications, and is not to be construed as a limitation on the scope of the claimed subject matter.
22,713
PRIORITY & CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Application No. 60/267,359, filed Feb. 8, 2001. Other features of the present invention are discussed and claimed in commonly assigned copending U.S. application Serial No. 09/______,______ entitled Pneumatic Fastening Tool. FIELD OF THE INVENTION [0002] The present invention generally relates to a fastening tool for dispensing fasteners from a magazine assembly into a workpiece and more specifically to an improved magazine assembly for a fastening tool. BACKGROUND OF THE INVENTION [0003] A number of pneumatically operated devices have been developed for use in driving fasteners, such as staples and nails, into workpieces. These tools typically employ a magazine assembly for holding a plurality of the fasteners and feeding the fasteners into the nose of the tool prior to the installation of the fasteners into a workpiece. [0004] Despite the wide spread use of such tools, several drawbacks have been noted. One such drawback concerns the dry-firing of the tool when an insufficient number of fasteners are contained in the magazine assembly. As is known in the art, the dry-firing of such tools tends to be harmful to the tool. [0005] Another drawback relates to situations wherein one or more fasteners are jammed in the nose of the tool. In such situations, the magazine assembly is typically removed from the fastening tool so as to provide sufficient space to permit the operator to remove the jammed fasteners from the nose of the fastening tool. Often times, tools, such as pliers, are employed in this task, so that the amount of space that is required for servicing the nose of the tool can be significant. Unfortunately, the complete removal of the magazine assembly from the remainder of the tool is often times very time consuming and may also require the use of additional tools to physically disconnect the magazine assembly. SUMMARY OF THE INVENTION [0006] In one preferred form, the present invention provides a fastening tool for holding a plurality of fasteners and selectively setting a first one of the fasteners into a workpiece. The fastening tool includes a fastening tool portion and a magazine assembly. The fastening tool portion includes a handle, a clamp mechanism, an actuating trigger and a nose structure. The handle is configured to be gripped by an operator when using the fastening tool. The clamp mechanism is coupled to the handle and includes a clamp pin with a head portion and a body portion. The clamp pin is movable between an engaged condition and a disengaged condition. The actuating trigger is positionable in an unactuated condition, wherein the fastening tool portion is not be cycled to set a fastener. The actuating trigger is also positionable in an actuated condition, wherein the fastening tool portion is cycled to set the fastener. The nose structure includes a magazine flange, a nose body, and at least one elongated magazine guide post. The nose body is coupled to the magazine flange and extends generally forwardly therefrom. The nose body is configured to hold at least the first one of the fasteners and to guide the first one of the fasteners into the workpiece when the trigger is positioned in the actuated condition and the fastening tool is actuated to set the first one of the fasteners. The at least one elongated magazine guide post extends downwardly from the magazine flange. The magazine assembly has an upper surface and at least one guide port. The upper surface is configured to abut a bottom surface of the magazine flange. Each of the guide ports is sized to receive an associated one of the guide posts. The magazine assembly further includes a magazine housing, a coupling bracket, a follower structure and a follower spring. The magazine housing has a sidewall that at least partially defines a follower cavity. The coupling bracket is coupled to the magazine housing and includes a slotted coupling aperture having a first portion, which is sized larger than the head portion of the clamp pin, a second portion, which is sized to engage the head portion, and a slotted portion interconnecting the first and second portions of the slotted coupling aperture. The slotted portion of the slotted coupling aperture is sized larger than the body portion of the clamp pin and smaller than the head portion of the clamp pin. The follower structure has a follower body and a guide tab. The follower body is slidably disposed in the follower cavity, the guide tab is coupled to the follower body and configured to support the fasteners in the magazine assembly, and the follower spring is coupled to both the magazine body and the follower structure and biases the follower body upwardly in the follower cavity. The magazine assembly is positionable relative to the fastening tool portion in an uncoupled condition, wherein the magazine assembly is separated from the fastening tool portion. The magazine assembly is also positionable relative to the fastening tool portion in a coupled condition, wherein the magazine assembly is fixed to the fastening tool portion such that the at least one elongated magazine guide post is engaged to an associated guide port, the upper surface of the magazine assembly is abutted to the bottom surface of the magazine flange, the clamp pin is disposed in the second portion of the slotted coupling aperture and the clamp mechanism is positioned in the engaged position and generating a clamping force that is applied through the head portion of the clamp pin and against the coupling bracket to thereby secure the magazine assembly to the handle. The magazine assembly if further positionable relative to the fastening tool portion in a semi-coupled condition, wherein the at least one elongated magazine guide post is engaged to the associated guide port, the clamp mechanism is positioned in the disengaged position, and the clamp pin is disposed in the slotted portion of the slotted coupling aperture to thereby permit the magazine assembly to be slid relative to the fastening tool portion. The slotted portion is sized to limit sliding movement of the magazine assembly so that the at least one elongated magazine guide post does not disengage the associated guide port. [0007] In another preferred form, the present invention provides a fastening tool for holding a plurality of fasteners and selectively setting a first one of the fasteners into a workpiece. The fastening tool includes a fastening tool portion and a magazine assembly. The fastening tool portion has an actuating trigger, a nose structure, a contact trip and a trigger lever. The actuating trigger is positionable in an unactuated condition, wherein the fastening tool portion cannot be cycled to set the first one of the fasteners, and an actuated condition, wherein the fastening tool portion can be cycled to set the first one of the fasteners. The nose structure includes a magazine flange and a nose body. The magazine flange includes a lock-out aperture. The nose body is coupled to the magazine flange and extends generally forwardly therefrom. The nose body is configured to hold at least the first one of the fasteners and to guide the first one of the fasteners into the workpiece when the trigger is positioned in the actuated condition to thereby actuate the fastening tool portion to set the first one of the fasteners. The contact trip is coupled to the nose structure and is slidable between an extended position and a retracted position. The contact trip is biased into the extended position and slides into the retracted position or rearwardly therefrom in response to contact with the workpiece. The trigger lever is coupled to the contact trip for movement therewith. The trigger lever interacts with the actuating trigger such that the actuating trigger is positionable in the actuated condition only when the contact trip is positioned in or rearward of the retracted position to thereby push the trigger lever into engagement with the actuating trigger. The magazine assembly holds at least a portion of the plurality of fasteners. The magazine assembly has an upper surface that is configured to abut a bottom surface of the magazine flange. The magazine assembly further includes a magazine housing, a follower structure and a follower spring. The magazine housing has a sidewall that at least partially defines a follower cavity. The follower structure has a follower body, a guide tab and a lock-out dog. The follower body is slidably disposed in the follower cavity, the guide tab is coupled to the follower body and configured to support the plurality of fasteners in the magazine assembly, and the lock-out dog is coupled to the follower body and extends upwardly therefrom. The follower spring is coupled to both the magazine body and the follower structure and biases the follower body upwardly in the follower cavity. The lock-out dog is sized to extend through the lock-out aperture only when the quantity of fasteners in the magazine assembly is less than a predetermined quantity and contacts at least one of the contact trip and the trigger lever and inhibits the trigger lever from interacting with the actuating trigger to position the actuating trigger in the actuated condition. [0008] Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS [0009] Additional advantages and features of the present invention will become apparent from the subsequent description and the appended claims, taken in conjunction with the accompanying drawings, wherein: [0010] [0010]FIG. 1 is a left side view of a tool constructed in accordance with the teachings of a preferred embodiment of the present invention; [0011] [0011]FIG. 2 is a right side view of the tool of FIG. 1; [0012] [0012]FIG. 3 is an exploded perspective view of the tool of FIG. 1; [0013] [0013]FIG. 4 is a sectional view of the tool of FIG. 1 taken through its longitudinal axis; [0014] [0014]FIG. 4 a is a section view taken along the line 4 a - 4 a of FIG. 4; [0015] [0015]FIG. 5 is a top view of the tool of FIG. 1; [0016] [0016]FIG. 6 is a sectional view taken along the line 6 - 6 of FIG. 5; [0017] [0017]FIG. 7 is an enlarged portion of FIG. 4 illustrating the nose assembly in greater detail; [0018] [0018]FIG. 8 is a front view of a portion of the tool of FIG. 1 illustrating the nose body and the contact tip in greater detail; [0019] [0019]FIG. 9 is a sectional view taken along the line 9 - 9 of FIG. 2; [0020] [0020]FIG. 9 a is sectional view of a portion of the magazine clamp assembly illustrating the spring collar in greater detail; [0021] [0021]FIG. 9 b is a sectional view of a portion of the magazine clamp assembly illustrating the clamp pin in greater detail; [0022] [0022]FIG. 10 is an enlarged portion of FIG. 4 illustrating the trigger assembly in greater detail; [0023] [0023]FIG. 11 is an exploded view of the tool of FIG. 1; [0024] [0024]FIG. 12 is an enlarged portion of FIG. 4 illustrating the rear of tool in greater detail; [0025] [0025]FIG. 13 is a sectional view of a portion of the exhaust manifold illustrating the construction of the exhaust ports in greater detail; [0026] [0026]FIG. 14 is an enlarged portion of FIG. 4 illustrating the engine assembly in greater detail; [0027] [0027]FIG. 15 is an enlarged portion of FIG. 11 illustrating the engine assembly in greater detail; [0028] [0028]FIG. 16 is a sectional view of the sleeve taken along its longitudinal axis; [0029] [0029]FIG. 17 is a sectional view taken along the line 17 - 17 of FIG. 16; [0030] [0030]FIG. 18 is a sectional view similar to that of FIG. 10 but illustrating the trigger assembly in an actuated condition; [0031] [0031]FIG. 19 is an exploded perspective view of the magazine assembly; [0032] [0032]FIG. 20 is a sectional view taken along the line 20 - 20 of FIG. 1 and illustrating the construction of the magazine body assembly; [0033] [0033]FIG. 21 is a rear view of a portion of the magazine body assembly; [0034] [0034]FIG. 22 is a side view of a portion of the magazine body assembly illustrating the L-shaped pin aperture in greater detail; [0035] [0035]FIG. 23 is a top view of a guide structure; [0036] [0036]FIG. 24 is a front view of the bracket structure; [0037] [0037]FIG. 25 is a rear view of a portion of the bracket structure; [0038] [0038]FIG. 26 is a side view of a portion of the bracket structure; [0039] [0039]FIG. 27 is a side view of the follower structure; [0040] [0040]FIG. 28 is a top view of a portion of the follower structure illustrating the construction of a portion of the follower body, the follower guide and the actuating lever; [0041] [0041]FIG. 29 is a view of a portion of the follower structure illustrating the configuration of the forward leg of the follower body; [0042] [0042]FIG. 30 is a view of a portion of the follower structure illustrating the configuration of the rearward leg of the follower body; [0043] [0043]FIG. 31 is a front view of a portion of the follower structure; [0044] [0044]FIG. 32 is a partial view of the follower structure from a side opposite the side which is illustrated in FIG. 27; [0045] [0045]FIG. 33 is a side view of the follower spring; [0046] [0046]FIG. 34 is a side view of the magazine end cap assembly; [0047] [0047]FIG. 35 is a sectional view of a portion of the end cap structure taken along the line 35 - 35 in FIG. 34; [0048] [0048]FIG. 36 is a sectional view of a portion of the end cap structure taken along the line 36 - 36 in FIG. 35; [0049] [0049]FIG. 37 is a top view of a portion of the end cap structure; [0050] [0050]FIG. 38 is a front view of the cam follower; [0051] [0051]FIG. 39 is a partial side view of the cam follower; [0052] [0052]FIG. 40 is an enlarged portion of the cam follower illustrated in FIG. 38; [0053] [0053]FIG. 41 is a partial side view of the cam follower illustrating the follower hook in greater detail; [0054] [0054]FIG. 42 is a partial section view illustrating the position of the cam follower on the pivot structure just prior to contact between the loading cam and the follower hook; [0055] [0055]FIG. 43 is a partial section view similar to that of FIG. 42 but illustrating the cam follower when the follower hook is contacting the first loading cam portion; [0056] [0056]FIG. 44 is a side view of the follower structure engaged to the magazine end cap assembly; [0057] [0057]FIG. 45 is a section view taken along the line 45 - 45 illustrating the follower hook disposed within the capture aperture; [0058] [0058]FIG. 46 is a side view of a portion of a tool constructed in accordance with the teachings of the an alternate embodiment of the present invention illustrating the magazine assembly removed from the tool; and [0059] [0059]FIG. 47 is a side view similar to that of FIG. 46 but illustrating the magazine assembly coupled to the tool. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0060] With reference to FIG. 1 of the drawings, a fastening tool constructed in accordance with the teachings of the present invention is generally indicated by reference numeral 10 . Fastening tool 10 is illustrated to include a detachable magazine assembly 20 and a fastening tool portion 30 . The fastening tool portion 30 includes a nose assembly 40 , a housing assembly 42 , a cap assembly 44 , an engine assembly 46 and a trigger assembly 48 . [0061] Nose Assembly [0062] With reference to FIGS. 1 through 9, the nose assembly 40 is illustrated to include a nose structure 50 , a contact trip 52 , a trigger lever 54 and a contact trip-return spring 56 . The nose structure 50 includes a nose body 60 , a pair of magazine stabilizing tabs 62 , a magazine flange 64 , a pair of magazine guide posts 66 , a mounting base 68 , a spring post 70 and a pair of contact trip guides 72 . The nose body 60 is generally U-shaped, with the legs 80 of the “U” being inwardly offset to form a semi-circular blade cavity 82 . The inwardly offset legs 80 of the nose body 60 also serve as a guide surface 84 for guiding the lower front portion 86 of the contact trip 52 . The contact trip guides 72 are coupled to the top of the nose body 60 and form a guide surface for guiding the portion 88 of the contact trip 52 that extends over the nose body 60 . [0063] The magazine stabilizing tabs 62 are situated on opposite sides of the nose body 60 and are spaced apart by a predetermined distance. The magazine flange 64 is a generally flat structure that is coupled to the bottom of the nose body 60 and that includes a lock-out dog aperture 90 . The magazine guide posts 66 , which are cylindrically shaped in the particular embodiment illustrated, extend downwardly and rearwardly from the magazine flange 64 . The magazine stabilizing tabs 62 , magazine flange 64 and magazine guide posts 66 are discussed in greater detail, below. [0064] The mounting base 68 is coupled to the magazine flange 64 and the nose body 60 and includes a pair of mounting apertures 94 , a nose seal groove 96 and a nose guide 98 . The nose guide 98 is generally cylindrically shaped and includes an internal cavity 100 that having a cross-section that is configured to receive the fastener F and which may include a fastener stop 102 which is configured to prevent the fasteners F from traveling rearwardly toward the engine assembly 46 . In the embodiment illustrated, the internal cavity 100 is generally semi-circular in shape but which includes a key-shaped fastener stop 102 . The nose seal groove 96 is formed around the outer perimeter of the nose guide 98 and is sized to receive a nose seal 104 , which is an O-ring seal in the particular embodiment illustrated. The spring post 70 is coupled to the top of the mounting base 68 and includes a boss 108 that is sized to fit within the contact trip-return spring 56 . [0065] The contact trip 52 is fit over and slides on the nose body 60 , being guided thereon by the inwardly offset legs 80 of the nose body 60 and the contact trip guides 72 . Preferably, the effective length of the contact trip 52 is adjustable so as to permit the tool operator to vary the depth at which the tool 10 sets the fasteners F. A spring protrusion 110 , which is sized to engage the inside diameter of the contact trip-return spring 56 , is formed in the rear of the contact trip 52 . The contact trip-return spring 56 is set over the boss 108 on the spring post 70 and the spring protrusion 110 on the contact trip 52 and exerts a spring force that biases the contact trip 52 away from the spring post 70 . Forward motion of the contact trip 52 is checked by a contract trip stop 114 that is formed onto a side of the nose body 60 and which contacts the contact trip 52 at a predetermined point. [0066] The trigger lever 54 is fixedly coupled to the contact trip 52 at a first end 120 and extends rearwardly from the nose structure 50 where a second end 122 engages the trigger assembly 48 in a conventional manner that is well known in the art. Briefly, the trigger assembly 48 includes a primary trigger 126 , a secondary trigger 128 and a trigger valve 130 that selectively controls the flow of compressed air to the engine assembly 46 . The primary trigger 126 is pivotably mounted to the housing assembly 42 and movable in response to the tool operator's finger. Movement of the primary trigger 126 will not, in and of itself, alter the state of the trigger valve 130 . Rather, the second end 122 of the trigger lever 54 must also move rearwardly and into contact with the secondary trigger 128 before the state of the trigger valve 130 is changed to permit compressed air to flow to the engine assembly 46 . A stop member 134 , which is configured to interact with the magazine assembly 20 in a matter that will be discussed in greater detail below, is coupled to the trigger lever 54 below the magazine flange 64 and extends inwardly toward the nose body 60 . In the particular embodiment illustrated, the stop member 134 is die-punched into the trigger lever 54 and is offset inwardly therefrom toward the nose body 60 . [0067] Housing Assembly [0068] Housing assembly 42 includes a unitarily formed housing 150 , a piston bumper 152 , a magazine clamp assembly 154 and a housing seal 156 , which is illustrated to be an O-ring seal in the example provided. The housing 150 includes a housing body 160 , a trigger housing 162 , a nose housing 164 and a handle portion 166 . The housing body 160 is a container-like structure having a front base 170 and an outwardly tapering sidewall 172 that cooperate to form a housing cavity 174 . The outwardly tapering sidewall 172 terminates at the rear of the housing body 160 at a rear housing face 176 , which in the particular embodiment illustrated, includes a housing seal groove 178 that is configured to receive the housing seal 156 . A guide bore 180 is formed into the inside face 182 of the housing cavity 174 and terminates at its forward end at a guide stop 184 . A nose guide aperture 188 is formed through the front base 170 of the housing body 160 . [0069] The nose housing 164 is coupled to the front base 170 of the housing body 160 and extends forwardly therefrom. The nose housing 164 includes an upper shroud 200 , a pair of sidewalls 202 and a pair of spaced apart bosses 204 , each of which having a threaded aperture 206 . The upper shroud 200 , sidewalls 202 and spaced apart bosses 204 cooperate to locate the nose assembly 40 to the housing 150 and the nose guide 98 is inserted into the nose guide aperture 188 . Threaded fasteners 210 are placed through each of the mounting apertures 94 in the mounting base 68 and threadably engaged to the threaded apertures 206 in the spaced apart bosses 204 to fixedly but removably couple the nose assembly 40 to the housing 150 . The axis 212 of the threaded fasteners 210 is skewed toward the rear of the tool 10 , causing the threaded fasteners 210 to exert a clamping force that pushes the nose assembly 40 downwardly onto the spaced apart bosses 204 and rearwardly against the front face of the front base 170 to thereby compress the nose seal 104 and sealingly engage the nose structure 50 to the housing body 160 . The upper shroud covers the spring post 70 , the contact trip-return spring 56 and a portion of the rear of the contact trip 52 to prevent foreign objects from lodging between the rear of the contact trip 52 and the spring post 70 . [0070] The handle portion 166 is preferably non-circular in shape and contoured to comfortably fit the hand of a tool operator. The distal end 250 of the handle portion 166 is enlarged so as to render the handle portion 166 less prone to slipping out of the tool operator's hand. With additional reference to FIG. 4 a , a clamp boss 252 is coupled to the forward face of the distal end 250 of the handle portion 166 . The clamp boss 252 includes a clamp boss base 254 that extends toward the front of the tool 10 , a clamp boss sidewall 256 that wraps around the perimeter of the clamp boss base 254 and an annular intermediate clamp boss wall 258 that cooperates with a portion of the clamp boss sidewall 256 to form a circular spring cavity 260 . The clamp boss base 254 and the clamp boss sidewall 256 cooperate to form a clamp cavity 262 into which the magazine clamp assembly 154 is disposed. A pair of U-shaped pin apertures 264 , which will be discussed in further detail below, are formed into an end of the clamp boss sidewall 256 . [0071] The handle portion 166 intersects both the housing body 160 and the trigger housing 162 and includes an air inlet cavity 270 which extends through the distal end 250 of the handle portion 166 to receive a supply of compressed air. The air inlet cavity 270 extends through the handle portion 166 and into both the housing cavity 174 and the trigger housing 162 to permit the compressed air to be directed through the tool 10 in a predetermined manner that will be described in detail, below. [0072] In the example provided, the magazine clamp assembly 154 is illustrated to include a clamp pin 300 , a compression spring 302 , a spring collar 304 , an actuating cam 306 and a coupling pin 308 . The clamp pin 300 includes a head portion 322 , a first body section 324 , which is coupled to the head portion 322 , and a second body section 326 that is coupled to the opposite end of the first body section 324 . The first body section 324 is generally cylindrically shaped and includes a pair of parallel flats 328 . The second body section 326 is generally cylindrically shaped but has an outer diameter that is smaller than that of the first body section 324 . The head portion 322 includes a frusto-conical abutting face 330 . [0073] The spring collar 304 includes a first annular portion 340 having a diameter that is sized to fit within the compression spring 302 , and a second annular portion 342 that is relatively larger in diameter than the compression spring 302 and which has a flat contact surface 344 . A pin aperture 346 is formed through the spring collar 304 that is sized to receive the second body section 326 of the clamp pin 300 . [0074] The actuating cam 306 has a base portion 350 and a leg portion 352 which are arranged relative to one another in an L-shape. The end of the base portion 350 opposite the intersection point 354 between the base and leg portions 350 and 352 includes a coupling pin aperture (not specifically shown) which is sized to engage the coupling pin 308 . The leg portion 352 of the actuating cam 306 is arcuate in shape and includes a plurality of gripping protrusions 356 or is otherwise textured on its inside surface so as to improve the tool operator's ability to move the actuating cam 306 in a desired direction. A slot 358 , which is sized to engage the second body segment 326 of the clamp pin 300 in a slip-fit manner, is formed into the actuating cam 306 through the base portion 350 and a portion of the leg portion 352 . [0075] The clamp pin 300 extends through a pin aperture 360 formed into the clamp boss base 254 of the clamp boss 252 such that the second body section 326 extends into the spring cavity 260 . The compression spring 302 is positioned over the second body section 326 and into the spring cavity 260 . The spring collar 304 is placed over the second body section 326 such that the first annular portion 340 is disposed inside the compression spring 302 . The base portion 350 of the actuating cam 306 is positioned into contact with the flat contact surface 344 such that the second body segment 326 extends into the portion of the slot 358 that is formed into the base portion 350 of the actuating cam 306 . The coupling pin 308 , which is a roll-pin in the example illustrated, is positioned into one of the U-shaped pin apertures 264 and driven through the base portion 350 of the actuating cam 306 and into engagement with a pin aperture 364 in the second body segment 326 of the clamp pin 300 . Accordingly, the coupling pin 308 pivotably couples the actuating cam 306 to the clamp pin 300 . Rotation of the actuating cam 306 about the coupling pin 308 places the intersection point 354 into contact with the flat contact surface 344 , causing the spring collar 304 to compress the compression spring 302 and transmit a clamping force to the head portion 322 of the clamp pin 300 . When the actuating cam 306 has been pivoted sufficiently so as to place the leg portion 352 into contact with the flat contact surface 344 , the force exerted by the compression spring 302 urges the spring collar 304 against the leg portion 352 to releasably lock the actuating cam 306 in place. The clamp cavity 262 protects the actuating cam 306 from being contacted during the operation of the tool 10 , thereby guarding against the inadvertent unlocking or releasing of the actuating cam 306 . [0076] In FIG. 10, the trigger housing 162 is configured to receive the trigger assembly 48 and includes a supply port 370 , which is coupled to the air inlet cavity 270 to provide the trigger assembly 48 with a source of compressed air. A biasing port 372 extends from the trigger housing 162 through the guide bore 180 in the housing cavity 174 that permits the trigger assembly 48 to direct air to or exhaust air from the housing cavity 174 . [0077] As shown in FIGS. 7 and 11, the piston bumper 152 is a unitarily formed molded elastomeric structure. In the particular example illustrated, the piston bumper 152 has a cylindrical body portion 390 and an annular lip 392 . The cylindrical body portion 390 preferably includes a first annular bumper portion 396 and a second annular bumper portion 398 that is generally larger in diameter than the first annular bumper portion 396 and which is disposed between the first annular bumper portion 396 and the annular lip 392 . The annular lip 392 extends radially outwardly of the body portion 390 and includes a front abutting face 400 that is configured to abut the inside surface 402 of the housing body 160 and sealingly engage the front base 170 of the housing body 160 . The annular lip 392 also includes a rear abutting face 404 having a first annular lip portion 406 and a second annular lip portion 408 that lies radially outwardly of and recessed forwardly relative to the first annular lip portion 406 . The rear abutting face 404 and a cylindrically-shaped driver blade aperture 410 that extends through the center of the piston bumper 152 will be described in detail, below. [0078] Cap Assembly [0079] With reference to FIGS. 11 and 12, the cap assembly 44 includes a cap housing 420 , an exhaust manifold 422 and a top bumper 424 . The cap housing 420 includes an outer cap wall 430 that is generally flat at the rear of the tool 10 , but folds over on its sides to form a cup-like container having a generally flat forward face 432 that is configured to engage the housing seal 156 to permit the cap housing 420 to be sealingly coupled to the rear of the housing 150 . [0080] The cap housing 420 also includes a plurality of foot tabs 434 , a plurality of strengthening gussets (not specifically shown), an annular exhaust port wall 438 , an exhaust button 440 and a cylindrical locating hub 442 having a threaded aperture 444 formed therethrough. The foot tabs 434 extend forwardly from the flat portion of the outer cap wall 430 beyond the front face 432 by a predetermined distance. The outside diameter of the foot tabs 434 is sized such that the foot tabs 434 fit within the housing cavity 174 . The foot tabs 434 will be discussed in greater detail, below. The strengthening gussets are employed to couple both the foot tabs 434 or the outer cap wall 430 to the annular exhaust port wall 438 , which extends forwardly from the flat rear portion 446 of the outer cap wall 430 . The exhaust button 440 is an annular member that also extends forwardly from the flat rear portion 446 of the outer cap wall 430 but which is spaced apart from the annular exhaust port wall 438 and the locating hub 442 . A plurality of primary exhaust ports 450 are formed through the exhaust button 440 and a plurality of secondary exhaust ports 452 are formed through the portion of the outer cap wall 430 between the annular exhaust port wall 438 and the exhaust button 440 . [0081] The exhaust manifold 422 is preferably unitarily formed from a molded from a plastic material and includes a center hub 460 , an annular spacing wall 462 and an annular manifold wall 464 . The center hub 460 is configured to fit between the exhaust button 440 and the locating hub 442 and includes a hub aperture 468 that is configured to engage the locating hub 442 in a slip fit manner. The annular spacing wall 462 is coupled to the forward-most portion of the center hub 460 and is spaced apart from the exhaust button 440 . The annular manifold wall 464 is coupled to the outer perimeter of the annular spacing wall 462 and includes a plurality of circumferentially extending exhaust slots 470 that are spaced around the circumference of the annular manifold wall 464 . The exhaust slots 470 are generally U-shaped and as best shown in FIG. 13, have a rear edge 472 that tapers rearwardly and inwardly toward the center hub 460 . [0082] Returning to FIGS. 11 and 12, the top bumper 424 preferably includes a dampening member 480 that is molded from an elastomeric material, such as urethane, and a structural member 482 , such as a washer, that is molded into the dampening member 480 . The dampening member 480 is a cup-shaped structure that is sized to fit within the center hub 460 of the exhaust manifold 422 . The dampening member 480 includes an annular wall 484 that extends forwardly from the base 486 of the dampening member 480 . A ridge 488 is formed into the forward end of the annular wall 484 , thereby creating a groove 490 between the base 486 of the dampening member 480 and the ridge 488 . A plurality of slits 492 are formed into the annular wall 484 , creating a plurality of wall segments 494 that are flexibly coupled to the base 486 . A threaded fastener 496 is threadably engaged to the threaded aperture 444 in the locating hub 442 to fixedly but removably couple the top bumper 424 to the cap housing 420 . The structural member 482 is employed so as to permit the clamping force that is exerted by the threaded fastener 496 to be transmitted through the top bumper 424 without crushing the base 486 of the dampening member 480 . A portion of the clamping force is transmitted through the base 486 of the dampening member 480 and into the center hub 460 of the exhaust manifold 422 to maintain the exhaust manifold 422 in a stationary position relative to the cap housing 420 . [0083] Engine Assembly [0084] Engine assembly 46 is shown to include a cylinder assembly 500 , a piston assembly 502 , a rod or driver blade 504 . The cylinder assembly 500 includes a hollow, cylindrical, and unitarily constructed sleeve 510 , an inner exhaust port seal 512 , an outer exhaust port seal 514 , a cap flange seal 516 , rear and front guide seals 518 and 520 , a guide assembly 522 , a compensating valve 524 , a rear spring flange 526 , a spring 528 , a front spring flange 530 and a front spring flange seal 532 . In the particular embodiment illustrated, inner exhaust port seal 512 , outer exhaust port seal 514 , rear and front guide seals 518 and 520 and front spring flange seal 532 are conventional, commercially available O-ring seals. The cap flange seal 516 is a molded elastomeric seal having an outside surface with a generally flat seal face 540 and first and second radially inwardly extending flanges 542 and 544 , respectively, that are spaced apart from one another to form an engagement groove 546 therebetween. [0085] With additional reference to FIG. 16, the sleeve 510 is shown to include a first sleeve body portion 550 , an annular sleeve flange 552 , a second sleeve body portion 554 having a maximum outer diameter that is generally the same as that of the first sleeve body portion 550 and a third sleeve body portion 556 having a maximum outer diameter that is generally larger than that of the first sleeve body portion 550 . The first sleeve body portion 550 includes a first U-shaped seal groove 560 , which is sized to receive the front spring flange seal 532 , a plurality of circumferentially-spaced front exhausting ports 562 , a spring flange groove 564 , which is sized to receive the rear spring flange 526 , a valve groove 566 , which is discussed in greater detail, below, and a second U-shaped seal groove 568 , which is sized to receive the front guide seal 520 . [0086] The valve groove 566 has a first U-shaped portion 570 , a second U-shaped portion 572 and a plurality of valve apertures 574 . The first U-shaped portion 570 is sized to receive the compensating valve 524 , which in the particular embodiment illustrated, is a flat elastomeric band 580 . The second U-shaped portion 572 is disposed within the first U-shaped portion 570 , but has a diameter that is somewhat smaller than that of the first U-shaped portion 570 so as to define an annular ring that extends around the circumference of the first U-shaped portion 570 . In the particular embodiment illustrated, the diameter of the second U-shaped portion 572 is about 0.010 inches to about 0.030 inches smaller in diameter than the first U-shaped portion 570 . The valve apertures 574 are illustrated to be relatively small diameter holes that are located within the second U-shaped portion 572 and which are drilled through the sleeve 510 . The valve apertures 574 will be discussed in greater detail, below, as will the set of front exhausting ports 562 that are located between the first U-shaped seal groove 560 and the spring flange groove 564 . [0087] The annular sleeve flange 552 extends radially outwardly from the first sleeve body portion 550 of the sleeve 510 and separates the first and second sleeve body portions 550 and 554 from one another. A third U-shaped seal groove 584 , which is sized to receive the rear guide seal 518 is formed into the outer surface of the annular sleeve flange 552 . [0088] The majority of the second sleeve body portion 554 of the sleeve 510 is of approximately the same outer diameter as the first sleeve body portion 550 . The rear end of the second sleeve body portion 554 , however, includes a flange portion 590 that extends radially outwardly to form a seal lip 592 and a fourth U-shaped seal groove 594 prior to its connection with the third sleeve body portion 556 . The seal lip 592 is configured to engage the engagement groove 546 formed into the cap flange seal 516 and abut the first and second radially inwardly extending flanges 542 and 544 . The fourth U-shaped seal groove 594 is configured to receive a portion of the first radially inwardly extending flange 542 . [0089] The third sleeve body portion 556 is fixedly coupled to the end of the second sleeve body portion 554 and is larger in diameter than the outer diameter of the first sleeve body portion 550 . A fifth U-shaped seal groove 600 is formed into the outer surface of the third sleeve body portion 556 and is sized to receive the outer exhaust port seal 514 . A plurality of circumferentially extending rear exhaust slots 604 are disposed around the perimeter of the third sleeve body portion 556 . The rear exhaust slots 604 are located between the fourth and fifth U-shaped seal grooves 594 and 600 . A sixth U-shaped seal groove 608 , which is configured to receive the inner exhaust port seal 512 , is formed into the inner diameter of the third sleeve body portion 556 . [0090] The hollow cavity 610 that is formed through the sleeve 510 has a first cavity portion 612 that is generally of a constant diameter over the portion of its length that includes the first and second sleeve body portions 550 and 554 and the annular sleeve flange 552 . The hollow cavity 610 also has a second cavity portion 614 having a larger diameter than that of the first cavity portion 612 . [0091] In FIG. 14, the guide assembly 522 is shown to include a guide 650 and first and second housing seals 652 and 654 , which in the particular embodiment illustrated, are O-ring seals. The guide 650 is a molded plastic component, having a stepped-diameter body portion 660 , a plurality of longitudinally extending legs 662 , a locating tab 664 and a plurality of stop tabs 668 . The stepped-diameter body portion 660 includes a flange bore 670 , which is sized to receive the annular sleeve flange 552 and sealingly engage the rear guide seal 518 , a body bore 672 , which is sized to receive the first sleeve body portion 550 and sealingly engage the front guide seal 520 , and an abutting flange 676 that forms the transition between the flange bore 670 and the body bore 672 . [0092] The longitudinally extending legs 662 extend away from the stepped-diameter body portion 660 and are spaced apart circumferentially in equal amounts. The locating tab 664 is positioned on the same side of the stepped-diameter body portion 660 as the longitudinally extending legs 662 between two of the longitudinally extending legs 662 . The locating tab 664 is employed to signify the presence of an air gallery 680 and locate the guide assembly 522 relative to the housing assembly 42 . The air gallery 680 is configured to permit air to flow through the stepped-diameter body portion 660 from a point between the first and second housing seals 652 and 654 through the stepped-diameter body portion 660 and out the abutting flange 676 . [0093] The rear and front guide seals 518 and 520 and the elastomeric band 580 that forms a portion of the compensating valve 524 are initially installed to the sleeve 510 . Thereafter, the guide assembly 522 is positioned over the first sleeve body portion 550 and pushed onto the sleeve 510 such that the flange bore 670 and body bore 672 are sealingly engaged to the rear and front guide seals 518 and 520 , respectively, and the abutting flange 676 abuts the annular sleeve flange 552 . [0094] The rear spring flange 526 is next installed to the sleeve 510 . The rear spring flange 526 is a plastic collar that is split on one side to permit the ends of the rear spring flange 526 to be spread apart so that it may be loaded onto the first sleeve body portion 550 of the sleeve 510 and into the spring flange groove 564 . The rear spring flange 526 has a cylindrically shaped body portion 690 and a flange portion 692 that extends radially-outwardly from the body portion 590 in a manner that provides the rear spring flange 526 with a L-shaped cross-section. The rear spring flange 526 is located to the spring flange groove 564 such that the flange portion 692 is nearest the annular sleeve flange 552 . [0095] The front spring flange 530 is a plastic collar having a tapering outside diameter 596 and a generally flat rear face 698 . The inside surface 700 of the front spring flange 530 is generally cylindrical, but includes an annular protrusion 702 that extends radially inwardly of the remainder of the inside surface 700 and which engages the first sleeve body portion 550 of the sleeve 510 in a slip-fit manner. [0096] The spring 528 is a conventional compression spring having both ends ground flat. The spring 528 is disposed over the first sleeve body portion 550 of the sleeve 510 such that its rear end abuts the flange portion 692 of the rear spring flange 526 . Thereafter, the front spring flange 530 is positioned such that its rear face 698 contacts the second end of the spring 528 . The front spring flange 530 is pushed toward the annular sleeve flange 552 to compress the spring 528 a sufficient distance to permit the front spring flange seal 532 to be inserted into the first U-shaped seal groove 560 . Thereafter, the front spring flange 530 is moved toward the front of the sleeve 510 such that the front spring flange seal 532 is sealingly engaged with the inside surface 700 of the front spring flange 530 . The rear side of the front spring flange seal 532 contacts the annular protrusion 702 to limit the forward travel of the front spring flange 530 prior to the installation of the engine assembly 46 to the housing assembly 42 . Forward motion of the guide assembly 522 along the sleeve 510 is checked by contact between the stop tabs 668 and the rear surface of the flange portion 692 of the rear spring flange 526 to thereby prevent the guide 650 from becoming disengaged from the rear and front guide seals 518 and 520 . Construction in this manner is highly advantageous in that it permits the entire cylinder assembly 500 to be pre-assembled outside of the housing assembly 42 in a relatively easy and cost efficient manner. [0097] The piston assembly 502 includes a piston 720 and a ring 722 . In the example provided, the piston 720 is shown to include a first piston portion 730 and a second piston portion 732 . The first piston portion 730 in an annular member that is smaller in diameter than the first cavity portion 612 of the hollow cavity 610 in the sleeve 510 . A U-shaped annular ring groove 734 is formed around the circumference of the first piston portion 730 that is sized to receive the ring 722 . In the embodiment illustrated, the ring 722 is shown to be fabricated from a plastic material and have a rectangular cross-section. The ring 722 is split to permit its ends of the ring 722 to be spread apart so that it may be loaded around the first piston portion 730 and into the ring groove 734 . The second piston portion 732 is an annular member that is smaller in diameter than the first piston portion 730 . The second piston portion 732 is coupled to the rear end of the first piston portion 730 and includes a pair of wrench flats 740 and a locking protrusion 744 , both of which will be discussed in more detail, below. A generous fillet radius 746 is employed at the intersection between the first and second piston portions 730 and 732 so as to reduce the concentration of stress within the piston 720 . [0098] The construction of the driver blade 504 is largely conventional and as such, a detailed discussion of it is neither required nor within the scope of this disclosure. Briefly, the driver blade 504 is shown to include a coupling portion 760 and a driver body 762 . In the example provided, the coupling portion 760 includes a collar 764 and a threaded portion 766 which are formed into the rear end of the driver blade 504 . The wrench flats 740 on the second piston portion 732 are employed to facilitate relative rotation between the driver blade 504 and the piston 720 to permit the threaded portion 766 to threadably engage a threaded aperture 768 that is formed through the piston 720 and to permit the collar 764 to engage the front surface 770 of the piston 720 to generate a clamping force that fixedly but removably couples the piston 720 and the driver blade 504 together. Coupling of the piston 720 and the driver blade 504 via a threaded connection is presently preferred so as to permit the servicing and replacement of the driver blade 504 , since this portion of the tool 10 is essentially perishable. Those skilled in the art will understand, however, that other coupling mechanisms, such as press-fitting, shrink fitting, welding, or any other mechanical coupling method may also be employed. [0099] The driver body 762 is sized to fit in the blade cavity 82 and is shown to include a keyway 774 , a slide surface 776 , a loading groove 778 and a tip portion 780 . The keyway 774 is illustrated to be a cut that is formed into the surface of the driver body 762 along its longitudinal axis. The fastener stop 102 that is formed into the internal cavity 100 in the nose guide 98 is disposed within the keyway 782 to guard against a situation wherein fasteners F feed rearwardly into the tool 10 . The slide surface 776 is generally flat and provides the driver body 762 with a relatively large surface that will consistently slide over the fasteners F that are loaded into the magazine assembly 20 . The tip portion 780 is formed at the front end of the driver body 762 and is operable for contacting the fasteners F and driving them into a workpiece. The loading groove 778 is cylindrically shaped and is formed along an axis that is skewed to the longitudinal axis of the driver blade 504 such that it intersects both the tip portion 780 and the slide surface 776 . The loading groove 778 is tapered such that it is deepest at the front of the driver blade 504 . The loading groove 778 ensures that only one fastener F is sheared from the remaining fasteners F in the magazine assembly 20 . The loading groove 778 also permits the fasteners F in the magazine assembly 20 to move upwardly toward the nose body 60 of the tool 10 prior to the time at which the driver blade 504 has stroked back to its rear-most (i.e., retracted) position to thereby minimize the lag time between the point at which the driver blade 504 has moved to its retracted position and the point at which the driver blade 504 can be moved forwardly to drive another fastener F. [0100] With additional reference to FIGS. 16 and 17, the driver blade 504 and the piston assembly 502 , once coupled to one another, are inserted into the second cavity portion 614 of the hollow cavity 610 in the sleeve 510 . The diameter of the second cavity portion 614 is larger than the diameter of the piston assembly 502 (with the ring 722 in an expanded condition). A chamfer 790 is employed at the front of the second cavity portion 614 to facilitate the transition to the smaller-diameter first cavity portion 612 . With the exertion of light force onto the rear of the piston assembly 502 , the piston assembly 502 is moved forwardly in the hollow cavity 610 and into contact with the chamfer 790 . The chamfer 790 is operable for compressing the ring 722 to permit the piston assembly 502 to travel into the first cavity portion 612 . [0101] Once assembled, the engine assembly 46 is placed into the housing cavity 174 such that the locating tab 664 is aligned to a tab slot 800 formed into the housing cavity 174 and the driver blade 504 is inserted through the driver blade aperture 410 in the piston bumper 152 and into the internal cavity 100 in the nose guide 98 . The engine assembly 46 is pushed forwardly into the housing cavity 174 to engage the guide assembly 522 against the guide stop 184 . In this position, the first and second housing seals 652 and 654 sealingly engage the guide bore 180 that is formed into the inside surface 182 of the outwardly tapering sidewall 172 . The first and second annular bumper portions 396 and 398 extend through the front face 810 of the sleeve 510 and into the hollow cavity 610 . The front face 820 of the front spring flange 530 sealingly contacts the second annular lip portion 408 on the piston bumper 152 . The cap assembly 44 is thereafter placed onto the rear end of the housing assembly 42 such that each of the longitudinally extending legs 662 contacts one of the foot tabs 434 . The foot tabs 434 cooperate with the longitudinally extending legs 662 to prevent the guide assembly 522 from moving along the longitudinal axis of the tool 10 . The sleeve 510 , however, is slidable within the guide assembly 522 , as will be discussed in greater detail, below. [0102] Alternatively, the piston assembly 502 and driver blade 504 may be inserted into the housing cavity 174 such that the driver blade 504 is inserted through the driver blade aperture 410 in the piston bumper 152 and into the internal cavity 100 in the nose guide 98 . The cylinder assembly 500 is then loaded into the housing cavity 174 in the manner discussed above. A lead L formed into the front face 810 of the sleeve 510 that permits the ring 722 to be compressed so that the piston assembly 502 can travel rearwardly into the first cavity portion 612 of the hollow cavity 610 in the sleeve 510 . [0103] Engine Operation [0104] With reference to FIGS. 10, 14 and 16 , when the tool 10 has been coupled to a source of compressed air, the trigger assembly 48 maintains the trigger valve 130 in an unactuated state wherein compressed air is directed from the supply port 370 to the biasing port 372 where it enters the air gallery 680 at a point between the first and second housing seals 652 and 654 . Compressed air flows through the stepped-diameter body portion 660 and exits from the abutting flange 676 where it enters a sleeve return chamber 850 that is defined by the forward face 852 of the annular sleeve flange 552 , the rear guide seal 518 , the flange bore 670 , the body bore 672 , the front guide seal 520 and the first sleeve body portion 550 of the sleeve 510 . As the guide 650 is not movable within the housing 150 , the pressure of the air that is in the sleeve return chamber 850 is exerted against the front face 852 of the annular sleeve flange 552 to bias the sleeve 510 in a rearward direction. [0105] The air inlet cavity 270 also provides compressed air to a sleeve extend chamber 860 that is defined by the rearward face 862 of the annular sleeve flange 552 , the rear guide seal 518 , the guide 650 , the second housing seal 654 , the portion of the outwardly tapering sidewall 172 that is situated rearwardly of the second housing seal 654 , the outer portion of the cap housing 420 that includes the annular exhaust port wall 438 , the cap flange seal 516 and the second sleeve body portion 554 of the sleeve 510 . Compressed air in the sleeve extend chamber 860 directs force to both the rearward face 862 of the annular sleeve flange 552 and the front face 864 of the flange portion 590 of the second sleeve body portion 554 of the sleeve 510 . [0106] The forces that act on the annular sleeve flange 552 and the front face 864 of the flange portion 590 , in cooperation with the force that is exerted by the spring 528 , bias the sleeve 510 in a rearward direction into its retracted position such that the flat seal face 540 of the cap flange seal 516 sealingly engages the front face 866 of the annular exhaust port wall 438 . [0107] With reference to FIGS. 10 and 12, when the sleeve 510 is in the retracted position, a primary exhaust chamber 870 is defined by the cap flange seal 516 , the inside surface 872 of the annular exhaust port wall 438 , the outer exhaust port seal 514 , the third sleeve body portion 556 of the sleeve 510 , the inner exhaust port seal 512 , the exhaust manifold 422 , the second sleeve body portion 554 of the sleeve 510 , the piston assembly 502 and the driver blade 504 . The position of the sleeve 510 relative to the cap assembly 44 is such that the air that is in the primary exhaust chamber 870 is permitted to flow between the third sleeve body portion 556 and exhaust manifold 422 , through the exhaust slots 470 in the exhaust manifold 422 and out the primary exhaust ports 450 in the exhaust button 440 where this air is vented to atmosphere. [0108] With the sleeve 510 in the retracted position, a secondary exhaust chamber 880 is formed by the annular exhaust port wall 438 , the outer exhaust port seal 514 , the third sleeve body portion 556 of the sleeve 510 , the inner exhaust port seal 512 , the exhaust manifold 422 , the exhaust button 440 and the portion of the outer cap wall 430 between the annular exhaust port wall 438 and the exhaust button 440 . Air that is in the secondary exhaust chamber 880 is vented to the atmosphere through the primary exhaust ports 450 in the exhaust button 440 and through the secondary exhaust ports 452 in the portion of the outer cap wall 430 between the annular exhaust port wall 438 and the exhaust button 440 . [0109] With reference to FIGS. 12, 14 and 18 , when the trigger assembly 48 is actuated to change the state of the trigger valve 130 to an actuated state, air in the sleeve return chamber 850 is vented through the trigger assembly 48 to the atmosphere. Consequently, the force that is exerted onto the rear face 862 of the annular sleeve flange 552 causes the sleeve 510 to slide forwardly relative to the housing assembly 42 . When the sleeve 510 slides in a forward direction, the seal between the cap flange seal 516 and the front face 866 of the annular exhaust port wall 438 is broken, permitting compressed air to flow through the rear exhaust slots 604 in the third sleeve body portion 556 of the sleeve 510 . As the area of the front surface 900 of the rear exhaust slots 604 is larger than the area of its rear surface 902 , the pressure of the air flowing through the rear exhaust slots 604 also tends to push the sleeve 510 in a forward direction. The piston bumper 152 checks forward travel of the sleeve 510 . More specifically, forward travel of the sleeve 510 is checked when the front face 810 of the sleeve 510 contacts the first annular lip portion 406 of the piston bumper 152 . [0110] Simultaneous with the forward motion of the sleeve 510 , the inner exhaust port seal 512 slides forwardly by an equal amount to sealingly engage the outer circumference 910 of the exhaust manifold 422 at a point forward of the exhaust slots 470 to thereby prevent air from flowing to the atmosphere through the exhaust slots 470 . Pressure acts on the rear surface 920 of the piston assembly 502 to disengage the locking protrusion 744 in the second piston portion 732 from the groove 490 in the top bumper 424 . The pressure acts on the piston assembly 502 to drive the piston assembly 502 and the driver blade 504 forwardly through the first cavity portion 612 of the hollow cavity 610 in the sleeve 510 . Air in the first cavity portion 612 is compressed by the forward motion of the piston assembly 502 , causing it to be expelled from the hollow cavity 610 through the internal cavity 100 in the nose guide 98 , as well as through the front exhausting ports 562 and into a frontal air chamber 940 . The frontal air chamber 940 is defined by the first sleeve body portion 550 of the sleeve 510 , the front guide seal 520 , the guide 650 , the first housing seal 652 , the outwardly tapering wall 172 of the housing body 160 , the second annular lip portion 408 of the annular lip 392 in the piston bumper 152 , the front spring flange 530 and the front spring flange seal 532 . [0111] The piston bumper 152 checks the forward motion of the sleeve 510 . Thereafter, the piston assembly 502 pushes the driver blade 504 forwardly so that the tip portion 780 drives a fastener F into a workpiece (not shown). With the piston bumper 152 also checks the forward motion of the piston assembly 502 and effectively seals against the front surface 770 of the piston assembly 502 to seal the frontal air chamber 940 . In this condition, the piston assembly 502 is positioned forwardly of the valve apertures 574 in the first sleeve body portion 550 of the sleeve 510 . Accordingly, if the pressure of the air in the portion of the hollow cavity 610 that is rearward of the piston assembly 502 is greater than the pressure of the air in the frontal air chamber 940 , the compensating valve 524 permits air to flow through the sleeve 510 and into the frontal air chamber 940 so as to balance the air pressure that is acting on the front and rear surfaces 770 and 920 of the piston assembly 502 . The compensating valve 524 , however, is a one-way valve that does not permit air to flow from the frontal air chamber 940 through the valve apertures 574 and into the hollow cavity 610 . [0112] Referring back to FIGS. 10, 12, 14 and 16 , when the state of the trigger valve 130 is changed to its unactuated state, compressed air is once again routed to the sleeve return chamber 850 where it applies a force against the front face 852 of the annular sleeve flange 552 . The balance of the forces on the sleeve 510 is such that the sleeve 510 is pushed in a rearward direction until the cap flange seal 516 sealingly engages the front face 866 of the annular exhaust port wall 438 . Air in the primary and secondary exhaust chambers 870 and 880 is then vented to the atmosphere in the manner discussed above. [0113] The piston assembly 502 , immediately prior to the exhausting of the air in the primary and secondary exhaust chambers 870 and 880 , was such that it remained in sealed engagement with the piston bumper 152 . When the air in the primary exhaust chamber 870 is vented to the atmosphere, however, the pressure in the frontal air chamber 940 generates a force on the front surface 770 of the piston assembly 502 that exceeds the force that is acting on its rear face 920 . As mentioned above, the compensating valve 524 is a one-way valve that prevents air from flowing through the valve apertures 574 and into the hollow cavity 610 and as such, the pressure of the air to the rear of the piston assembly 502 is less than the pressure of the air in the frontal air chamber 940 . Accordingly, the pressure acting on the front surface 770 of the piston assembly 502 drives the piston assembly 502 rearwardly until the locking protrusion 744 in the second piston portion 732 engages the groove 490 in the top bumper 424 . [0114] Those skilled in the art will understand that while the above-described configuration of the engine assembly 46 results in a relatively lighter-weight tool as compared with pneumatic fastening devices that employ a conventional head valve, the reduction in the weight of the tool 10 does not come at the expense of increased recoil that is felt by the tool operator. In this regard, the felt force that is exerted onto the cap assembly 44 when a fastener F is driven into a workpiece is counteracted by the felt force that is exerted by the sliding of the sleeve 510 in a forward direction. [0115] Magazine Assembly [0116] The magazine assembly 20 is shown to include a magazine body assembly 1000 , a follower structure 1002 , a follower spring 1004 and a magazine endcap assembly 1006 . The magazine body assembly 1000 includes a magazine housing 1010 , a pair of guide structures 1012 a and 1012 b and a coupling bracket 1014 . In the example illustrated, the magazine housing 1010 is extruded from a lightweight material, such as aluminum and includes a wall member 1020 that defines a fastener head portion 1022 , a follower housing portion 1024 , a pair of guide housing portions 1026 and a fastener body portion 1028 . [0117] The fastener head portion 1022 is generally rectangular in shape, defining a fastener head chamber 1030 that is open at its top and bottom ends so as to permit the head portion H of the fasteners F to travel through the fastener head portion 1022 . The fastener head portion 1022 is also open along a portion of one of its sides 1032 so as to permit the follower structure 1002 to travel upwardly within the magazine housing 1010 . With additional reference to FIG. 21, a threaded fastener 1034 is threadably engaged to the wall member 1020 , forming a contact surface 1036 that checks the upward travel of the follower structure 1002 . [0118] As shown in FIGS. 19, 20 and 22 , the follower housing portion 1024 is coupled to the forward side of the fastener head portion 1022 and defines a generally rectangular follower cavity 1040 that is sized to receive the follower structure 1002 and the follower spring 1004 . A slot 1042 is formed into the rear surface 1044 of the follower housing portion 1024 . The slot 1042 interconnects the follower cavity 1040 to the fastener head chamber 1030 . An L-shaped pin aperture 1050 is formed into a side of the follower housing portion 1024 . The L-shaped pin aperture 1050 includes a relatively narrow first portion 1052 that extends generally parallel the longitudinal axis of the follower housing portion 1024 and a second portion 1054 that is skewed to the first portion 1052 . The L-shaped pin aperture 1050 will be discussed in greater detail, below. [0119] In FIGS. 19 and 20, each guide housing portion 1026 is shown to include a pair of spaced apart and arcuate protrusions 1060 a and 1060 b that are coupled to the wall member 1020 . The arcuate protrusions 1060 a and 1060 b cooperate with the wall member 1020 to define a guide structure cavity 1062 that extends over the length of the magazine housing 1010 and which is configured to receive one of the guide structures 1012 a and 1012 b . In the particular embodiment illustrated, the guide structure cavity 1062 includes a first cavity portion 1064 that is generally cylindrically shaped and located proximate the follower housing portion 1024 , and a second cavity portion 1066 that is shaped as a generally flat void that is generally tangent to the cylindrically shaped first cavity portion 1064 . [0120] The fastener body portion 1028 is generally U-shaped, being coupled to the forward portion of the pair of guide housing portions 1026 . The fastener body portion 1028 includes a U-shaped fastener body cavity 1070 that is configured to receive the body B of the fasteners F. A plurality of oval windows 1072 are formed into the sides 1074 of the fastener body portion 1028 which permit the tool operator to monitor the quantity of fasteners F that are housed in the magazine assembly 20 , as well as to reduce the overall weight of the magazine assembly 20 . [0121] As guide structures 1012 a and 1012 b are generally identical in construction, reference numerals may occasionally be shown on only of the guide structure 1012 a and 1012 b . Those skilled in the art will understand, however, that guide structure 1012 b is a mirror image of guide structure 1012 a . In the embodiment illustrated in FIGS. 19, 20 and 23 , each of the guide structures 1012 a and 1012 b includes a cylindrically-shaped guide port 1100 , first and second retention tabs 1102 and 1104 , respectively, an intermediate member 1106 and an end member 1108 . The guide port 1100 is generally hollow, having an outside diameter that is sized to slip fit into the first cavity portion 1064 of an associated one of the guide housing portions 1026 and an inside diameter that is to engage an associated one of the magazine guide posts 66 . The first retention tab 1102 is coupled to the guide port 1100 on one side and to the intermediate member 1106 on the opposite side. The second retention tab 1104 is coupled to the intermediate member 1106 on the side opposite the first retention tab 1102 . The intermediate member 1106 is sized to fit between the arcuate protrusions 1060 a and 1060 b in the guide housing portion 1026 as well as to space the first and second retention tabs 1102 and 1104 apart from one another by a predetermined distance that permits the first and second retention tabs 1102 and 1104 to engage the arcuate protrusions 1060 a and 1060 b when the guide structures 1012 a and 1012 b are inserted into the guide structure cavities 1062 . The inner surface 1110 of the second retention tab 1104 extends inwardly further toward the centerline 1112 of the magazine housing 1010 than the inside surfaces of the U-shaped fastener body cavity 1070 so as to form a wear surface 1114 against which the body B of the fastener F is permitted to rub. The end member 1108 is coupled to the end of the guide structures 1012 a and 1012 b opposite the end to which the guide port 1100 is coupled. The end member 1108 is configured to abut the ends of the arcuate protrusions 1060 a and 1060 b so as to prevent the guide structures 1012 a and 1012 b from moving upwardly out of the top of the magazine housing 1010 . [0122] In FIGS. 24 and 25, the coupling bracket 1014 is shown to have a pair of threaded bushings 1200 and a bracket structure 1202 having a pair of mounting flanges 1204 and a U-shaped body portion 1206 that is coupled to one of the mounting flanges 1204 at each of its opposite ends. Each of the threaded bushings 1200 is coupled to one of the mounting flanges 1204 . The mounting flanges 1204 abut the side of the follower housing portion 1024 and threaded fasteners 1210 (FIG. 2) are employed to engage the threaded bushings 1200 to fixedly but removably couple the coupling bracket 1014 to the magazine housing 1010 . [0123] The U-shaped body portion 1206 includes a base 1220 and a plurality of legs 1222 , with each of the legs 1222 coupling a side of the base 1220 to an associated one of the mounting flanges 1204 . The base 1220 includes a slotted pin aperture 1230 that includes a circular portion 1232 , a slotted portion 1234 that is spaced apart from the circular portion 1232 , and a necked-down slotted portion 1236 having a width that is smaller than that of the slotted portion 1234 and which interconnects the circular and slotted portions 1232 and 1234 . The circular portion 1232 is sized to receive the head portion 322 of the clamp pin 300 , the slotted portion 1234 is sized to slidingly receive the first body section 324 of the clamp pin 300 , and the necked-down slotted portion 1236 is sized to receive the second body section 326 of the clamp pin 300 but not the first body section 324 . With specific reference to FIG. 25, the back side of the base 1220 is illustrated in pertinent detail. The end of the slotted portion 1234 is shown to include a conical detent 1238 which is configured to confront the frusto-conical abutting face 330 of the head portion 322 of the clamp pin 300 . [0124] With reference to FIGS. 19, 20 and 27 through 32 , the follower structure 1002 is illustrated to have a follower body 1300 , a front guide tab 1302 , a lock-out dog 1304 , a loading cam 1306 , a follower guide 1308 and an actuating lever 1310 . The follower body 1300 is generally U-shaped, having a base 1320 and a pair of follower legs 1322 a and 1322 b . The lock-out dog 1304 extends upwardly from the base 1320 in a direction opposite that of the follower legs 1322 a and 1322 b . The front guide tab 1302 is also coupled to the base 1320 but extends upwardly and forwardly therefrom in the same plane as the base 1320 . Accordingly, when the follower structure 1002 is installed to the magazine housing 1010 , the front guide tab 1302 extends forwardly from the follower housing portion 1024 , past the pair of guide housing portions 1026 and into the fastener body portion 1028 where the U-shaped tip portion 1330 of the front guide tab 1302 supports the body B of the fasteners F. [0125] The loading cam 1306 is formed into follower leg 1322 a and includes a first loading cam portion 1350 , a second loading cam portion 1352 and a third loading cam portion 1354 . The first loading cam portion 1350 is a tapered ramp that extends outwardly and upwardly from the distal end of the follower leg 1322 a . The second loading cam portion 1352 includes an oval follower capturing portion 1360 , a downwardly and forwardly extending intermediate portion 1362 and a forwardly and upwardly extending catch portion 1364 and a catch aperture 1368 that is formed at the lower-most portion of the catch portion 1364 . The follower capturing portion 1360 and the intermediate portion 1362 are formed into a first side of the follower leg 1322 a at a first depth, and the catch portion 1364 is formed into the first side of the follower leg 1322 a at a second depth that is greater than the first depth. The third loading cam portion 1354 is a generally flat portion of the front surface 1370 of the follower leg 1322 a. [0126] The follower guide 1308 is formed onto the outside surface of follower leg 1322 b . The follower guide 1308 includes a V-shaped flange 1380 , an end member 1382 and a connector portion 1384 that couples the V-shaped flange 1380 and the end member 1382 . The connector portion 1384 is configured to fit into the slot 1042 in the follower housing portion 1024 such that the V-shaped flange 1380 and the end member 1382 confront the rear inside surface 1044 and the rear outside surface 1388 , respectively, of the follower housing portion 1024 . [0127] The actuating lever 1310 extends outwardly from the end member 1382 and thereafter bends inwardly toward the follower legs 1322 a and 1322 b . The distal end of the actuating lever 1310 forms an engagement surface 1390 that is configured for receiving an input from the tool operator's thumb. A protrusion 1392 that is configured to contact the contact surface 1036 in the fastener head portion 1022 is also formed onto the actuating lever 1310 . [0128] With reference to FIGS. 19, 20, 29 , 30 and 33 , the follower spring 1004 is illustrated to include a spring hook 1400 , a coiled, flat band spring 1402 , a cylindrically-shaped spring roller body 1404 and a spring roller pin 1406 . The spring roller pin 1406 extends through and rotatably supports the spring roller body 1404 . The band spring 1402 is a type of torsion spring, being coupled to and wound around the spring roller body 1404 . The free end of the band spring 1402 is coupled to the spring hook 1400 . Each end of the spring roller pin 1406 is set into a generally U-shaped spring roller slot 1410 that is formed into each inside surface of the follower legs 1322 a and 1322 b to couple the follower spring 1004 to the follower structure 1002 . [0129] When the follower structure 1002 is disposed within the follower housing portion 1024 , the band spring 1402 is unwound to permit the C-shaped spring hook 1400 to be engaged to the side of the follower housing portion 1024 opposite the side in which the L-shaped pin aperture 1050 is formed. The torsion exerted by the band spring 1402 is converted to a force that is exerted through the spring roller pin 1406 to the follower structure 1002 , thereby biasing the follower structure 1002 in an upward direction toward the spring hook 1400 . [0130] In the particular embodiment illustrated in FIGS. 1, 19 and 35 through 45 , the magazine endcap assembly 1006 includes a molded end cap structure 1600 , a crush tube 1602 , a pivot structure 1604 , a cam follower 1606 , a cam follower spring 1608 and a thrust member 1610 . The end cap structure 1600 is configured to mate against the bottom of the magazine housing 1010 to close off the follower housing portion 1024 and the fastener body portion 1028 . [0131] The end cap structure 1600 includes a bushing trunnion 1620 for receiving the crush tube 1602 , a fastener trunnion 1622 for receiving a fastener 1623 a (FIG. 1) that couples the nose 1623 b of the end cap structure 1600 to the fastener body portion 1028 and a pair of pivot trunnions 1624 for receiving the pivot structure 1604 , which is illustrated to be a threaded fastener 1626 that is secured to the end cap structure 1600 via a threaded nut 1628 in the example provided. The crush tube 1602 , which is retained by the bushing trunnion 1620 , prevents the end cap structure 1600 form being overstressed as well as the follower housing portion 1024 from being deformed as a result of the clamping force that is exerted by the threaded fastener 1630 (FIG. 1) that couples the end cap structure 1600 to the follower housing portion 1024 . [0132] The end cap structure 1600 also includes a follower directing wall 1640 , a thrust flange 1642 and a spring flange 1644 . The follower directing wall 1640 extends upwardly from the base 1646 of the end cap structure 1600 and includes a ramped portion 1650 , which tapers outwardly and downwardly from the top end 1652 of the follower directing wall 1640 , and a generally flat portion 1654 that interconnects the ramped portion 1650 to the base 1646 of the end cap structure 1600 . The spring flange 1644 is located proximate one of the pivot trunnions 1624 , extending upwardly from the base 1646 of the end cap structure 1600 behind one of the pivot trunnions 1624 . The thrust flange 1642 is located between the spring flange 1644 and the follower directing wall 1640 and includes a first U-shaped aperture 1660 that is configured to receive the pivot structure 1604 and a second U-shaped aperture 1662 that is configured to receive the hollow thrust member 1610 . [0133] In the particular embodiment illustrated, the cam follower 1606 includes a lever 1670 and a follower hook 1672 . The lever 1670 includes a slotted pivot aperture 1680 that is sized to receive and rotate as well as pivot in a lateral (side-to-side) direction on a portion of the pivot structure 1604 . The lever 1670 extends beyond the slotted pivot aperture 1680 to form a spring follower hook 1672 that can be employed during the assembly of the magazine endcap assembly 1006 . The follower hook 1672 includes a cylindrical body portion 1690 that is coupled to the distal end of the lever 1670 and a leg member 1692 that is coupled to the outer end of the body portion 1690 and which extends downwardly from the body portion 1690 generally parallel to the lever 1670 . The outside face 1694 of the leg member 1692 is heavily chamfered such that the leg member 1692 terminates at a rounded tip portion 1696 . The intersection between the body portion 1690 and the leg member 1692 is undercut by a radius 1698 . [0134] The cam follower spring 1608 is illustrated to be a combination compression and torsion spring having a spring body 1700 that wraps around a portion of the pivot structure 1604 , a bent end 1702 for contacting the front face of the lever 1670 and a straight end 1704 for contacting the spring flange 1644 . The cam follower spring 1608 is operable for exerting a rotational biasing force onto the cam follower 1606 which biases the cam follower 1606 toward the rear of the tool 10 . The cam follower spring 1608 is also operable for exerting a lateral force onto the cam follower 1606 which biases the cam follower 1606 toward the thrust member 1610 . [0135] The pivot structure 1604 is positioned through the pivot trunnion 1624 that is adjacent the spring flange 1644 . The cam follower spring 1608 is positioned over a portion of the pivot structure 1604 such that the straight end 1704 is in contact with the spring flange 1644 . The cam follower 1606 is positioned into the end cap structure 1600 such that the lever 1670 will contact the thrust member 1610 and the follower hook 1672 will be proximate the follower directing wall 1640 . The spring follower hook 1672 of the cam follower 1606 is employed to lift the bent end 1702 of the cam follower spring 1608 onto the lever 1670 . The pivot structure 1604 is then pushed through the slotted pivot aperture 1680 . The hollow thrust member 1610 , which is a washer in the embodiment illustrated, is positioned in the second U-shaped aperture 1662 in the thrust flange 1642 and the pivot structure 1604 is pushed entirely through the end cap structure 1600 and secured in place with the threaded nut 1628 . [0136] With additional reference to FIGS. 27, 31 and 32 , when fasteners F are to be loaded into the magazine assembly 20 , the tool operator presses the engagement surface 1390 of the actuating lever 1310 to move the follower structure 1002 downward toward the end cap structure 1600 . The ramped portion 1650 of the follower directing wall 1640 directs the follower leg 1322 a of the follower structure 1002 toward the cam follower 1606 and the flat portion 1654 of the follower directing wall 1640 ensure that proper contact is established and maintained between the loading cam 1306 and the cam follower 1606 . [0137] When the first loading cam portion 1350 of the loading cam 1306 contacts the leg member 1692 of the follower hook 1672 on the cam follower 1606 , the ramp of the first loading cam portion 1350 pushes the follower hook 1672 in a side-to-side motion along the axis of the pivot structure 1604 in the direction of Arrow R (FIG. 43), permitting the leg member 1692 to travel over the first loading cam portion 1350 and into the oval follower capturing portion 1360 of the second loading cam portion 1352 of the loading cam 1306 . With the leg member 1692 being positioned in the oval follower capturing portion 1360 , the follower structure 1002 cannot be moved further down the magazine housing 1010 . When pressure on the engagement surface 1390 of the actuating lever 1310 is released, the force generated by the follower spring 1004 is employed to lift the follower structure 1002 within the magazine housing 1010 so as to simultaneously cause the cam follower 1606 to pivot about the axis of the pivot structure 1604 , thereby permitting the leg member 1692 to travel through the intermediate portion 1362 and into the catch portion 1364 of the second loading cam portion 1352 of the loading cam 1306 . When the leg member 1692 is positioned in the catch portion 1364 of the loading cam 1306 , the leg member 1692 extends through the catch aperture 1368 and around the follower leg 1322 a of the follower structure 1002 thereby securely coupling the cam follower 1606 to the follower structure 1002 and inhibiting upward travel of the follower structure 1002 within the magazine housing 1010 . In this condition, fasteners F may be readily loaded into the magazine assembly 20 . [0138] If the magazine assembly 20 is not already coupled to the fastening tool portion 30 , this operation is performed next. This is accomplished by positioning the top end of the magazine assembly 20 relative to the nose assembly 40 such that the holes in the guide ports 1100 are proximate an associated one of the magazine guide posts 66 , the stop member 134 on the trigger lever 54 is positioned directly above the first portion 1052 of the L-shaped pin aperture 1050 , and the head portion 322 of the clamp pin 300 is engaged to the circular portion 1232 of the slotted pin aperture 1230 in the base 1220 of the bracket structure 1202 . The actuating cam 306 is then pushed toward the clamp boss 252 to compress the compression spring 302 and extend the clamp pin 300 in an outward direction so that the second body section 326 of the clamp pin 300 extends through the slotted pin aperture 1230 . With the clamp pin 300 in this condition, the magazine assembly 20 is slid upwardly until the clamp pin 300 is fully positioned into the slotted portion 1234 of the slotted pin aperture 1230 . Simultaneously, the guide ports 1100 are slid further onto the magazine guide posts 66 so that the top of the magazine assembly 20 cannot pivot relative to the nose assembly 40 and the stop member 134 on the trigger lever 54 is disposed in the second portion 1054 of the L-shaped pin aperture 1050 . [0139] Thereafter, the tool operator releases the actuating cam 306 , causing the compression spring 302 to retract the clamp pin 300 somewhat so that the first body section 324 of the clamp pin 300 is disposed within the slotted portion 1234 of the slotted pin aperture 1230 . In this condition, the parallel flats 328 that are formed onto the first body section 324 abut the parallel sides of the slotted portion 1234 of the slotted pin aperture 1230 , thereby permitting the magazine assembly 20 to be slid along an axis defined by the magazine guide posts 66 and the slotted portion 1234 of the slotted pin aperture 1230 . The magazine assembly 20 is pushed upwardly into contact with the magazine flange 64 that is formed into the nose structure 50 . The actuating cam 306 is then pivoted to place the leg portion 352 in contact with the flat contact surface 344 . More specifically, the frusto-conical abutting face 330 of the head portion 322 of the clamp pin 300 engages the conical detent 1238 that is formed into the end of the slotted portion 1234 to both locate the magazine assembly 20 relative to the tool portion 30 as well as to mechanically lock the clamp pin 300 to the coupling bracket 1014 . [0140] In this condition, the compression spring 302 exerts a clamping force that is transmitted through the clamp pin 300 to fixedly but removably couple the coupling bracket 1014 to the clamp boss 252 . The magazine stabilizing tabs 62 extend downwardly from the magazine flange 64 and abut the opposite sides of the fastener body portion 1028 of the magazine housing 1010 to inhibit excessive rotation of the magazine assembly 20 relative to the nose assembly 40 . [0141] With the magazine assembly 20 attached, the fasteners F are fed into the magazine assembly 20 such that the body B of the fasteners F enter the follower cavity 1040 via the slot 1042 . Typically, the fasteners F are collated (usually at an angle of 20° or 31°) in “sticks”, which permits the magazine assembly 20 to be loaded relatively rapidly. [0142] The follower structure 1002 is released from the cam follower 1606 by pressing downwardly on the engagement surface 1390 of the actuating lever 1310 . The body portion 1690 of the follower hook 1672 rides on the upper surface of the forwardly and upwardly extending catch portion 1364 , causing the cam follower 1606 to rotate forwardly. The simultaneous downward movement of the follower structure 1002 and the forward rotation of the cam follower 1606 continues until the leg member 1692 slips out of the catch portion 1364 and the body portion 1690 of the follower hook 1672 slides onto the third loading cam portion 1354 of the loading cam 1306 . As the leg member 1692 of the follower hook 1672 is not contacting the side of the leg 1322 a of the follower structure 1002 , the follower spring 1004 exerts a force against the lever 1670 that pushes the follower hook 1672 in a side-to-side motion so that the lever 1670 abuts the thrust member 1610 . With the body 1690 of the follower hook 1672 engaged against the third loading cam portion 1354 of the loading cam 1306 , the body 1690 of the follower hook 1672 prevents the cam follower 1606 from engaging the follower structure 1002 and the upward motion of the follower structure 1002 is controlled by the follower spring 1004 . The upward movement of the follower structure 1002 brings the tip portion 1330 of the front guide tab 1302 into contact with the bottom-most fastener F in the magazine assembly 20 which urges the fasteners F upwardly and into the nose assembly 40 . The force exerted by the follower structure 1002 onto the fasteners F, along with the configuration of the fastener head portion 1022 , ensures that fasteners F will not slip rearwardly out of the magazine assembly 20 during the operation of the tool 10 . [0143] As discussed above, the tool operator must push the contact trip 52 against the workpiece to cause the trigger lever 54 to push the secondary trigger 128 in to contact with the trigger valve 130 to permit the state of the trigger valve 130 to be changed. With the magazine assembly 20 fully engaged against the magazine flange 64 , the stop member 134 on the trigger lever 54 is free to move in a direction parallel to the longitudinal axis of the tool 10 (i.e., rearwardly-forwardly) within the second portion 1054 of the L-shaped pin aperture 1050 . [0144] In the event of a “jam” condition wherein fasteners F have not fed properly through the nose assembly 40 , the tool operator need only rotate the actuating cam 306 such that its base portion 350 is abutted against the flat contact surface 344 to release the clamping force that is exerted through the clamp pin 300 . The magazine assembly 20 may then be slid downwardly from the magazine flange 64 to permit the tool operator to service the nose assembly 40 . The magazine assembly 20 , however, is constrained by the magazine guide posts 66 and the clamp pin 300 so that it can only move in a predetermined linear direction. The predetermined linear direction is cooperatively defined by the magazine guide posts 66 , which remain engaged in the holes 1800 in the guide ports 1100 , and the first body section 324 of the clamp pin 300 , which remains engaged in the slotted portion 1234 of the slotted pin aperture 1230 . Downward movement of the magazine assembly 20 is checked when the first body section 324 of the clamp pin 300 contacts the necked-down slotted portion 1236 of the slotted pin aperture 1230 . Accordingly, the nose assembly 40 may be serviced without completely removing the magazine assembly 20 from the magazine flange 64 . Furthermore, when the magazine assembly 20 is moved downwardly into this condition, the stop member 134 is moved out of the second portion 1054 of the L-shaped pin aperture 1050 and into the first portion 1052 of the L-shaped pin aperture 1050 . With the stop member 134 located in this manner, rearward motion of the contact trip 52 relative to the nose body 60 is limited such that the stop member 134 contacts the rearward edge 1820 of the first portion 1052 of the L-shaped pin aperture 1050 , thereby preventing the trigger lever 54 from pushing the secondary trigger 128 sufficiently rearward so that the state of the trigger valve 130 cannot be changed (i.e., actuated). Accordingly, the stop member 134 and the L-shaped pin aperture 1050 cooperate to selectively prevent the trigger valve 130 from being actuated depending upon the position of the magazine assembly 20 relative to the magazine flange 64 . [0145] Those skilled in the art will understand that as fasteners F are dispensed from the tool 10 , the follower spring 1004 will force the follower structure 1002 in an upwardly direction so as to continue to feed fasteners F into the nose body 60 . When the magazine assembly 20 is empty of fasteners F, the follower structure 1002 will be raised within the magazine housing 1010 to a point wherein the lock-out dog 1304 extends through the lock-out dog aperture 90 that is formed into the magazine flange 64 so that it inhibits sufficient rearward motion of the contact trip 52 so as to prevent the trigger lever 54 from changing the state of the trigger valve 130 . Accordingly, the lock-out dog 1304 inhibits the tool 10 from cycling when the magazine assembly 20 is empty of fasteners F and coupled to the magazine flange 64 . [0146] In an alternate embodiment of the present invention illustrated in FIGS. 46 and 47, the nose assembly 40 includes a pivoting lock-out tab 2000 that is rotatably coupled to the nose structure 50 and pivotable between a first position, which is illustrated in FIG. 47, that permits the contact trip 52 to move rearwardly a sufficient amount that permits the trigger lever 54 to change the state of the trigger valve 130 , and a second position, which is shown in FIG. 46, that inhibits rearward motion of the contact trip 52 by an amount wherein the trigger lever 54 cannot change the state of the trigger valve 130 . As illustrated in FIG. 47, when the magazine assembly 20 abuts the magazine flange 64 , the top surface 2010 of the magazine housing 1010 contacts the lock-out tab 2000 and rotates it into the first position. When the magazine assembly 20 is not abutted against the magazine flange 64 as illustrated in FIG. 46, however, the lock-out tab 2000 is rotated by a torsion spring (not specifically shown) into the second position to prevent the tool 10 from being cycled. [0147] While the invention has been described in the specification and illustrated in the drawings with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention as defined in the claims. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment illustrated by the drawings and described in the specification as the best mode presently contemplated for carrying out this invention, but that the invention will include any embodiments falling within the foregoing description and the appended claims.
A magazine assembly for a fastening tool. The magazine assembly slides on guide posts that are formed into the nose assembly of the fastening tool and is clamped to the fastening tool via a magazine clamp assembly that requires no tools to operate. The magazine clamp assembly may be partially released to permit the magazine assembly to be partially withdrawn from the nose assembly so that the nose assembly may be maintained without the complete removal of the magazine assembly. The construction of the nose assembly is such that when the magazine assembly is placed in a partially withdrawn state, a portion of the nose assembly mechanically inhibits actuation of the fastening tool trigger system.
96,186
BACKGROUND OF THE INVENTION The present invention relates generally to an analog electronic timepiece in which optical pointers indicate the time with the aid of liquid crystal or the like, and more particularly to an analog electronic clock which can display a short pointer separately even when both short and long pointers are superimposed. In a clock where the time is indicated analogously with the aid of liquid crystal, for instance, a part of the displaying segment for the long pointer is used also as the displaying segment for the short pointer and then the long and short pointers are displayed in the same width. Thus, when the displayed segments for the long and short pointers are superimposed once an hour, by way of example at the time 1:05 as shown in FIG. 6, the short pointer does not appear on the clock and the long pointer is displayed alone. In such a case a glance at the clock often leads to the misunderstanding that it might be malfunctioning or have failed. SUMMARY OF THE INVENTION An object of the present invention is to provide a novel analog electronic timepiece in which a plurality of optical displaying elements having the form to display both long and short pointers are disposed radially, the time is indicated through the display of the long and short pointers in response to clocking output, and either of the short pointer displaying segments adjacent to the segment that otherwise should be displayed lights up when the long and short pointers to be displayed are superimposed, thereby enabling to be indicated the time in a natural manner with ease to see. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a plan view showing an embodiment of a display device used in the present invention; FIG. 2 is a block diagram of an electric circuit for operating the display device; FIG. 3 is a logic circuit diagram showing the principal part of FIG. 2 in more detail; FIGS. 4 and 5 are front views showing embodiments for indicating the time according to the present invention; and FIG. 6 is a front view showing the manner of indicating the time in the prior art when the displaying segments for the long and short pointers to be lighted up are superimposed. DESCRIPTION OF THE PREFERRED EMBODIMENT In the following a preferred embodiment of the present invention is described with reference to the drawings. FIG. 1 shows a liquid crystal display device, in which two glass plates 1 and 2 are disposed oppositely and liquid crystal is interposed therebetween. 60 pieces of segment electrodes S 0 -S 59 each of which is in the form of pointers are provided radially on the glass plate 1, and in opposition to the segment electrodes are provided common electrodes C 1 and C 2 ring form at outer and inner sides on the other glass plate 2, respectively. A liquid crystal displaying element for a short pointer consists of each segment electrode, the common electrode C 2 and the liquid crystal located therebetween, while a liquid crystal displaying element for a long pointer consists of each segment electrode, the common electrodes C 1 , C 2 and the liquid crystal located therebetween. The common electrodes C 1 , C 2 and the segment electrodes S 0 -S 59 have lead wires l 1 , l 2 and e 0 -e 59 respectively and signal voltage as described hereinafter is supplied to each terminal of the lead wires. FIG. 2 shows a circuit diagram for clocking electronically and then lighting up the liquid crystal display device illustrated in FIG. 1 in response to a clocking output. A clock pulse generator 3 produces a series of pulses at the interval of 1 minute and the clocking for minute order is made at a counter 4. A counter 5 receives the clocking output at the interval of 12 minutes from the counter 4 and carries out the clocking for hour order. A decoder 6 receives the output from the counter 4 and generates a pulse at each terminal of p 0 , p 1 , . . . , p 58 and p 59 in turn for each 1 minute, while a decoder 7 generates a pulse at each terminal of q 0 , q 1 , . . . , q 58 and q 59 in turn for each 12 minutes. A control circuit 8 receives the outputs from the decoders 6 and 7 and generates an output to light up the short pointer displaying element with shift in its position when the displaying elements for the long and short pointers to be lighted up are superimposed. A voltage supply circuit 9 for the liquid crystal display device consists of analog switches, for example, and analog switches 9a-9h are provided to connect with terminals p 0 -p 59 and r 0 -r 59 respectively. Each analog switch turns on when a selective output is applied to the corresponding terminal and either of the voltages applied on terminals N 1 and N 2 is then produced at one of terminals e 0 -e 59 . When the selective output is not applied to any terminal, the analog switches 9a-9h are kept off. FIG. 3 shows the control circuit 8 illustrated in FIG. 2 in more detail, in which the reference numbers 10-12 designate AND gate circuits, 13-15 designate inhibit gate circuits and 16-17 designate OR gate circuits. The operation will be described hereinafter. To simplify the followed description, it is assumed here that the liquid crystal display device lights up at the voltage over Vo, voltages 0 and Vo are applied on the terminals l 1 and l 2 of the common electrodes C 1 and C 2 , and voltages 2 Vo and Vo are applied on the terminals N 1 and N 2 , respectively. Now, since the selective output is produced at one of the terminals p 0 -p 59 of the decoder 6 every 1 minute clocking by the counter 4 in turn, the analog switches 9a, 9b . . . 9c and 9d in the voltage supply circuit 9 turn on correspondingly in due order and the applied voltage 2 Vo on the terminal N 1 is given to each terminal of the segment e1 electrodes S 0 -S 59 shown in FIG. 1 by turns. This lights up the selected displaying element by applying the voltages Vo, 2 Vo across its segment electrodes and common electrodes C 1 , C 2 , respectively. In such a manner, the long pointer or the minute pointer is advanced step by step at intervals of 1 minute. When the short and long pointers are not superimposed, the short pointer is displayed as follows: the counter 5 changes its output every 12 minutes and then the selective output is produced at each terminal q 0 -q 59 of the decoder 7 by turns. However, the displayed position of the short pointer is superimposed with that of the long pointer 12 times for its every turn at each of the following times: 12:00, 1:05, 2:10, 3:16 4:21, 5:27,6:32, 7:38, 8:43, 9:49, 10:54 and 11:59. The circuit diagram of FIG. 3 is arranged so as to display the short pointer adjacent to one otherwise to be displayed without lighting up the displaying element for the latter. At the time except for the above, since the levels at the terminals p 0 and q 0 , p 5 and q 5 , p 10 and q 10 . . . of the decoders 6 and 7 never show logic "1" simultaneously, the inhibit gate circuits 13,14,15 . . . are opened and then the selective outputs given at the terminals q 0 , q 5 , q 10 . . . pass through them. Thus, when both pointers are not superimposed, each selective output comes out at the corresponding terminal and the analog switches 9e,9f, . . . 9h turn on in due order, thereby introducing the voltage Vo applied on the terminal N 2 to the terminal of the segment electrode. Then, the voltage 0 is applied across the outer common electrodes C 1 and the opposing segment electrode, and the voltage Vo is applied across the inner electrode C 2 and the opposing electrode. As a result, the displaying element opposing to the inner electrode C 2 or the same for the short pointer is lighted up alone. In the following, the operation will be described when the positions of both pointers to be displayed are superimposed, taking 1:15 as an example. At the time of 1:05, the selective outputs are produced from the terminal p 5 , q 5 of the decoders 6 and 7. Accordingly, the output from the inhibit circuit 14 shown in FIG. 3 is blocked and an output is produced at a terminal r 6 of the OR gate circuit 16 simultaneously. The output from the terminal r 6 produces the voltage for displaying the short pointer at the terminal e 6 of the voltage supply circuit 9, while the output from the terminal p 5 produces the voltage for displaying the long pointer at the terminal e 3 of the voltage supply circuit 9. As a result, the time 1:05 is indicated with the shift of the displayed position of the short pointers S from that of the long pointers L in a natural manner, as shown in FIG. 4. At the time 1:06, outputs are produced from the terminals p 6 and q 5 and this makes the output logic from the AND gate 11 in FIG. 3 into "0" and then the output is produced from the terminal r 5 of the inhibit gate circuit 14, while stopping the output from the OR gate circuit 16. Therefore, the time 1:06 is indicated normally as shown in FIG. 5. Similarly, at each time as indicated above in which the positions of both pointers to be displayed are superimposed, the time is indicated with the short pointer advancing by one step temporarily. However, at the time 12:00, only the long pointer is displayed due to the fact that the shift in displayed position of the short pointers would look rather strange. More specifically, the outputs produced from the terminals p 0 and q 0 at the time 12:00 make the output logic from the AND gate circuit 10 in FIG. 3 into "1" and then the output from the inhibit gate circuit 13 is blocked, while effecting the display of the long pointer through the output from the terminal p o alone. At any time except for the aforementioned each time when the displayed position of the pointers are superimposed, the outputs appeared which appear on the respective terminals q 0 . . . q 59 of the decoder 7 are directly produced at the respective terminals r 0 . . . r 59 of the control circuit 8, so that the display of the short pointer is effected. Though the aforementioned explanation has been made with respect to the embodiment in which the display of the short pointer is effected by turning on the position immediately after the superimposed displayed position, in the case that the displayed positions are superimposed at a time during from 7:38 till 11:59, it may be also possible to turn on the position immediately before the superimposed displayed position. In this case, a part of the circuit shown in FIG. 3 should be modified. This is achieved by connecting each OR gate circuit to the terminal just prior to one at which both pointers are superimposed. Taking the gate circuits 11, 14 and 16 as an example, although the terminal inputs are not same, the above modification can be made by removing the OR gate circuit 16, connecting the terminals q 6 to the terminal r 6 directly and providing an OR gate circuit so that it receives the outputs from the AND gate circuit 11 and the terminal q 4 and produces its output at the terminal 4. This explanation is made referring to the terminal numbers different from the practice, but the modified circuit can be similarly arranged from the terminals corresponding to the above each time after 7:38, too. Furthermore, it is a matter of course that the form of electrode used in the display device, wiring system for leads and others are not restricted to the afore-mentioned embodiment. As will be clear from what has been described heretofore, according to the present invention, the short pointer is displayed with a shift in its position temporarily when the long and short pointers to be displayed are superimposed, thereby enabling to indicate the time in a natural manner with ease to see.
In an analog electronic timepiece where a plurality of optical displaying elements in the form of pointers are disposed radially and the pointers are displayed optically in response to a clocking output, the short pointer is displayed separately by lighting up either one of the short pointer displaying segments adjacent to the lighted long pointer displaying segment in order to prevent the long pointer from being displayed alone when the displaying segments for the long and short pointers to be lighted up coincide thereby enabling the long and short pointers to be easily distinguished.
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CROSS REFERENCE TO RELATED APPLICATIONS This application is a divisional of U.S. patent application Ser. No. 09/923,924 filed Aug. 6, 2001, now U.S. Pat. No. 7,406,539, which claims the benefit of U.S. Provisional Applications No. 60/241,450, filed Oct. 17, 2000 and 60/275,206 filed Mar. 12, 2001, and is a continuation-in-part of U.S. application Ser. No. 09/903,441, filed Jul. 10, 2001, now U.S. Pat. No. 7,080,161, and is a CIP of Ser. No. 09/903,423, filed Jul. 10, 2001, now U.S. Pat. No. 7,363,367 which are all hereby incorporated by reference in their entireties. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to the field of networking. In particular, the invention relates to prioritizing and queuing updated routing information. 2. Description of the Related Art Internetworks such as the Internet currently comprise Autonomous Systems, which exchange routing information via exterior gateway protocols. Amongst the most important of these protocols is the Border Gateway Protocol, or BGP. BGPv4 constructs a directed graph of the Autonomous Systems, based on the information exchanged between BGP routers. Each Autonomous System in identified by a unique 16 bit AS number, and, by use of the directed graphs, BGP ensures loop-free routing amongst the Autonomous Systems; BGP also enables the exchange of additional routing information between Autonomous Systems. BGP is further described in several RFCs, which are compiled in The Big Book of Border Gateway Protocol RFCs , by Pete Loshin, which is hereby incorporated by reference. The Border Gateway Protocol provides network administrators some measure of control over outbound traffic control from their respective organizations. For instance, the protocol includes a LOCAL_PREF attribute, which allows BGP speakers to inform other BGP speakers within the Autonomous System of the speaker's preference for an advertised route. The local preference attribute includes a degree of preference for the advertised route, which enables comparison against other routes for the same destination. As the LOCAL_PREF attribute is shared with other routers within an Autonomous System via IBGP, it determines outbound routes used by routers within the Autonomous System. A WEIGHT parameter may also be used to indicate route preferences; higher preferences are assigned to routes with higher values of WEIGHT. The WEIGHT parameter is a proprietary addition to the BGPv4 supported by Cisco Systems, Inc. of San Jose, Calif. In typical implementations, the WEIGHT parameter is given higher precedence than other BGP attributes. The performance knobs described above are, however, rather simple, as they do not offer system administrators with sufficiently sophisticated means for enabling routers to discriminate amongst routes. There is a need for technology that enables greater control over outbound routing policy. In particular, there is a need to allow performance data about routes to be exchanged between routers. Additionally, system administrators should be able to fine tune routing policy based upon sophisticated, up-to-date measurements of route performance and pricing analysis of various routes. SUMMARY OF THE INVENTION The invention includes routing intelligence for evaluating routing paths based on performance measurements. In some embodiments of the invention, the routing intelligence may include processes executed in a self-contained device. This device may control one or more edge routers, based on performance data from end users. In other embodiments of the invention, the routing intelligence device may be used solely to monitor one or more edge routers, producing reports but not effecting any changes to routing. Routing decisions may be injected to the edge routers via BGP updates. The devices may be stationed at the premises of a multihomed organization, such as an enterprise, ISP, government organization, university, or other organization supporting a sub-network coupled to an internetwork. In other embodiments, the routing intelligence comprises processes executed on a router. In some embodiments, the routing intelligence unit may be a self-contained device controlling a single edge router. In other embodiments, a single routing intelligence unit controls multiple edge routers. Though the collection of routers is coupled to one or more Internet Service Provider (ISP) links, the individual routers may be coupled to one or more ISP links, or to no ISP links. In some embodiments of the invention, the routing intelligence unit includes a main memory database for storing information on network prefixes. In some embodiments, a plurality of geographically dispersed routing intelligence devices are coupled to a Routing Intelligence Exchange (RIX), which transmits performance data for network prefixes between the routing intelligence devices. These and other embodiments are described further herein. BRIEF DESCRIPTION OF THE FIGURES FIG. 1-FIG . 4 illustrate different configurations of routing intelligence units and edge routers, according to some embodiments of the invention. FIG. 5 schematically illustrates an internal architecture of a routing intelligence unit according to some embodiments of the invention. FIG. 6 illustrates a queuing and threading structure used in the routing intelligence unit in some embodiments of the invention. DETAILED DESCRIPTION A. System Overview In some embodiments of the invention, one or more routing intelligence units are stationed at the premises of a multi-homed organization, each of which controls one or more edge routers. These devices inject BGP updates to the Edge Routers they control, based on performance data from measurements obtained locally, or from a Routing Intelligence Exchange—Routing Intelligence Exchanges are further described in U.S. applications 60/241,450, 60/275,206, Ser. Nos. 09/903,441, and 09/903,423 which are hereby incorporated by reference in their entirety. Different configurations of these routing intelligence units and edge routers are illustrated in FIGS. 1 through 4 . In some embodiments illustrated in FIG. 1 , one edge router 102 with multiple ISPs 104 and 106 is controlled by a single device 100 . FIG. 2 illustrates embodiments in which the routing intelligence unit 200 controls multiple edge routers 202 and 204 , each of which in turn links to multiple ISPs 206 , 208 , 210 , and 212 ; FIG. 2 also illustrates embodiments in which routers 203 205 controlled by the routing intelligence unit 200 are not coupled to SPALs. In FIG. 3 , a single routing intelligence unit 300 controls multiple edge routers 302 and 304 , each of which is linked to exactly one ISP 306 and 308 . In additional embodiments illustrated in FIG. 4 , different routing intelligence units 400 and 402 , each connected to a set of local edge routers 404 , 406 , 408 , and 410 , may coordinate their decisions. In some embodiments of the invention, the routing intelligence units comprise processes running within one or more processors housed in the edge routers. Other configurations of routing intelligence units and edge routers will be apparent to those skilled in the art. B. Architecture of Routing Intelligence Units The routing intelligence units include a Decision Maker resource. At a high level, the objective of the Decision Maker is to improve the end-user, application level performance of prefixes whenever the differential in performance between the best route and the default BGP route is significant. This general objective has two aspects: One goal is to reach a steady state whereby prefixes are, most of the time, routed through the best available Service Provider Access Link (i.e., SPAL), that is, through the SPAL that is the best in terms of end-to-end user performance for users belonging to the address space corresponding to that prefix. To achieve this goal, the Decision Maker will send a significant amount of updates to the router (over a tunable period of time) until steady state is reached. This desirable steady state results from a mix of customer-tunable criteria, which may include but are not limited to end-to-end user measurements, load on the links, and/or cost of the links. Current measurements of end-to-end user performance on the Internet show that fluctuations in performance are frequent. Indeed, the reasons for deterioration of performance of a prefix may include, but are not limited to the following: The network conditions can vary along the path used by the packets that correspond to that prefix on their way to their destination. Alternatively, the access link through which the prefix is routed can go down. The Service Provider to which the prefix is routed can lose coverage for that prefix. In such occurrences, the routing intelligence unit should detect the deterioration/failure, and quickly take action to alleviate its effect on the end-user. In order to optimize application performance, the routing intelligence unit converts measurements on the performance of routes traversing the edge-routers into scores that rate the quality of the end-to-end user experience. This score depends on the application of interest, namely voice, video and HTTP web traffic. In some embodiments of the invention, by default, the routing intelligence unit attempts to optimize the performance of web applications, so its decisions are based on a score model for HTTP. However, in such embodiments, the customer has the choice between all of voice, video, and HTTP. In order to avoid swamping routers with BGP updates, in some embodiments of the invention, the maximum rate of update permitted by the prefix scheduler is offered as, for example, a control, such as a knob that is set by the customer. The faster the rate of updates, the faster the system can react in the event of specific performance deteriorations or link failures. However, the rate of updates should be low enough not to overwhelm the router. In some embodiments, the selected rate will depend on the customer's setting (e.g., the traffic pattern, link bandwidth, etc.); for example, faster rates are reserved to large enterprises where the number of covered prefixes is large. Even when the rate of updates is slow, in some embodiments of the invention, the most urgent updates are still scheduled first: this is performed by sorting the prefix update requests in a priority queue as a function of their urgency. The priority queue is then maintained in priority order. The most urgent events (such as loss of coverage, or link failure) bypass this queue and are dealt with immediately. In case interface statistics are available, the Decision Maker may directly use the corresponding information to function in an optimized way. For example, in some embodiments of the invention, the Decision Maker can use bandwidth information to make sure that a link of lower bandwidth is not swamped by too much traffic; in a similar manner, link utilization can be used to affect the rate of BGP updates sent to the router. Finally, the prefix scheduler may use per-link cost information, as provided by the user to tailor its operation. For example, assume that the router is connected to the Internet through two links: Link 1 is a full T3, while Link 2 is a burstable T3, limited to 3 Mbit/sec. That is, whenever load exceeds the 3 Mbit/sec mark on Link 2, the user incurs a penalty cost. Combining information pertaining to per-link cost and utilization, the Decision Maker can attempt to minimize the instances in which load exceeds 3 Mbit/sec on Link 2, thus resulting in reduced costs to the user. In some implementations, the Decision Maker may also use configurable preference weights to adjust link selection. The cost of carrying traffic may vary between links, or a user may for other reasons prefer the use of certain links. The Decision Maker can attempt to direct traffic away from some links and towards others by penalizing the measurements obtained on the less preferred links; this encourages use of the preferred links, but still allows the less preferred links to carry any traffic which receives great benefit. Even though information about SPALs (e.g., the bandwidth and utilization of each of the access links) and prefixes (e.g., the load profile of a particular prefix) is valuable and can be used effectively (as described above) to achieve a more optimal results (according to the algorithm's objective), the Decision Maker is designed to work well even if the only available information is provided by edge stats measurements. In case the routing intelligence unit fails, the design is such that the edge router falls back to the routing that is specified in the BGP feed. The same behavior occurs in case performance routes fail. Finally, in some embodiments of the invention, a flapping control algorithm is included in the design, avoiding the occurrence of undesirable excessive flapping of a prefix among the different access links. A diagram showing the high-level architecture of Routing Intelligence Unit, and focused on its BGP settings is shown in FIG. 5 . In the embodiments illustrated in FIG. 5 , three BGP peering types may exist between a given Routing Intelligence Unit 500 and the external world: one to control the local edge router or routers 502 that this particular Routing Intelligence Unit 500 is optimizing, one to a Routing Infrastructure Exchange (RIX) 504 , and one to every other Routing Intelligence Unit device with which it coordinates 506, as further described in U.S. applications 60/241,450, 60/275,206, Ser. Nos. 09/903,441, and 09/903,423, which are hereby incorporated by reference in their entirety. In the diagram shown in FIG. 5 , the three external peering types are shown as the arrows at far left (to the Edge Routers 502 and to RIX 504 ) and far right 506 . In order for BGP updates to be propagated to the appropriate devices, some devices are configured to be route reflectors, and others as route reflector clients. In some embodiments of the invention, the Decision Maker is a reflector client on all its iBGP peering types. C. Queuing Architecture A diagram showing the high level mechanics of the decision maker prefix scheduler is shown in FIG. 6 . As illustrated in FIG. 6 , two threads essentially drive the operation of the scheduler. The first thread 600 polls the database for changes in terms of per-SPAL performance, load, or coverage, and decides on which prefix updates to insert in a Priority Queue that holds prefix update requests. The second thread 602 takes items out of the queue in a rate-controlled fashion, and converts the corresponding update requests into an appropriate set of NLRIs (Network Layer Reachability Information) that it sends to the local routers, and an appropriate set of NLRIs that it sends to the back channel for communication to other Routing Intelligence Units. In the following, we describe each thread separately. In the description, we will refer to tables in the database, and to fields within these tables. The contents of this database are also explicated in U.S. applications 60/241,450, 60/275,206, Ser. Nos. 09/903,441, 09/903,423 which are hereby incorporated by reference in their entirety. Thread 1 This first thread 600 polls the database for changes in terms of per-SPAL performance, load, or coverage, and decides on which prefix updates to insert in a Priority Queue that holds prefix update requests. In some embodiments of the invention, such changes are checked for in 2 passes. The first pass looks for group level changes, wherein a group comprises an arbitrary collection of prefixes. Groups are also described in U.S. applications 60/241,450, 60/275,206, Ser. Nos. 09/903,441, 09/903,423 which are hereby incorporated by reference in their entirety. In case a significant change in performance for a group is noticed, the group is unpacked into its individual prefixes; the corresponding prefixes are checked and considered for insertion in the priority queue. The second pass captures prefixes for which there are no group-level performance changes. The circumstances under which an update request for a prefix is made may include any one or more of the following: 1. In case a significant change in its performance score is witnessed on at least one of its local SPALs. 2. In case a significant change in its performance score is witnessed on a foreign SPAL (that is, a SPAL that is controlled by a different Routing Intelligence Unit box in a coordinated system). 3. In case any of the local SPALs becomes invalid. 4. In case an update pertaining to this prefix was received from the router. Note that measurements reside at the group level; hence, Check 1 can be done in the first pass. On the other hand, all of Checks 2 , 3 , and 4 are prefix-specific and may be performed in Pass 2 : indeed, foreign performance updates are transferred through the back channel in BGP messages, and hence correspond to particular prefixes. Also, SPALs may become invalid for some, and not necessary all prefixes in a group. Finally, updates from the router relate to the change of winner SPALs for some prefixes, or to the withdrawal of other prefixes. (In fact, any information that is transferred by BGP relates to prefixes.) Pass 1 : In some embodiments of the invention, in the first pass, an asynchronous thread goes through all groups in the GROUP_SPAL table, checking whether the NEW_DATA bit is set. This bit is set by the measurement listener in case a new measurement from a/32 resulted in an update of delay, jitter, and loss in the database. Delay, jitter, and loss, also denoted as d, v, and p, are used to compute an application-specific score, denoted by m. The scalar m is used to rate application-specific performance; MOS stands for “Mean Opinion Score”, and represents the synthetic application-specific performance. In embodiments of the invention, MOS may be multiplied by a degradation factor that is a function of link utilization, resulting in m. (That is, the larger the utilization of a given SPAL, the larger the degradation factor, and the lower the resulting m.) In embodiments of the invention, users of the device may also configure penalty factors per SPAL. Non-limiting examples of the uses of such penalty features include handicapping some links relative to others, to achieving cost control, or accomplishing other policy objectives. As a non-limiting example, Provider X may charge substantially more per unit of bandwidth than Provider Y. In such a situation, the penalty feature allows the user to apply an m penalty to SPAL X. This will cause Provider Y to receive more traffic, except for those prefixes in which the performance of Provider X is substantially better. One implementation of this embodiment is to subtract the penalty for the appropriate SPAL after m is computed. Other implementations of the penalty feature will be apparent to those skilled in the art. Even when NEW_DATA is set, the variation in d, v, and p can be small enough so that the change in the resulting scalar m is insignificant. Hence, in some embodiments of the invention, the prefix is only considered for insertion in the queue in case the change in m is significant enough. The corresponding pseudo-code is shown below. for each group { // First pass: only consider groups for which there is a change in the group pref data compute_winner_set = 0; for each spal (<> other) { // check whether there is new data for this group if (new_data(group, spal) = = 1) { compute m (spal, d, v, p, spal-penalty), store in local memory new_data(group, spal) = 0; if (significant change in m) { store m (spal, d, v, p) in group_spal compute_winner_set = 1; break; } } } if (compute_winner_set) for each prefix schedule_prefix(prefix) // see below In some embodiments of the invention, rolling averages are used to update measurements of delay, jitter, and loss, i.e., d =alpha* d +(1−alpha)* d new v =beta* v +(1−beta)* v new p =gamma* p +(1−gamma)* p new, where dnew, vnew, pnew represent the new delay, jitter, and loss measurements. Algorithms for calculating MOS for HTTP (1.0 and 1.1) and for voice and video are also presented in U.S. Provisional Application 60/241,450, filed Oct. 17, 2000 and 60/275,206 filed Mar. 12, 2001. Values used for the models employed by these algorithms in embodiments of the invention are presented in an XML format below. Note that since MOS is computed per group, a selection from the sets of the following parameters may be made to allow different optimization goals for each group. <module> <engine slot=”1”> <application model=”http1.0” [alpha=”0.9” beta=”0.9” gamma=”0.9” theta=”1.18” phi=”0.13” omega=”0.15” psi=”0.25”] /> </engine> </module> <module> <engine slot=”1”> <application model=”http1.1” [alpha=”0.9” beta=”0.9” gamma=”0.9” theta=”1 .3” phi=”0.31” omega=”0.41” psi=”1.0”] /> </engine> </module> <module> <engine slot=”1”> <application model=”voice” [alpha=”0.9” beta=”0.9” gamma=”0.9” theta =”1 .5” phi=”6.0” omega=”23.0” psi=”0.0”] /> </engine> </module> <module> <engine slot=”1”> <application model=”video” [alpha=”0.9” beta=”0.9” gamma=”0.9” theta=”1.0” phi=”4.0” omega=”69.0” psi=”0.0”] /> </engine> </module> The values presented above are given as examples only. Many different models for deriving MOS scores for different applications will be apparent to those skilled in the art. Pass 2 In the second pass, an asynchronous thread goes through all prefixes in the PREFIX table. For each prefix, Checks 2 , 3 , and 4 are made: NEW_INCOMING_BID in the PREFIX table indicates that a new bid was received from the coordination back channel; NEW_INVALID in the PREFIX_SPAL table indicates, for a particular (Prefix P, SPAL x) pair a loss of coverage for Prefix P over SPAL x. NEW_NATURAL_DATA indicates the receipt by Routing Intelligence Unit of an update message from a router, notifying it of a change in its natural BGP winner. In fact, the Decision Maker only asserts a performance route in case it is not the same as the natural BGP route; hence, it can potentially receive updates concerning the natural BGP winners of given prefixes from routers to which it has asserted no performance route for those prefixes. (If Routing Intelligence Unit were to assert performance routes regarding a given prefix P to all routers irrespectively of the current BGP winner for that prefix, it will never receive an update from the router pertaining to changes in the natural BGP winner for Prefix P. Indeed, the performance route would always be the winner, so the router would assume there is nothing to talk about.) The following example illustrates the usefulness of the NEW_NATURAL_DATA flag: Assume that the Decision Maker controls 3 routers, each of which controls its individual SPAL. Assume that the Decision Maker has just determined that Prefix P will move to SPAL 1 . Assume that Prefix P believes that the natural BGP route for Prefix P as saved by Router 1 is SPAL 1 , the same as its current performance assertion. The Decision Maker's logical operation is to withdraw Prefix P's last performance route (say SPAL 3 ). However, it turned out that this BGP natural route has, in fact changed to SPAL 2 ; indeed, this could have happened during the previous assertion of a performance route for Prefix P (since, in this case, as mentioned above, the Decision Maker receives no updates for Prefix P from the router, despite potential changes in Prefix P's natural BGP winner). As a result of this discrepancy, all traffic pertaining to Prefix P will be routed through SPAL 2 , the current natural BGP winner for Prefix P, which is not the desired behavior. This is the primary reason for NEW_NATURAL_DATA: as such an event occurs, the router sends an update back to the Decision Maker, communicating to it the change in natural route. The Peer Manager sees the change in natural BGP route and sets the NEW_NATURAL_DATA flag to 1; consequently, the prefix is considered for rescheduling during this pass, in Thread 1 , as described above. Note that in case of changes in the natural BGP route for a given prefix, the Decision Maker will need two passes through the Priority Queue before the prefix is routed through its appropriate performance route. Finally, the ACCEPTING_DATA bit in the prefix table is checked. ACCEPTING_DATA is set to 0 by the peer manager to notify the decision maker not to assert performance routes for this prefix. This would primarily occur in case the prefix is withdrawn from the BGP tables in all local routers. In this case, in the ROUTER_PREFIX_SPAL table, the ANNOUNCED bit would be set to 0 on all routers and all SPALs for that prefix. Clearly, a prefix is only considered for insertion in the queue in case ACCEPTING_DATA is set to 1. for each prefix { //Checks 2 and 4: scan the prefix_group table get new_bid, new_natural, and accepting_data from prefix group if (new_bid) ∥ (new_natural) { if (accepting_data) { schedule_prefix(prefix) // see below } } //Check 3: scan the prefix_spal table get new_invalid, from prefix_spal if (new_invalid) { schedule_prefix(prefix) } } Note that asserting a performance route about a prefix that does not exist in any of the routers' BGP tables could be problematic, depending on the surrounding network environment. If the set of controlled routers do not emit routes to any other BGP routers, then it is acceptable to generate new prefixes. But if any propagation is possible, there is a danger of generating an attractor for some traffic. Specifically, if the new route is the most specific route known for some addresses, then any traffic to those addresses will tend to forward from uncontrolled routers towards the controlled routers. This can be very disruptive, since such routing decisions could be very far from optimal. The mechanism can cope with this in a number of ways: Prevent any use of a prefix unknown to BGP. This is achieved using the ACCEPTING_DATA check included in some embodiments of the invention. Permit all such use, in a context where new routes cannot propagate Permit such use, but mark any new prefix with the well-known community value no-advertise to prevent propagation Permit such use, but configure the routers to prevent any further propagation (in some embodiments, by filtering such prefixes) Deciding to Insert a Prefix Update Request in the Priority Queue: the Schedule_Prefix Function Once a prefix P makes it through the checks imposed in either Pass 1 or Pass 2 , it is considered for insertion into the prefix update priority queue. schedule_prefix includes the related functionality, described below: First of all, a winner set of SPALs is re-computed for P; this set includes SPALs for which the performance is close to maximal. After the winner set W is computed for P, the decision maker determines whether the current route for P is included in W. In case of a coordinated Routing Intelligence Unit system, in some embodiments of the invention, the back channel is sent updates pertaining to Prefix P even if the local prefix update request is dropped. For example, the performance on local links could have changed dramatically since the last time a bid was sent to the back channel for this prefix; in the event of such an occurrence, an updated bid is sent to the back channel (through the BGP peering set up for this purpose). In case the current route is not part of the newly computed winner set, it is clear that Prefix P is not routed optimally. Before going ahead and inserting an update request for Prefix P in the queue, the Routing Intelligence Unit performs a check of the flapping history for Prefix P. In case this check shows that Prefix P has an excessive tendency to flap, no prefix update request is inserted in the queue. In some embodiments of the invention, before the prefix is inserted in the queue, a SPAL is chosen at random from the winner set. In case the winner set includes a remote SPAL controlled by a coordinated Routing Intelligence Unit as well as a local SPAL, the local SPAL is always preferred. Also, in some embodiments of the invention, the randomness may be tweaked according to factors pertaining to any one or more of the following: link bandwidth, link cost, and traffic load for a given prefix. Finally, the state in the database is updated, and the element is inserted in the Priority Queue. The rank of the prefix update in the priority queue is determined by computing the potential percent improvement obtained from moving the prefix from its current route to the pending winner route. At the outset, a winner set of SPALs is re-computed for P; this set includes SPALs for which the performance is close to maximal. In some embodiments of the invention, invalid SPALs are excluded from the winner set computation. Bids from remote SPALs under the control of coordinated Routing Intelligence Units may, in embodiments, be included in the winner set computation. Since the bids corresponding to such remote routes are filtered through BGP, they are in units which are compatible with iBGP's LOCAL_PREF, which in some implementations is limited to 0-255. Therefore, one possible implementation is to multiply m by 255. The converted quantity is referred to as MSLP. For consistency, the m values computed for local SPALs are also are also converted to LOCAL_PREF units. The new winner is then determined to be the set of all SPALs for which MSLP is larger than MSLP max —winner-set-threshold, where MSPL max represents the maximum MSLP for that prefix across all available SPALs, and winner-set-threshold represents a customer-tunable threshold specified in LOCAL_PREF units. The related pseudo-code is shown below. for each spal (<> other) { get invalid bit from prefix_spal if (invalid) { mark spal as invalid, not to be used in winner_set computation continue } convert m (spal) to MSLP Store MSLP in prefix_spal table } for spal=other { get MSLP_other = other_bid in prefix_group table } compute winner_set(prefix) // considers winners among all valid spals and other_bid After the winner set W is computed for P, the decision maker determines whether the current route for P is included in W. Indeed, in such a case, the performance of that prefix can't be improved much further, so no prefix update request needs to be inserted in the queue. Even though an update request for a given prefix is ignored, the Decision Maker may still send an update to the back channel in certain embodiments. For example, even though the current route for Prefix P is still part of the winner set, performance degradation could have affected all SPALs at once, in which case the bid that was previously sent to the back channel for Prefix P is probably inaccurate. In some embodiments, one may solve this problem by implementing the following: the last bid for a given prefix is saved as MY_BID in the PREFIX table; a low and high threshold are then computed using two user-configurable parameters, bid-threshold-low and bid-threshold-high. In case of a significant difference between the MSLP score on the current route and the last score sent to the back channel for that prefix (i.e., MY_BID) is witnessed (that is, if the new score falls below (1−bid-threshold-low)*100% or jumps to a value that is larger than (1+bid-threshold-high)*100% of MY_BID), a BGP message is sent to the back channel, carrying the new bid for Prefix P to remote coordinated Routing Intelligence Units. Pseudo-code illustrating the functionality described here is shown below. //First, detect non-communicated withdrawal of a prefix if winner_set only comprises remote link { for all local routers if performance route exists for that (prefix, router) pair in the ROUTER_PREFIX_SPAL table send urgent withdrawal of this route to edge router continue } get current_winner(prefix) and pending_winner(prefix) from prefix_spal table if (pending_winner != current_winner) { if (current_winner in winner_set) { update pending_winner = current_winner in database continue } if (current_winner not in winner set) && (pending_winner in winner_set) { continue } //if (current_winner not in winner_set) && (pending_winner not in winner_set) //{ //} } if (current_winner == pending_winner) { if (new_natural) { for all routers { current_route_per_router = SPAL (prefix, router, type = natural, state = latest_ON) if (current_route_per_router exists) && (current_route_per_router != current_winner) { special_route = current_route_per_router set local special_route_flag = 1; break; } } } else { current_route = current_winner } if (current_route in winner_set) ∥ (special_route == current winner) { get bid_low_threshold and bid_high_threshold from prefix_group table if ((MSLP(prefix, current_spal) < bid_low_threshold) ∥ (MSLP(prefix, current_spal) bid_high_threshold)) { compute bid_low_threshold and bid_high_threshold from MSLP (prefix) store bid_low_threshold and bid_high_threshold in prefix_group form NLRI to send to backchannel SBGP } continue } } At this point, it is clear that Prefix P is not routed optimally. In some embodiments of the invention, before proceeding with sending the update request to the edge router, the Routing Intelligence Unit performs a check of the flapping history for Prefix P. An algorithm whose operation is very close to the flapping detection algorithm in BGP monitors the flapping history of a prefix. The algorithm can be controlled by, in one embodiment, three user-controlled parameters flap_weight, flap_low, and flap_high and works as follows: the tendency of a prefix to flap is monitored by a variable denoted FORGIVING_MODE that resides in the PREFIX table. FORGIVING_MODE and other flapping parameters are updated in Thread 2 right before a performance route pertaining to Prefix P is asserted to the local routers. In case FORGIVING_MODE is set to 1, the tendency for Prefix P to flap is considered excessive, and the prefix update request is ignored. Conversely, in case FORGIVING_MODE is set to 0, Prefix P has no abnormal tendency to flap, so it is safe to consider its update request. get flapping state for prefix from prefix_group table if (excessive flapping) { continue } If a prefix survives to this point in Thread 1 , it will deterministically be inserted in the queue. Hence, all bits that were checked should be reset at this point so that some other pass on the prefixes does not reconsider and reschedule the prefix update request. For example, in case the prefix belongs to a group for which there was a significant change in m, the prefix will be considered for insertion in the queue in Pass 1 , and should not be reconsidered in Pass 2 . //reset prefix level bits, if necessary for each spal (<> other) { get new_invalid bit from prefix spal if (new_invalid) reset new_invalid to 0 in prefix_spal } get new_bid and new_natural bits from prefix_group if (new_bid) reset new_bid to 0 in prefix_group if (new_natural) reset new_natural to 0 in prefix_group In some embodiments of the invention, before the prefix is inserted in the queue, a SPAL is chosen at random from the winner set. This way, traffic is spread across more than one SPAL, hence achieving some level of load balancing. In order to achieve some set of desirable policies, randomness can be tweaked in order to favor some SPALs and disregard others. For example, in case the winner set includes a remote SPAL controlled by a coordinated Routing Intelligence Unit as well as a local SPAL, the local SPAL is always preferred. In other words, a remote SPAL is only the winner in case it is the only available SPAL in the winner set. Also, depending on the weight of a prefix and the observed load on different links, one can tweak the probabilities in such a way that the prefix is routed through a SPAL that fits it best. (This feature corresponds to the “Saturation Avoidance Factor”—SAF, described later in this document) After a winner is selected, PENDING_WINNER in PREFIX_SPAL is updated to reflect the new potential winner. Finally, the element is inserted in the Priority Queue. The rank of the prefix update in the priority queue is determined by computing the percent improvement; that is, the percent improvement obtained from moving the prefix from its current route to the pending winner route. That is, percent-improvement=[score(pending_winner)−Score(current_route)]/Score(current_route). The special-spal-flag is part of the data structure for the update, as it will be used in the determination of which messages to send to the local routers. if ((winner_set_size>1) and (other in winner_set)) remove other from winner_set select spal from winner_set at random update PENDING_WINNER in PREFIX_SPAL table compute percent_improvement for prefix insert prefix in prefix update queue Thread 2 In this thread 602 , elements are taken out of the queue in a rate-controlled manner. In some embodiments of the invention, this rate is specified by the customer. The update rate is often referred to as the token rate. Tokens are given at regular intervals, according to the update rate. Each time a token appears, the head of the queue is taken out of the queue, and considered for potential update. In case the database shows that more recent passes in Thread 1 have canceled the update request, it is dropped without losing the corresponding token; the next update request is then taken out from the head of the queue; this procedure is performed until either the queue empties, or a valid request is obtained. In some embodiments of the invention, when an update request that corresponds to Prefix P is determined to be current (thus, valid), one or more of the following tasks are performed: The flapping state is updated for Prefix P. The database is updated to reflect the new actual winner; more specifically, the pending winner, chosen before inserting the prefix update request at the end of the first thread now becomes the current winner. The database is checked to determine the current state of each of the individual routers. Accordingly, individual NLRIs are formed and sent to each of the routers. For example, no performance route is sent to an edge router in case the BGP winner for Prefix P, according to that router is found to be the same. An NLRI is sent to the back channel, describing the new local winner. Finally, the database is updated to keep track of the messages that were sent to each of the routers, as well as the expected resulting state of these routers. In this thread 602 , elements are just taken out from the queue in a rate-controlled manner, according to an update rate that may be set by the customer. The update rate is often referred to as the token rate: indeed, tokens are given at regular intervals, according to the update rate. Each time a token appears, the head of the queue is taken out, and considered for potential update. Assume that the update request concerns Prefix P. The PREFIX_SPAL table is checked to obtain the PENDING_WINNER and CURRENT_WINNER for Prefix P. In case PENDING_WINNER and CURRENT_WINNER correspond to the same SPAL, this is an indication that a more recent pass in Thread 1 has canceled the update request; in this case, the update request is dropped, without losing the corresponding token; the next token request is then polled from the head of the queue; this procedure is performed until either the queue empties, or a valid request, for which PENDING_WINNER and CURRENT_WINNER are different, is obtained. Having different pending and current winners reflects a valid update request. In this case, the Decision Maker should assert the winning route for Prefix P; correspondingly, a series of tasks are performed. First, the flapping state is updated for Prefix P. In some embodiments of the invention, the tendency of a prefix to flap is monitored by a variable denoted INTERCHANGE_RATE that resides in the PREFIX table. The flap_weight parameter dictates the dynamics of INTERCHANGE_RATE; more specifically, at this point in the algorithm thread, INTERCHANGE_RATE is updated using the last value of INTERCHANGE_RATE, as stored in the table, LAST_ICR_TIME, also stored in the PREFIX table, and flap_weight. In case the new computed INTERCHANGE_RATE is below flap_low, Routing Intelligence Unit considers the tendency for that prefix to flap to be low. On the other hand, when INTERCHANGE_RATE exceeds flap_high, the Routing Intelligence Unit considers the tendency for that prefix to flap to be high. That is, the algorithm functions in the following fashion: In case FORGIVING_MODE (also in the PREFIX table) is set to 0, and INTERCHANGE_RATE exceeds flap_high, FORGIVING_MODE is set to 1. In case FORGIVING_MODE is set to 1, but INTERCHANGE_RATE drops below flap_low, FORGIVING_MODE is set to 0 again, and the prefix update request survives this check. In case FORGIVING_MODE is set to 1 and INTERCHANGE_RATE is larger than flap_low, or FORGIVING_MODE is set to 0, and INTERCHANGE_RATE is below flap_high, FORGIVING_MODE does not change. Note that the method presented above is only one technique for controlling flapping; others will be apparent to those skilled in the art. In some embodiments of the invention, the two parameters flap_low, and flap_high are separated by an amount to avoid hysterisis between the two values. Then, the Decision Maker updates the PREFIX_SPAL table to reflect this change; more specifically, CURRENT_WINNER is moved to PENDING_WINNER in the table. At this time, the ROUTER_PREFIX_SPAL table is queried to capture the current state of each router in regards to Prefix P. Accordingly, different NLRIs are formed and sent to each of the routers. In some embodiments of the invention, the Decision Maker only asserts a performance route in case it is not the same as the natural BGP route; indeed, if Routing intelligence Unit were to assert performance routes regarding a given prefix P to all routers irrespectively of the current BGP winner for that prefix, it will never receive an update from the router pertaining to changes in the natural BGP winner for Prefix P. (Indeed, the performance route would always be the winner, so the router would assume there is nothing to talk about.) Also, an NLRI is sent to the back channel, describing to other Routing Intelligence Units in a coordinated system the new local winner. Finally, the database is updated to keep track of the messages that were sent to each of the routers, as well as the expected resulting state of these routers. Prior to forming the NLRIs, the database is updated to include the new flap parameters and prefix-SPAL information (i.e., the new current SPAL for that prefix). The BGP update sent to an edge router may be filtered out by the policy on the router. However, assuming the update is permissible, it may be made to win in the router's BGP comparison process. One implementation is to have the edge router apply a high Weight value to the incoming update. (Weight is a common BGP knob, supported in most major implementations of the protocol, but it is not in the original protocol specification.) This technique constrains the update so that it gains an advantage only on the router or routers to which the update is directly sent; this is desirable if some other routers are not controlled by a device such as the one described here. It is also possible to send the update with normal BGP attributes which make the route attractive, such as a high LOCAL_PREF value. if (local_token available) { get prefix at the head of the local update queue updatePrefixSpal (prefix, spal) updateFlapStats (prefix) compute bid_low_threshold and bid_high_threshold from MSLP (prefix) store bid_low_threshold and bid_high_threshold in prefix_group form NLRI to send to local SBGP form NLRI to send to backchannel SBGP } D. Technical Considerations Queue Size In some embodiments of the invention, a maximum queue size is to be chosen by the customer. In some embodiments, a small queue size may be chosen, so the maximum delay involved between the time instant a prefix update request is queued and the time instant it is considered by the second thread as a potential BGP update is small. For example, in case the token rate corresponding to a given link is 10 tokens per second, and we choose not to exceed a 2 second queuing delay, the queue should be able to accommodate 20 prefix update requests. Note that this method is simple, and only requires the knowledge of the token rate and the maximum acceptable delay. Maximum Rate of Prefix Updates It is desirable for the Routing Intelligence Unit to remain conservative in the rate of updates it communicates to the edge-router. This is the function of the token rate, which acts as a brake to the whole system. In some embodiments of the invention, the responsibility for setting the token rate is transferred to the customer, who selects a token rate that best fits her bandwidth and traffic pattern. E. Feedback from the Listener BGP The feedback from the listener BGP is valuable as it describes the actual current state of the local edge routers. Accordingly, in some embodiments of the invention, a separate routing intelligence unit thread modifies the content of the database according to the state it gets from the router(s). The Routing Intelligence Unit can operate more subtly in case it is a perfect listener; we consider the Routing Intelligence Unit to be a perfect listener if it has knowledge of the individual BGP feeds from each individual SPAL. That is, in case the Routing Intelligence Unit is connected to three access links, each connecting to a separate provider, the Routing Intelligence Unit is a perfect listener if it has access to each of the three feeds handed by each of these providers. Configuring Routing Intelligence Unit as a Perfect Listener is desirable, as it allows the support of private peerings. For example, unless Routing Intelligence Unit is configured as a Perfect Listener, when Routing Intelligence Unit hears about a prefix, it can't assume that coverage exists for that prefix across all SPALs. Considering the scenario described above, a prefix that the Routing Intelligence Units learns about could be covered by any of the three SPALs the router is connected to. For example, assume that only SPAL 1 has coverage for a given prefix P; in case the Routing Intelligence Unit asserts a performance route for that prefix across SPAL 2 , there is no guarantee that the traffic pertaining to that prefix will be transited by the Service Provider to which SPAL 2 is connected (which we denote Provider 2 ). In case Provider 2 actually has a private peering with Provider X that obeys some pre-specified contract, Provider X could well monitor the traffic from Provider 2 , and filter all packets that do not conform to that contract. In case this contract namely specifies that Provider X will only provide transit to customers residing on Provider X's network, then the traffic pertaining to Prefix P will be dropped. If Routing Intelligence Unit were a Perfect Listener, it would only assert performance routes for prefixes across SPALs that are determined to have coverage for these prefixes. This behavior may be referred to as “extremely polite.” In some embodiments, the Routing Intelligence Unit is capable of avoiding the “Rocking the boat” problem, which stems from unwanted propagation of prefixes which did not already exist in BGP. The Routing Intelligence Unit can operate in “impolite” mode, where any prefixes may be used, or in “polite” mode, where only those prefixes which were previously present in BGP can be used. An ANNOUNCED bit resides in the ROUTER PREFIX SPAL table, and is set by the Peer Manager in case the Routing Intelligence Unit hears about a prefix from any of the Routers. This bit allows use of “polite” mode by the following procedure: in case the ANNOUNCED bit is set to 0 for all (router, SPAL) combinations in the ROUTER_PREFIX_SPAL table, then ACCEPTING_DATA is set to 0 in the PREFIX table. F. Urgent Events In case a catastrophic event occurs, such as a link going down, some embodiments of the invention send urgent BGP updates to the router. These urgent updates have priority over the entire algorithm described above. For example, in case a SPAL has lost coverage for a prefix, an urgent BGP message should be sent to the router, requesting to move the prefix to other SPALs. A list of urgent events upon which such actions may be taken, and a description of the algorithms pertaining to these actions, are described below. Algorithm for the Detection of an Invalid SPAL In some embodiments of the invention, a specific (Prefix P, SPAL x) pair is invalidated in case there are reasons to believe that SPAL x no longer provides coverage to Prefix P. One possible implementation is described as follows. Measurements corresponding to a (Prefix, SPAL) pair are assumed to arrive to the Decision Maker at something close to a predictable rate. A background thread that is independent from Threads 1 and 2 computes this update rate, and stores a time of last update, the LAST_UPDATE_TIME. Another background thread verifies that LAST_ICR_TIME is reasonable given UPDATE_RATE. For example, assuming that measurements come in following a Poisson distribution, it is easy to verify whether LAST_ICR_TIME exceeds a fixed percentile of the inter-arrival interval. As LAST_UPDATE_TIME increases, the Decision Maker becomes more and more worried about the validity of the path. In the current design, there are two thresholds: at the first threshold, the NEW_INVALID and INVALID flags are set in the PREFIX_SPAL table. As described in Thread 1 above, setting the NEW_INVALID flag for a (Prefix P, SPAL x) pair will prevent any new update requests for Prefix P to be routed through SPAL x. At this stage, no other action is taken. At the second threshold, the Decision Maker becomes “very concerned” about routing Prefix P through SPAL x; hence, an urgent check is made to see whether Prefix P is currently routed through SPAL x, in which case an urgent NLRI is created (that is, an NLRI that bypasses the entire queue system) in order to route Prefix through a different SPAL. G. Saturation Avoidance Factor Some embodiments of the invention support a Saturation Avoidance Factor, which measures the effect of a prefix on other prefixes. In some embodiments of the invention, the “Saturation Avoidance Factor” (SAF) pertaining to a given prefix may be taken into account when prefixes are sorted in the Priority Queue. This SAF measures the effect of a prefix on other prefixes. That is, if, upon scheduling a prefix on a given link, its effect on the other prefixes already scheduled on that link is high (i.e., this effectively means that the aggregate load for this prefix is large), its SAF should be low. The lower the SAF of a prefix, the lower its place in the Priority Queue. This way, the algorithm will always favor low load prefixes rather than high load prefixes. Note that in some embodiments, the SAF is not directly proportional to load. For example, a prefix that has a load equal to 0.75 C has a different SAF whether it is considered to be scheduled on an empty link or on a link which utilization has already reached 75%. In the later case, the SAF should be as low as possible, since scheduling the prefix on the link would result in a link overflow. At times, the token rate may be slower than the responded feedback. In case link utilization information is obtained through interface-stats, the token rate may be slower than the rate at which utilization information comes in. Also, the token rate may be slower than the rate at which edge-stats measurements come in. Additionally, in some embodiments, each prefix is considered at a time. That is, PQServiceRate is small enough so that no more than one token is handed at a time. For example, denoting by T the token rate obtained from the above considerations, PQServiceRate is equal to 1/T. If more than one token were handed at one time, two large prefixes could be scheduled on the same link, just as in the example above, potentially leading to bad performance. In some embodiments of the invention, the SAF is a per-prefix, per-SPAL quantity. For example, assume that a prefix carries with it a load of 75% the capacity of all SPALs. If we have a choice between two SPALs, SPAL 1 and SPAL 2 , SPAL 1 already carrying a load of 50%, the other having a load of 0%. In this case, moving Prefix p to SPAL 1 will result in bad performance not only for itself, but also for all other prefixes already routed through SPAL 1 . In this case, the SAF is close to 0, even if performance data across SPAL 1 seems to indicate otherwise. On the other hand, the SAF of moving Prefix p to SPAL 2 is, by contrast, very good, since the total load on the link will remain around 75% of total capacity, so delays will remain low. If, instead of carrying a load of 75% capacity, Prefix p carried a load of 10% capacity, the results would have been different, and the SAF of Prefix p across SPALs 1 and 2 would have been close. In some embodiments of the invention, without knowing the load of a link, we can still measure the effect of moving a given prefix to a given SPAL through RTT measurements. That is, instead of measuring the load directly, we measure the end result, that is the amount by which performance of prefixes across a link worsens as a result of moving a prefix to it. Modifying the Schema for the Support of SAF In order to support SAF, the schema may be include a load field in the SPAL table, and an SAF field in the PREFIX_SPAL table. In some embodiments, the SAF field is a per-prefix, per-SPAL information. H. Available Bandwidth Edge-stats measurements may include measurements of delay, jitter, and loss; using these measurements, an application-specific performance score may be obtained based on which a decision is made on whether to send an update request for this prefix. Available bandwidth is a valuable quantity that is measured and included in the computation of the performance score in some embodiments of the invention. I. Differentiated Queues and Token Rates per Link In some embodiments of the invention, token rates may differ on a per-link basis (which dictates the use of different queues for each link). In some embodiments, the token rate may be tailored to total utilization. Lowly utilized links can afford relatively higher token rates without fear of overflow, whereas links close to saturation should be handled more carefully. Some embodiments of the invention provide one or more of the following modes of operation: 1. The default mode: the user specifies one token rate (and, optionally, a bucket size), shared equally among the prefixes updates destined to the different links. 2. The enhanced performance mode: the user specifies a minimum token rate (and, optionally, a bucket size). Depending on factors such as the total bandwidth utilization and the bandwidth of individual links, the prefix scheduler takes the initiative to function at a higher speed when possible, allowing better performance when it is not dangerous to do so. 3. The custom mode: in this case, the user can specify minimum and maximum token rates (and, optionally, bucket sizes), as well as conditions on when to move from one token rate to another. Using this custom mode, customers can tailor the prefix scheduler to their exact needs. J. Prefix Winner set Re-computation Even though the priority queue is sized in such a way that the delay spent in the queue is minimized, there is still an order of magnitude between the time scale of the BGP world, at which level decisions are taken, and the physical world, in which edge stats and interface stats are measured. That is, even though the queuing delay is comparable to other delays involved in the process of changing a route, prefix performance across a given link or the utilization of a given link can change much more quickly. For example, a 2 second queuing delay could be appropriate in the BGP world, while 2 seconds can be enough for congestion to occur across a given link, or for the link utilization to go from 25% to 75%. For this reason, in some embodiments of the invention, the winner set is re-evaluated at the output of the priority queue. K. Conclusion The foregoing description of various embodiments of the invention has been presented for purposes of illustration and description. It is not intended to limit the invention to the precise forms disclosed. Many modifications and equivalent arrangements will be apparent.
Systems and methods are described for supporting routing intelligence for evaluating routing paths based on performance measurements. The routing intelligence may include processes executed in a self-contained device. This device may control one or more edge routers, based on performance data from end users. In other embodiments, the routing intelligence device may be used solely to monitor one or more edge routers, producing reports but not effecting any changes to routing. Routing decisions may be injected to the edge routers via BGP updates. The devices may be stationed at the premises of a multihomed organization, such as an enterprise, ISP, government organization, university, or other organization supporting a sub-network coupled to an internetwork. In other embodiments, the routing intelligence comprises processes executed on a router.
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BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a zero edge aquarium or an infinity aquarium which is an aquarium without visible structures. 2. Description of Related Art Aquariums often have rims, supports, covers or edges that obstruct the view of the contents. Additionally the surface of the water of most aquariums is disturbed by the flow of bubbles or other discharges. The turbulence obstructs the view of the contents and can create noises that detract while viewing contents of the aquarium. SUMMARY OF THE INVENTION An aquarium according to this invention is useful for containing and viewing aquatic life. A preferred embodiment of this invention offers unobstructed viewing through a smooth lens of water on the sides and the top. This is often referred to as a zero edge aquarium or an infinity aquarium. The aquarium is constructed of at least partially from a transparent material and water is circulated over the top of and along the outside of the sidewall before being collected in a gutter and a drain box and optionally a drain channel. The top edge and corners of the aquarium are rounded to aid in the flow of water. The water is then returned to the interior of the aquarium via an infeed. The infeed may comprise a sump, pump, piping, valving, and a return outlet. The aquarium can be virtually any shape or size. It offers a unique view of the contents as there appears to be no lid, edge, or structure within the water. Additional prefiteration or filtration is employed per the needs of the aquarium. Another preferred embodiment provides a smooth fluid surface and smooth flow over the sides to offer clean and quiet viewing of the contents. This is done by the design of the aquarium tank and the flow components. BRIEF DESCRIPTION OF THE DRAWINGS The above-mentioned and other features of this invention will be better understood from the following detailed description taken in conjunction with the drawings wherein: FIG. 1 is a partial exploded view of an aquarium according to a preferred embodiment of the invention; FIG. 2 shows a detail view of a radiused upper edge of a sidewall according to a preferred embodiment of the invention; FIG. 3 shows a partial side view of an aquarium according to a preferred embodiment of the invention; FIG. 4 shows a partial side view of a drain channel and a sump according to a preferred embodiment of the invention; FIG. 5 shows a partial side view of a drain channel and a prefilter according to a preferred embodiment of the invention; and FIG. 6 is a perspective view an aquarium according to a preferred embodiment of the invention. DESCRIPTION OF PREFERRED EMBODIMENTS FIG. 1 shows a partial exploded view of aquarium 20 . Both fresh and saltwater aquariums 20 typically have sidewalls 22 where fluid 62 , typically water, occupies at least a part of interior volume 34 . Fluid 62 may have a saline nature from the addition of salts or minerals or variations in pH according to the practices of keeping aquatic life. Aquatic life is diverse ranging from, but not limited to, plankton, algae, corals, crustaceans, muscles, fish, sharks, reptiles, amphibians, and mammals. Aquarium 20 is made of any suitable at least partially transparent or substantially transparent material adapted for viewing. These are such as, but not limited to, glass, acrylics, polycarbonates, etc. According to at least one preferred embodiment of the invention, materials of construction have a refractive index that approximates that of fluid 62 . Sidewall 22 can be a variety of thickness depending on the shape, size, height of aquarium 20 . According to one embodiment of the invention, sidewall 22 has a thickness of about ⅛″ to 2″ or more. In at least one embodiment of the invention sidewall 22 is ½″ thick acrylic. In another embodiment of the invention the sidewall 22 is 5 mm glass. One or more sidewalls 22 preferably form interior volume 34 along with bottom. Interior volume 34 is adaptable to aquarium 20 needs and ranges from a fraction of a gallon to thousands of gallons. According to at least one of the preferred embodiments of the invention, aquarium 20 does not have a top, lid, roof, or cover. This allows unobstructed viewing of contents of aquarium 20 . Other embodiments of the invention may include a partial or total cover with or without the addition of lighting. According to other preferred embodiments of the invention, sidewalls 22 are constructed without supports or structures that block views of aquarium 20 contents. Sidewalls 22 are capable of taking on any of a number of shapes as viewed from top perimeter 36 . Such shapes include, but are not limited, to circle, triangle, square, rectangle, trapezoid, pentagon, hexagon, octagon, decagon, regular polygon, irregular polygons, combinations of arcs/curves of equal or varying diameters, or combinations of curves/arc and straight segments/lengths. According to one embodiment of the invention, at least a part of sidewall 22 is not transparent. This is beneficial when placing aquarium 20 against another surface such as a wall. According to at least one preferred embodiment of the invention, sidewalls 22 are substantially vertical. According to other embodiments of the invention, sidewalls 22 are inwardly and/or outwardly angled. Angles of the sidewalls 22 may be adjusted depending upon the properties of fluid 62 such as viscosity, surface tension, and affinity for materials of sidewall 22 . As shown FIG. 2 , according to a preferred embodiment of the invention, at least a part of sidewall 22 has radiused upper edge 28 which allows fluid 62 to flow over radiused upper edge 28 without creating significant ripples or turbulence in fluid surface 70 or on outer surface 26 of sidewall 22 . Radiused upper edge 28 creates a smooth lens of fluid 62 on fluid surface 70 and sidewall 22 . Smooth lens creates a zero edge aquarium or an infinity aquarium. Curvature of radiused upper edge 28 , or bullnose edge, maybe may be varied depending on viscosity of fluid 62 . As shown in FIG. 2 , in at least one of the embodiment of the invention, some of corners 38 formed by the union of sections of sidewalls 22 are rounded to minimize ripples or turbulence of fluid 62 . Corners 38 allow for containment of fluid 62 to avoid escaping or leakage and enhance viewing of contents of the aquarium 20 since there is a smooth lens of fluid on top and sides. An additional benefit is that noise of fluid 62 splashing or gurgling is minimal. Attention is given while producing corner 38 or seam to minimize visual impact. According to at least one embodiment of this invention, square or right angle corners 38 have one or both of the two adjoining pieces of material rounded off and then bull nosing outer corner 38 where two radiused upper edges 28 meet. Fluid 62 preferably flows along at least a portion of outer surface 26 of sidewall 22 . According to one embodiment of the invention, entire top perimeter 36 of aquarium 20 includes fluid 62 flowing over radiused upper edge 28 . As shown in FIG. 6 , according to other embodiments of this invention, at least one backwall 66 replaces a sidewall 22 with varying height so that fluid 62 does not flow over on all sides. According to this embodiment of the invention, top edge 68 of backwall 66 is preferably above fluid surface 70 . The open top and overflowing sidewalls 22 create a large surface area which allows oxygen to become dissolved in fluid 62 . According to a preferred embodiment of the invention, outer surface 26 of sidewall 22 is smooth so as to maintain virtually ripple-free flow of fluid 62 . Alternatively, sidewall 22 of aquarium 20 may include texture/uneven surfaces or even protuberances to produce a more rippled flow. According to a preferred embodiment of this invention, gutter 24 is positioned along bottom perimeter of sidewall 22 . Fluid 62 flows over radiused upper edge 28 and along sidewall 22 to gutter 24 . Gutter 24 is in fluid communication with sidewall 22 . This allows gutter 24 to collect fluid 62 from outer surface 26 of sidewall 22 . In at least one preferred embodiment of this invention, gutter 24 extends entire length of lower perimeter of sidewall 22 . Other embodiments of this invention, may include gutter 24 along only a portion of lower perimeter of sidewall 22 . According to one embodiment of this invention, gutter 24 is positioned above or below bottom of sidewall 22 of aquarium 20 . Gutter 24 is a suitable size to contain the volume of fluid 62 flowing down sidewall 22 as it flows to drain box 30 . Gutter 24 is made of materials relatively impervious to fluid 62 such as: glass, metal, plastic, wood, etc. Gutter 24 may be of various shapes including, but not limited to, square or U-shaped troughs/conduit. According to an embodiment of the invention, gutter 24 is integral to aquarium 20 . According to other embodiments of the invention, gutter is detachable relative to sidewalls 22 . According to one embodiment of this invention, filler material such as gravel is positioned in gutter 24 and allows fluid 62 to flow on, through, or below filler material. According to a preferred embodiment of the invention, fluid 62 in gutter 24 flows to at least one drain box 30 . Drain box 30 is preferably integral to aquarium 20 . Still other embodiments of this invention may include drain box 30 affixed with suitable fasteners such as adhesive or screws. Drain box 30 may be made of materials relatively impervious to fluid 62 such as: glass, metal, plastic, wood, etc. In at least one embodiment of the invention, fluid 62 flows in drain box 30 in a step-like fashion and drain box 30 directs fluid 62 away from outer perimeter of aquarium 20 . Other embodiments of this invention may include fluid 62 flowing into gooseneck within drain box 30 . As shown in FIG. 5 , according to a preferred embodiment of the invention, prefilter 48 is installed in the drain box 30 . Prefilter 48 removes particles from fluid 62 and minimizes splashing or gurgling of fluid 62 in drain box 30 . According to a preferred embodiment of this invention, prefilter 48 is installed adjacent or touching drain aperture 70 or a hole in the gutter. This additionally minimizes splashing or gurgling of fluid 62 . Suitable material for prefilter 48 include, but are not limited to, sponge (natural or man-made), foam, sand, activated carbon, etc. According to a preferred embodiment of this invention, fluid 62 from drain box 30 flows to infeed 32 for return to aquarium 20 . As shown in FIG. 4 , according to a preferred embodiment of this invention, fluid 62 flows from drain box 30 through drain channel 40 before infeed 32 . Drain channel 40 may be made of materials that are relatively impervious to fluid 62 such as: glass, metal, plastic, wood, etc. According to a preferred embodiment, drain channel 40 has legs on a side which are positionable between engaged and disengaged position that facilitates maintenance of aquarium 20 or infeed 32 . As shown in FIG. 4 , according to one preferred embodiment of this invention, filter media 44 is positioned in drain channel 40 . Suitable material of filter media 44 include, but are not limited to, sponge (natural or man-made), foam, sand, activated carbon, etc. Selection of filter media 44 is made by one skilled in keeping of aquariums 20 . According to one embodiment of the invention, filter media 44 is placed on lattice structure or egg crate for support. An additional benefit of filter media 44 is reduced splashing and gurgling of fluid 62 . According to one embodiment of the invention, baffle 46 is positioned in drain channel 40 to direct flow and minimize splashing and gurgling of fluid 62 . An additional benefit of baffle 46 is minimizing evaporation of fluid 62 . According to one embodiment of the invention, baffle 46 is horizontal. According to additional embodiments of this invention, baffle 46 is sloped. Baffle 46 is made of same or similar materials to drain channel 40 . As shown in FIG. 3 , according to one embodiment of the invention, fluid 62 then reaches infeed 32 which returns fluid 62 to aquarium 20 . According to one embodiment of the invention, infeed 32 includes sump 50 . Sump 50 collects fluid 62 before returning to aquarium 20 . In at least one embodiment of the invention, sump 50 includes weir element 52 to separate sump 50 into two or more sections. Weir element 52 is an arrangement of flow modifiers including, but not limited, to baffles, weirs, and dams. Weir element 52 is useful for providing calm fluid 62 to inlet of a circulating force. According to one embodiment of the invention, a circulating force is pump 54 . Pump 54 is in fluid communication with sump 50 and may be internal or external to sump 50 . Pump 54 provides motive force to fluid 62 . Typical motive force means include, but are not limited to, centrifugal pumps, rotary pumps, submersible pumps, positive displacement pumps, diaphragm pumps, peristaltic pumps, and ejectors/eductors. According to a preferred embodiment of this invention, pump 54 is a mag 12 . According to a preferred embodiment of the invention, pump 54 has a discharge pressure and flowrate sufficient to return fluid 62 to aquarium 20 including head and line losses while creating desired flows over radiused upper edge 28 . As shown in FIG. 3 , according to one embodiment of this invention, infeed 32 further comprises check valve 56 or other back flow preventing device. Check valve 56 reduces loss of fluid 62 if pump 54 is not in operation. According to other embodiments of this invention, infeed 32 includes isolation valve 58 . Isolation valve 58 is located after fluid 62 flows through check valve 56 . Isolation valve 58 allows for maintenance on check valve 56 . A type of isolation valve 58 maybe, but is not limited to, gate, globe, plug, ball, butterfly, or pinch. According to one preferred embodiment of the invention, fluid 62 flows from pump 54 through check valve 56 and then through isolation valve 58 before returning to aquarium 20 . Return outlet 60 is located at aquarium 20 and provides a means for returning fluid 62 to aquarium 20 . According to one embodiment of the invention, return outlet 60 may be a simple bulkhead fitting or hose. According to other embodiments of this invention, return outlet 60 has diffusing characteristics that minimize rippling of fluid surface 70 . According to one preferred embodiment of this invention, return outlet 60 comprises orifices as shown in FIG. 3 . According to other embodiments of the invention, return outlet 60 includes the use of cover plates, baffles, goosenecks, and/or porous media such as pebbles/rocks. According to other embodiments of the invention a combination of nozzles, flow modifiers and/or media comprise return outlet 60 . According to a preferred embodiment of the invention, return outlet 60 is substantially centrally positioned on bottom of aquarium 20 . According to an embodiment of this invention, return outlet 60 is positionable anywhere in fluid communication with interior volume 34 . According to an embodiment of this invention, return outlet 60 may also be positioned on sidewalls 22 as shown in FIG. 6 . According to other embodiments of the invention, return outlet 60 creates turbulence and/or bubbles with nozzles for a fountain-like or agitation effect. In fluid communication is defined as liquid flowing between two components with little loss of liquid. Some common means of providing fluid communication include but are not limited to pipe, tube, hose, fittings, and valves with joints that are welded, threaded, glued, interference fit, coupled, or other mechanically fastened means. Materials of construction of fluid communication means are compatible with fluid 62 and include, but not limited to, plastics (PVC, CPVC, ABS, HDPE, rubber, neoprene, etc.) and metals (iron, steel, stainless steel, brass, copper, alloys, etc.). Often physically placing two objects next to each other can be sufficient to result in fluid communication. According to an embodiment of the invention, aquarium 20 maybe positioned on suitable stand that conceals drain box 30 and infeed 32 . Stand is constructed of wood, metal, plastic or other material capable of bearing the mass of filled aquarium 20 at a convenient height. According to one embodiment of the invention, stand uses hingeless doors to conceal the internals. According to one embodiment of this invention, stand includes ability to level aquarium 20 with respect to floor. Additional embodiments of this invention include light fixture mounted from stand and/or aquarium 20 . While in the foregoing specification this invention has been described in relation to certain preferred embodiments thereof, and many details have been set forth for purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details described herein can be varied considerably without departing from the basic principles of the invention.
The invention is a zero edge or infinity aquarium for viewing aquatic life. The design offers unobstructed viewing through a smooth lens of water on the sides and the top. The aquarium is constructed of a transparent material and water is circulated over the top of and along the outside of the sidewall before being collected in a gutter and drain box. The top edge and corners of the aquarium are rounded to aid in the flow of water. The water is then returned to the interior of the aquarium via an infeed. The infeed may comprise a sump, pump, piping, valving, and a return outlet. It offers a unique view of the contents as there appears to be no lid, edge, or structure within the water.
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BACKGROUND OF THE INVENTION [0001] The present invention relates to a three-dimensional sensor array suitable in particular for receiving electrical signals that occur in natural cell connections. The cell assemblies to be measured are, for example, tissue sections in the animal or human organism. In particular, the invention makes possible the recording of electrical or electromagnetic signals that are generated by neurons and are forwarded to surrounding neurons or to muscular cells. The sensor array in accordance with the invention is also used in the examination of cell cultures cultivated outside of an organism, for example, in a culture system. [0002] In order to detect electrical signals occurring in biological tissue, two basically different solution approaches were pursued in the past. It has been possible for a long time to record a summation signal such as occurs on the surface of a biological tissue with areally applied electrodes, for example, on the surface of the skin of a patient when recording an EEG. The precise position of the production and forwarding of such signals inside the biological tissue cannot be examined with this method. The attempt has been recently made to examine more closely the signals produced in the biological tissue and the processes of biological ion conduction occurring there in that measuring electrodes are positioned at individual positions inside a three-dimensional tissue body in order to record the signals punctually. However, this has the problem that the precise production site of the signals and the path of their forwarding are not known so that the positioning of the electrodes is very difficult. The signal distribution in space can also not be determined with such probes. Furthermore, there is basically the problem in the detection of signals inside biological tissue that a corrosion of the electrodes and/or in the medium range a tissue change occurs on account of the electrochemical series that is being built up, as a result of which the detected signals are falsified. This problem is present if electrical signals are to be fed via the electrodes into the biological tissue for purposes of stimulation. [0003] Sensors have been recently suggested that should mitigate the problem of the exact positioning of the electrodes inside the tissue. For example, the so-called Utah electrode array has been described which concerns a miniaturized sensor array that comprises numerous sensor needles on a carrier that each have an electrode on their sensor tip. In order to make possible the detection of signals in tissue layers at different depths (Z direction) the sensor needles can have http://www.medgadget.com/archives/print/002076print.html). different lengths so that when they penetrate into the tissue they penetrate into it with different depths (“Utah Electrode Array to Control Bionic Arm”; May 24, 2006; [0004] However, even with this sensor array the spatial distribution of electrical signals in biological tissue can be detected only to a very limited extent because each sensor needle of the array detects signals only at a certain depth in the tissue. Furthermore, there is the problem, due to the construction of the sensor array, that an unhindered fluid flow through the array is hindered by the continuous carrier plate, as a result of which the supplying of cell cultures with nutrients in culture systems is significantly adversely affected. [0005] A three-dimensional sensor array with sensor needles arranged in a comb-like manner and mutually spaced in the x and the y direction is known from JP 2004237077A. Each sensor needle has several electrode surfaces distributed in the longitudinal direction on the sensor needle. [0006] US 2003/0100823 A1 shows a three-dimensional sensor array with several sensor needles arranged in a comb-like manner. Each sensor needle is provided with several electrode surfaces arranged distributed in the longitudinal direction on the sensor needle. [0007] WO 2010/005479 A1 describes a three-dimensional sensor array for measuring electrical signals in biological cell assemblies. In the sensor array previously known from this publication each sensor needle has only one electrode surface. SUMMARY OF THE INVENTION [0008] Thus, one task of the present invention consists in making available an improved three-dimensional sensor array with which electrical signals can be precisely detected in a three-dimensional biological cell combination, in particular as concerns the time and place of the occurrence of such signals. A partial task is seen in modifying a sensor array in such a manner that a currentless measuring in tissue structures becomes possible in order to prevent the corrosion of electrodes and tissue changes. Finally, another partial task consists in modifying the sensor array in such a manner that it is not only suitable for being used in the living organism but is also suitable in particular for the measuring of cell combinations cultivated in a bioreactor and does not adversely affect the supplying of the cultivated cells with nutrients. [0009] The previously cited main task is solved by a three-dimensional sensor array in accordance with the attached claim 1 . The cited partial tasks are solved in particular by preferred embodiments in accordance with the subclaims. [0010] The sensor array in accordance with the invention is composed of several micro-structured sensor plates that each comprises a carrier section on which several sensor needles are arranged in a comb-like manner. The sensor needles are spaced from each other in a first direction (X direction) and carry several electrode surfaces distributed in the longitudinal direction of the sensor needles (Z direction). Each of the electrode surfaces is contacted via its own conducting track, whereby all conducting tracks run over the carrier section to a contacting section. Spacer elements are located between the several sensor plates which elements serve for the spacing of the sensor plates and preferably at the same time for the fastening of these plates. In this manner the carrier sections and the sensor needles formed on them are spaced from the adjacent sensor plates in a second direction (Y direction) that runs vertically to the first direction and to the longitudinal direction of the sensor needles (Z). Passages are formed between the spacer elements and the carrier sections which passages allow a fluid running through the sensor array to flow between the sensor plates in the longitudinal direction of the sensor needles. [0011] Numerous electrode surfaces that are spatially arranged distributed in a grid are formed by the buildup of the sensor array in accordance with the invention. If the sensor array is introduced into a biological tissue, occurring electrical signals regarding the location can be precisely determined in the space in which the sensor needles extend. Since all electrode surfaces are individually contacted and therefore the particular signals detected can be forwarded to an evaluation unit, the signal amount being produced can be solved in time and in space so that the point of production as well as the types of the forwarding of signals in the tissue combination can be recorded. [0012] The sensor needles in the sensor array can be manufactured as needle structures preferably consisting of silicon or vitreous silicon dioxide surfaces with a metallic core by known methods of nanotechnology. For example, self-organizing processes of etching, overgrowth and forming can be used. It is also possible to form surface structures on the sensor needles which structures facilitate an anchoring in biological tissue. Microstructural components with such formed, nanostructured surfaces are known, for example, from WO 2007/017458 A1, which is referred to regarding the production of such surface structures. [0013] According to a preferred embodiment of the present invention the spacer elements extend exclusively between the carrier sections of the sensor plates, so that free spaces remain between the sensor needles of adjacent sensor plates which spaces can be filled by the biological tissue to be examined. A flow of liquid through the sensor array in the Z direction is made possible by the passages formed between spacer elements and the carrier sections. Thus, the sensor array can be designed in a very simple manner as a component of a culture system, whereby the supplying of nutrients to the individual tissue layers is not adversely affected or is even facilitated by the positioning of the sensor arrays. [0014] The essential elevation of the sensitivity of the electrical measuring by the needle-like, grass-like nanostructures on the surface of the sensor needles is advantageous. At the same time, these nanostructures can be attached on the surface of the joint to the next sensor plate and thus contribute to the novel buildup and connection technique to the real 3-D-MEA in that they are pressed into the plastic maintaining the spacing. Such novel buildup and connection techniques used on materials that are additionally effective in a capacitive manner make possible the three-dimensionality of the described sensors. [0015] An advantageous embodiment is distinguished in that the surface of the sensor needles is rendered biologically passive. The creation of electrochemical series can be prevented by applying appropriate coatings. The procedure for a biological passivation of semiconductor materials such as can be used for the manufacture of sensor needles is basically known to the person skilled in the art so that a detailed description will not be given. However, it is especially advantageous in this connection if even the electrode surfaces are coated with an electrically insulating, in particular biologically passivated covering. The signal detection takes place in this case by capacitive measuring methods, whereby the individual electrode surfaces form an electrode of a measuring capacitor. The required counterelectrode can be realized by opposing electrode surfaces on the sensor needles or also by a common capacitor plate, which represents an independent component of the sensor array. In order to reduce the cross talk during the signal detection the conducting tracks in the sensor array can be provided with an electromagnetically active screening. [0016] The above-cited task is also solved in accordance with the invention by a measuring assembly in accordance with the coordinate claim 7 . This measuring assembly comprises a previously described sensor array as well as an evaluation unit connected to it which evaluation unit detects and processes in time and as to location the signals delivered from the several electrode surfaces of the sensor array. The evaluation unit or parts of it can be constructed as an on-chip-signal processing circuit and be arranged in the direct vicinity of the electrode surfaces on the sensor array. As a result, a data reduction can be carried out on-chip so that a reduced amount of data can be transmitted, for example, by a wireless communication connection to an external data processing unit. Moreover, the measuring assembly can preferably comprise a signal generator that can supply an electrical stimulation signal to one or more electrode surfaces of the sensor array. Thus, not only the signals naturally produced in the biological tissue can be detected but a purposeful stimulation is also possible, for example, in order to activate muscle cells or to simulate other processes in the tissue combination. BRIEF DESCRIPTION OF THE DRAWINGS [0017] Further advantages, details and further developments of the present invention result from the following description of preferred embodiments with reference made to the drawings. In the drawings: [0018] FIG. 1 shows a simplified view of the sensor plate for several sensor needles in a top view; [0019] FIG. 2 shows an arrangement of several sensor plates on a wafer during a manufacturing step; [0020] FIG. 3 shows a perspective view of a spacer element; [0021] FIG. 4 shows a perspective view of a first embodiment of a three-dimensional sensor array; [0022] FIG. 5 shows an assembly drawing with modified embodiments of the components of the sensor array; [0023] FIG. 6 shows a perspective view of a cell cultivation system with integrated sensor array. DETAILED DESCRIPTION [0024] FIG. 1 shows a first component of the sensor array in accordance with the invention in a simplified top view. It concerns a sensor plate 01 that is manufactured by micro-structuring and comprises a carrier section 02 as well as numerous sensor needles 03 . The sensor needles 03 are arranged in a comb-like manner on the carrier section 02 and spaced from each other in the X direction. The space between the individual sensor needles is, for example, 50 to 1000 μm. Several electrode surfaces 04 are arranged on each sensor needle 03 and are spaced from each other in the Z direction (longitudinal direction). Each electrode surface is connected to its own conducting track 06 so that numerous conducting tracks 06 run on the sensor plate that are guided via the carrier section 02 to a contacting section 07 . [0025] FIG. 2 shows the arrangement of several sensor plates 01 on a wafer 08 during a manufacturing step. In this phase of the manufacture the sensor needles 03 are at first still surrounded by a structuring area 09 that must later be removed, e.g., by etching or sandblasting in order to expose the comb-like structure of the sensor needles. The at first two-dimensional production of the structures on the individual sensor plates preferably takes place by standard MEMS technologies. For example, an insulating substrate (glass, Borofloat 33) in wafer form is used as starting material. Metallic layers are separated off with the aid of thin-layer technologies (sputtering, vaporization) which layers can subsequently be structured by lithography and etching. In order to keep low the influencing of the cell cultures to be examined later by the sensor array, an insulating, biocompatible passivation layer (preferably Si 3 N 4 or SiO 2 ) is separated off over the entire structure with a low-temperature separating method (PECVD). The electrode surfaces 04 are subsequently exposed again by a further etching step in as far as a capacitive measuring is not preferred. Corresponding structuring steps can be carried out on both sides of the wafer disk in order to apply electrode surfaces on both sides of the sensor needles. Deviating manufacturing steps are necessary if the conducting tracks 06 are to be additionally provided with a screening. [0026] After the electrode surfaces and the conducting tracks have been manufactured the comb structure for the individual sensor needles must be manufactured, for which a structuring through the complete wafer is required. Net- and dry chemical etching processes can be used for this. A micro-sandblasting is also possible when using pre-structured masks, which drastically reduces the working time. The sensor plates manufactured in this manner are subsequently singled so that several sensor plates are present. [0027] FIG. 3 shows a perspective view of a preferred embodiment of a spacer element 11 that forms another component of the sensor array of the invention. The spacer element 11 preferably consists of plastic, in particular polycarbonate. The spacer element corresponds in its dimensions as regards width and length approximately to the measurement of the carrier section 02 of the sensor plate. The thickness of the spacer element determines the later spacing of the individual sensor plates in the Y direction and is, for example, 50 to 1000 μm. Several passages 12 are formed as groove-shaped recesses in the spacer element 11 , preferably on both sides. In the assembled sensor array these passages 12 bring it about that a fluid current, for example, a nutrient solution, can flow through and is thus maintained between the individual sensor plates. [0028] FIG. 4 shows a perspective view of a first embodiment of the sensor array. The latter obviously consists of several sensor plates 01 that are spaced from each other by intermediate spacer elements 11 in the Y direction so that numerous sensor needles 03 are arranged in a matrix fashion. The electrode surfaces 04 attached on the sensor needles 03 are distributed over the space defined by the sensor needles. The hybrid three-dimensional buildup of the sensor array preferably takes place by thermal compression bonding. To this end the spacer elements 11 are alternatingly stacked with the sensor plates 01 , heated in a thermal press to approximately 90% of the softening temperature of the material of the spacer elements and loaded with a pressure of, for example, 5 MPa. The surfaces of the spacer elements and of the sensor plates standing in contact can be previously pre-treated by a plasma activation. The required thermal bond time is approximately 3 min. [0029] If the spacer elements do not consist of plastic but rather of silicon in alternative embodiments the connection between the spacer elements and the sensor plates can be produced by anodic bonding. In this case the stack of spacer elements and sensor plates must be sequentially bonded. [0030] It is apparent that as a result of the buildup in accordance with the invention sufficient space remains between the sensor needles 03 so that biological cells can settle there. The sensor array can be introduced into natural cell surroundings in that the sensor needles are pushed into the tissue. In distinction to other matrix-like sensor arrays a flow of fluid even in the Z direction remains possible since, in spite of the required shunting of the numerous conducting tracks on the carrier sections between the individual sensor plates, flow conduits are formed with the aid of the passages 12 . Such a flowing through is required in particular in the cultivation of biological cells in order to supply sufficient nutrient solution to all cells in a three-dimensional combination. [0031] FIG. 5 shows a modified embodiment of the components of the sensor array in an assembly drawing. The sensor plates 01 as well as the spacer elements 11 have in this embodiment separating webs 13 that have approximately the length of the sensor needles 03 in the Z direction. In the X direction the separating webs 13 are uniformly positioned so that they lie tightly on the particular separating webs of the adjacent plates (sensor plate and spacer element) after the assembly of the plate stack. Furthermore, additional covering plates 14 are provided on the edges of the plate stack that enclose the space of the intermediate sensor needles. [0032] FIG. 6 shows a perspective view of the largely assembled state of a modified embodiment of the sensor array, that in this case is an integral component of a cell cultivation system. A cultivation space is created by the outer separating webs 13 as well as by the cover plates 14 in which space several sensor needles 03 are arranged, whereby a cell culture can be cultivated between the latter. In the embodiment shown the cultivation space is divided into two chambers separated by central separating webs 13 . A communication can take place between the two chambers via conduits provided in the central separating webs so that fluids can flow and/or a cell emigration can take place. For example, neurons can be cultivated in one chamber while muscle cells grow in the other chamber. Axons of the neurons can grow through the conduits in the central separating webs and dock on the muscle cells. The signals being produced and their propagation can be determined in a resolved manner locally and in time in both chambers with the aid of the sensor array.
The invention relates to a hybrid three-dimensional sensor array, in particular for measuring biological cell assemblies. The sensor array has a plurality of microstructured sensor plates, each having one carrier section on which a plurality of sensor needles are arranged in a comb-like manner, which carry a plurality of electrode surfaces. Furthermore, a plurality of spacer elements are provided, which are fastened between the sensor plates so that both the carrier sections and the sensor needles of adjacent sensor plates are at a distance from each other. The invention further relates to a measuring assembly for measuring electrical activities of biological cell assemblies using such a sensor array.
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FIELD OF THE INVENTION [0001] The present invention relates to the field of sampling devices and methods for mixed bulk material, and more particularly to sampling devices and methods for mixed powder ingredients for pharmaceutical preparations. BACKGROUND OF THE INVENTION [0002] In the manufacture of dosage forms, in the pharmaceutical, food and chemical industries, e.g. tablets, capsules, permeable pouches, cans etc., active and inactive ingredients are blended in a suitable blender. Such blends of materials are routinely sampled and tested for homogeneity. Blended bulk materials may be liquid, powder, or a suspension of a powder in a liquid. A proper sampling technique requires unit-dose or bulk quantity sampling to be acquired from different areas of the batch, e.g., top, middle and bottom of the blender or storage container. A unit-dose sample is defined as a quantity of mixed material that is of sufficient size to provide one dose of the active ingredient, whereas a bulk sample is defined as a sample size large enough to provide multiple doses of the active ingredient. Conventionally, samples are obtained by inserting a tubular sampling device having multiple cavities into a batch of mixed materials in the blender. However, such a sampling procedure disturbs the blend during insertion by creating localized pressure spots, thus affecting the test results. This is especially true in case of powder blends. In addition, this sampling technique requires samplers of different lengths to accommodate different size blenders or storage containers. Further, in closed flow streams of powder from a blender or container, there is no provision for compacting the samples into tablets or collecting the samples directly into gelatin capsules in order to eliminate or reduce the post-sampling error caused by transfer handling of small quantities of loose powder. [0003] U.S. Pat. No. 5,974,900, issued on Nov. 2, 1999 to the present inventor, describes a manually operated stream sampling device and method. This device does offer the possibility of compacting the powder samples into tablets or collecting the samples directly into gelatin capsules. However, this device can be used only with open streams of material, and it is desirable to keep mixed powder materials in closed streams to avoid spreading powder dust into the ambient atmosphere. [0004] U.S. Pat. Nos. 5,440,941, 5,337,620 and 6,339,966 each disclose a tube-and-shaft type sampling device as may be employed in the invention described and claimed herein. Each of these patents is incorporated herein in its entirety by reference. [0005] The present invention offers the following advantages over the currently available samplers: (a) the sampler does not have to be inserted into the powder bed; (b) a closed stream of material may be sampled without exposing personnel to powder dust; (c) unit-dose samples may be obtained and processed into the form of tablets or capsules (d) multiple sample collectors are provided for efficiency; and (f) the devices are easily assembled, disassembled, operated and cleaned. SUMMARY OF THE INVENTION [0006] The present invention is a sampling device and a method for obtaining samples from a falling closed stream of mixed material. The sampling device consists of a sleeve, a guide ring and one or more sample collectors. [0007] The sleeve has holes on its top flange for being bolted to a discharge port of a blender or storage container. The bottom flange of the sleeve is formed to engage a flow skirt to convey the powder material into a drum or a bin without distributing any dust into the surrounding environment. The mixed powder flows through a sleeve formed with one or more radially aligned holes adapted for inserting a number of collectors. [0008] The guide ring is formed with radially aligned holes on its side surface to match the holes on the cylinder's surface. Collectors are guided through these holes to retrieve samples. Each of these holes is configured to prevent the sampler shaft from rotating [0009] Each collector has an outer tube and an inner shaft and an end piece. The outer tube and the inner shaft have corresponding openings. The inner shaft and the outer tube each have a handle so that they can be rotated individually to open and close sample-collection cavities. The end piece has a curvature that matches the inner surface of the sleeve so that the falling powder material is minimally disturbed. The end piece is larger than the hole in the sleeve to prevent unintended removal. The tube is turned to expose holes in the shaft and collect sample material, and turned back to the original position, to close the dies as described in U.S. Pat. Nos. 5,337,620 and 5,440,941, noted above. The collector shaft may be modified to accommodate empty gelatin capsules instead of holes or sample dies. BRIEF DESCRIPTION OF THE DRAWINGS [0010] [0010]FIG. 1 is a side elevation view of a blender to which the sampling device of the invention is mounted. [0011] [0011]FIG. 2 is a perspective view of a sleeve of the invention sampling device. [0012] [0012]FIG. 3 is a top plan view of a collar adapted for being mounted around the sleeve of FIG. 1 with a plurality of collectors assembled thereto. [0013] [0013]FIG. 3A is an enlarged segmented view similar to that in the dashed circle of FIG. 3 with the sleeve tube added for detail. [0014] [0014]FIG. 4 is a top plan view of the collar of FIG. 3 shown in opened condition without the collectors. [0015] [0015]FIG. 4A is a section view taken along line 4 A- 4 A of FIG. 4. [0016] [0016]FIG. 5 is an exploded perspective view of the collector shown in FIG. 3, comprising a tube with an end cap, a shaft, and a plurality of dies. [0017] [0017]FIG. 6 is a diagrammatic representation of the top of the invention sleeve showing the location from which samples are obtained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT [0018] The following description depicts the preferred embodiment as illustrated in the accompanying drawing figures. The described embodiment is provided as an example, not a limitation, of the principles of the invention. [0019] Referring now to FIG. 1, a commercial tumbling blender 10 , as is known in the trade, is shown in upright orientation at the termination of the blending operation during which blender 10 is rotated, or tumbled, around shaft S to thoroughly mix powder ingredients to a homogeneous batch. The bulk material, typically a powder, consists essentially of active and inactive components to be mixed together. The speed of rotation of the blender and the length of the tumble cycle depends upon the tumbler geometry and capacity as well as the properties of the components being mixed. Blender 10 is fitted with a discharge port 12 having a discharge valve 14 by which the mixed batch may be allowed to flow out of blender 10 . [0020] The apparatus of the invention is generally depicted as sampler 20 , comprising sleeve 24 and collectors 60 , to be described in detail below. An upper flange of sleeve 24 is attached by means of bolts or otherwise, to discharge valve 12 . A shroud 16 is mounted to encompass a lower end of sleeve 24 so that the mixed powder material is discharged from blender 10 into receptacle 18 without sending dust into the surrounding environment. The relative size of illustrated blender 10 and sampler 24 is not intended to represent actual equipment. Sampler 20 may connect to other supply apparatus, such as a duct or storage tank. [0021] [0021]FIG. 2 shows a detail of sleeve 24 in perspective view. Sleeve 24 is formed with a circumferential wall 29 , an upper flange 26 and a lower flange 28 . Circumferential wall 29 defines a throat portion 30 , having axis 31 , through which the mixed bulk powder materials are conveyed following the blending operation. Upper flange 26 is formed with a plurality of bolt holes 32 which match with the location of a similar set of bolt holes in the under side of discharge port 12 (FIG. 1). Lower flange 28 is provided and sized to securely hold shroud 16 as described above. One or more collector holes 34 are formed through circumferential wall 29 in orientations so that each is along a radius of throat 30 . As will be noted below in reference to FIG. 3, collector holes 34 are uniformly spaced around the periphery of circumferential wall 29 . Sleeve 24 is preferably formed of an inert, easily cleanable material, for example stainless steel. [0022] Referring now to FIGS. 3 and 4, a guide ring 42 depicted in closed and open condition, respectively. Guide ring 42 is split into two hemi-rings 42 a and 42 b . The two hemi-rings 42 a and 42 b are connected at a mutual end by hinge 54 and are closeable at an opposite end by engagement of latch 50 with hook 52 . An elevation view of hemi-ring 42 a is shown in FIG. 4A, as taken in the direction of line 4 A- 4 A of FIG. 4. [0023] The inside diameter D of guide ring 42 is sized to snugly encircle the periphery of tube 29 of sleeve 24 (see FIG. 2). Guide ring 42 has a diametral thickness of T. Guide ring 42 has a vertical thickness t, as shown in FIG. 4A. Vertical thickness t and diametral thickness T are each sufficient to receive and slidingly support collectors 60 in a guide hole 44 , 46 , 48 , respectively. Thickness t is preferably on the order of double the outside diameter of collector 60 or greater. Diametral thickness T is preferably about 2-3 times the outside diameter of collector 60 . Ring 42 is formed of a plastic resin, for example nylon, according to the preferred embodiment. [0024] A plurality of radially aligned holes 44 , 46 and 48 are formed through guide ring 42 so as to be separated from each other by substantially equal angles α, when ring 42 is closed around circumferential wall 29 . In the case of the illustrated embodiment, guide holes 44 , 46 and 48 are separated by angles α of 120°. Each guide hole 44 , 46 and 48 is formed with an enlarged entry on the outer side of guide ring 42 and a slot 44 s (shown in FIG. 4A) to accommodate a collar portion and pin of collector 60 , as will be described below. Since each of collectors 60 a , 60 b and 60 c are shown in FIG. 3 to be oriented on co-planar radii, only one of collectors 60 a , 60 b and 60 c , for example collector 60 a , can be positioned through the center of ring 42 at any one time. With collector 60 a positioned across throat 30 , alternate collectors 60 b and 60 c are retracted to reside mainly outside of ring 42 with their respective inner end caps 78 a (see FIG. 6) adjacent the inner wall of ring 42 . [0025] Typical collector 60 is illustrated in exploded perspective view in FIG. 5. Collector 60 is made up of tube 62 , shaft 82 , dies 90 a , 90 b and 90 c , and plug 78 . For purposes of description, tube 62 is assumed to have an outer end, shown on the left as illustrated FIG. 5 and an inner end, shown on the right. Outer end and inner end also refers to the radial representation of collectors 60 a , 60 b and 60 c shown assembled to guide ring 42 in FIG. 3. Tube 62 is sized in diameter to slidingly ride in guide hole 44 and collector hole 34 , with a collar 64 located adjacent the outer end of tube 62 sized to snugly engage the enlarged entry of guide hole 44 . A flange 70 is formed at the outer end of tube 62 to control the depth to which tube 62 , including mounted plug 78 , may be inserted into sleeve 24 and serve as a connecting point for rotator 68 . Rotator 68 extends radially outwardly from flange 70 and serves as a control of the angular orientation of tube 62 . Tube 62 is formed with a set of apertures 80 a , 80 b and 80 c which, when tube 62 is appropriately oriented on shaft 82 , are positioned above dies 90 a , 90 b and 90 c , respectively. As will be apparent to those skilled in the art, apertures 80 are slightly smaller than respective dies 90 so as to retain dies 90 seated in slot 88 during operation, as described below. Plug 78 is formed with a threaded end to snugly engage a matching thread within the inner end of tube 62 . The outer end of plug 78 is formed with a cap 78 a that has an end shape that is preferably spherical with a radius r that is parallel to the radius R of throat 30 , as shown most clearly in FIG. 3A. Cap 78 a is formed larger in diameter than collector holes 34 in sleeve 24 . The spherical radius r of cap 78 a is smaller than radius R of collar by a space Z between cap 78 a and tube 29 when tube 62 is fully inserted and flange 70 contacts guide ring 42 . In this configuration, cap 78 a disturbs the flow of passing mixed powder material to only a minimal degree. The spherical radius r of cap 78 a is similarly effective in minimizing powder flow disturbance when collector 60 is retracted outwardly as in the case of collectors 60 b and 60 c in FIG. 3. [0026] Shaft 82 is sized to slidingly insert into bore 72 in tube 62 and to extend, when fully inserted, substantially the full length of tube 62 . Shaft 82 is configured with a slot 88 that receives a plurality, for example 3, of dies 90 . As described in the prior patents cited hereinabove, dies 90 each have a cavity 92 that has an internal volume sized to contain a selected quantity, equal to a unit dose of the powder mix. As an alternate choice of the user, dies 90 are adapted to hold a half gelatin capsule to catch the powder mix directly in the capsule, avoiding the need for transfer of the powder samples. Dies are designed to be readily replaced in shaft 82 so that a unit dose of the specific powder mix being processed may be collected. A series of pairs of holes 89 are provided through shaft 82 such that each pair of holes 89 is positioned beneath a respective one of dies 92 a , 92 b and 92 c . By inserting a tool (not shown) through each pair of holes 89 , the proximate die 92 is lifted out of shaft 82 enough so that it may be grasped by the fingers or an appropriate tool. The distance between the holes in each pair of holes 89 is greater than the distance between adjacent holes 89 in sequential pairs so that the tool cannot be inserted into holes affecting two adjacent dies. Shaft 82 is further formed with a pin 86 extending radially therefrom and positioned near a handle 84 at the outer end of shaft 82 . Pin 86 is sufficiently long to extend beyond the outer diameter of collar 64 and to engage slot 44 s in guide ring 42 when assembled. When dies 90 are placed within slot 88 with cavities 92 exposed and oriented to be open upwardly, shaft 82 is placed into bore 72 of tube 62 and pin 86 enters keyway 74 in flange 70 . A slot 66 is formed as a “T,” with its stem parallel to the axis of tube 62 and its cross-bar circumferential thereto. After pin 86 passes through flange 70 into slot 66 in collar 64 , tube 62 is rotated so that pin 86 rides along the cross-bar of slot 66 and cavities 92 are covered by the portion of tube 62 without apertures. The combined length of tube 62 and cap 78 a is slightly less than the distance from the outside of guide ring 42 to the opposed inside surface of circumferential wall 29 (see FIG. 3A) when assembled. [0027] The method of operation of the sampling apparatus of the invention is typically as follows. Guide ring 42 is placed around circumferential wall 29 of sleeve 24 and locked in place with guide holes 44 aligned with collector holes 34 . The operator pushes a first tube 62 (see FIG. 3A) into sleeve 24 and threads a mating plug 78 to the inner end thereof. A shaft 82 is prepared for sample collecting by placing a number of dies 90 with cavities 92 exposed into open slot 88 . Shaft 82 is then slidingly inserted into tube 62 . Handle 84 is held still to keep cavities 92 facing up as rotator 68 is turned to close apertures 80 . Additional collectors 60 are assembled to sampler 20 as described above. Each collector 60 is retracted so as to be positioned out of throat 30 to the extent possible. Sleeve 24 is assembled to discharge port 12 on the bottom of blender 10 by threaded fasteners or other means (not shown). Shroud 16 is connected to the bottom of sleeve 24 and its lower open end is placed into receptacle 18 . Valve 14 is opened to allow mixed powdered material to flow from blender 10 through sleeve 24 and into receptacle 18 . At an appropriate time in the process of transfer of the mixed bulk material from blender 10 to receptacle 18 , the operator pushes a handle 84 so as to insert a selected sampler 60 across the width of throat 30 . In so doing, collar 64 (see FIG. 5) enters the enlarged entry portion of guide hole 44 , and pin 86 , extending upward beyond collar 64 , enters slot 44 s . Being engaged in slot 44 s , pin 86 prevents unwanted rotation of shaft 82 , maintaining cavities 92 facing upward. The operator turns rotator 68 clockwise to rotate tube 62 and expose dies 90 , allowing a quantity of bulk mixed material to fill each cavity 92 a , 92 b and 92 c . Rotator 68 is turned counterclockwise to close tube 62 over cavities 92 a , 92 b and 92 c . The operator pulls handle 84 without rotation so as to retract assembled collector 60 to the extent possible until cap 78 a contacts the near-inner side of circumferential wall 29 . The operator rotates handle 84 clockwise, to turn both shaft 82 and tube 62 , causing dies 90 a , 90 b and 90 c to be oriented downwardly. The operator holds handle 84 still while rotating rotator 68 further clockwise to move apertures 80 a , 80 b and 80 c of tube 62 to expose dies 92 a , 92 b and 92 c , while positioning a container beneath each die to transfer the sample from each die into individual containers for quality testing, as is known. Optionally, the samples obtained may be pressed into tablets prior to testing, which may be done in dies 92 . [0028] In the alternate process whereby samples of bulk mixed materials are caught in capsules that have been placed in cavities 92 , shaft 82 is kept in its orientation with cavities 92 facing upward as handle 84 is pulled to retract collector 60 . Rotator 68 is turned so that shaft 82 can be withdrawn from tube 62 . A pair of pins of a tool (not shown) is inserted through holes 89 in tube 62 to sequentially lift each die 90 sufficiently so that the operator can remove dies 90 from slot 88 with cavity 92 and the capsule it contains remains upright. The use of a capsule half is preferred in certain circumstances, such as where the finished dosage form is a capsule or where sample compaction is not required. [0029] To further clarify an objective of the present invention, FIG. 6 shows a diagrammatic representation of a top view of sleeve 24 , with the nine positions indicated from which samples are obtained. Each of the sample positions adjacent the wall of sleeve 24 is marked with an “X” and the three sample positions at the center of sleeve 24 are marked with a single “O.” [0030] The samples acquired above are from each edge and the center of sleeve 24 along the axis of collector 60 a . Leaving collector 60 a in its retracted position, the procedure described above is repeated with collector 60 b and then again with collector 60 c . At the end of this cycle, six samples have been collected from angularly dispersed peripheral locations and three samples from the center of sleeve 24 for comparison of product uniformity or other properties. [0031] While the present invention is described with respect to specific embodiments thereof, it is recognized that various modifications and variations may be made without departing from the scope and spirit of the invention, which is more clearly and precisely defined by reference to the claims appended hereto.
The present invention provides apparatus and method for sample acquisition from an active flow of mixed powder material being transferred from a blender. The apparatus includes a sleeve that is assembled co-axially to a discharge port of the blender and a number of sample collectors which each include a shaft with sample cavities and a tube that is rotatable around the shaft for exposing and covering the cavities. The sample collectors are alternately inserted through a bearing collar into the sleeve. The tubes are plugged at their respective outer ends to prevent accidental removal from the sleeve. The method includes inserting and opening each of the sample collectors in turn and removing the collected samples for analysis.
20,774
CROSS-REFERENCE TO RELATED APPLICATIONS/INCORPORATION BY REFERENCE This application is a continuation of U.S. application Ser. No. 11/935,105 filed on Nov. 5, 2007, which in turn makes reference to and claims priority to U.S. Provisional Application Ser. No. 60/944,011, filed on Jun. 14, 2007, which is hereby incorporated herein by reference in its entirety. FIELD OF THE INVENTION Certain embodiments of the invention relate to wireless communication. More specifically, certain embodiments of the invention relate to a method and system for 60 GHz antenna adaptation and user coordination based on base station beacons. BACKGROUND OF THE INVENTION The field of wireless communication has seen dramatic growth the last few years. In today's world, most people use their mobile devices, be it cellular phones, PDA's, laptops, media players and/or other devices for business and personal use on a constant and daily basis. Often multiple users within a local environment operate on a plurality of wireless interfaces. In addition to voice and data communication such as email and internet browsing, these devices may enable high speed data transfer such as video streaming or multi-user gaming wherein multiple users interact with one or more video display applications. Wireless service providers may offer links via various wireless technologies such as GSM, CDMA or WIMAX for wide area communications while links utilized within a local region or interior space may comprise technologies such as wireless local area networks (WLAN) and wireless personal area networks (WPAN). Many service providers offer location based services for hand held wireless devices. These location based services may utilize satellite reference systems such as the Global Positioning system (GPS). The GPS system comprises 24 medium orbit satellites that enable devices comprising GPS receivers to determine position and time. The devices may calculate their position by measuring their distance from three or more GPS satellites. In some instances, the GPS system may be utilized as a clock reference for a plurality of devices that depend on a known time reference. Further limitations and disadvantages of conventional and traditional approaches will become apparent to one of skill in the art, through comparison of such systems with the present invention as set forth in the remainder of the present application with reference to the drawings. BRIEF SUMMARY OF THE INVENTION A system and/or method for 60 GHz antenna adaptation and user coordination based on base station beacons, substantially as shown in and/or described in connection with at least one of the figures, as set forth more completely in the claims. Various advantages, aspects and novel features of the present invention, as well as details of an illustrated embodiment thereof, will be more fully understood from the following description and drawings. BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS FIG. 1A is a block diagram that illustrates an exemplary system for 60 GHz antenna adaptation and user coordination based on base station beacons, in accordance with an embodiment of the invention. FIG. 1B is a block diagram that illustrates an exemplary wireless base station and mobile station communicating via one or more wireless links comprising a 60 GHz wireless link and a plurality of lower frequency wireless links, in accordance with an embodiment of the invention. FIG. 2A is a block diagram that illustrates an exemplary system that may perform location determination measurements via one or more 60 GHz wireless links and/or one or more lower frequency links, in accordance with an embodiment of the invention. FIG. 2B is a block diagram that illustrates an exemplary system that may perform location determination measurements via one or more 60 GHz wireless links and/or one or more lower frequency links, in accordance with an embodiment of the invention, in accordance with an embodiment of the invention. FIG. 2C is a block diagram that illustrates an exemplary system that may communicate via one or more 60 GHz wireless links via highly directional adaptive antennas, in accordance with an embodiment of the invention. FIG. 3 is a flow chart that illustrates exemplary steps for location determination and antenna adaptation utilizing a 60 GHz wireless link, in accordance with an embodiment of the invention. DETAILED DESCRIPTION OF THE INVENTION Certain aspects of the invention may be found in a method and system for 60 GHz antenna adaptation and user coordination based on base station beacons. Various aspects of the invention may enable communication between two or more wireless devices via a 60 GHz wireless link. In this regard, 60 GHz transmissions may utilize any available unlicensed millimeter wave frequency band within the range of 57 to 66 GHz. Due to the characteristics of radio wave propagation at extremely high frequencies, 60 GHz wireless links may be best utilized for communication over short distances and may be transmitted in highly directional beams. Accordingly, a pair of antennas enabled as 60 GHz, transmitting and receiving link partners may need to be precisely aligned in order to maintain communication. Adaptive antennas may be utilized to maintain such an alignment between two 60 GHz link partners during transmissions. However, determining the initial alignment via adaptive antenna signal processing may be time consuming. Therefore, various location determination techniques may be utilized to aid in the initial alignment of antennas utilized in 60 GHz communications. For example, a beacon signal may be transmitted from a base station to aid in location determination of one or more mobile devices. The beacon may be transmitted via a directional radiation pattern that may be swept through an angle over azimuth or altitude for example. The base station and mobile stations may utilize angle and/or distance measurements based on the beacon to locate the mobile stations and map their positions. In some embodiments of the invention, the location determination process may be aided by global positioning system (GPS) data, a terrestrial reference system, and/or a compass for position and/or time references. The base station and mobile stations may share location determination information in order to enable 60 GHz transmissions via adaptive antennas. In this regard, the base station and mobile stations may comprise a plurality of wireless interfaces for communication tasks such as device discovery, initial connection, security operations, application operations, location determination enablement and location information sharing for example. In some embodiments of the invention, antenna arrays may be utilized that enable beamforming such as in phased arrays, for example, to modify the direction of transmission and/or reception. Beamforming may be based on improving signal to noise ratio (SNR) and/or received signal strength. Accordingly, signal processing may be utilized to adjust the amplitude and/or phase of signal components and therefore modify beam or sensitivity direction via the antenna array. Adaptive beamforming may enable modification of the beam direction according to perceived varying spatial relationships between wireless devices. In some aspects of the invention, switched beamforming may be utilized. In this regard, the direction of radiation may be switched through a plurality of fixed beam patterns. FIG. 1A is a block diagram that illustrates an exemplary system for 60 GHz antenna adaptation and user coordination based on base station beacons, in accordance with an embodiment of the invention. Referring to FIG. 1A , there is shown two wireless devices, a base station 102 and a mobile station 104 . The two wireless devices 102 and 104 may each comprise at least a processor block 112 , a memory block 114 , a 60 GHz block 110 a and antenna interfaces 116 and 118 respectively. In addition, the base station 102 and mobile station 104 may each comprise one or more of a wireless local area network (WLAN) block 110 b , a wireless personal area network (WPAN) block 110 c , and/or a global positioning system (GPS) receiver 110 d . The base station 102 and mobile station 104 are not limited to these specific wireless technology interfaces and may comprise any suitable wireless interface, for example, any type of cellular and/or WIMAX technologies may be utilized. The base station 102 and mobile station 104 may comprise suitable logic, circuitry and/or code that may enable wireless communication via one or more of the wireless interfaces 60 GHz 110 a , WLAN 110 b , WPAN 110 c and/or GPS receiver 110 d . For example, the highly directional 60 GHz interface 110 a may be utilized for location determination operations and or data transfer. Communications via one or more of the lower frequency band interfaces, for example, WLAN 110 b and/or WPAN 110 c may enable tasks such as device discovery, connection initiation, security operations, data transfer, service coordination and/or location determination for example. In some embodiments of the invention, the base station 102 , may control and coordinate operations among one or more mobile stations such as mobile station 104 . For example, the base station 102 may communicate mobile station position information to one or more mobile stations that may enable mobile stations to adapt antennas for highly directional 60 GHz communications. The base station 102 and/or mobile station 104 may not be limited with regard to any specific software application. For example, the 60 GHz wireless interfaces 110 a may be utilized for high speed multi user video gaming or video streaming for example and the base station 102 and/or mobile station 104 may comprise video displays. In addition, the mobile station 104 and/or base station 102 may be enable internet access for browsing, gaming, data retrieval and/or voice over internet protocol (VoIP). The wireless multimode devices 102 and/or 104 may enable wireless phone connections for example. The base station 102 may be a stand-alone stationary device or may be substantially the same as or similar to the mobile station device 104 . In some embodiments of the invention, the base station 102 may be incorporated into a device such as a set-top box, a home gateway or gaming console for example. Moreover, the base station 102 may act as a residential gateway and may connect to the internet or another network via a line and/or wireless connection. Furthermore, the base station 102 may comprise suitable logic, circuitry and or code to transmit a beacon signal via the 60 GHz link 110 a or via a lower frequency wireless interface for example WLAN 110 b or WPAN 110 c. The processor blocks 112 may comprise suitable logic, circuitry and or code to enable a plurality of tasks for the base station 102 and mobile station 104 . For example the processor block 112 may enable location determination tasks that may comprise processing spatial information and mapping mobile station positions. The processor block 112 may enable coordination of communication operations for one or more mobile stations 104 . Antenna management and signal processing, for example beamforming, may be enabled within the processor block 112 . In addition, the processor block 112 may enable applications operations, for example, gaming or digital image rendering processes. In this regard, the processor block 112 may comprise one or more general purpose processors and/or one or more special purpose processors. The processor block 112 may be communicatively coupled to the memory block 114 , the antenna block 116 or 118 , the 60 GHz block 110 a , WLAN block 110 b , WPAN block 110 c and or the GPS receiver 110 d. The memory blocks 114 may comprise suitable logic, circuitry and or code to store and retrieve data for the base station 102 and mobile station 104 . In addition to supporting communications, gaming and/or image processing operations, the memory block 114 may support location determination operations. The memory block 114 may be communicatively coupled with the processor block 112 , the antenna block 116 or 118 , the 60 GHz block 110 a , WLAN block 110 b , WPAN block 110 c and or the GPS receiver 110 d. The antenna block 116 in the base station 102 may comprise suitable logic, circuitry and or code to enable transmission and/or reception of signals between the base station 102 and one or more mobile stations such as mobile station 104 . The antenna block 116 may comprise one or more antenna elements and/or antenna arrays. In this regard, beamforming via adaptive signal processing and/or beam switching may be utilized for 60 GHz communications. Antennas may be wide band and/or narrow band and may vary with respect to radiation pattern according to the needs of a specific design. In addition, the antenna block 116 may enable transmission of a pilot or beacon signal which may be radiated in an omni directional pattern or may be radiated in a directional pattern and may be swept through an angle over azimuth or altitude for example. In this regard, the beacon may be transmitted on the 60 GHz wireless interface 110 a or on a lower frequency interface such as WLAN 110 b or WPAN 110 c via a 2.4 GHz or 5 GHz band carrier for example. The antenna block 116 may be communicatively coupled with the 60 GHz block 110 a , the WLAN block 110 b , the WPAN block 110 c , the GPS receiver 110 d and/or any other wireless transceiver suitable for the base station 102 . In addition, the antenna block 116 may be communicatively coupled with the processor block 112 and the memory block 114 . The antenna block 118 in the mobile station 104 may comprise suitable logic, circuitry and or code to enable transmission and/or reception of signals between the mobile station 104 and the base station 102 as well as between two or more mobile stations such as the mobile station 104 . The antenna block 118 may comprise one or more antenna elements and/or antenna arrays and may enable beamforming for example via adaptive signal processing or beam switching for 60 GHz communications between two or more mobile stations and/or between a mobile station and a base station 102 . Antennas may be wide band and/or narrow band and may vary with respect to radiation pattern according to the needs of a specific design. In addition, the antenna block 118 may enable reception of a pilot or beacon signal from the base station 102 . The pilot signal may be received via an omni directional pattern antenna or a directional pattern antenna as well as an antenna enabled to adapt to varying signal direction. In this regard, the beacon may be received on the 60 GHz wireless interface 110 a or on a lower frequency interface such as WLAN 110 b or WPAN 110 c via a 2.4 GHz or 5 GHz band carrier for example. The antenna block 118 may be communicatively coupled with the 60 GHz block 110 a , the WLAN block 110 b , the WPAN block 110 c , the GPS receiver 110 d and/or any other wireless transceiver suitable for the mobile station 104 . In addition, the antenna block 118 may be communicatively coupled with the processor block 112 and the memory block 114 within the mobile station 104 . The 60 GHz physical interface 110 a may comprise suitable logic, circuitry and/or code to enable communications within a local region relative to the base station 102 and mobile station 104 . The 60 GHz interface may, for example, enable local file transfers, video connections and/or high speed gaming for one or more users. The 60 GHz block may comprise a physical layer interface or a physical layer interface and a medium access control (MAC) layer. 60 GHz signals may be transmitted short distances, point to point, in a highly directional radiating pattern. In addition, the 60 GHz interface 110 a may enable location determination operations for the base station 102 and/or the mobile station 104 . In addition, the 60 GHz physical interface may support high speed data transfer via an ultra wide band (UWB) technology for example, or other wireless technologies. The wireless local area network (WLAN) block 110 b may comprise suitable logic, circuitry and or code to enable communications within a local region relative to the base station 102 and mobile station 104 . The WLAN block 110 b may support an IEEE 802.11 physical layer (PHY) or a PHY and a media access control (MAC) layer. In addition, the WLAN block 110 b may operate on a lower portion of spectrum, for example, near 2.4 GHz and/or 5 GHz for example. The WLAN block 110 b may be utilized to communicate and/or retrieve data from a computer or network, for example video and/or audio data. Moreover, the WLAN block 110 b may be utilized to access the Internet for retrieval of audio/video data, web surfing and/or voice over IP for example. In some embodiments of the invention, the WLAN may be utilized to support location determination by sharing geo-location information obtained via the 60 GHz block 110 a and/or GPS block 110 d with one or more devices. The wireless personal area network (WPAN) block 110 c may comprise suitable logic, circuitry and or code to enable communications within a local region relative to the base station 102 and/or 104 . The WPAN block 110 c may comprise for example, a Bluetooth transceiver comprising a physical layer interface or a physical layer interface and a medium access control (MAC) layer. The WPAN block 110 c may support operations in the 2.4 GHz and/or 5 GHz frequency bands or may operate in other suitable spectrum. The WPAN block 110 c is not limited with regard to wireless technologies and may, for example, support frequency hopping or UWB technology capable of high speed file transfer such as Wimedia. The WPAN block 110 c may enable device discovery, security operations and/or general administrative activity among the base station 102 and mobile station 104 . The WPAN block 110 c may be communicatively coupled with the processor block 112 , the memory block 114 and/or the antenna blocks 116 and/or 118 . The GPS block 110 d may comprise suitable logic, circuitry and or code to enable communications with Global Positioning System (GPS) satellites. The GPS block 110 d may comprise a GPS receiver enabling reception of spread spectrum signals carrying information that enables clock synchronization and/or coarse position determination for civilian applications or more precise position determination for military applications. GPS information comprising satellite position, current time and measured delay of the received signal, may be utilized to calculate a position fix for the base station 102 and/or the mobile station 104 . Position errors caused by atmospheric conditions, multi-path signals, clock errors and other physical conditions may be processed for improved accuracy. The GPS block 110 d may be communicatively coupled with the processor block 112 , the memory block 114 and the antenna block 116 and/or 118 . In operation, the base station 102 and mobile station 104 may communicate via multiple wireless interfaces comprising a 60 GHz interface 110 a and one or more lower frequency wireless interfaces 110 b and/or 110 c . Moreover, the base station 102 and/or one or more mobile stations may communicate via adaptive antennas. The 60 GHz block 110 a , WLAN block 110 b , WPAN block 110 c and/or the GPS block 110 d may enable location determination operations. In this regard, the 60 GHz block 110 a may improve the precision of location information that may be based on lower bandwidth measurements. In addition, high speed data transfer, for example audio and/or video data, may be transmitted between the base station 102 and mobile station 104 or between two or more mobile stations such as mobile station 104 via the 60 GHz physical interface 110 a. The lower frequency interfaces, for example WLAN 110 b and/or WPAN 110 c , may be utilized to enable application and communication operations among the base station 102 and mobile station 104 . For example, lower frequency interfaces may be utilized to transfer data with regard to security and/or coordination among devices. A WPAN interface 110 c may, for example, enable discovery of devices within a local region. A WLAN interface 110 b may, for example, enable sharing of location determination information among devices. In addition, the lower frequency interfaces WLAN 110 b and/or WPAN 110 c may enable location determination of mobile stations. In this regard, location information gathered via the lower frequency interfaces WLAN 110 b and/or WPAN 110 c interfaces for example, may be utilized to aid in establishing highly directional 60 GHz connections via adaptive antennas between the base station 102 and mobile station 104 or between two or more mobile stations 104 . In another aspect of the invention, the WLAN physical interface 110 b and/or WPAN 110 c interfaces may be utilized by applications running on the base station 102 to distribute information retrieved from a network. The base station 102 and/or mobile station 104 may be utilized in a plurality of applications that may comprise multi-user high speed wireless gaming and/or audio/video wireless data transfer and rendering for example. The invention is not limited with regard to specific applications and the base station 102 and/or mobile station 104 may support a plurality of applications. FIG. 1B is a block diagram that illustrates an exemplary wireless base station and mobile station communicating via one or more wireless links comprising a 60 GHz wireless link and a plurality of lower frequency wireless links, in accordance with an embodiment of the invention. Referring to FIG. 1B , there is shown a base station 102 and mobile station 104 , a lower frequency wireless link 106 , a 60 GHz wireless link 108 , an optional line or wireless communications link 154 and an optional network 120 . The base station 102 may be the same or similar to the base station 102 described in FIG. 1A . The base station 102 may comprise suitable logic, circuitry and/or code to enable wireless communication via one or more wireless interfaces as well as enable location determination of one or more mobile stations 104 via a 60 GHz wireless link 108 and/or a lower frequency wireless link 108 . In addition, the base station 102 may be capable of receiving GPS information for location determination assistance. In one embodiment of the invention, the base station 102 may be connected to a line and/or wireless network 120 that may be, for example, the Internet Accordingly, the base station 102 may act as an access point and/or a gateway to a network for one or more local devices such as the mobile station 104 . In addition, the base station 102 may serve as a coordinator and/or controller of operations in relation to one or more devices such as mobile station 104 and may change roles with another device such as the mobile station 104 , wherein the other device becomes the coordinator and/or controller of operations. Moreover, the base station 102 may handle peer to peer relationships with one or more devices such the mobile station 104 . The base station 102 may be a stationary unit or may be portable or mobile. In this regard, the base station 104 may be a stand alone unit or may, for example, be incorporated in a WLAN access point, a set top box, a game console, a computer, a video server or video recorder/player device. The base station 102 may enable location determination for one or more devices such as the mobile station 104 . In this regard, the base station 102 may transmit a 60 GHz pilot or beacon signal via the wireless link 108 to enable position measurements and/or location determination for one or more devices such as mobile station 104 . The base station 102 may utilize wireless technologies on lower operating frequencies, for example, utilizing WLAN 110 b or WPAN 110 c via wireless link 106 to share location determination information with one or more devices such as mobile station 104 . Moreover, the lower frequency link 106 may be utilized for device position measurements. In this regard, position measurements may be utilized to enable highly directional antenna orientation for 60 GHz transmissions between the base station 102 and mobile station 104 and/or between two or more mobile stations such as the mobile station 104 . The mobile station 104 may be the same or similar to the mobile station 104 described in FIG. 1A . The mobile station 104 may comprise suitable logic, circuitry and/or code to enable communication via one or more wireless links such as the 60 GHz wireless link 108 and/or the lower frequency link 106 and may utilize adaptive antennas. The mobile station 104 may enable location determination via the 60 GHz link 108 and/or one or more lower frequency links 106 . In addition, the wireless mobile station 104 may be capable of receiving and processing GPS information for location determination assistance. In one embodiment of the invention, the mobile station 104 may receive coordination and/or control information from the base station 102 . In some embodiments of the invention, the mobile station 104 may be enabled to change roles with base station 102 wherein mobile station 104 may become the coordinator and/or controller of operations among a plurality of devices. Moreover, the mobile station 104 may handle peer to peer relationships with one or more devices such as base station 102 and/or mobile station 104 . The mobile station 104 may enable location determination for base station 102 and/or one or more mobile stations 104 . In this regard, the mobile station 104 may receive and/or may transmit a pilot or beacon signal via the 60 GHz wireless link 108 and/or the lower frequency link 106 to enable location determination. The mobile station 104 may utilize wireless technologies on lower operating frequencies for example WLAN or WPAN to share information for example information regarding discovery, location determination, security operations, application data, control and/or coordination information with base station 102 and/or other mobile stations such as mobile station 104 . The wireless link 106 may communicatively couple two or more wireless devices such as base station 102 and mobile station 104 and/or two or more mobile stations such as the mobile station 104 . Accordingly, the base station 102 and mobile station 104 may comprise suitable logic, circuitry and/or code to generate the lower frequency link 106 . Accordingly, the wireless link 106 may be enabled to share data, perform discovery, initiate connections and/or facilitate operations for example. Moreover, the lower frequency link may comprise suitable logic, circuitry and/or code to transmit and/or receive a pilot or beacon signal between the base station 102 and/or mobile station 104 . The wireless link 106 may support lower frequencies than the 60 GHz link 108 , for example 2.4 GHz and/or 5 GHz and may be communicatively connected with the WPAN 110 c and/or WLAN 110 b interfaces for example. However, the invention is not limited with regard to specific carrier frequencies and any suitable frequency may be utilized. These lower frequency wireless links 106 may be radiated in a directional pattern, a broad-angle pattern or even in an omni directional pattern and may be scanned over an angle for example. Achievable transmission distance or range, supported by the lower frequency wireless link 106 , may vary depending on a plurality of factors comprising carrier frequency, wireless technology, radiating power as well as physical environment (for example, an interior space versus an exterior space). Ranges may vary from approximately 10 m to over 100 m. In some embodiments of the invention, ultra-wideband (UWB) technology may be utilized for short range communications among the base station 102 and one or more mobile stations 104 . Accordingly, UWB links may support high speed data transfers. Moreover, worldwide interoperability for microwave access (WIMAX) or various other cellular connections may be utilized and may enable longer range communications. The 60 GHz wireless link 108 may communicatively couple two or more wireless devices such as base station 102 and mobile station 104 and/or between two or more mobile stations such as the mobile station 104 . Accordingly, the base station 102 and mobile station 104 may comprise suitable logic, circuitry and/or code to generate the 60 GHz wireless link 108 . Moreover, the 60 GHz link 108 may be communicatively connected with the 60 GHz interface 110 a in the base station 102 and/or mobile station 104 for example. The 60 GHz wireless link 108 may be enabled to support location determination operations, video streaming, high speed video for multi-user gaming connections and/or high speed data transfers between base station 102 and mobile station 104 and/or between two or more mobile stations such as the mobile station 104 . Accordingly, the 60 GHz wireless links may be radiated in highly directional patterns over short ranges. In some embodiments of the invention, adaptive antenna arrays or other intelligent antenna technologies may be utilized for transmitting and/or receiving the 60 GHz link within the base station 102 and/or one or more mobile stations 104 . Highly directional 60 GHz transmissions may comprise point to point communication between two devices such as between participating devices such as two mobile stations 104 or between the base station 102 and mobile station 104 . In this regard, a participating device may have or gain knowledge of the relative positions or absolute locations of one more other devices participating in the communication. In another embodiment of the invention, the 60 GHz wireless link 108 may support location determination operations. In this regard, the 60 GHz wireless link may for example be utilized to transmit and receive a pilot or beacon signal. The pilot or beacon signal may radiate in a stationary pattern or, the direction of radiation may be varied, for example, may be swept over an angle for example. The network 120 may be a private, public or ad hoc network for example that may support applications running on the base station 102 and/or mobile station 104 . The network 120 may comprise suitable logic, circuitry and or code to handle data that may be utilized by one or more of the base station 102 and mobile station 104 . For example, audio and/or video (A/V) data may be transferred to one or more of the base station 102 and mobile station 104 from the network 120 and may be rendered. The network 120 may be communicatively coupled with the base station 102 via the communications link 154 . The communications link 154 may comprise suitable logic, circuitry and/or code that may enable the transfer of data between the base station 102 and the network 120 . Accordingly, any suitable communications network technology and communications protocol may be utilized. In operation, the base station 102 and mobile station 104 may communicate via a plurality of wireless interfaces such as 60 GHz 110 a , WLAN 110 b and/or WPAN 110 c and over a plurality of wireless links 60 GHz link 108 and lower frequency link 108 . In this regard, high bandwidth, highly directional, short range tasks such as location determination and high speed data transfers may be enabled via the 60 GHz wireless link 108 . Moreover tasks supporting the 60 GHz wireless link 108 , for example, sharing location information and other administrative tasks such as device discovery, connection initiation and security operations may be enabled via the lower frequency wireless link 106 . Upon receiving a request for service, the base station 102 may utilize a lower frequency wireless link 106 to enable discovery of devices within a local region. In addition, a lower frequency wireless link 106 may enable connection and security communications for the base station 102 and/or mobile station 104 via WPAN 110 c and/or WLAN 110 b wireless interfaces for example. Moreover, software and/or information regarding one or more applications running on the base station 102 and/or mobile station 104 may be received by the base station 102 from the network 120 via the communications link 154 and may be distributed via the lower frequency wireless link 106 to mobile station 104 for example. The 60 GHz link 108 may be utilized to enable location determination with an improved level of precision and may enable high speed communications between the base station 102 and mobile station 104 or between two or more mobile stations such as the mobile station 104 . In some embodiments of the invention, an initial reference position for one or more devices may be known based upon GPS information or another source of location information such as user configuration data for example. Subsequently, a position for the base station 102 and/or one or more mobile stations 104 , within a local region may be determined relative to one or more known reference positions. Millimeter waves from the 60 gigahertz physical interface 110 a may be used to augment GPS or other position information and may improve precision of position measurements. Furthermore, antenna arrays or directional antennas that may be swept over an angle may be utilized to support angle of arrival and or time of arrival measurements. FIG. 2A is a block diagram that illustrates an exemplary system that may perform location determination measurements via one or more 60 GHz wireless links and/or one or more lower frequency links, in accordance with an embodiment of the invention. Referring to FIG. 2A , there is shown a base station 102 , a plurality of mobile stations 104 a , 104 b 104 c , a plurality of wireless links 108 a , 108 b and 108 c and a plurality of angles 210 a , 210 b , 210 c. The base station 102 may be similar or substantially the same as the base station 102 described in FIGS. 1A and 1B . The mobile stations 104 a , 104 b and 104 c may be similar or substantially the same as the mobile station 104 in FIGS. 1A and 1B . The wireless links 108 a , 108 b and 108 c may be similar to or substantially the same as the 60 GHz link 108 described in FIG. 1B and/or the lower frequency link 106 described in FIG. 18 . The wireless links 108 a , 108 b and/or 108 c may be communicatively coupled with the mobile stations 104 a , 104 b and/or 104 c respectively and the base station 102 and may be enable a pilot or beacon signal between the base station 102 and the mobile stations 104 a , 104 b and/or 104 c . In some embodiments of the invention, the pilot or beacon signal may be swept over an angle around the base station 102 , spanning an arc that originates from a determined reference point or direction. In this regard the wireless links 108 a , 108 b and 108 c may indicate an angle at which the one or more mobile devices 104 a , 104 b and 104 c receive the pilot or beacon signal. The angles 210 a , 210 b and/or 210 c may be angles measured between the determined reference point or direction and a wireless link 108 a , 108 b and/or 108 c . The angles 210 a , 210 b and/or 210 c may indicate a line on which the mobile stations 104 a , 104 b and/or 104 c may be located in relation to the base station 102 . In operation, the base station 102 may for example function as control and coordination device for one or more participating mobile stations 104 a , 104 b and/or 104 c . The base station 102 may for example, coordinate location determination operations for the one or more mobile stations 104 a , 104 b and/or 104 c . In this regard the base station 102 may calculate positions and/or may generate maps of participating device positions. In some embodiments of the invention, the base station 102 may utilize location information received from other internal or external sources such as a compass, the GPS system, a terrestrial reference system, user configuration data and/or other suitable sources. The base station 102 and/or mobile stations may map device positions according to any suitable coordinate system, for example, polar coordinates or Cartesian coordinates may be utilized depending on time or spatial references available to the system. The base station 102 and/or mobile stations 104 a , 104 b and/or 104 c may share information regarding location determination via a 60 GHz link 108 and/or a lower frequency link 106 as described in FIG. 2A . Furthermore, information regarding the positions of the base station 102 and/or the one or more mobile stations 104 a , 104 b and/or 104 c may be utilized to enable adaptive antenna orientation processes for communication via the 60 GHz links 108 of the participating devices. A pilot or beacon signal between the base station 102 and one or more mobile stations 104 a , 104 b and/or 104 c may be utilized to measure the angle subtended by an arc between a reference direction and the direction of the wireless links 108 a , 108 b and/or 108 c at the time of reception of the pilot or beacon signal. FIG. 2B is a block diagram that illustrates an exemplary system that may perform location determination measurements via one or more 60 GHz wireless links and/or one or more lower frequency links, in accordance with an embodiment of the invention. Referring to FIG. 2B , there is shown a base station 102 , a plurality of mobile stations 104 a , 104 b 104 c and a plurality of wireless links 108 a , 108 b and 108 c. The base station 102 may be similar or substantially the same as the base station 102 described in FIGS. 1A , 1 B and 2 A. The mobile stations 104 a , 104 b and 104 c may be similar or substantially the same as the mobile stations 104 , 104 a , 104 b and 104 c described in FIGS. 1A , 1 B and 2 A. The wireless links 108 a , 108 b and 108 c may be similar to or substantially the same as the wireless links 106 , 108 , 108 a , 108 b and 108 c described in FIGS. 1B and 2A . In addition to the operations described in FIG. 2A , the wireless links 108 a , 108 b and/or 108 c may be utilized to determine a relative distance from the base station 102 and one or more mobile stations 104 a , 104 b and 104 c . In this regard, a signal that may be a pilot or beacon or may be another communication signal between the base station 102 and one or more mobile stations 104 a , 104 b and/or 104 c may be utilized to measure the time delay from the base station 102 and one or more mobile stations 104 a , 104 b and/or 104 c . In this regard, a round trip delay time or time of arrival may be measured. The measurements may be referenced to a shared time reference, for example, from the GPS system or a terrestrial reference system for example. The distance information may be utilized to enhance the mapping of devices as described in FIG. 2A . FIG. 2C is a block diagram that illustrates an exemplary system that may communicate via one or more 60 GHz wireless links via highly directional adaptive antennas, in accordance with an embodiment of the invention. Referring to FIG. 2C , there is shown a base station 102 , a plurality of mobile stations 104 a , 104 b 104 c and a plurality of wireless links 108 a , 108 b and 108 c , a plurality of 60 GHz links 230 a , 230 b and 230 c and a plurality of angles 240 a , 242 a , 240 b , 242 b , 240 c and 242 c. The base station 102 may be similar or substantially the same as the base station 102 described in FIGS. 1A , 1 B, 2 A and 2 B. The mobile stations 104 a , 104 b and 104 c may be similar or substantially the same as the mobile stations 104 , 104 a , 104 b and 104 c described in FIGS. 1A , 1 B, 2 A and 2 B. The wireless links 108 a , 108 b and 108 c may be similar to or substantially the same as the wireless links 106 , 108 , 108 a , 108 b and 108 c described in FIGS. 18 , 2 A and 2 B. The angles 240 a , 242 a , 240 b , 242 b , 240 c and 242 c may enable location determination of the mobile stations 104 a , 104 b and/or 104 c relative to each other. These angles may be determined from angle and time measurements described in FIGS. 2A and/or 2 B as well as from other sources of location and/or time reference information described in FIGS. 2A and 2B . The angles 240 a , 242 a , 240 b , 242 b , 240 c and 242 c are shown in FIG. 2C on a two dimensional plane however angles in a third dimension or other coordinate systems may be determined and utilized. Accuracy of the of determined relative positions of the mobiles stations may depend on variables such as the directivity of the antennas utilized, the bandwidth of the signals utilized and the synchronization of a time reference. The 60 GHz links 230 a , 230 b and 230 c may be similar or substantially the same as the 60 GHz links 108 , 108 a , 108 b and 108 c described in FIGS. 1B , 2 A and 2 B however, 60 GHz links 230 a , 230 b and 230 c may be transmitted and received between mobile stations 104 a , 104 b and/or 104 c . Moreover, the 60 GHz links may be transmitted via adaptive antennas that may modify the direction of transmission and/or reception according to variations in spatial relationships between among the mobile stations 104 a , 104 b and 104 c. In operation, the base station 102 and/or one or more of the mobile stations 104 a , 104 b and 104 c may participate in communications via adaptive antennas over one or more 60 GHz wireless links 230 a , 230 b and 230 c and 60 GHz links on 108 a , 108 b and/or 108 c . The 60 GHz wireless links may comprise highly directional beams that may be difficult or time consuming to detect for antenna adaptation processes utilized among the participating devices. Prior knowledge of a general direction or bearing from one participating device to another, may reduce the time needed to detect signal sources and determine the direction for radiation intensity. Accordingly, the time to make a connection via the 60 GHz wireless links 230 a , 230 b and 230 c as well as 60 GHz links on 108 a , 108 b and/or 108 may be improved. Therefore, estimated location information such as relative positions or directions from one participating device to another may be determined via the methods described in FIGS. 1A , 1 B, 2 A and 2 B as well as for determining the angles 240 a , 242 a , 240 b , 242 b , 240 c . The determined location estimations may be more or less accurate and precise depending on the quality of measurements and reference frames utilized. Accordingly, one or more of the base station 102 and mobile stations 104 a , 104 b and 104 c may utilize the estimated location information to enable timely connections via the 60 GHz wireless links 230 a , 230 b and 230 c and 60 GHz links on 108 a , 108 b and/or 108 c . Furthermore, if a connection fails or is lost during communications, the process may repeat to determine a new position fix and subsequent wireless connection. The invention is not limited to any specific number of base stations 102 and/or mobile stations 104 and may comprise any suitable number and combination thereof. FIG. 3 is a flow chart that illustrates exemplary steps for location determination and antenna adaptation utilizing a 60 GHz wireless link, in accordance with an embodiment of the invention. Referring to FIG. 3 , the process begins in step 300 . In step 302 , a beacon signal is transmitted via a 60 GHz link or lower frequency link, for example, wireless links 108 a , 108 b and/or 108 c . In step 304 , the direction and/or distance from of one or more mobile stations 104 a , 104 b and/or 104 c relative to the base station 102 may be determined. In step 306 , the direction and/or distance from one mobile to another mobile station may be determined. In step 308 , the determined directions and/or distances may be utilized to inform antenna adaptation processes such as signal detection and/or direction of radiation that may be utilized for establishing connections via 60 GHz wireless links. In step 310 , adaptive antennas may track the movements of radiation sources and/or radiation targets to maintain communications between two or more mobile stations such as 104 a , 104 b and 104 c or with one or more base stations such as base station 102 until a connection is terminated. In step 312 , if the connection has not been terminated due to error, the process may proceed to step 314 . Step 314 , is the end step. In step 312 , if the connection has been terminated in error, proceed to step 302 . In an embodiment of the invention, information may be communicated between two or more wireless devices such as the mobile station 104 and/or the base station 102 . Location information regarding the two or more wireless devices may be based on the transmission and reception or detection of a beacon signal. In this regard, the location information may enable communication between the two or more devices via adaptive or steered antennas or antenna systems 118 and/or 116 and 60 GHz band signals 108 . The beacon signal may be swept through an angle such as 210 a , 210 b and/or 210 c and may be utilized along with reference system information to determine the direction and/or distance between the two or more wireless devices. The determined direction and/or distance may be utilized to initialize adaptive or steered antennas or antenna systems 118 and/or 116 that enable transmission and/or reception of the 60 GHz band signals such as the wireless link 108 . Spatial relationships between the two or more wireless devices may vary. Furthermore, the two or more wireless devices may communicate and coordinate communications between the two or more wireless devices via alternate lower frequency signals such as the wireless link 106 . A first method is disclosed for enabling communication between a plurality of devices, the method comprises: in a 60 GHz communication system comprising a plurality of 60 GHz wireless devices that utilize adaptive or steered antennas or antenna systems for communication, communicating location information to at least one of the plurality of 60 GHz wireless devices via beacon signals to enable communication between the at least one of the plurality of 60 GHz wireless devices and at least one other of the plurality of 60 GHz wireless devices. The first method may also comprise sweeping a direction of a beam comprising the beacon signal over one or more angles. The first method may also comprise determining direction and/or distance between the plurality of wireless devices based on the beacon signal. The first method may also comprise determining direction and/or distance between the plurality of wireless devices based on the beacon signal and initializing the adaptive or steered antennas or antenna systems for transmission and/or reception of 60 GHz band signals based on the determined direction and/or distance between the two or more wireless devices. The first method may also comprise varying spatial relationships between the plurality of wireless devices. The first method may also comprise communicating control information via an 802.11 WLAN, a Bluetooth WPAN and/or a Wimedia UWB between the plurality of wireless devices. The first method may also comprise coordinating the communication between the plurality of wireless devices via an 802.11 WLAN, a Bluetooth WPAN and/or a Wimedia UWB. The first method may also comprise communicating one or more of identity information, configuration information, timing information and spatial information via the beacon signals. Certain embodiments of the invention may comprise a machine-readable storage having stored thereon, a computer program having at least one code section for 60 GHz antenna adaptation and user coordination based on base station beacons, the at least one code section being executable by a machine for causing the machine to perform one or more of the steps described herein. Accordingly, aspects of the invention may be realized in hardware, software, firmware or a combination thereof. The invention may be realized in a centralized fashion in at least one computer system or in a distributed fashion where different elements are spread across several interconnected computer systems. Any kind of computer system or other apparatus adapted for carrying out the methods described herein is suited. A typical combination of hardware, software and firmware may be a general-purpose computer system with a computer program that, when being loaded and executed, controls the computer system such that it carries out the methods described herein. One embodiment of the present invention may be implemented as a board level product, as a single chip, application specific integrated circuit (ASIC), or with varying levels integrated on a single chip with other portions of the system as separate components. The degree of integration of the system will primarily be determined by speed and cost considerations. Because of the sophisticated nature of modern processors, it is possible to utilize a commercially available processor, which may be implemented external to an ASIC implementation of the present system. Alternatively, if the processor is available as an ASIC core or logic block, then the commercially available processor may be implemented as part of an ASIC device with various functions implemented as firmware. The present invention may also be embedded in a computer program product, which comprises all the features enabling the implementation of the methods described herein, and which when loaded in a computer system is able to carry out these methods. Computer program in the present context may mean, for example, any expression, in any language, code or notation, of a set of instructions intended to cause a system having an information processing capability to perform a particular function either directly or after either or both of the following: a) conversion to another language, code or notation; b) reproduction in a different material form. However, other meanings of computer program within the understanding of those skilled in the art are also contemplated by the present invention. While the invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present invention without departing from its scope. Therefore, it is intended that the present, invention not be limited to the particular embodiments disclosed, but that the present invention will include all embodiments falling within the scope of the appended claims.
A first device wirelessly transmits and/or receives swept 60 GHz beacon signals to and/or from other devices. Beacon signals indicate angle of reception and/or relative direction with respect to other devices. Knowing reception angle and/or relative direction enables beamforming of adaptive and/or steered antennas for communication. 60 GHz beacons are swept over one or more angles. Identity information, configuration information, timing information and/or spatial information are communicated via 60 GHz beacons. Control and/or coordination information are transmitted and/or received. Reception angle, relative direction and/or distance between devices are determined based on 60 GHz beacons. Adaptive and/or steered antennas used for communication are initialized and/or undergo beamforming for 60 GHz, based on the angle, direction and/or distance between devices. Devices are mobile and/or stationary. Devices comprise mobile stations, base stations, wireless phones, access points, set-top-boxes, computers, game consoles, video servers, video recorders, video playback devices, residential gateways and internet browsing devices.
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RELATED APPLICATIONS The present application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/460,640 filed on Apr. 4, 2003. FIELD OF THE INVENTION The present invention relates to wireless data communication networks and, more specifically, to location-based testing for wireless data communication networks. BACKGROUND TO THE INVENTION Wireless Local Area Networks (WLANs) have recently gained in popularity and importance. These networks are a special case of standard computer Local Area Networks (LANs), where the wires or optical fibers interconnecting computers have been partially or completely replaced by radio frequency (RF) data links. WLANs may also be viewed as a special case of commonly encountered cellular telephone networks, where the relatively large distances in the order of tens of miles covered by cellular telephones have been significantly reduced to hundreds of feet, (within buildings) in exchange for much higher data transmission rates. WLANs offer the possibility of interconnecting information technology devices at relatively high speeds without wires, and hence yield significant reductions in installation cost together with significant improvements in user convenience. The increased usage and reliance upon WLANs has in turn dictated an increase in the level of performance and functionality testing that must be carried out in order to ensure that the WLAN protocol has been properly implemented and that WLAN equipment will function predictably, reliably and robustly under all circumstances. Without a significant level of testing, it is not possible to guarantee this reliability and performance. In general, WLAN testing and characterization seeks to achieve the same goals as traditional wired LAN testing. The following categories of tests must be carried out: (a) Performance measurements. These tests seek to determine some metrics of network performance, such as data rate (typically measured in bits per second), bit or frame error ratios, system utilization, latency, burst tolerance, etc. Performance measurements are normally carried out by transmitting test stimulus data at various speeds to the device under test and making quantitative measurements on the response from the device. (b) Conformance tests. These tests attempt to quantify the level of adherence of the device to a set of specifications or requirements. These specifications may include published standards (e.g., the IEEE 802.11 standard for WLANs). They are usually carried out by presenting a set of well-defined patterns or stimuli to the device under test and verifying that the device responds as per the specification to each set of stimuli. (c) Interoperability tests. These tests are used to ensure that two or more devices from different sources can intercommunicate without problems. Interoperability tests can be done by utilizing test equipment to simulate or emulate devices with which interoperability is desired, and measuring the responses of the device under test to ensure that the expected values are matched. (d) Diagnostic tests. Diagnostic tests are performed during design and development to expose any faults or design errors in the device that may be causing performance, conformance or interoperability tests to fail. These are typically performed with the same test equipment, but set up instead to generate arbitrary stimuli to the device under test and record its responses. Unlike wired LANs, however, WLANs have created a number of significant problems related to performance and functionality testing and characterization. The complexity of the protocol required to implement the high-speed data transfers is quite high, requiring correspondingly more complex and detailed testing capability. A single piece of WLAN equipment may need to communicate with multiple computers or end-stations, all sharing the same spectrum and in close proximity to each other. This renders the interactions observed between the equipment and the end-stations more complex and less predictable. The attenuation and multipath characteristics of the RF channel used to communicate between the WLAN equipment and the end-stations can cause significant variations in behavior and performance. Interference can also occur between WLAN equipment located in the same or adjacent buildings, even though they are physically isolated. All of these render the WLANs testing many times more complex than the testing for traditional wired or fiber-optic LANs. Implementation and testing of WLAN networks, equipment and components is hence very different from that of standard wired LANs such as Ethernet. An important difference is that location is a significant parameter within the test environment; changing the location of equipment has virtually no impact on a wired LAN, but creates a huge impact on a WLAN system. Therefore, wired LAN testing methods and test equipment are quite unsuitable for WLAN testing, and a substantially new approach is required. This new approach, and the apparatus required to realize it, are the subjects of the present invention. The key factor that distinguishes protocol testing of wireless data communication networks such as WLANs from that of wired LANs is the concept of location aware protocol testing. Location awareness here refers to the fact that the exact three-dimensional spatial location of a WLAN device, relative to the other WLAN devices and to the environment in which it is placed, is of great significance in the performance and functioning of the WLAN and must be accounted for. For example, shifting the position of a WLAN device by a few feet (e.g., placing it in a different room) can materially affect the throughput or interference seen by the device. This is clearly not the case for wired LAN technologies, which operate using copper or fiber optic links that are substantially insensitive to changes in physical location. This means that WLAN test systems must support the ability to account for the three-dimensional spatial location of the device or system being tested. In addition, the tests performed upon a device or system at a particular location cannot be reproduced at a different location without also duplicating some or all of the characteristics of the original location. Such duplication may be performed either directly (i.e., re-creating the physical environment of the device or system) or indirectly (i.e., by simulating the characteristics of the physical environment, without duplicating it in its entirety). The latter is clearly much simpler. SUMMARY OF THE INVENTION It is an object of the invention to provide an improved wireless data communication protocol tester. It is a further object of the invention to provide a wireless data communication protocol tester that enables the location-dependent characteristics of wireless data communication networks to be accounted for during protocol testing. It is yet a further object of the invention to provide a wireless data communication protocol tester that enables the location-dependent characteristics of a wireless data communication network environment to be simulated at a different location without reproducing the entire physical environment. In a first aspect, the present invention provides a test unit for testing operation and measuring performance of wireless data communication systems and equipment, comprising: a protocol test unit for generating test stimulus data, executing a sequence of test steps selected for testing operation and measuring performance of said wireless data communication systems, and processing test result data; a location processor, operatively coupled to said protocol test unit, for generating spatial location data providing the location of said protocol test unit relative to a preset point; and a first interface unit, operatively coupled to said protocol test unit, for converting said test stimulus data to a first format specific to said object under test and for converting said test result data to a second format specific to said protocol test unit. In a second aspect, the present invention provides a test system for testing operation and measuring performance of wireless data communication systems and equipment, comprising: n test units, each test unit for selectively testing a specific parameter and data protocol pertinent to an object under test, where n is an integer nε[1, N]; a location processor on each said test units for determining the location of each said test unit relative to a pre-set point; a central controller for monitoring, controlling and coordinating operation of said test units and collecting test results data associated with said respective spatial location data; and a user interface for enabling selection of test sequences, configuration of traffic generation and of test parameters. In a third aspect, the present invention provides a method of testing operation and measuring performance of wireless data communication systems and equipment, comprising: a) providing n test units in the proximity of an object under test and connecting said test units to a central controller, where n in an integer nε[1, N]; b) initializing a connection between said test units and said central controller; c) configuring at each said test unit traffic generation, a test sequence, and a set of reporting parameters according to said test sequence; d) operatively controlling said test units for executing said test sequence; e) collecting test result data at said test units and associating said test result data with a respective test unit; and f) organizing, reviewing and analyzing said test result data. In a fourth aspect, the present invention provides a test system for testing operation and measuring performance of wireless data communication systems having both a wireless network portion and a wired network portion, comprising: n test units, each test unit for selectively testing a specific parameter and data protocol pertinent to an object under test in said wireless data communication systems, where n is an integer nε[1, N]; a location processor on each said test units for determining the location of each said test unit relative to a pre-set point; a central controller for monitoring, controlling and coordinating operation of said test units and collecting test results data associated with said respective spatial location data; and a user interface for enabling selection of test sequences, configuration of traffic generation and of test parameters; wherein at least one of said n test units includes a wireless network interface unit for testing a wireless object in said wireless network portion, and wherein at least one of said n test units includes a wired network interface unit for testing a wired object in said wireless network portion. Advantageously, the test units may be responsive to high-level instructions for performing protocol tests or sequences of protocol tests from the central controller, and process these high-level instructions in order to generate data bit patterns, analysis functions and control functions that are required by the protocol generation and processing means. BRIEF DESCRIPTION OF THE DRAWINGS The description of the preferred embodiments is taken in conjunction with the accompanying drawings, wherein: FIG. 1 is a diagram illustrating a general arrangement of the test units and the central controller in relation to the device or system under test; FIG. 2 is a schematic block diagram showing the details of a single test unit; FIG. 3 is a schematic block diagram of the RF interface unit circuitry; FIG. 4 is a schematic block diagram of the circuitry for the location determining means; FIG. 5A is a schematic block diagram of the circuitry for the Ethernet LAN interface that may be used to implement the communication means with the central controller; FIG. 5B is a schematic block diagram of the circuitry for the UHF radio data link that may be used to implement the communication means with the central controller; FIG. 6 is a representation of the user interface implemented by the central controller; FIG. 7 is a diagram illustrating an arrangement of test units and the central controller wherein the air interfaces between the test units and a device under test have been replaced by cables; FIG. 8 depicts the process of setting up, initializing, configuring and operating the test units and analyzing the results; FIG. 9 depicts an example of a sequence of instructions executed by a test unit when carrying out a specific protocol test; and FIG. 10 is a schematic block diagram showing the details of a single test unit with a wired network interface. DESCRIPTION OF THE PREFERRED EMBODIMENTS With reference to FIG. 1 , the wireless data communication protocol test system comprises a general-purpose computer 14 that is programmed to act as a central controller, and a plurality of identical test units 10 , 11 , 12 , 13 that perform the actual traffic generation and reception functions during the process of protocol testing of device or system under test 15 . Term “object under test” is also used for item 15 , to collectively designate a device or a system under test. As all of the test units 10 , 11 , 12 , 13 are preferably identical, it is understood that a reference to an aspect of any specific test unit, e.g. 10 , shall be hereinafter taken to apply to all of the other test units in the system, e.g., 11 , 12 , 13 . It is further understood that the number of test units 10 in the system may range from 1 to any arbitrary number required to perform a specific test or to simulate a specific wireless data communications network. The central controller 14 communicates with each test unit as shown at 17 . Each test unit 10 is a compact device that can be placed at various locations around or within the device or system under test 15 and generates and receives wireless data streams 16 to and from the latter. Each test unit 10 may be programmed to simulate a WLAN access point (AP), a WLAN endstation (STA), or both, or may be set up to simply monitor traffic being generated or received by the device or system under test 15 . The central controller 14 preferably utilizes a standard host computer or workstation, such as a personal computer, and executes user-interface and control software. A comprehensive control and analysis program is implemented on the central controller 14 in order to control and co-ordinate the test units. User control of the test units is accomplished through a Graphical User Interface (GUI). An example of a GUI window 100 is shown in FIG. 6 , and described in detail in the accompanying text. In general, GUI 100 provides the user with access to analysis tools (filters, statistics calculation, charting etc.) as well as provides the ability to format and output analysis reports, and communicate with the test units 10 , 11 , 12 , 13 via UHF or Ethernet communication means 17 . With reference to FIG. 2 , each test unit 10 preferably comprises a protocol test generation and processing unit 20 , an RF interface unit 21 coupled to antenna 22 , either directly or indirectly, that generates and receives wireless data streams to and from the device or system being tested; a communications interface unit 23 coupled to communications link 17 that serves to communicate with the central controller 14 , and a location processor 27 , coupled to location processor antenna 28 . Test generation and processing unit 20 executes the test unit control software 26 and includes a storage 25 for tests and test results. Location processor 27 calculates the spatial location of the test unit 10 in three dimensions relative to the central controller 14 in order to determine the position of the test unit 10 within the environment surrounding the device or system under test 15 . The location processor 27 , RF interface unit 21 , and communications interface unit 23 are operatively coupled to protocol test generation and processing unit 20 , and are preferably implemented as plug-in cards to allow simple upgrading, either during manufacturing or in the field. For instance, future support for newer WLAN protocols may be accomplished by inserting a different RF interface unit 21 . The protocol test generation and processing unit 20 is preferably constructed around a high-speed embedded CPU 30 and associated peripherals that are operatively coupled to CPU bus 31 . The CPU 30 is interfaced to program storage 33 and data storage 34 . Program storage 33 may be implemented using Flash Electrically Erasable Programmable Read-only Memory (Flash EEPROM), while data storage 34 may advantageously be implemented using Synchronous Dynamic RAM (SDRAM) for maximum speed and data capacity. At least 32 megabytes of Flash EEPROM, plus at least 64 MB of SDRAM, may be implemented. The CPU 30 is also interfaced to bus control logic 32 that is operatively coupled to synchronization logic 35 as well as to interfaces 37 , 38 and 39 . Location interface 37 couples to location processor 27 ; RF interface 38 couples to RF interface unit 21 ; and communication interface 39 couples to communications interface unit 23 . The CPU utilizes bus control logic 32 to implement the control and data transfer functions required to support location processor 27 , RF interface unit 21 and communications interface unit 23 . The CPU 30 exercises overall control and co-ordination of location processor 27 and RF interface unit 21 , maintains the communication link 17 to central controller 14 via communications interface unit 23 (preferably supporting a TCP/IP protocol stack in order to simplify the communications functions), and communicates with the central controller 14 to perform test set-up and report test results. The CPU 30 may also implement firmware programs required for performing the protocol testing and analysis functions. Synchronization logic 35 is operative to provide a clock reference frequency for use by RF interface unit 21 in generating wireless data bit streams of the proper data rate and phase alignment. It is coupled to synchronization inputs and outputs 36 , which may be advantageously connected to the corresponding synchronization inputs and outputs 36 of other test points in order to align all the data bit streams produced by these test points. In addition, synchronization logic 35 provides the timing reference required to mark the times at which wireless data bit streams have been received by RF interface unit 21 . Synchronization logic 35 is preferably implemented using a temperature-compensated high-stability Voltage Controlled Crystal Oscillator (VCXO), implemented as part of a Phase Locked Loop (PLL), that generates a stable and precise 10 MHz clock reference locked to a 100 pulse-per-second (PPS) signal that is either generated internally or received from another test unit via synchronization inputs and outputs 36 . With reference to FIG. 3 , RF interface unit 21 comprises a WLAN RF front-end unit 42 , a WLAN baseband processor unit 41 , and protocol pre-processing logic 40 . WLAN RF front-end unit 42 is operative to implement the radio frequency amplification, frequency conversion, and analog signal processing functions such as Automatic Gain Control (AGC), as required by the physical layer of the wireless data communication protocol. Further, WLAN RF front-end unit 42 implements attenuation functions such that the RF signal output by RF interface unit 21 to antenna 22 may be controlled to a high degree of precision, and the detection threshold for the RF signal input to RF interface unit 21 by antenna 22 may also be controlled to a high degree of precision. These attenuation functions permit the RF interface unit 21 to simulate the effect of increased attenuation of radio signals through the environment, as would be found, for example, if the test unit 10 and the device under test 15 were separated by a greater distance. Also, antenna 22 coupled to WLAN RF front-end circuitry 42 may advantageously be replaced with a connectorized coaxial cable in situations requiring direct connection from test unit 10 to device under test 15 , as for example when device under test 15 is to be tested as a closed system and not as part of a larger environment, or for example when it is desired to exclude external signal interference from various sources. WLAN baseband processor 41 is operative to perform the signal modulation and demodulation functions required by the physical layer of the wireless data communication protocol. These functions may advantageously be implemented using digital signal processing circuitry. Protocol pre-processing logic 40 provides hardware acceleration functions to assist protocol test generation and processing unit 20 , of FIG. 2 , in carrying out the required protocol tests. In addition, it may contain the timing logic necessary for the precise bit-level timing requirements of WLAN baseband processor 41 , and may further implement a serial control interface to support the configuration and monitoring of WLAN baseband processor 41 and WLAN RF front-end 42 . In one embodiment, protocol pre-processing logic 40 may include on the receive side a deserializer (serial to parallel converter) 53 , a timing marker 52 , a receive First In First Out (FIFO) buffer 51 , and a protocol processor interface logic 50 . On the transmit side, protocol pre-processing logic 40 may include a transmit FIFO buffer 54 , an output timer logic 55 , and a serializer (parallel to serial converter) 56 . The clocking and synchronization of the protocol pre-processing logic 40 is controlled by a master clock logic and clock offset control logic 57 . The logic interfaces with the WLAN baseband processor 41 via baseband receive input 58 and baseband transmit output 59 , both of which convey serial data. Deserializer 53 converts the incoming serial data stream demodulated by the baseband processor 41 into a parallel data stream of preferably 8 bits in width. This data stream is passed to timing marker logic 52 , which detects the start and end of the data stream constituting each received frame and time-stamps the start and end points with an accurate time indication derived from master clock logic 57 . The time-stamped data stream is then placed in receive FIFO 51 , and subsequently passed to the protocol test generation and processing logic 20 by protocol processor interface logic 50 through RF interface bus 38 . Transmit data, preferably in 8-bit byte format, are obtained from the protocol test generation and processing logic 20 , of FIG. 2 , by protocol processor interface logic 50 via RF interface bus 38 and placed into transmit FIFO 54 . The data are then passed to output timer logic 55 , which controls the precise time at which each word of transmit data will be passed to serializer 56 . Timing references are provided by master clock logic 57 to output timer logic 55 . The parallel data presented to serializer 56 are then converted to serial form and placed on baseband transmit output 59 for later modulation and transmission by WLAN baseband processor 41 . The master clock logic 57 is responsible for generating the clock signals required by the receive and transmit paths of protocol pre-processing logic 40 . These clock references are phase-locked to the accurate clock reference generated by synchronization logic 35 . In addition, master clock logic 57 is capable of adding or subtracting an adjustable offset delay to the clock reference obtained from synchronization logic 35 prior to creating the actual receive and transmit clock signals. This enables the protocol pre-processing logic 40 to simulate the effect of propagation delays through the environment. For instance, an increased offset delay is equivalent to the effect of increasing the distance between the test unit 10 and the device or system under test 15 . It is understood that different air interface standards (IEEE 802.11 Wireless LAN, Bluetooth, HiperLAN, etc.) may be accommodated by substituting the appropriate baseband processing function 41 and RF front-end function 42 in RF interface 21 . It will be apparent to persons skilled in the art that the protocol test generation and processing unit 20 is realized in a general fashion using firmware running on CPU 30 , and hence support of wireless data communications protocols is simply a matter of replacing RF interface 21 and reprogramming the firmware. With reference to FIG. 4 , location processor 27 may be advantageously implemented using the Global Positioning System (GPS) to determine the absolute three-dimensional spatial co-ordinates of test unit 10 , and subsequently computing the three-dimensional vector from the test unit 10 to the central controller 14 in order to ascertain the relative position of test unit 10 . The location processor 27 consists of GPS RF front end unit 81 , operatively coupled to location processor antenna 28 , and GPS baseband processor 80 . Standard GPS processing is performed on the GPS satellite navigation signals received by location processor antenna 28 to compute the three-dimensional co-ordinates of test unit 10 , and these co-ordinates are passed to protocol test generation and processing logic 20 by means of location interface 37 . A communications link is required between the test unit 10 and the central controller 14 in order for the central controller 14 , of FIG. 1 , to configure and control test unit 10 and also to receive test results. This communications link may preferably be implemented using either Ethernet or a dedicated UHF radio link. The communications link is supported by implementing one instance of communications interface unit 23 in each test unit 10 , and one similar instance of communications interface unit 23 in the central controller 14 . If Ethernet is being used, a standard Ethernet repeater or switch (not shown) may preferably be used to permit all of the test units 10 , 11 , 12 , 13 to communicate with the central controller 14 . If a UHF radio link is being used, the central controller 14 may advantageously implement a polling or time-division-multiplexing protocol to allow communications with all of test units 10 , 11 , 12 , 13 without requiring multiple instances of communications interface unit 23 to be present at the central controller 14 . The realization of such polling or time-division-multiplexing protocols in radio links is well understood and will not be described further. With reference to FIG. 5A , communications interface unit 23 may be implemented using the standard Ethernet communications protocol. In this case, Ethernet MAC logic 60 performs the required Ethernet packet processing and medium access control functions, and Ethernet Physical Layer Device (PHY) logic 61 implements the Ethernet physical layer functions required to interface to Ethernet link 62 , which in turn is used to communicate with central controller 14 . Ethernet MAC logic 60 is operatively coupled to protocol test generation and processing logic 20 , of FIG. 2 , by means of communications interface 39 . With reference to FIG. 5B , communications interface unit 23 a is an alternative implementation using a dedicated UHF radio data link operating in a suitable frequency band, preferably 430 MHz. The dedicated UHF radio data link comprises UHF antenna 75 coupled to RF filters and transmit/receive switch 73 , which is in turn coupled to UHF serial data transmitter 71 and UHF serial data receiver 72 . Serializer/deserializer (SERDES) and data processor 70 converts between parallel data transferred to or from the protocol test generation and processing logic 20 via communications interface 39 and serial data streams that are generated by UHF serial data receiver 72 and accepted by UHF serial data transmitter 71 . Clock generator 74 implements a clock synthesis function that generates the necessary bit-clock, carrier and frequency conversion signals required by the UHF serial data transmitter 71 and UHF serial data receiver 72 . Multiple UHF channels may be supported by reconfiguring clock generator 74 to generate different carrier frequencies. With reference to FIG. 6 , the software program executed by central controller 14 displays and maintains a Graphical User Interface (GUI) 100 that interacts with the user of the protocol test system and controls the operation of test units 10 through communication links 17 , together with an underlying control program supporting GUI 100 . The specific capabilities of GUI 100 and underlying control program preferably include: (a) Detection, checking, initialization and configuration of the test units in the system; (b) Display of test unit status; (c) Grouping of test units under user command to simulate Basic Service Sets in the WLAN protocol; (d) Configuration of traffic generation parameters; (e) Display and editing of test control sequences; (f) Configuration of traffic monitoring and capture filters; (g) Display of traffic counters, and support of a traffic counter spreadsheet; (h) Display of test unit location in a 3-D window; (i) Display of captured frame data; (j) Saving, restoring and execution of test control sequences; (k) Display of measured traffic characteristics in charts and histograms; (l) Saving and restoring of frame, counter and chart/histogram log files; (m) Download and update of firmware on the test units; and (n) Inter-test unit synchronization during startup. GUI 100 and associated control program may advantageously enable the user to download firmware images stored on the central controller to the test units 10 , 11 , 12 , 13 , thereby allowing the test units to be upgraded in capabilities and features in the field. GUI 100 display preferably includes a menu bar 101 that displays menus of commonly used commands, a test unit selection and grouping window 102 , a test setup and results window 103 , a test sequence control window 104 , a statistics counter window 105 , a 3-D view window 106 and a test unit status window 107 . Test unit selection and grouping window 102 shows the plurality of test units 10 available to the user for the test, and permits the user to select and group these test units in any arbitrary combination in order to perform test setup and execution. Test setup and results window 103 enables the user to set up test units and monitor their results, either singly or in groups. Test sequence control window 104 allows the user to define and execute sequences of protocol test actions on one or more test units, and to organize these sequences in a hierarchical manner so as to construct complex test sequences from blocks of simpler test sequences. Statistics counter window 105 displays the statistics (packets or bytes transmitted and received, errors, histograms of packet lengths, etc.) accumulated by test units, either singly or in groups. The 3-D view window 106 displays a three-dimensional view (as a 2-D projection) of the set of test units and the device under test, using the spatial location information gathered from the test points. Finally, test unit status window 107 displays the status of individual test units that are selected via test unit selection and grouping window 102 or via 3-D view window 106 . User interactions with GUI 100 are translated by the underlying control program into sets of instructions that are transferred to test units 10 via communications links 17 . Each set of instructions is executed by CPU 30 in the corresponding test unit 10 in order to perform a specific protocol test or tests. The results are returned to GUI 100 via communications links 17 and subsequently displayed in one or more of the windows of GUI 100 . With reference to FIG. 7 , test units 10 , 11 , 12 , 13 may advantageously support an auxiliary arrangement whereby microwave-rated cables 81 , 82 , 83 , 84 are used instead of an air interface (i.e., without utilizing antennas) to carry signals between the test units 10 , 11 , 12 , 13 and a device under test 15 . This arrangement makes use of a standard passive microwave power splitter/combiner module 85 to combine the signals from multiple test units 10 , 11 , 12 , 13 and drive them to the device under test 15 via cable 86 , as well as to split the signals from the device under test 15 equally among the test units 10 , 11 , 12 , 13 . This type of cabled setup is only feasible if the device under test 15 supports connectorized antenna inputs (e.g., an auxiliary RF input, or removable antennas with standard connectors) or if device under test 15 can be placed in an RF-shielded chamber to which cables 81 , 82 , 83 , 84 are coupled. When cabled in this manner, synchronization between test units 10 , 11 , 12 , 13 is preferably accomplished by means of cables running directly between the synchronization inputs and outputs 36 coupled to synchronization logic 35 implemented in each test unit. A mechanical mounting in the form of a chassis or rack may advantageously be provided to further facilitate convenient operation of test units 10 , 11 , 12 , 13 using cabled setups. Operation of the wireless data communication protocol test system depicted in FIG. 1 is completely initiated and controlled via GUI 100 running on the host computer serving as central controller 14 . GUI 100 converts operator commands that are input via a keyboard and mouse into high-level command messages directed at one or more of the test units 10 , 11 , 12 , 13 ; these command messages are then passed to the specified test units via the appropriate communications links 17 (i.e., Ethernet or UHF radio). System operation preferably begins with an initialization phase, followed by the actual test configuration and execution phase. Post-processing and report generation may then follow the test phase, after tests have been executed and results gathered by GUI 100 from the test units. With reference to FIG. 8 , a typical usage scenario may include the steps of: (a) At step 111 , setting up the test units 10 , 11 , 12 , 13 at the desired locations around the device or system under test 15 and powering them on. (b) At step 112 , starting up GUI 100 on the central controller 14 to display the top-level screen, verifying that the required test units 10 , 11 , 12 , 13 have been detected and initialized, and then optionally grouping them into logical groups as desired using the test unit selection and grouping window 102 of GUI 100 . (c) At step 113 , configuring parameters, if necessary, for the traffic generation to be performed by the groups of test units, and then setting up sequences of traffic to be generated by each test unit, using test setup and results window 103 . The user may also optionally set up capture and monitoring filters controlling the data capture by each test unit using the same window. (d) At step 114 , executing the sequence(s) on the test units that have been selected to participate in the test, using test sequence control window 104 . (e) At step 115 , reviewing the data captured by the test units and presented on statistics counter window 105 , test unit status window 107 , and test setup and results window 103 , in order to ascertain whether the device or system under test 15 is functioning properly, whether additional tests need to be run, and, further, optionally invoking post-processing analysis and report generation functions on the captured data. (f) At step 116 , checking to see if more tests need to be run; if not, at step 117 terminating the test procedure by exiting GUI 100 and powering down the test units. Initialization of the wireless data communication protocol test system at step 112 takes place immediately after GUI 100 is started, may include three stages: test unit polling and discovery, timing synchronization, and test unit location. The system initialization process preferably happens automatically (when the GUI 100 is started); however, it may also be initiated and controlled by the user via the GUI 100 . Also, the initialization phase may advantageously include firmware upgrades to the test units 10 , 11 , 12 , 13 under user control. The first stage in the initialization process preferably includes polling for and discovering all of the test units that are available. The set of test units thus found is reported to the user, who may then be allowed to modify the set by removing or reassigning test units that are not intended to participate in the subsequent tests. The process of polling for test units may advantageously occur at regular intervals while GUI 100 is running, in order to detect when new test units have been added to the system, or if an existing test unit has been removed or has failed during a test. The initialization process preferably then ensures that the internal real-time clock within each of the test units 10 , 11 , 12 , 13 are synchronized. This is done with the aid of synchronization logic 35 that is implemented as a part of protocol test generation and processing unit 20 , of FIG. 2 . Synchronization inputs and outputs 36 coupled to synchronization logic 35 in each test unit are used to exchange timing signals between the test units in order to bring the clock references generated by master clock 57 , of FIG. 3 , of all of the test units into synchronism. After synchronization has been performed, the final stage of initialization preferably includes obtaining the precise three-dimensional location of each of the test units by means of location processor 27 . Central controller 14 may poll for the three-dimensional coordinates of each test unit 10 , and report the results to the user via test unit status window 107 . The central controller 14 may advantageously improve location accuracy by transmitting differential GPS (DGPS) corrections to the test units 10 , 11 , 12 , 13 , at this time, if DGPS information is available. Subsequent to initialization 112 , each test unit 10 is preferably configured from central controller 14 prior to running tests, as shown in step 113 . Configuration may include the steps of setting up RF interface unit 21 to match the test requirements, configuring traffic patterns and monitoring parameters to be used during the tests by protocol test generation and processing unit 20 , and defining reporting options for test results to be sent back to central controller 14 . Configuration of RF interface unit 21 , of FIG. 3 , is relatively straightforward and may include writing parameters to its internal registers. The parameters to be written preferably cover such aspects as data rate, preamble length, scrambler seeds, antenna selection controls, tone generation, receiver AGC control, and transmitter power level. All of these parameters may be advantageously adjustable by the user via GUI 100 . Traffic patterns and monitoring configuration at step 113 comprises at least two aspects: traffic monitoring configuration and traffic generation configuration. Traffic monitoring configuration parameters set up each test unit 10 to gather traffic streams and characteristics, and may include error filters, frame capture filters, event filters (e.g., inter-frame spacing thresholds) and counter update controls. Traffic generation configuration parameters may be used to determine the nature of traffic (frames or interference) that will be transmitted by the test units, and preferably include frame data values, data payload patterns, error injection parameters, traffic stream parameters (e.g., inter-frame spacing, burst lengths, etc.) and test sequence scripts. Reporting configuration parameters may be advantageously specified during step 113 in order to reduce the amount of data that has to be returned to the central controller 14 when test results are downloaded from the test units 10 , 11 , 12 , 13 . These configuration parameters may control the counters that maintain traffic statistics, as well as the types of frames that may be captured and reported during the test, plus the fields within captured frames that are actually stored. Reporting configuration parameters preferably takes the general form of pattern-matching filters, which specify frame data patterns and event conditions on which to update specific counters and also to capture data. Additional pattern-matching filters may be used to define the portions of captured frames that have to be retained in internal buffers. The use of such pattern-matching filters for frame analysis is well-known in the prior art and will not be described further herein. Execution of the test procedure configured at step 113 is accomplished at step 114 by protocol test generation and processing unit 20 , and may consist of generating traffic for stimulating the device or system under test 15 as well as recording its responses. During the execution of the test procedure, each test unit 10 may perform continuous, real-time traffic monitoring, and record a comprehensive set of events, statistics and traffic data within its on-board memory. The types of records maintained in the memory of each test unit 10 preferably include: (a) event records, such as clear-channel assessment, acquisition, coding violations, etc.; (b) captured wireless data frames (in whole or in part), selected according to filters defined during configuration step 113 ; (c) interface-dependent parameters associated with captured wireless data frames, such as total length, data rate, received signal strength, signal quality, etc.; (d) error parameters associated with captured wireless data frames, such as CRC errors, illegal frame lengths, illegal frame types, and illegal frame field values; (e) predefined statistics counters that accumulate counts of different events, including received and transmitted data and control frames of various types, received and transmitted octets, frame size histograms, frames received from specific addresses, etc.; and (f) user-defined auxiliary statistics counters that accumulate counts of the number of frames that match set of user-configured filter parameters, as well as the number of frame octets corresponding to those frames. The following additional types of records may advantageously be maintained in the memory: (a) predefined min/max variables that record various extrema pertaining to the transmitted and received traffic streams, including the maximum medium busy time, the minimum IFS, the maximum and minimum packet lengths, etc.; (b) user-defined auxiliary min/max variables that record the minimum and maximum time interval between any two types of user-selectable packet filters; and (c) tables that record wireless data frame fields, including addresses, that are associated with the received traffic, with each table being preferably of a predefined maximum size, and new entries added to a table preferably overwriting the oldest entries when the table becomes full. Each record may be associated with a timestamp that indicates when it was created or updated. The timestamp preferably has a precision of 1 nanosecond and an accuracy no worse than that of the master clock 57 within each test unit 10 . The information gathered during the execution of the test procedure at step 114 may advantageously be placed into a database maintained by CPU 30 in protocol test generation and processing unit 20 for retrieval by the user via GUI 100 on the central controller 14 . The user is preferably provided with a single view of the databases in all of the active test units, to simplify the process of retrieving and analyzing data. The test units 10 , 11 , 12 , 13 therefore comprise a single distributed database of monitored information that can be queried at will. During execution of the test procedure at step 114 , the protocol generation and test processing unit 20 in each test unit 10 may further generate wireless data traffic for device and system testing as well as network performance analysis. Such traffic may include three categories: specific frame sequences used to test device functions and protocol compliance, continuous traffic generated to measure system throughput, and illegal data generated to test the robustness of the device or system under test 15 . Compliance testing of device or system under test 15 to a particular wireless data communication standard is preferably performed by creating specific command sequences on GUI 100 and executing them on test units 10 , 11 , 12 , 13 in order to generate traffic to exercise various aspects of the protocol. Examples of such protocol compliance test sequences for the Wireless LAN protocol include association and authentication handshakes, RTS/CTS handshakes, inter-frame spacing tolerance sequences. FIG. 9 depicts an example of a test sequence as displayed on test sequence control window 104 of GUI 100 . This sequence illustrates the process of generating a WLAN frame transfer protocol compliance check, including the steps of waiting for a Request To Send (RTS) frame, sending a Clear To Send (CTS) frame, waiting for a Data frame to arrive within the specified interval of 10 microseconds, sending an Acknowledge (ACK) frame in response, and then repeating the process 100 times to ensure that the device under test 15 is compliant to this portion of the WLAN protocol. It is clear from FIG. 9 that each test unit 10 is capable of conditioning the execution of test sequences based on responses from the device under test; for instance, the sequence illustrated causes the test unit 10 to wait for a specific frame to be transmitted by the device under test 15 before proceeding with the rest of the sequence, which allows complex protocol handshakes to be properly supported. Throughput measurements on device or system under test 15 may further be supported by test units 10 , 11 , 12 , 13 . Throughput measurements require the test units to continuously generate back-to-back frames with the minimum interframe spacing specified by the wireless data communications protocol, while supporting all of the handshaking requirements of the protocol. In the case of WLANs, such handshaking requirements may include association, authentication, RTS/CTS exchanges, Data/ACK exchanges, and so on. The throughput measurements supported by the wireless data communication protocol test system include: sustained traffic throughput, burst traffic throughput, traffic focusing (multiple endstations to one access point or endstation) throughput, database capacity tests (addresses, association IDs, etc.), frame size handling and interframe gap tolerance. Interference tests on device or system under test 15 may further be supported by test unit 10 , 11 , 12 , 13 . Such interference tests include: (a) Collision interference. Test units 10 , 11 , 12 , 13 may monitor transmissions from device or system under test 15 and deliberately collide at specified locations within specified frames transmitted by the device, in order to permit the measurement of the device's ability to perform retransmissions. In addition, the test units 10 , 11 , 12 , 13 may advantageously be set up to collide with each other, to allow the collision detection capabilities of the device under test 15 to be verified. Collisions are preferably performed by simply transmitting a random bit pattern via RF interface unit 21 while the device under test 15 is still transmitting a data packet. (b) Continuous wave interference. Test units 10 , 11 , 12 , 13 may be configured to generate a continuous unmodulated carrier at the center frequency of any given wireless data communications channel, in order to simulate the effect of a tone jammer on the operation of device under test 15 . (c) Spread-spectrum interference. Test units 10 , 11 , 12 , 13 may be configured to output a continuous pseudorandom bitstream, not organized as valid wireless data frames, and confined to a specific channel. This measures the ability of the device under test 15 to cope with signal-to-noise ratio impairments. (d) Adjacent-BSS interference. A subset of test units may be configured to simulate a distant BSS operating within the same channel as a local BSS of which the device under test 15 is a part. Simulation of a distant BSS is performed by configuring the subset of test units to operate at reduced power and larger delay relative to the remainder of the test units, thereby emulating the attenuation and path delay experienced in the actual environment. The synchronization logic 35 , together with master clock and clock offset control 57 in each test unit 10 may be advantageously used to permit the rigid alignment of sequences among test units 10 , 11 , 12 , 13 , so that any test unit, e.g. 10 , generates traffic at precisely determined times with respect to all other test units, e.g. 11 , 12 , 13 . This permits the user to simulate specific traffic patterns, perform throughput and latency tests, and simulate interference in a highly deterministic and repeatable manner. As an example, two or more such synchronized test units 10 , 11 may be configured to perform closely aligned back-to-back transactions with one device under test 15 in order to measure performance in a traffic focusing scenario. Reporting of test results to the user via GUI 100 for review and analysis may take place continuously during the test execution, or may take place after the test execution has completed. Reported results include statistics counters, transmitted and received frames, and the real-time status of each test unit 10 . Each test unit 10 should preferably report a user-selectable set of statistics counters to the controller for display in the statistics counter window 105 of GUI 100 . These statistics counters include counts of received and transmitted frames, counts of transmitted multicast frames, counts of failed transmits, counts of retried transmits, counts of duplicate frames received, counts of control frames received and transmitted, counts of errored frames received, counts of bytes received and transmitted, and counts of fragmented frames received and transmitted. The protocol test generation and processing unit 20 preferably ensures that the counters are coherent, i.e., the values being displayed are all measured at the same instant in time. GUI 100 may advantageously support a display mode wherein counters from multiple test units 10 , 11 , 12 , 13 are displayed simultaneously, in a side-by-side organization to permit the user to make quick comparisons of counter values from the different test units. In place of a side-by-side display, GUI 100 may further support a spreadsheet form of counter display that permits the user to perform arithmetic operations using one or more counter values from one or more test units, the results of which are displayed and updated concurrently with the counters themselves. This form of display is very useful for making throughput, packet loss and error rate measurements. Each test unit 10 should preferably transfer the frames received by RF interface unit 21 and filtered by protocol test generation and processing unit 20 to the GUI 100 on the central controller 14 under user command during or after the test execution, for display on test setup and results window 103 . GUI 100 may advantageously support a further display mode wherein frames from multiple test units 10 , 11 , 12 , 13 are displayed simultaneously, in a side-by-side organization to permit quick comparisons. Each test unit 10 should preferably present its operational status continuously to the central controller 14 for display in the test unit status window 107 of GUI 100 . The status information displayed includes: the health of the test unit (whether running, idle or faulty); the current location of the test unit in three dimensions; the current transmit power setting; key fields of the last frame received by the test unit (addresses, received power, etc.); and the group to which the test unit belongs. The wireless data communication protocol test system may further support the following special functions to aid the user in setting up and monitoring tests, and handling the location-sensitive nature of wireless data communication networks: (a) 3-D display window 106 in GUI 100 . This window is used to display all of the test units in their 3-dimensional spatial locations relative to the central controller 14 , and may also be used to display the computed location of the device under test 15 . The spatial locations are obtained from location processor 27 . The 3-D window 106 may be coupled into the remainder of the underlying control program running on central controller 14 and GUI 100 , such that test units can be selected by clicking on them in the window. In addition, the system may support the automatic specification of artificial delays and attenuation factors introduced into sequences run by different test units 10 , 11 , 12 , 13 (thereby simulating the effect of locating test units at different positions within the environment) by permitting the user to drag the icons associated with the test units to different locations within the 3-D window. This in turn causes the configuration of RF interface unit 21 in each of the test units 10 , 11 , 12 , 13 to be updated automatically such that the transmitted power and receiver thresholds are modified to reflect the effect of the different channel attenuation, and the master clock and clock offset control 57 is adjusted to reflect the effect of the different path delay. (b) Test unit selection and grouping window 102 in GUI 100 . This window allows the user to group test units 10 , 11 , 12 , 13 into one or more subsets, assign names to each group, and then manipulate all of the test units in each group as a unit. For instance, it is advantageous to start and stop all of the test units in a group simultaneously, thereby repeatably emulating the effect of stations at multiple points in a wireless network beginning their transmissions simultaneously. The grouping of test units may also be used to apply traffic generation and monitoring parameters to all of the test units in a group, if the group is first selected prior to modifying the parameters, thereby simplifying the task of setting up the parameters for a group. It is apparent that the teachings of the present invention enable the protocol testing of wireless data communication devices or networks having location sensitive characteristics to be performed in a simpler and more deterministic manner, with a higher degree of reliability and a reduced burden upon the user. It is further apparent that the location-sensitive characteristics of the wireless data communication device or network may be accounted for and tested during the protocol testing process. It is further apparent that the present invention provides for the simulation of the location-dependent characteristics of a wireless data communications network during protocol testing of wireless data communication devices or systems. The present invention may also be modified to provide the following embodiments: (a) Inclusion of record/replay functions. With reference to FIG. 2 , RF interface unit 21 is capable of continuously receiving wireless data communication signals from antenna 22 , and passing these signals to protocol test generation and processing unit 20 for storage in test and result storage memory 25 . Further, RF interface unit 21 is capable of continuously accepting bit data from protocol test generation and processing unit 20 for transmission as wireless data communication signals from antenna 22 . These functions can be advantageously coupled to permit recording and future replay of wireless data communication signals, such that a sequence of signals may be initially recorded in permanent or semi-permanent form in test and result storage 25 and later replayed via RF interface unit 21 to regenerate the same sequence of signals exactly. Such record/replay functions are very useful for diagnostic purposes, wherein a signal or packet sequence evoking a defect in a device or system under test may be captured and recorded, and later replayed as many times as necessary to re-create the defect and permit it to be fixed. In addition, such record/replay functions are useful for capturing a sequence of signals at one location (for example, a user environment) and later reproducing the same sequence of signals at another environment (for example, a laboratory). The ability of the present invention to emulate the location-sensitive characteristics of an environment is of significant benefit in this case. (b) Provision of a multi-protocol RF interface unit 21 in test unit 10 . The present invention may be extended to support the testing of multiple wireless data communication protocols without requiring multiple types of test units by modifying RF interface unit 21 to support these different protocols. For example, it is possible to support the IEEE 802.11b and IEEE 802.11a, both WLAN data communication protocols, by adapting RF interface unit 21 to support the physical layers specific to both IEEE 802.11b and IEEE 802.11a; as the underlying MAC protocol is identical for both, it is possible to simultaneously test devices conforming to either or both protocols by using only one set of test units 10 , 11 , 12 , 13 . (c) Provision of a channel simulator 130 in front of RF interface unit 21 in test unit 10 . A channel simulator is a device, well known in the prior art, that emulates the physical characteristics of a wireless transmission channel, including the various types of impairments that may be present in the channel, such as attenuation, phase shifts, fading, multipath effects, noise and interference. With reference to FIG. 2 , the placement of a channel simulator 140 , as alternatively shown with dashed lines, between RF interface 21 and antenna 22 would permit the physical aspects of the wireless channel to be exactly emulated, rather than the approximate emulation possible by adjusting the delay, output power and receiver threshold of RF interface 21 . This, in turn, would allow more accurate emulation of the location-sensitive properties of a wireless data communication environment to be performed. (d) Provision of a wired network interface unit. Most wireless data communication networks incorporate a wired portion as well; for instance, the access points of a WLAN are linked together using a wired network (typically Ethernet), and the basestations of a cellular network are connected to the cellular switching system via wired transmission trunks. With reference to FIG. 10 , the present invention may be extended to include the testing of the wired portion of the wireless data communication networks by providing a wired network interface unit 140 in test unit 11 , in place of RF interface unit 21 in test unit 10 of FIG. 2 . This would enable simultaneous testing of the wired and wireless portions of a wireless data communications network; the test units with standard RF interface units 21 would be positioned and configured to generate wireless test data signals, and the test units, such as test unit 11 with wired network interfaces shown in FIG. 10 , would be attached to the wired network portions of the data communications network. Communications unit 23 depicted in FIG. 5A may be utilized with the wired network interface unit 140 in a test unit to support an Ethernet test interface, for example. Accordingly, while this invention has been described with reference to illustrative embodiments, this description is not intended to be construed in a limiting sense. Various modifications of the illustrative embodiments, as well as other embodiments of this invention, will be apparent to persons skilled in the art upon reference to this description.
Apparatus and methods facilitating a distributed approach to performance and functionality testing of location-sensitive wireless data communication systems and equipment are described. A plurality of test units, geographically distributed at arbitrary points in a three-dimensional volume surround the system or equipment under test. Each test unit generates test stimuli and records responses from the device under test, and emulates the effects of changes in spatial location within an actual wireless network environment. A central controller co-ordinates the set of test units to ensure that they act as a logical whole, and enables testing to be performed in a repeatable manner in spite of the variations introduced by the location sensitive characteristics of wireless data communication networks. The central controller also maintains a user interface that provides a unified view of the complete test system, and a unified view of the behavior of the system or equipment under test. For diagnostic purposes, the recorded responses may be regenerated to view any defects as many times as necessary to correct them. Alternatively, each test unit may have either wired network interface units, instead of a wireless interface unit to test systems or equipment forming part of a wired network portion in the wireless data communication system.
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CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a Continuation of U.S. application Ser. No. 14/936,088, filed Nov. 9, 2015, which is a Continuation of U.S. application Ser. No. 10/535,918, filed Mar. 16, 2006, which is a U.S. National Phase of PCT/US2002/37948, filed Nov. 26, 2002, the disclosures of which are incorporated herein by reference in their entirety. FIELD OF INVENTION [0002] The present invention relates to materials and methods for preventing or treating microbe-mediated epithelial disorders, such as gut-derived sepsis. BACKGROUND [0003] Microbe-mediated epithelial disorders, or abnormal conditions, present a significant threat to the health of man and animals, imposing a burden on healthcare systems worldwide. One example of such disorders, gut-derived sepsis, is a major cause of mortality among organisms, such as human patients, that suffer from any of a variety of diseases, disorders or afflictions, such as burn injuries, neonatal enterocolitis, severe neutropenia, inflammatory bowel disease, and organ rejection following transplantation. The intestinal tract reservoir has long been recognized to be a potentially lethal focus of bacterial-mediated sepsis in, e.g., critically ill, hospitalized patients. The ability of microbial pathogens such as the Pseudomonads (e.g., Pseudomonas aeruginosa ) to perturb the regulatory function of the intestinal epithelial barrier may be a defining characteristic among opportunistic organisms capable of causing gut-derived sepsis. In many of these infections, Pseudomonas aeruginosa has been identified as the causative pathogen. Significantly, the intestinal tract has been shown to be the primary site of colonization of opportunistic pathogens such as P. aeruginosa. [0004] Conventional therapeutic approaches to the prevention or treatment of microbe-mediated epithelial disorders such as gut-derived sepsis have met with incomplete success. Antibiotic-based approaches are compromised by the difficulty in tailoring antibiotics to the intestinal pathogen in a manner that does not impact the remaining intestinal flora. In addition, many of the intestinal pathogens, as typified by P. aeruginosa , often become resistant to antibiotic challenges, resulting in a costly, ongoing and incompletely successful approach to prevention or treatment. [0005] Problems also plague immunotherapeutic approaches. Particularly, many intestinal pathogens such as P. aeruginosa , are immunoevasive, rendering such approaches minimally effective. [0006] Another approach to the prevention or treatment disorders such as gut-derived sepsis is intestinal lavage. In the past several years, intestinal lavage using polyethylene glycol (PEG) solutions has been attempted, with some anecdotal reports suggesting that PEG may show some promise in treating gut-derived sepsis across a variety of clinical and experimental circumstances. The PEG in these solutions has an average molecular weight of 3,500 daltons and the solutions are commercially available (e.g., Golytely). The mechanisms by which these relatively low molecular weight (LMW) solutions of PEG provide a therapeutic benefit in treating or preventing gut-derived sepsis is unknown. Typically, these solutions are used to wash or flush the intestinal tract of organisms at risk of developing, or suffering from, gut-derived sepsis. As a result of administering these LMW PEG solutions to the intestinal tract, there is a variable change in the floral composition of the treated intestine depending on the method of concentration and the molecular weight of the compounds used. For example, solutions having concentrations of PEG higher than about 20% can result in a microbiocidal action resulting in the elimination of potentially protective microorganisms in the intestinal tract of a stressed host. Also, solutions of low molecular weight PEG can lose their efficacy in attenuating the virulence capacity of certain organisms, despite preserving them. Therefore, a need exists in the art for a solution that inhibits microbial virulence expression (the harmful properties of a microbe) while not killing the microbe or neighboring microbes, thereby providing the benefit of preserving the natural ecosystem of the intestinal microflora. For example, preservation of the native floral composition would provide competition for opportunistic pathogens that might otherwise colonize the intestine. [0007] Concomitant with a change in floral composition is a change in the physiology of the organism. These physiological changes may be monitored by assaying any number of characteristic enzymatic activities, such as lactate dehydrogenase levels. Consequently, LMW PEG treatments of the intestine produce significant changes in the physiology of the treated organisms, with unpredictable, and thus potentially deleterious, longer-term consequences for the health and well-being of the treated organism. Moreover, such treatments provoke physically demanding reactions in the form of massive intestinal voiding in critically ill organisms such as hospitalized human patients. [0008] Thus, there remains a need in the art to provide a composition effective in preventing, or treating, a microbe-mediated epithelial disorder (e.g., gut-derived sepsis) and/or a symptom associated with such a disorder, along with methods for achieving such benefits, without creating the potential for further complications through significant alteration of the physiology of the treated organism. SUMMARY OF THE INVENTION [0009] The present invention satisfies the aforementioned need in the art by providing a high molecular weight (HMW) polyethylene glycol composition that provides effective protection against an abnormal condition characterized by an epithelial surface at risk of developing a microbe-mediated disorder. Exemplary abnormal conditions include gut-derived sepsis, and other intestinal disorders/diseases associated with intestinal flora, due to intestinal pathogens including, but not limited to, P. aeruginosa . The HMW PEG inhibits or prevents contact of such pathogens as P. aeruginosa with the intestinal epithelial surface. In addition, high molecular weight PEG suppresses virulence expression in these pathogens (e.g., P. aeruginosa ) responsive to a variety of signals that may involve quorum sensing signaling networks. The ability of HMW PEGs to interdict at the infectious interface between the intestinal pathogen and the intestinal epithelium provides an alternative approach to preventing or treating gut-derived sepsis, e.g., following catabolic stress. Importantly, treatments with HMW PEGs would be cost effective and relatively simple to perform on human patients as well as a variety of other organisms such as agriculturally significant livestock (e.g., cattle, pigs, sheep, goats, horses, chickens, turkeys, ducks, geese, and the like), pets, and zoo animals. [0010] One aspect of the invention provides a method of reducing the likelihood of mortality in an animal with an abnormal condition, including a disease condition, comprising an epithelial surface at risk of developing a microbe-mediated disorder selected from the group consisting of gut-derived sepsis, a burn injury, neonatal necrotizing enterocolitis, severe neutropenia, toxic colitis, inflammatory bowel disease, enteropathy, transplant rejection, pouchitis, and pig belly, comprising administering an effective dose of polyethylene glycol (PEG) to an animal in need thereof, wherein the PEG has an average molecular weight of at least 5,000 daltons. Suitable animals include, but are not limited to, dog, cat, sheep, goat, cow, pig and human. In the aforementioned method, the PEG preferably has an average molecular weight of at least 15,000 daltons, and is preferably between 5,000 and 20,000 daltons, or between 15,000 and 20,000 daltons. Also preferred is PEG having an average molecular weight of 6,000, of 7,000, of 8,000, of 9,000, of 10,000, of 11,000, of 12,000 of 13,000, of 14,000, and of 25,000 daltons. Further, the PEG may be in an aqueous solution comprising 5-20% PEG, and preferably 10-20% PEG (e.g., 10% PEG). In one embodiment of the method, the condition is associated with the presence of a Pseudomonas aeruginosa organism in the intestine and the cell membrane integrity of such P. aeruginosa is not detectably altered. In another embodiment of the method, the growth pattern of Pseudomonas aeruginosa is not detectably altered. [0011] Another aspect of the invention is a method of inhibiting gut-derived sepsis comprising contacting a mammalian epithelium, such as an intestine, with polyethylene glycol (PEG), wherein the PEG has an average molecular weight of at least 5,000 daltons, and preferably at least 15,000 daltons. In one embodiment of this method, the mammalian intestine contacts the PEG for at least 30 minutes. [0012] Further aspects of the invention include a method of inhibiting PA-I lectin/adhesin expression in a pathogen of the epithelia, e.g., an intestinal pathogen, comprising administering an effective dose of polyethylene glycol to an animal in need thereof; a method of inhibiting epithelium-induced (e.g., intestinal epithelium-induced) activation of PA-I lectin/adhesin comprising administering an effective dose of polyethylene glycol to an animal in need thereof; a method of inhibiting C4-HSL-induced morphological change of a pathogen of the epithelia (e.g., an intestinal pathogen) comprising administering an effective dose of polyethylene glycol to an animal in need thereof; a method of reducing virulence expression in a pathogen of the epithelia (e.g., an intestinal pathogen) comprising administering an effective dose of polyethylene glycol to an animal in need thereof; a method of reducing or preventing interaction of an epithelial surface with a microbial virulence factor comprising administering an effective dose of polyethylene glycol to an animal in need thereof; a method of ameliorating epithelial (e.g., intestinal) pathogenesis by preventing formation of pathogenic quorum-sensing activation comprising administering an effective dose of polyethylene glycol to an animal in need thereof; and a method of inhibiting interaction between epithelium (e.g., intestinal epithelium) of a vertebrate and a bacterium, such as a Pseudomonad (e.g., Pseudomonas aeruginosa ), comprising contacting the epithelium with polyethylene glycol. In all of these aspects of the invention, the PEG has an average molecular weight of at least 5,000 daltons, and preferably at least 15,000 daltons. [0013] A still further aspect of the invention is a method of inhibiting a Pseudomonas aeruginosa -induced reduction in the transepithelial electrical resistance of a mammalian epithelial layer, such as an intestinal epithelial layer, comprising contacting the (intestinal) epithelial layer with polyethylene glycol, wherein the PEG has an average molecular weight of at least 5,000 daltons, and preferably at least 15,000 daltons. Preferably, the PEG has an average molecular weight of 15,000 to 20,000 daltons. In a preferred embodiment, the integrity of the membrane of the microbe (e.g., P. aeruginosa ) is not detectably altered. [0014] Yet another aspect of the invention is a method of inhibiting adherence of a bacterial cell to a mammalian epithelium, such as a mammalian intestine, comprising contacting the intestine with polyethylene glycol, wherein the PEG has an average molecular weight of at least 5,000 daltons, and preferably at least 15,000 daltons. With this method as well, it is preferred that the PEG has an average molecular weight of 15,000 to 20,000 daltons. The PEG may be in an aqueous solution comprising 5-20% PEG, and preferably 5-10% PEG. An exemplary bacterial cell contemplated as amenable to inhibition of adherence by this method is a Pseudomonad, such as P. aeruginosa. [0015] Another aspect of the invention is a method of reducing the expression of PA-I lectin/adhesin in a bacterial cell comprising contacting the bacterial cell with polyethylene glycol, wherein the PEG has an average molecular weight of at least 5,000 daltons, and preferably 15,000 daltons, and is preferably between 15,000 and 20,000 daltons. Again, the PEG may be in an aqueous solution comprising 5-20% PEG, and preferably 5-10% PEG. [0016] In another aspect, the invention provides a method of reducing the likelihood of mortality in an animal exhibiting a microbe-mediated epithelial disorder selected from the group consisting of gut-derived sepsis, a burn injury, neonatal necrotizing enterocolitis (NEC), severe neutropenia, toxic colitis, inflammatory bowel disease, enteropathy (e.g., in the critically ill), transplant rejection, pouchitis and pig belly comprising administering an effective amount of a compound (e.g., PEG) that adheres to a cell selected from the group consisting of a mammalian intestinal epithelial cell and an intestinal bacterial cell, wherein the compound adheres to the cell in a topographically asymmetrical manner, thereby inhibiting interaction of the mammalian intestinal epithelial cell and the bacterial cell. A preferred compound is a surfactant. In one embodiment of this method, the compound is PEG, preferably having an average molecular weight of at least 15,000 daltons. In another embodiment of this method, the inhibition is determined by atomic force microscopy. In yet another embodiment of this method, the bacterial cell is an intestinal pathogen and there is no detectable modification of its growth characteristics. In related aspects, this method further comprises introducing an effective amount of dextran into the intestine of the animal and/or introducing an effective amount of L-glutamine, dextran-coated L-glutamine, dextran-coated inulin, dextran-coated butyric acid, one or more fructo-oligosaccharides, N-acetyl-D-galactosamine, dextran-coated mannose and galactose, lactulose and balancing buffers and stabilizing agents, known in the art, into the intestine of the animal. When administered together as a single composition, this multicomponent single-solution administration will treat and prepare the intestinal tract in anticipation of a disruption in the intestinal flora and barrier function of the intestine, such as occurs following severe catabolic-, surgical- and traumatic-type stresses. [0017] Another aspect of the invention is a method of ameliorating a symptom associated with any disease or condition arising from, or characteristic of, an abnormal condition of the epithelium, such as gut-derived sepsis, comprising administering polyethylene glycol to the intestine, wherein the PEG has an average molecular weight of at least 5,000 daltons, preferably at least 15,000 daltons, and is preferably between 15,000 and 20,000 daltons. The PEG may be in an aqueous solution comprising 5-20% PEG, and preferably 5-10% PEG. The invention comprehends ameliorating a symptom associated with any disease or condition disclosed herein. [0018] Still another aspect of the invention is a method of preventing loss of lactating capacity in an animal exhibiting an abnormal condition in the form of an epithelial surface of a mammary gland at risk of developing a microbe-mediated disorder affecting milk output, comprising administering, e.g., topically, an effective dose of a polyethylene glycol of at least 5,000 daltons, and preferably at least 15,000 daltons, to the epithelial surface of a mammary gland. Exemplary animals include mammals, such as sheep, goats, cows, pigs, horses and humans. In a related aspect, the invention provides a method of treating a loss of lactating capacity in an animal characterized by a microbe-mediated disorder of an epithelial surface of a mammary gland affecting milk output, comprising administering, e.g., topically, an effective dose of a polyethylene glycol of at least 5,000 daltons and, preferably, at least 15,000 daltons to a mammary gland. In another related aspect, the invention provides a method of preventing development of a microbe-mediated epithelial disorder in an animal of nursing age comprising administering an effective dose of polyethylene glycol of at least 5,000 daltons, and preferably at least 15,000 daltons, to the animal. Suitable animals include mammals, such as humans, livestock, domesticated pets, and zoo animals. In one embodiment, the PEG is admixed with any infant formula known in the art. [0019] A related aspect of the invention is a composition comprising infant formula and polyethylene glycol (PEG), wherein the PEG has an average molecular weight of at least 5,000 daltons. Again, any infant formula known in the art may be used, including formulas based on the milk of a mammal, such as cow's milk, goat's milk, and the like, as well as formulas based on soy milk. The formula may also be enriched with any vitamin and/or element, including fortification with iron. The PEG preferably has an average molecular weight of at least 15,000 daltons, and is preferably present in the range of 5-20% upon reconstitution or hydration of the infant or baby formula. The invention further provides a method of providing nutrition to an animal, preferably of nursing age, comprising administering an effective dose of the composition comprising infant formula and PEG to the animal. [0020] Yet another aspect of the invention is a pharmaceutical composition comprising polyethylene glycol of at least 5,000 daltons, and preferably 15,000 daltons, average molecular weight and a suitable adjuvant, carrier or diluent. In a related aspect, the composition further comprises a compound selected from the group consisting of dextran-coated L-glutamine, dextran-coated inulin, dextran-coated butyric acid, one or more fructo-oligosaccharides, N-acetyl-D-galactosamine, dextran-coated mannose and galactose, lactulose and balancing buffers and stabilizing agents known in the art. [0021] An additional aspect of the invention is a kit for the therapeutic treatment or prevention of an abnormal condition characterized by an epithelial surface at risk of developing a microbial-mediated disorder, such as gut-derived sepsis, comprising one of the above-described pharmaceutical compositions and a protocol describing use of the composition in therapeutic treatment or prevention of the abnormal condition. Protocols suitable for inclusion in the kit describe any one of the therapeutic or preventive methods disclosed herein. [0022] Still other aspects of the invention are drawn to methods of preventing an abnormal condition characterized by an epithelial surface at risk of microbe-mediated disorder, including diseases. For example, the invention comprehends a method of preventing a disease or an abnormal condition comprising administering a composition comprising an effective dose of polyethylene glycol (PEG) to an animal, wherein the PEG has an average molecular weight of at least 5,000 daltons. A suitable disease or abnormal condition, amenable to the preventive methods of the invention, is selected from the group consisting of swimmer's ear, acute otitis media, chronic otitis media, ventilator-associated pneumonia, gut-derived sepsis, necrotizing enterocolitis, antibiotic-induced diarrhea, pseudomembranous colitis, an inflammatory bowel disease, irritable bowel disease, neutropenic enterocolitis, pancreatitis, chronic fatigue syndrome, dysbiosis syndrome, microscopic colitis, a chronic urinary tract infection, a sexually transmitted disease, and infection. An animal suitable as a subject for such preventive methods is selected from the group consisting of dog, cat, sheep, goat, cow, pig, chicken, horse and human. The PEG preferably has an average molecular weight of at least 15,000 daltons; also preferred is PEG having an average molecular weight between 15,000 and 20,000 daltons. Further, the PEG may be an aqueous solution comprising 10-20% PEG, and preferably 10% PEG. The composition being administered may further comprise a vehicle selected from the group consisting of a liquid solution, a topical gel, and a solution suitable for nebulizing. Additionally, the composition may further comprise a compound selected from the group consisting of dextran-coated L-glutamine, dextran-coated inulin, dextran-coated butyric acid, a fructo-oligosaccharide, N-acetyl-D-galactosamine, dextran-coated mannose, galactose and lactulose. In one embodiment, the composition comprises PEG, dextran-coated L-glutamine, dextran-coated inulin, dextran-coated butyric acid, a fructo-oligosaccharide, N-acetyl-D-galactosamine, dextran-coated mannose, galactose and lactulose. [0023] Yet another aspect of the invention is a method of preventing skin infection comprising the step of applying a composition comprising an effective amount of polyethylene glycol (PEG) to an animal, wherein the PEG has an average molecular weight of at least 5,000 daltons. The composition may further comprise a vehicle selected from the group consisting of an ointment, a cream, a gel and a lotion. The invention contemplates that an agent causing the infection is selected from the group consisting of Bacillus anthracis , Small Pox Virus, enteropathogenic E. coli (EPEC), enterohemorrhagic E. coli (EHEC), enteroaggregative E. coli , (EAEC), Clostridium difficile , rotavirus, Pseudomonas aeruginosa, Serratia marcescens, Klebsiella oxytocia, Enterobacteria cloacae, Candida albicans and Candida globrata. [0024] Another aspect of the invention is a method of preventing respiratory infection comprising the step of administering an effective amount of polyethylene glycol (PEG) to an animal, wherein the PEG has an average molecular weight of at least 5,000 daltons. A respiratory infection amenable to the preventive methods of the invention may arise from contact with an infectious agent via any route known in the art, including pneumonias associated with ventilators (e.g., ventilator-associated pneumonia), air-borne infectious agents, infectious agents dispersed in a nebulized fluid such as by sneezing, and the like. In some embodiments, the method prevents respiratory infection by an agent selected from the group consisting of Bacillus anthracis and Small Pox Virus. [0025] Yet another aspect of the invention is a method for irrigating at least a portion of the urinary tract in order to prevent a chronic urinary tract infection, comprising the step of delivering an effective amount of a composition comprising PEG to a urethra, wherein the PEG has an average molecular weight of at least 5,000 daltons. In one embodiment, the composition is administered to a portion of the urinary tract that includes at least the bladder. [0026] Another aspect of the invention is a method of preventing a sexually transmitted disease comprising the step of applying polyethylene glycol (PEG) to a condom, wherein the PEG has an average molecular weight of at least 5,000 daltons. A related aspect of the invention is a condom comprising at least a partial coating with PEG having an average molecular weight of at least 5,000 daltons. Yet another related aspect is a kit comprising a condom and polyethylene glycol (PEG) having an average molecular weight of at least 5,000 daltons. [0027] The invention also comprehends a method of preventing a digestive tract disorder comprising administering an effective dose of a composition comprising polyethylene glycol (PEG) to an animal in need thereof, wherein the PEG has an average molecular weight of at least 5,000 daltons. Exemplary digestive tract disorders amenable to the preventive methods of the invention may be selected from the group consisting of neonatal necrotizing enterocolitis, antibiotic-induced diarrhea, pseudomembranous colitis, an inflammatory bowel disease, irritable bowel disease, neutropenic enterocolitis, pancreatitis, dysbiosis syndrome and microscopic colitis. [0028] Another aspect of the invention is a method for monitoring the administration of polyethylene glycol (PEG) to an animal in need thereof, comprising administering an effective amount of a composition comprising labeled PEG, wherein the PEG has an average molecular weight of at least 5,000 daltons, to an animal in need thereof, and detecting the labeled PEG, whereby the quantity and/or location of the labeled PEG (e.g., associated with a microbe) provides information useful in assessing the efficacy of administration. In one embodiment of the monitoring method, the label is a fluorophore (e.g., fluorescein, rhodamine, Cy3, Cy5). In another embodiment of the method, detecting the labeled PEG comprises endoscopic inspection. The monitoring method also contemplates that the labeled PEG is detected in a stool sample (i.e., the labeled PEG associates with a component such as a microbe, whose source is a stool sample). In addition, the monitoring method may further comprise administering a second label specific for a microbe and detecting the second label. “Specific” as used in this context means that the label is detectably associable with at least one microbe. [0029] Another aspect of the invention is a method for monitoring the administration of polyethylene glycol (PEG) to an animal in need thereof, comprising obtaining a sample from an animal receiving polyethylene glycol, wherein the PEG has an average molecular weight of at least 5,000 daltons, contacting the sample with an epithelial cell, and measuring the adherence of a microbe in the sample to the epithelial cell, whereby the quantity and/or location of the PEG provides information useful in assessing the efficacy of administration. The measuring may be accomplished by microscopic examination. [0030] Another monitoring method according to the invention is a method for monitoring the administration of polyethylene glycol (PEG) to an animal in need thereof, comprising obtaining a sample from an animal receiving polyethylene glycol, wherein the PEG has an average molecular weight of at least 5,000 daltons, contacting the epithelial cell layer with the sample, and measuring a trans-epithelial electrical resistance of the epithelial layer, whereby effective administration is indicated by a reduced decrease in trans-epithelial electrical resistance relative to a control value. The control value may be internal (i.e., measuring the TEER prior to PEG administration) or external (i.e., a value developed in other studies that is reliably used for comparison). [0031] Yet another monitoring method of the invention is a method for monitoring the administration of polyethylene glycol (PEG) to an animal in need thereof, comprising obtaining a sample from an animal receiving polyethylene glycol, wherein the PEG has an average molecular weight of at least 5,000 daltons, isolating a microbe from the sample, and measuring the hydrophobicity of the cell surface of the microbe, whereby the hydrophobicity of any microbe in the sample provides information useful in assessing the efficacy of administration. “Isolating,” as used in this context, means separated from other components of the sample (e.g., solid matter) sufficiently to permit hydrophobicity measurements, as would be understood in the art. [0032] A related aspect of the invention is a kit for monitoring the administration of polyethylene glycol, comprising a labeled PEG and a protocol describing use of the labeled PEG in monitoring administration thereof. Suitable protocols include any of the methods disclosed herein or known in the art relating to the administration, delivery or application of PEG. In some embodiments of this aspect of the invention, the kit further comprises a free label. [0033] Still another monitoring method of the invention is a method for monitoring the administration of polyethylene glycol (PEG) to an animal in need thereof, comprising obtaining a sample from an animal receiving polyethylene glycol, wherein the PEG has an average molecular weight of at least 5,000 daltons, and detecting PA-I lectin/adhesin activity in the sample, whereby the PA-I lectin/adhesin activity provides information useful in assessing the efficacy of administration. In one embodiment of this method, the PA-I lectin/adhesin is detected by binding to a PA-I lectin/adhesin binding partner, such as any known form of a specific anti-PA-I lectin/adhesin antibody or a carbohydrate to which the lectin/adhesin specifically binds. A related aspect of the invention is a kit for monitoring the administration of polyethylene glycol (PEG) comprising a PA-I lectin/adhesin binding partner and a protocol describing use of the binding partner to detect PA-I lectin/adhesin in the sample. Suitable protocols include any of the methods disclosed herein or known in the art relating to the use of PEG. [0034] Other features and advantages of the present invention will be better understood by reference to the following detailed description, including the drawing and the examples. BRIEF DESCRIPTION OF THE DRAWING [0035] FIG. 1 provides mortality rates in mice at 48 hours subjected to either sham laparotomy or 30% surgical hepatectomy followed by direct injection of P. aeruginosa PA27853 into the cecum. Mice underwent a 30% bloodless left lobe hepatectomy immediately, followed by direct cecal injection of 1×10 7 cfu/ml of PA27853. Each group contained 7 mice. Control mice underwent sham laparotomy followed by injection of equal amounts of PA27853 into the cecum. For mice in the PEG groups, 1×10 7 cfu/ml of PA27853 was suspended in either PEG 3.35 (LMW PEG 3,350) or PEG 15-20 (HMW PEG 15,000 to 20,000 daltons) prior to cecal injection. Dose response curves for PEG 15-20 are seen in panel b. a. A statistically significant protective effect of PEG 15-20 was determined by the Fisher Exact Test (P<0.001). b. The minimum protective concentration of PEG 15-20 was determined to be 5% (P<0.05). c. Quantitative bacterial cultures of cecal contents (feces), washed cecal mucosa, liver, and blood 24 hours following 30% surgical hepatectomy and direct cecal injection of 1×10 7 cfu/ml of PA27853. One-way ANOVA demonstrated a statistically significant increase in bacterial counts in cecal contents, mucosa, liver, and blood in mice following hepatectomy (P<0.001). A significant decrease (P<0.05) in the liver and blood bacterial counts was observed for PEG 3350, while PEG 15-20 completely prevented PA27853 from disseminating to the liver and blood of mice. [0036] FIG. 2 shows the protective effect of PEG 15-20 against PA27853-induced epithelial barrier dysfunction as assessed by transepithelial electrical resistance (TEER). a. Data represent the mean±SEM % maximal fall in TEER from baseline of triplicate cultures (n=7) observed during 8 hours of apical exposure to 1×10 7 cfu/ml of PA27853. A statistically significant decrease in TEER was demonstrated (one-way ANOVA (P<O.001)) in Caco-2 cells exposed to PA27853. A statistically significant protective effect on the fall in TEER induced by PA27853 was demonstrated for PEG 15-20 (P<O.001). b. Image of Caco-2 cells in the presence of PEG 3.35 and apical exposure to PA27853. Images taken after 4 hours of co-culture demonstrated loss of monolayer integrity with cells floating 30-40 microns above the cell scaffolds displaying adherence of PA27853 to cell membranes. c. Caco-2 cells apically exposed to PA27853 after 4 hours in the presence of PEG 15-20 showed no evidence of floating cells in any of the planes examined. [0037] FIG. 3 illustrates the inhibitory effect of PEGs on PA-I expression in PA27853. a. Western blot analysis. Exposure of PA27853 to 1 mM of the quorum-sensing signaling molecule C4-HSL resulted in a statistically significant increase (P<0.001 one-way ANOVA) in PA-I protein expression that was partially inhibited in the presence of 10% PEG 3.35 and much more inhibited with 10% PEG 15-20. a′. The minimum inhibitory concentration of PEG 15-20 on C4-HSL induced PA-I expression was 5% (P<0.01). b. Electron microscopy of individual bacteria cells exposed to C4-HSL in the presence and absence of PEGs, demonstrated that C4-HSL caused a morphological change in the shape and pili expression of P. aeruginosa . The C4-HSL-induced morphological effect was completely eliminated in the presence of PEG 15-20, but not PEG 3.35. A halo-type effect can be seen surrounding PA27853 exposed to PEG 15-20. c. Northern hybridization. Exposure of PA27853 to 0.1 mM of C4-HSL resulted in a statistically significant increase (P<0.001 one-way ANOVA) in PA-I mRNA expression that was greatly inhibited with 10% PEG 15-20. d. The increase in PA-I mRNA induced by 4 hours exposure to Caco-2 cell was inhibited in the presence of PEG 15-20, but not PEG 3.35 (P<0.001 one-way ANOVA). [0038] FIG. 4 shows the effect of PEG solutions on bacterial membrane integrity arid growth patterns of PA27853. a. The effect of the two PEG solutions on bacterial membrane integrity was assessed by a staining method consisting of SYTO 9 and propidium iodide. Neither PEG solution had any effect on bacterial membrane permeability. b. PA27853 growth patterns appeared identical in the two PEG solutions relative to the PEG-free TSB medium (control). [0039] FIG. 5 presents Atomic Force Microscopy (AFM) images of Caco-2 cells and bacterial cells exposed to PEGs. a-c. AFM images of Caco-2 cells in the presence of medium alone (a), medium with PEG 3.35 (b), and medium with PEG 15-20. PEG 3.35 was seen to form a smooth carpet over the Caco-2 cells (b), whereas PEG 15-20 formed a more topographically defined covering (c). d-f. AFM images of PA27853 in PEG 3.35 and PEG 15-20. PEG 3.35 formed a smooth envelope around individual bacterial cells (e) whereas PEG 15-20 not only tightly hugged the individual cells (f), but also increased the polymer/bacterial diameter (g,h), thereby distancing individual bacteria from one another. [0040] FIG. 6 shows the effect of PEG solution on the dispersion/clumping pattern of PA27853. The dispersion pattern of bacterial cells in dTC3 dishes was observed directly with an Axiovert 100 TV fluorescence inverted microscope using DIC and GFP fluorescence filter, at an objective magnification of 63×. Temperature was adjusted with a Bioptechs thermostat temperature control system. Tungsten lamps (100 V) were used for both DIC and the GFP excitation. The 3D imaging software (Slidebook) from intelligent Imaging Innovations was used to image the bacterial cell dispersion pattern in the Z plane using the GFP filter. Uniformly dispersed planktonic P. aeruginosa cells in the medium without Caco-2 cells were seen on DIC image (6a 1 ) and Z plane reconstruction (6a 2 ). In the presence of Caco-2 cells, bacterial cells developed a clumped appearance (6b 1 ) and were seen adherent to the Caco-2 cells (6b 2 ). 10% PEG 3350 decreased the motility of bacteria and induced immediate formation of mushroom-shaped bacterial microcolonies (6c 1 ) adhering to the bottom of the well (6c 2 ). In the presence of Caco-2 cells, bacterial microcolonies were on the order of 8 microns above the plane of the epithelial cells (6d 1,2 ). 10% PEG 15-20 greatly diminished the motility of P. aeruginosa cells. Nevertheless, for the first 0.5-1 hours of incubation in PEG 15-20-containing medium, bacterial cells formed spider-shaped microcolonies that were close to the bottom of the well (6e 1,2 ). Within several hours, spider leg-shaped microcolonies occupied the entire space/volume of the medium (not shown). In the presence of Caco-2 cells, P. aeruginosa cells lost the spider-like configuration and were seen elevated high above the plane of the epithelium (30-40 microns) (6f 1,2 ). DETAILED DESCRIPTION OF INVENTION [0041] The invention provides products and methods that collectively present simple and economical approaches to the treatment and/or prevention of a variety of microbe-mediated epithelial disorders, i.e., abnormal conditions and diseases, that afflict many mammals, including humans. By administering high molecular weight polar polymers such as HMW polyethylene glycol to an animal in need, including those at risk, any of a number of health- or life-threatening abnormal conditions, i.e., epithelial disorders and diseases, including gut-derived sepsis, can be treated with minimal cost and minimal training of practitioners. Without wishing to be bound by theory, the benefits provided by the invention are consistent with the principle that microbe-mediated epithelial disorders can be successfully prevented, ameliorated or treated by facilitating an environment conducive to the survival of such microbes. An understanding of the following more detailed description of the invention is facilitated by initially establishing the following meanings for terms used in this disclosure. [0042] An “abnormal condition” is broadly defined to include mammalian diseases, mammalian disorders and any abnormal state of mammalian health that characterized by an epithelial surface at risk of developing a microbial-mediated disorder. The abnormal conditions characterized by an epithelial surface at risk of developing a microbial-mediated disorder include conditions in which the epithelial surface has developed a microbial-mediated disorder. Exemplary conditions include human diseases and human disorders requiring, or resulting from, medical intervention, such as a burn injury, neonatal enterocolitis, severe neutropenia, inflammatory bowel disease, enteropathy (e.g., of the critically ill) and transplant (e.g., organ) rejection. [0043] “Burn injury” means damage to mammalian tissue resulting from exposure of the tissue to heat, for example in the form of an open flame, steam, hot fluid, and a hot surface. [0044] “Severe” neutropenia is given its ordinary and accustomed meaning of a marked decrease in the number of circulating neutrophils. [0045] “Transplant rejection” refers to any development of transplanted material (e.g., an organ) recognized as being associated with ultimate rejection of that material by the host organism. [0046] “Administering” is given its ordinary and accustomed meaning of delivery by any suitable means recognized in the art. Exemplary forms of administering include oral delivery, anal delivery, direct puncture or injection, topical application, and spray (e.g., nebulizing spray), gel or fluid application to an eye, ear, nose, mouth, anus or urethral opening. [0047] An “effective dose” is that amount of a substance that provides a beneficial effect on the organism receiving the dose and may vary depending upon the purpose of administering the dose, the size and condition of the organism receiving the dose, and other variables recognized in the art as relevant to a determination of an effective does. The process of determining an effective dose involves routine optimization procedures that are within the skill in the art. [0048] An “animal” is given its conventional meaning of a non-plant, non-protist living being. A preferred animal is a mammal, such as a human. [0049] In the context of the present disclosure, a “need” is an organismal, organ, tissue, or cellular state that could benefit from administration of an effective dose to an organism characterized by that state. For example, a human at risk of developing gut-derived sepsis, or presenting a symptom thereof, is an organism in need of an effective dose of a product, such as a pharmaceutical composition, according to the present invention. [0050] “Average molecular weight” is given its ordinary and accustomed meaning of the arithmetic mean of the molecular weights of the components (e.g., molecules) of a composition, regardless of the accuracy of the determination of that mean. For example, polyethylene glycol, or PEG, having an average molecular weight of 3.5 kilodaltons may contain PEG molecules of varying molecular weight, provided that the arithmetic mean of those molecular weights is determined to be 3.5 kilodaltons at some level of accuracy, which may reflect an estimate of the arithmetic mean, as would be understood in the art. Analogously, PEG 15-20 means PEG whose molecular weights yield an arithmetic mean between 15 and 20 kilodaltons, with that arithmetic mean subject to the caveats noted above. These PEG molecules include, but are not limited to, simple PEG polymers. For example, a plurality of relatively smaller PEG molecules (e.g., 7,000 to 10,000 daltons) may be joined, optionally with a linker molecule such as a phenol, into a single molecule having a higher average molecular weight (e.g., 15,000 to 20,000 daltons). [0051] “Cell membrane integrity” means the relative absence of functionally significant modifications of a cell membrane as a functional component of a living cell, as would be understood in the art. [0052] “Detectably altered” is given its ordinary and accustomed meaning of a change that is perceivable using detection means suitable under the circumstances, as would be understood in the art. [0053] “Growth pattern” refers collectively to the values of those properties of a cell, or group of cells (e.g., a population of cells), that are recognized in the art as characterizing cell growth, such as the generation or doubling time of the cell, the appearance of topography of a nascent group of cells, and other variables recognized in the art as contributing to an understanding of the growth pattern of a cell or group of cells. [0054] “Inhibiting” is given its ordinary and accustomed meaning of inhibiting with, reducing or preventing. For example, inhibiting morphological change means that morphological change is made more difficult or prevented entirely. [0055] “PA-I, or PA-I lectin/adhesin, expression means the production or generation of an activity characteristic of PA-I lectin/adhesin. Typically, PA-I lectin/adhesin expression involves translation of a PA-I lectin/adhesin-encoding mRNA to yield a PA-I lectin/adhesin polypeptide having at least one activity characteristic of PA-I lectin/adhesin. Optionally, PA-I lectin/adhesin further includes transcription of a PA-I lectin/adhesin-encoding DNA to yield the aforementioned mRNA. [0056] “Epithelium-induced activation” refers to an increase in the activity of a given target (e.g., PA-I lectin/adhesin) through direct or indirect influence of an epithelial cell. In the context of the present invention, for example, epithelium-induced activation of PA-I lectin/adhesin refers to an increase in that polypeptide's activity attributable to the indirect influence of an epithelium manifested through the direct contact of an epithelial cell or cells with an intestinal pathogen. [0057] “Morphological change” is given its ordinary and accustomed meaning of an alteration in form. [0058] “Intestinal pathogen” means a pathogenic microbe capable of causing, in whole or part, gut-derived sepsis in an animal such as a human. Intestinal pathogens known in the art are embraced by this definition, including gram negative bacilli such as the Pseudomonads (e.g., Pseudomonas aeruginosa ). [0059] “Ameliorating” means reducing the degree or severity of, consistent with its ordinary and accustomed meaning. [0060] “Pathogenic quorum” means aggregation or association of a sufficient number of pathogenic organisms (e.g., P. aeruginosa ) to initiate or maintain a quorum sensing signal, as would be known in the art. [0061] “Interaction” is given its ordinary and accustomed meaning of interplay, as in the interplay between or among two or more biological products, such as molecules, cells, and the like. [0062] “Transepithelial Electrical Resistance,” or TEER, is given the meaning this phrase has acquired in the art, which refers to a measurement of electrical resistance across epithelial tissue, which is non-exclusively useful in assessing the status of tight junctions between epithelial cells in an epithelial tissue. [0063] “Adherence” is given its ordinary and accustomed meaning of physically associating for longer than a transient period of time. [0064] “Topographically asymmetrical” refers to an image, map or other representation of the surface of a three-dimensional object (e.g., a cell) that is not symmetrical. [0065] “Atomic force microscopy,” also known as scanning force microscopy, is a technique for acquiring a high-resolution topographical map of a substance by having a cantilevered probe traverse the surface of a sample in a raster scan and using highly sensitive means for detecting probe deflections, as would be understood in the art. [0066] “Pharmaceutical composition” means a formulation of compounds suitable for therapeutic administration, to a living animal, such as a human patient. Preferred pharmaceutical compositions according to the invention comprise a solution balanced in viscosity, electrolyte profile and osmolality, comprising an electrolyte, dextran-coated L-glutamine, dextran-coated inulin, lactulase, D-galactose, N-acetyl D-galactosamine and 5-20% PEG (15,000-20,000). [0067] “Adjuvants,” “carriers,” or “diluents” are each given the meanings those terms have acquired in the art. An adjuvant is one or more substances that serve to prolong the immunogenicity of a co-administered immunogen. A carrier is one or more substances that facilitate the manipulation, such as by translocation of a substance being carried. A diluent is one or more substances that reduce the concentration of, or dilute, a given substance exposed to the diluent. [0068] “HMW PEG” refers to relatively high molecular weight PEG defines as having an average molecular weight greater than 3.5 kilodaltons. Preferably, HMW PEG has an average molecular weight greater than 5 kilodaltons and, in particular embodiments, HMW PEG has an average molecular weight at least 8 kilodaltons, at least 15 kilodaltons, and between 15 and 20 kilodaltons. [0069] The following examples illustrate embodiments of the invention. Example 1 describes the protection against gut-derived sepsis provided to hepatectomized mice by high molecular weight PEG. Example 2 discloses how HMW PEG prevents pathogen adherence to intestinal epithelial cells. Example 3 reveals how HMW PEG inhibits pathogenic virulence expression generally, and PA-I lectin/adhesin expression specifically. Example 4 shows that PEG does not affect growth, or cell membrane integrity, of pathogens. Example 5 illustrates the unique topographical conformation of HMW PEG-coated pathogens using Atomic force microscopy. Example 6 describes the cell-cell interactions affected by HMW PEG. Example 7 describes preventive methods using the compositions of the invention. Example 8 discloses methods for monitoring administration of HMW PEG, such as in the treatment methods of the invention, and corresponding kits. Example 1 HMW PEG Protects Against Gut-Derived Sepsis Following 30% Hepatectomy [0070] Male Balb/c mice were anesthetized and subjected to hepatectomy using a conventional protocol. A 30% bloodless excision of the liver along the floppy left lobe was performed. Control mice underwent manipulation of the liver without hepatectomy. The experimental and control groups each contained seven mice. In all mice, a volume of 200 μl of 10 7 cfu/ml of Pseudomonas aeruginosa PA27853 was injected into the base of the cecum by direct needle puncture diluted in either saline, PEG 3.350 or PEG 15-20 (PEGs). The relatively low molecular weight PEGs are commercially available; PEG 15-20, having an average molecular weight of 15,000 to 20,000 daltons, is a combination of PEG 7-8 and PEG 8-10 covalently joined to a phenol ring. The PEG 7-8 has an average molecular weight of 7,000 to 8,000 daltons and the PEG 8-10 has an average molecular weight of 8,000 to 10,000 daltons. One of skill in the art will realize that HMW PEGs include compounds having any of a variety of PEG subunits with each subunit having any of a variety of average molecular weights joined, preferably covalently, to each other or to one or more linker molecules, which are relatively small molecules having functional groups suitable for joinder of PEG molecules. Suitable linkers substantially preserve the biological activity of HMW PEG (preservation of sufficient biological activity to realize a beneficial prophylactic or therapeutic effect as disclosed herein). [0071] In order to provide a constant source of PEG for the 48-hour duration of the experiment, the needle was directed into the small bowel (ileum) and 1 ml of saline, PEG 3.35 or PEG 15-20 was injected retrograde into the proximal bowel. The puncture site was tied off with a silk suture and the cecum swabbed with alcohol. Mice were returned to their cages and were given H 2 O only for the next 48 hours. [0072] Dose response curves for PEG 15-20 are seen in panel b of FIG. 1 . a. A statistically significant protective effect of PEG 15-20 was determined by the Fisher Exact Test (P<0.001). b. The minimum protective concentration of PEG 15-20 was determined to be 5% (P<0.05). c. Quantitative bacterial cultures of cecal contents (feces), washed cecal mucosa, liver, and blood 24 hours following 30% surgical hepatectomy and direct cecal injection of 1×10 7 cfu/ml of PA27853. One-way ANOVA demonstrated a statistically significant increase in bacterial counts in cecal contents, mucosa, liver, and blood in mice following hepatectomy (P<0.001). A significant decrease (P<0.05) in the liver and blood bacterial counts was observed for PEG 3350, while PEG 15-20 completely prevented PA27853 from disseminating to the liver and blood of mice. [0073] Pseudomonas aeruginosa strain ATCC 27853 (PA27853) is a non-mucoid clinical isolate from a blood culture. Direct cecal injection of strain PA27853 in mice previously subjected to a 30% bloodless surgical hepatectomy resulted in a state of clinical sepsis and no survivors at 48 hours. Mice subjected to sham laparotomy without hepatectomy (controls), who are similarly injected with P. aeruginosa , survive completely without any clinical signs of sepsis ( FIG. 1 a ). To determine the ability of PEG solutions to prevent or lower mortality in this model, 200 μl of PA27853 at a concentration of 1×10 7 cfu/ml, was suspended in one of two 10% (w/v) solutions of polyethylene glycol (PEG-3.35 versus PEG-15-20). PEG-3.35 was chosen as it represents the molecular weight of PEGs that have been available for clinical use for the last 25 years (Golytely®). In comparison, PEG solutions according to the invention that were used had molecular weights varying between 15-20 kDa. Suspended strains were introduced into the cecum by direct puncture. PEG 3.35 had no effect on mortality in mice following hepatectomy, whereas PEG 15-20 was completely protective. In fact, PEG 15-20 had a statistically significant protective effect, as determined by the Fisher Exact Test (P<0.001). Dose-response experiments demonstrated a 5% solution to be the minimal concentration of PEG 15-20 that was completely protective (P<0.05; see FIG. 1 b ), although one of skill in the art will recognize that HMW PEG solutions of less than 5% would be expected to provide some protection and, thus, fall within the scope of the present invention. With respect to bacterial counts in the experimental and control mice, a one-way analysis of variance (ANOVA) demonstrated a statistically significant increase in bacterial counts in the cecal contents, mucosa, liver, and blood in mice following hepatectomy (P<0.001). A significant decrease (P<0.05) in the liver and blood bacterial counts was observed for PEG 3350, while PEG 15-20 completely prevented PA27853 from disseminating to the liver and blood of mice. PEG 15-20 completely inhibited the dissemination of intestinal PA27853 to the liver and bloodstream ( FIG. 1 c ). The data indicate that the action of PEG solutions involves mechanisms that are non-microbiocidal. Given at PEG concentrations non-toxic to mammalian cells (i.e. ≦about 10%), no effect on bacterial growth patterns can be demonstrated. [0074] The example demonstrates that HMW PEG reduces the mortality rate attributable to gut-derived sepsis in mice subjected to surgical intervention in the form of a partial hepatectomy. This mouse model indicates that HMW PEG therapy is useful in reducing the mortality rate of an animal species (i.e., reducing the likelihood of mortality in any given organism), such as a mammal like man, subjected to a physiological stress such as invasive surgery (e.g., partial hepatectomy). It is expected that HMW PEG therapy will be effective in methods of preventing death or serious illness associated with sepsis when implemented following the physiological stress (e.g., during post-operative care). Further, HMW PEG therapy may be used prior to physiological stressing (e.g., pre-operative care), under circumstances where introduction of the stress is predictable, to lower the risk of serious illness or death. HMW PEG therapy is also useful in ameliorating a symptom associated with a disease or abnormal condition associated with gut-derived sepsis. Example 2 HMW PEG Prevents Pathogen Adherence to Intestinal Epithelia [0075] Tight junctions are dynamic elements of the epithelial cell cytoskeleton that play a key role in the barrier function of the mammalian intestinal tract. P. aeruginosa results in a profound alteration in tight junctional permeability as measured by the transepithelial electrical resistance (TEER) of both Caco-2 cells and T-84 cells. Caco-2 cells are well-characterized human colon epithelial cells that maintain a stable TEER in culture, and this cell line provides a recognized in vitro model of the in vivo behavior of intestinal pathogens. To determine the protective effect of PEG on P. aeruginosa PA27853-induced decreases in TEER of cultured Caco-2 monolayers, 1×10 7 cfu/ml of PA27853 was apically inoculated onto two Caco-2 cell monolayers in the presence of 10% PEG 3.35 or 10% PEG 15-20. TEER was serially measured for 8 hours and the maximal fall in TEER recorded. [0076] Only PEG 15-20 protected significantly against the P. aeruginosa -induced decrease in TEER ( FIG. 2 a ). The data presented in FIG. 2 represent the mean±SEM % maximal fall in TEER from baseline of triplicate cultures (n=7) observed during 8 hours of apical exposure to 1×10 7 cfu/ml of PA27853. A statistically significant decrease in TEER, as demonstrated in Caco-2 cells exposed to PA27853, was revealed by one-way ANOVA (P<O.001). A statistically significant protective effect on the fall in TEER induced by PA27853 was demonstrated for PEG 15-20 (P<O.001). FIG. 2 b shows Caco-2 cells in the presence of PEG 3.35 and with apical exposure to PA27853. After 4 hours of co-culture in the presence of PEG 3.35, disruption of the Caco-2 cell monolayers displaying focally adherent bacteria was observed, with cells floating 30-40 microns above the monolayer scaffolds ( FIG. 2 b ). In contrast, FIG. 2 c , showing images of Caco-2 cells apically exposed for 4 hours to PA27853 in the presence of PEG 15-20, shows no evidence of floating cells in any of the planes examined. The protective effect of PEG 15-20 on Caco-2 cell integrity was associated with less bacterial adherence, reflected by a 15-fold higher recovery of bacteria in the cell supernatants following a 4-hour exposure to 1×10 6 cfu/ml of PA27853. [0077] The resistance of PEG-cultured human intestinal epithelial cells to the barrier-disrupting effects of P. aeruginosa , as judged by the maintenance of TEER, offers a practical approach to stabilizing tight junctional barrier function in the face of a challenge from invading pathogens. Further evidence of the therapeutic value of PEG 15-20 is that epithelial transport function (Na + /H + exchange, glucose transport) is unaffected by this compound. [0078] Thus, HMW PEG is relatively inert to, and has a stabilizing effect on, the intestinal epithelial barrier. The invention comprehends methods of treating intestinal barrier abnormalities associated with intestinal pathogens such as P. aeruginosa by administering HMW PEG to an animal such as a mammal and, preferably, a human. An intestinal barrier abnormality may be revealed by any diagnostic technique, or other means, known in the art. It is not necessary to identify an intestinal barrier abnormality prior to HMW PEG treatment, however. The low cost and high degree of safety associated with HMW PEG treatment make this approach suitable for both prophylactic applications, preferably directed towards at-risk organisms, as well as treatment methods applied to animals exhibiting at least one symptom characteristic of an intestinal barrier abnormality. The HMW PEG treatment methods would ameliorate a symptom associated with an intestinal barrier abnormality; preferably, the methods would reduce or eliminate the effects of gut-derived sepsis from a treated organism. Example 3 HMW PEG Inhibits Virulence Expression in Pathogens [0079] The expression of the PA-I lectin/adhesin in P. aeruginosa PA27853 was increased in the cecum of mice following hepatectomy and played a key role in the lethal effect of P. aeruginosa in the mouse intestine. PA-I functions as a significant virulence determinant in the mouse intestine by facilitating the adherence of PA27853 to the epithelium as well as by creating a significant barrier defect to the cytotoxins, exotoxin A and elastase. PA-I expression in P. aeruginosa is regulated by the transcriptional regulator RhIR and its cognate activator C4-HSL. Expression of PA-I in PA27853 was not only increased by exposure to C4-HSL, but also by contact with Caco-2 cells, Caco-2 cell membrane preparations, and supernatants from Caco-2 cell cultures. [0080] Northern hybridization was used to analyze the expression of PA-I at the transcriptional level. Total RNA of P. aeruginosa was isolated by the modified three-detergent method. Probes were generated by PCR using PA-I primers: F(ACCCTGGACATTATTGGGTG) (SEQ ID NO: 1), R(CGATGTCATTACCATCG-TCG) (SEQ ID NO: 2) and 16S primers: F(GGACGGGTGAGTAATGCCTA) (SEQ ID NO: 3), R(CGTAAGGGCCATGATGACTT) (SEQ ID NO: 4), and cloned into the pCR2.1 vector (Invitrogen, Inc.). The inserts were sequences that matched the sequence of either PA-I or 16S. Specific cDNA probes for PA-I and 16S were radiolabeled with α 32 P-dCTP. The specific radioactivity was measured by a Storm 860 phosphorimager (Molecular Dynamics, CA), and relative percent changes compared to control were calculated based on the intensity ratio of PA-I and 16S. Western blot was used for PA-I protein analysis, using rabbit affinity-purified polyclonal anti-PA-I antibodies. One ml of P. aeruginosa cells was washed with PBS and heated at 100° C. in lysis buffer (4% SDS, 50 mM Tris-HCl, pH 6.8); immunoblot analysis was performed by electrotransfer of proteins after Tricine SDS-PAGE. The PA-I lectin was detected by the ECL reagent (Amersham, N.J.). [0081] Exposure of P. aeruginosa PA27853 to 1 mM of the quorum-sensing signaling molecule C4-HSL resulted in a statistically significant increase (P<0.001, one-way ANOVA) in PA-I protein expression that was partially inhibited in the presence of 10% PEG 3.35 and inhibited to a much greater extent by 10% PEG 15-20 ( FIG. 3 ). The minimum completely inhibitory concentration of PEG 15-20 on C4-HSL-induced PA-I expression was 5% (P<0.01, one-way ANOVA). Electron microscopic examination of individual bacterial cells exposed to C4-HSL in the presence and absence of PEG, demonstrated that C4-HSL caused a morphological change in the shape and pili expression of P. aeruginosa ( FIG. 3 b ). The C4-HSL-induced morphological effect was completely eliminated in the presence of PEG 15-20, but not completely eliminated in the presence of PEG 3.35. A halo-type effect was seen surrounding PA27853 exposed to PEG 15-20 ( FIG. 3 b ). Exposure of PA27853 to 0.1 mM of C4-HSL resulted in a statistically significant increase (P<0.001, one-way ANOVA) in PA-I mRNA expression assessed using Northern blots. The PA-I expression was greatly inhibited by 10% PEG 15-20. FIG. 3 d shows that the increase in PA-I mRNA induced by a 4-hour exposure to Caco-2 cells was inhibited by PEG 15-20, but not by PEG 3.35 (P<0.001 one-way ANOVA). [0082] The data presented herein show that a significant attenuation (3-4-fold decrease) of PA-I expression (protein and mRNA) in PA27853, induced by 100 μM-1 mM of C4-HSL, was observed when bacteria were pre-treated with 10% PEG 15-20. This effect was not observed with PEG 3.35 ( FIG. 3 a ). Attenuation of C4-HSL-induced PA-I expression was also observed for 10% PEG 3.35, although the degree of attenuation was significantly less than that for 10% PEG 15-20. The minimum concentration of PEG 15-20 that inhibited C4-HSL induced expression of PA-I protein was 5% ( FIG. 3 b ). Electron microscopy of individual bacterial cells exposed to C4-HSL demonstrated that C4-HSL caused a morphological change in the shape and pili expression of PA27853 ( FIG. 3 b ). The C4-HSL-induced morphological effect was completely eliminated in the presence of PEG 15-20, but not PEG 3.35 ( FIG. 3 b ). PA-I expression (mRNA), induced by 4 hours exposure to Caco-2 cells, was inhibited in the presence of PEG 15-20 but not PEG 3.35 ( FIG. 3 b ). The protective effect of Caco-2 cell-induced PA-I expression with PEG 15-20 persisted in experiments of overnight exposure. [0083] HMW PEG also affects the virulence expression of P. aeruginosa in response to known stimuli. The attenuation of C4-HSL-induced PA-I expression in PA27853 may be a major protective effect of PEG 15-20, given that quorum-sensing signaling is a well-established mechanism of virulence expression for this pathogen. The PEG 15-20-induced interference with Caco-2 cell-induced expression of PA-I is expected to be an important aspect of the protective effect of PEG 15-20. PEG 15-20 was found to have a protective effect on host animals through the attenuation of P. aeruginosa (PA27853) PA-I expression in response to filtered cecal contents (feces) from mice following 30% hepatectomy. The ability of PEG 15-20 to shield P. aeruginosa from host factors that increase its virulence expression is expected to be yet another mechanism by which organisms are protected from gut-derived sepsis. [0084] Accordingly, the invention includes materials in the form of kits and corresponding methods of administering an HMW PEG to an animal to prevent or treat a condition characterized by the expression of a virulence factor or determinant by an intestinal pathogen such as one of the Pseudomonads. A virulence determinant may contribute to virulence directly, or indirectly. An example of an indirect contribution is the effect of the PA/I lectin/adhesin of P. aeruginosa on intestinal pathogen adhesion to intestinal epithelia and/or the generation of a barrier defect to the cytotoxins, exotoxin A and elastase. Example 4 [0085] PEG does not Affect Cell Growth, or Cell Membrane Integrity, of Pathogens [0086] The effect of the two PEG solutions (PEG 3.35 and PEG 15-20) on bacterial membrane integrity was assessed by a staining method consisting of SYTO 9 and propidium iodide. Neither PEG solution had any effect on bacterial membrane permeability ( FIG. 4 a ). Membrane integrity was determined using a live/dead bacterial viability kit L-3152 (Molecular Probes). Bacteria were quantified and counts expressed as cfu/ml by plating 10-fold dilutions of samples taken at different incubation times. Growth curves for P. aeruginosa grown overnight in TSB media containing either of the two PEG solutions demonstrated no inhibitory effect by either PEG solution on bacterial quantity ( FIG. 4 b ). In fact, the growth pattern in each of the PEG-containing media was indistinguishable from the growth pattern in PEG-free TSB medium. The activity of a housekeeping enzyme involved in energy metabolism, lactate dehydrogenase (LDH), was measured at various time points during the exponential and stationary phases of growth. LDH activity was measured in a coupled diaphorase enzymatic assay using a substrate mix from CytoTox 96 (Promega). Protein concentration was determined using the BCA Protein Assay (Pierce). No change in LDH activity in cell-free supernatants of P. aeruginosa grown in the presence of PEGs was observed. The results of this experiment indicate that HMW PEG has a negligible effect on bacterial growth patterns. [0087] The methods of the invention, and corresponding products (e.g., kits), provide the benefit of preventing or treating diseases or abnormal conditions associated with gut-derived sepsis without significantly influencing the composition of the intestinal flora. Similarly, the methods and products of the invention may be used to ameliorate a symptom associated with such diseases or abnormal conditions without significant change to the microbial composition of the intestine. One of skill in the art recognizes that methods (and kits) that do not significantly disturb the composition of the intestinal flora are desirable insofar as such methods would not be expected to lead to secondary health complications arising from such a disturbance. Example 5 Atomic Force Microscopy of PEG-Coated Pathogen [0088] One percent aliquots of a culture of PA27853 grown overnight were subcultured in tryptic soy broth (TSB), with or without 10% HMW PEG, for 4 hours at 37° C. One drop of each subculture was withdrawn and the P. aeruginosa PA27853 cells were extensively washed with PBS, dried on top of mica in blowing air for 10 minutes, and imaged immediately. Imaging of the dried bacteria with tapping-mode AFM was performed in air with a Multimode Nanoscope IIIA Scanning Probe Microscope (MMAFM, Digital Instruments). Subconfluent Caco-2 cells were treated with 10% HMW PEG for 4 hours and washed with PBS extensively. AFM imaging of the cells was performed in PBS without using an O-ring. For electron microscopy, PA27853 was inoculated in TSB with or without 1 mM C4-HSL and 10% HMW PEG and incubated overnight. One drop of 1% P. aeruginosa was stained with uranyl acetate and washed with 0.5M NaCl before examination under the electron microscope. [0089] Atomic force microscopy of Caco-2 cells demonstrated a classical non-uniform surface with brush border microvili, while Caco-2 cells exposed to PEG 3.35 demonstrated a smooth planar appearance on the surface of the epithelial cells ( FIGS. 5 a, c ). PEG 15-20 appears to carpet the Caco-2 cells by filling the asymmetries along a topographically defined plane ( FIG. 5 e ), yielding a more complex topographically defined covering. In somewhat similar fashion, PA27853 cells exposed to PEG 3.35 demonstrate a pattern of smooth coating of the polymer to bacterial cells in a diffuse flat pattern ( FIG. 6 d ), whereas PEG 15-20 appears to surround and hug the bacteria circumferentially in a more topographically asymmetric fashion. Cross-sectional analysis of the atomic force measurement of the bacterial diameter in PEG 15-20 demonstrates a significant increase in the bacteria/PEG envelope within the PEG solution ( FIG. 5 e, f ). In other words, PEG 3.35 forms a smooth envelope around individual bacterial cells ( FIG. 5 e ), whereas PEG 15-20 tightly hugs individual cells ( FIG. 5 f ) and increases the polymer/bacterial diameter ( FIGS. 5 g , 5 h ), thereby distancing individual bacterial cells from each other. [0090] Without wishing to be bound by theory, HMW PEG may exert its beneficial effect by the mere physical distancing of P. aeruginosa away from the intestinal epithelium. Alternatively, HMW PEG may provide benefits by preventing formation of a pathogenic quorum-sensing activation signal arising from cell-cell interaction of the pathogenic cells. Again without wishing to be bound by theory, it is possible that the coating of biological surfaces with HMW PEG results in loss of conformational freedom of the coating PEG chains and the repelling of approaching proteins. Polar-polar interactions between HMW PEG and Caco-2 cells could affect the elasticity of the PEG chains, constraining certain HMW PEG side chains to a molecular construct which repels protein. Data presented herein support the conclusion that HMW PEG-coated Caco-2 cells are more repellant to P. aeruginosa than uncoated Caco-2 cells, perhaps owing to a loss of “conformational entropy” as a result of some dynamic interaction of HMW PEG with Caco-2 cells. [0091] The results of this experiment establish that HMW PEG treatment has an effect on treated cells, notably affecting the surface topology of such cells. Moreover, the effect of HMW PEG exposure on such cells is different from the effect that PEG 3.35 has on such cells. Although not wishing to be bound by theory, the results disclosed herein do provide a physical correlate for the markedly different effect on cells exhibited by HMW PEG relative to lower molecular weight PEGs, such as PEG 3.35. Example 6 HMW PEG Affects Cell-Cell Interactions [0092] To directly observe the effect of PEG solutions on the spatial orientation of P. aeruginosa , experiments were performed with live strains of P. aeruginosa PA27853/EGFP harboring the egfp gene encoding the green fluorescent protein. Experiments were performed in the presence and absence of Caco-2 cells. In order to image the effect of PEGs on both the bacteria and their interaction with the cultured epithelia, differential interference contrast (DIC) microscopy and GFP imaging were used. [0093] The EGFP gene encoding green fluorescent protein was amplified using the pBI-EGFP plasmid (Clontech) as a template. XbaI and PstI restriction sites were introduced using primers TCTAGAACTAGTGGATCCCCGCGGATG (SEQ ID NO: 5) and GCAGACTAGGTCGACAAGCTTGATATC (SEQ ID NO: 6). The PCR product was cloned directly into the pCR 2.1 vector using a TA-cloning kit (Invitrogen), followed by transformation of the pCR2.1/EGFP construct into E. coli DH5a. The EGFP gene was excised from this construct by digestion with XbaI and PstI and the fragment containing the excised gene was cloned into the E. coli - P. aeruginosa shuttle vector pUCP24, which had been digested with the same restriction enzymes. The resulting construct (i.e., pUCP24/EGFP), containing the EGFP gene in the shuttle vector, was electroporated at 25 μF and 2500 V into PA27583 electro-competent cells. PA27853/EGFP-containing cells were selected on LB-agar plates containing 100 μg/ml gentamicin (Gm). [0094] Cells harboring PA27853/EGFP were grown overnight in LB containing 100 μg/ml Gm, and 1% of the culture was used to inoculate fresh LB containing 50 μg/ml Gm. After 3 hours of growth, Isopropyl-β-D-thiogalactopyranoside (IPTG) was added to a final concentration of 0.5 mM, and cultures were incubated for 2 additional hours. 100 μl of the bacterial culture was mixed with 1 ml of HDMEM media (Gibco BRL) buffered with HEPES and containing 10% fetal bovine serum (HDMEM HF) and 10% HMW PEG. One ml of bacterial suspension was poured into a 0.15 mm-thick dTC3 dish (Bioptech). Four-day-old Caco-2 cells (p10-p30) grown in 0.15 mm-thick dTC3 dishes (Bioptech) in HDMEM HF were washed once in HDMEM HF with or without HMW PEG. One ml of bacterial suspension prepared as above was added to a dTC3 dish containing Caco-2 cells. The dispersion pattern of bacterial cells in dTC3 dishes was observed directly with an Axiovert 100 TV fluorescence inverted microscope using DIC and GFP fluorescence filters, at an objective magnification of 63×. The temperature was adjusted with a Bioptechs thermostat temperature control system. Tungsten lamps (100 V) were used for both DIC and the GFP excitation. The 3D imaging software (Slidebook) from Intelligent Imaging Innovations was used to image the bacterial cell dispersion pattern in the Z plane using the GFP filter. Uniformly dispersed planktonic P. aeruginosa cells in the medium without Caco-2 cells were seen on a DIC image ( FIG. 6 a 1 ) and Z plane reconstruction ( FIG. 6 a 2 ). In the presence of Caco-2 cells, bacterial cells developed a clumped appearance ( FIG. 6 b 1 ) and were seen adhering to the Caco-2 cells ( FIG. 6 b 2 ). A solution of 10% PEG 3350 decreased the bacterial motility and induced immediate formation of mushroom-shaped bacterial microcolonies ( FIG. 6 c 1 ) adhering to the bottom of the well ( FIG. 6 c 2 ). In the presence of Caco-2 cells, bacterial microcolonies were approximately 8 microns above the plane of the epithelial cells ( FIG. 6 d 1,2 ). A solution of 10% PEG 15-20 greatly diminished the motility of P. aeruginosa cells. Nevertheless, for the first 0.5-1 hour of incubation in PEG 15-20-containing medium, bacterial cells formed spider leg-shaped microcolonies that were close to the bottom of the well ( FIG. 6 e 1,2 ). Within several hours, spider leg-shaped microcolonies occupied the entire space/volume of the medium. In the presence of Caco-2 cells, P. aeruginosa cells lost the spider leg-like configuration and were seen elevated high above the plane of the epithelium (30-40 microns) ( FIG. 6 f 1,2 ). [0095] To determine the spatial orientation of the bacterial-epithelial cell interactions in three dimensions, Z plane re-constructions were performed. Images demonstrated that the two PEG solutions had different effects on the clumping behavior of P. aeruginosa and differentially affected the spatial orientation of the bacteria depending on the presence or absence of Caco-2 cells. In experiments with medium only, P. aeruginosa were seen to display a uniformly dispersed pattern ( FIG. 6 a ). Bacterial cells examined in the presence of Caco-2 cells, however, developed a clumped appearance and were seen adjacent to the plane of the epithelial cells at the bottom of the wells ( FIG. 6 b ). Bacterial cells examined in the presence of PEG 3.35 alone formed large clumped aggregates and remained in the bottom of the culture well ( FIG. 6 c ), whereas bacterial cells examined with Caco-2 cells in medium containing PEG 3.35, remained suspended above the plane of the epithelial cells (about 8 microns), maintaining their clumped appearance ( FIG. 6 d ). Bacterial cells examined in the presence of PEG 15-20 alone displayed a uniform pattern of microclumping ( FIG. 6 e ), whereas bacterial cells examined in the presence of Caco-2 in medium containing PEG 15-20 were suspended higher above the plane of the epithelium (˜32 microns) in clumped formation ( FIG. 6 f ). In timed experiments, bacterial motility was observed to be decreased by PEG 3.35 and, to an even greater degree, with PEG 15-20. [0096] In a manner analogous to the experiment disclosed in Example 5, this Example provides a physical correlate for the observed effect of HMW PEG on cell-cell interaction, consistent with its beneficial prophylactic and therapeutic activities as disclosed herein. It is expected that use of HMW PEG will reduce or eliminate deleterious cell-cell interactions in the intestine (e.g., between intestinal epithelial cells and intestinal pathogens such as the Pseudomonads), reducing the risk of diseases and/or abnormal conditions associated with gut-derived sepsis. Example 7 Methods of Preventing Disease/Abnormal Conditions [0097] The invention also provides methods of preventing a variety of diseases and/or abnormal conditions in humans and other animals, particularly other mammals. In these methods, an effective amount of HMW PEG is administered to a human patient or an animal subject in need thereof. The PEG may be administered using a schedule of administration that is determined using routine optimization procedures known in the art. Preferably, the PEG has an average molecular weight of 5,000-20,000 daltons, and more preferably between 10,000-20,000 daltons. It is contemplated that at least 5% HMW PEG is administered. The HMW PEG may be administered in any suitable form, e.g., as a solution, as a gel or cream, as a solution suitable for nebulizing (e.g., for inhalational use), in a pharmaceutical composition comprising the HMW PEG, and in a sterile, isotonic solution suitable for injection into an animal. administration may be accomplished using any conventional route; it is particularly contemplated that the HMW PEG is administered orally or topically. In some embodiments, the HMW PEG composition being administered further comprises a compound selected from the group consisting of dextran-coated L-glutamine, dextran-coated inulin, dextran-coated butyric acid, a fructo-oligosaccharide, N-acetyl-D-galactosamine, dextran-coated mannose, galactose and lactulose. In another embodiment, the administered HMW PEG composition further comprises dextran-coated L-glutamine, dextran-coated inulin, dextran-coated butyric acid, one or more fructo-oligosaccharides, N-acetyl-D-galactosamine, dextran-coated mannose, galactose and lactulose. [0098] The invention provides methods of preventing a variety of diseases and abnormal conditions, such as swimmer's ear, acute or chronic otitis media, ventilator-associated pneumonia, gut-derived sepsis, necrotizing enterocolitis, antibiotic-induced diarrhea, pseudomembranous colitis, inflammatory bowel diseases, irritable bowel disease, neutropenic enterocolitis, pancreatitis, chronic fatigue syndrome, dysbiosis syndrome, microscopic colitis, chronic urinary tract infection, sexually transmitted disease, and infection (e.g., exposure to an environment contaminated by a bioterror agent such as Bacillus anthracis , Small Pox Virus, enteropathogenic E. coli (EPEC), enterohemorrhagic E. coli (EHEC), enteroaggregative E. coli , (EAEC), Clostridium difficile , rotavirus, Pseudomonas aeruginosa, Serratia marcescens, Klebsiella oxytocia, Enterobacteria cloacae, Candida albicans, Candida globrata , and the like). In a preferred embodiment of the method of preventing chronic urinary tract infection, or treating such an infection, the HMW PEG is delivered in the form of a bladder irrigant. For sexually transmitted disease prevention, a composition of the invention is preferably used to lubricate a condom. In a preferred embodiment of a method of preventing infection by a bioterror agent, the composition according to the invention is provided in the form of a gel or cream, suitable for topical application. It is expected that such topical application will be useful in preventing a variety of diseases/abnormal conditions associated with any of the bioterror agents or associated with a variety of chemical or physico-chemical agents that pose a threat to man or animal in terms of survival, health or comfort. Such chemical or physico-chemical agents include those agents capable of burning or otherwise injuring skin and which are rendered inactive or are poorly soluble in the compositions of the invention. [0099] In one embodiment of the preventive methods, male Balb/c mice are anesthetized and an aqueous 5% solution of PEG 15-20 is injected into the base of the cecum by direct needle puncture. In order to provide a constant source of PEG for the 48-hour duration of the experiment, the needle is directed into the small bowel (ileum) and 1 ml of the PEG 15-20 is injected retrograde into the proximal bowel. The puncture site is tied off with a silk suture and the cecum swabbed with alcohol. Mice are returned to their cages and are given H 2 O only. Forty-eight hours later, the mice are subjected to a conventional hepatectomy procedure involving a 30% bloodless excision of the liver along the floppy left lobe. Control mice will experience manipulation of the liver without hepatectomy. The preventive treatment involving administration of HMW PEG is expected to reduce or eliminate the incidence of surgery-associated gut-derived sepsis in mice. [0100] These methods are applicable beyond the preventive care of such pets as mice, guinea pigs, dogs and cats to such agriculturally significant animals as cattle, horses, goats, sheep, pigs, chickens, turkeys, ducks, geese, and any other domesticated animal. Moreover, these preventive methods are expected to be applicable to humans, improving the health, and life expectancy, of many patients or candidates at risk of developing a disease and/or an abnormal condition, such as swimmer's ear, acute or chronic otitis media, ventilator-associated pneumonia, gut-derived sepsis, necrotizing enterocolitis, antibiotic-induced diarrhea, pseudomembranous colitis, an inflammatory bowel disease, irritable bowel disease, neutropenic enterocolitis, pancreatitis, chronic fatigue syndrome, dysbiosis syndrome, microscopic colitis, chronic urinary tract infections, sexually transmitted diseases, and infectious agents (e.g., bioterror compositions) that include, but are not limited to, anthrax and small pox. As noted above, the preventive methods comprise administration of a composition comprising at least 5% HMW PEG (5-20 kDa), by any known or conventional administration route, to man or another animal. Preferably, the preventive methods are practiced on those individuals at risk of developing one or more of the aforementioned diseases and/or abnormal conditions, but it is contemplated that the compositions and methods of the invention will be useful in either a prophylactic or therapeutic role to broadly treat or prevent such diseases or abnormal conditions in entire populations or sub-populations of man or other animals. Example 8 Methods of Monitoring Administration of HMW PEG [0101] The invention also contemplates methods for monitoring administration of HMW PEG, e.g., in a method of treatment. In such monitoring methods, labeled HMW PEG is administered, alone or in combination with unlabeled HMW PEG, and the label is detected during treatment on a continuous or intermittent schedule, including simple endpoint determinations. The term “labeled” HMW PEG means that a label, or detectable compound, is directly or indirectly attached to HMW PEG, or the HMW PEG is attached to a reporter compound that is capable of associating a label with HMW PEG (of course, labels not attached to HMW PEG or designed to be associated therewith are also contemplated by the invention, as noted below). The HMW PEG is labeled using any detectable label known in the art, and the PEG is labeled to a level sufficient to detect it. Those of skill in the art will recognize that the level will vary depending on the label and the method of detection. One of skill in the art will be able to optimize the degree of labeling using routine optimization procedures. The label is chemically bound to the HMW PEG by a non-covalent or a covalent bond that is stable in use and, preferably, in storage. Label covalently bound to HMW PEG is preferred. The density of label attachment is adjusted to substantially preserve the biological activity of HMW PEG (preservation of sufficient biological activity to realize a beneficial prophylactic or therapeutic effect as disclosed herein). This is typically achieved by adjusting the HMW PEG:label ratio, as would be known in the art. Given the relative size of the average molecule of HMW PEG, it is expected that a wide variety of labels will be suitable for attachment to HMW PEG with substantial preservation of the biological activity thereof. [0102] Labels contemplated by the invention are those labels known in the art, which include a radiolabel, a chromophore, a fluorophore, and a reporter (including an enzyme that catalyzes the production of a detectable compound and a binding partner such as an antibody that localizes a detectable compound in the vicinity of the reporter). Exemplary enzyme reporters include an enzymatic component of a luminescence system and a catalyst of a colorimetric reaction. More particularly, exemplary reporter molecules include biotin, avidin, streptavidin, and enzymes (e.g., horseradish peroxidase, luciferase, alkaline phosphatases, including secreted alkaline phosphatase (SEAP); β-galactosidase; β-glucuronidase; chloramphenicol acetyltransferase). The use of such reporters is well known to those of skill in the art and is described in, e.g., U.S. Pat. No. 3,817,837, U.S. Pat. No. 3,850,752, U.S. Pat. No. 3,996,345, and U.S. Pat. No. 4,277,437. Exemplary enzyme substrates, which may be converted to detectable compounds by reporter enzymes, include 5-bromo-4-chloro-3-indolyl β-D-galactopyranoside or XgaI, and Bluo-gal. Enzyme substrates, as compounds capable of conversion to detectable compounds, may also be labels in certain embodiments, as would be understood in the art. U.S. patents teaching labels, and their uses, include U.S. Pat. No. 3,817,837; U.S. Pat. No. 3,850,752; U.S. Pat. No. 3,939,350 and U.S. Pat. No. 3,996,345. Exemplary radiolabels are 3 H, 14 C, 32 P, 33 P, 35 S, and 125 I; exemplary fluorophores are fluorescein (FITC), rhodamine, Cy3, Cy5, aequorin, and green fluorescent protein. A preferred label is a fluorophore such as fluorescein. [0103] The monitoring methods of the invention may also involve more than one label. In one embodiment, one label serves to identify the location of the HMW PEG following or during treatment, while a second label is specific for one or more microbes insofar as the label detectably associates with at least one microbe. For example, a monitoring method may include fluorescein attached to HMW PEG in a manner that substantially preserves the biological activity of the HMW PEG, and free (i.e., unattached) XgaI or bluo-gal for detection of prokaryote-specific β-galactosidase activity. The fluorescein localizes the HMW PEG, while a colored (blue) product indicates the presence of a lactose-metabolizing prokaryotic microbe, such as a Pseudomonad. The invention also includes monitoring methods wherein a single label provides this information (i.e., the location of HMW PEG and an indication of the presence of a microbe). [0104] Any detection technique known in the art may be used in the monitoring methods of the invention. Several factors will influence the detection technique chosen, including the type of label, the biomaterial subjected to monitoring (e.g., epidermal cells of the skin, ear canal, or intestine; stool, mucus or tissue samples), the level of discrimination desired, whether quantitation is expected, and the like. Suitable detection techniques include simple visual inspection with the unaided eye, visual inspection with an instrument such as an endoscope, optionally equipped with a suitable light source and/or camera for recordation, the conventional use of Geiger counters, x-ray film, scintillation counters, and the like, and any other detection technique known in the art. [0105] One of skill will recognize that the monitoring methods of the invention are useful in optimizing the treatment methods. For example, a monitoring method may be used to optimize the quantity and/or concentration of HMW PEG (e.g., to achieve a desired viscosity for a solution or mixture of HMW PEG), which is delivered to an epithelial cell, such as the epithelial cells of the ear canal to prevent or to treat swimmer's ear. By way of additional examples, optimization of bowel or intestinal treatments may be facilitated by endoscopic inspection of an intestinal tract exposed to labeled HMW PEG or by monitoring stool samples. [0106] The monitoring methods of the invention include a stool assay for a microbe capable of adhering to an intestinal epithelial cell comprising contacting a microbe and an intestinal epithelial cell and detecting adherence of the microbe to the epithelial cell using any technique known in the art. In a preferred embodiment, the intestinal epithelial cell is immobilized on a suitable surface, such as the bottom and/or sides of a microtiter well. In another preferred embodiment, a direct label, or an indirect label such as a reporter capable of generating a detectable product, is added prior to, or during, the detecting step. The monitoring methods may further comprise addition of free label. For example, free Bluo-gal is added to a sample suspected of containing a lactose-metabolizing prokaryotic microbe; if present, the microbial enzyme β-galactosidase will cleave Bluo-gal to yield a detectable blue product. [0107] In one embodiment, commercially available intestinal epithelial cells (e.g., Caco-2 cells, ATCC HTB 37, and/or IEC-6 cells, ATCC CRL 1952) are fixed to the wells of a microtiter dish using a conventional technique. A stool sample is collected and mixed with a fluid such as phosphate-buffered saline. The liquid phase of the mixture, containing suspended microbes, is obtained (e.g., by suitable filtration (i.e., separation of gross solids from bacteria in fluid suspension), decanting, or the like) and diluted 1:100 in PBS. Bluo-gal is added to the live microbial suspension. The microbial suspension is added to microtiter wells for 1 hour at 24° C., followed by washing of the wells with a suitable fluid (e.g., PBS) to remove unbound microbes. Microbes unbound and/or bound to the immobilized epithelial cells are detected, e.g., by counting using polarized light microscopy. In alternative embodiments, an immunoassay is used to detect adherence, with suitable immunological reagents being a microbe(s)-specific monoclonal or polyclonal antibody, optionally attached to a label such as a radiolabel, a fluorophore or a chromophore. [0108] One of skill in the art will recognize that neither the intestinal epithelial cell nor the microbe is required to be immobilized, although such immobilization may facilitate accurate detection of microbes adhering to epithelial cells. For example, in one embodiment, an immobilized stool microbe is brought into contact with an intestinal epithelial cell that is not immobilized. Further, one of skill would recognize that any suitable fluid known in the art may be used to obtain the microbial suspension, with preferred fluids being any of the known isotonic buffers. Also, as noted above, any known label may be used to detect cell adherence. [0109] In a related aspect, the invention provides a kit for assaying for microbial cell adherence comprising an epithelial cell and a protocol for assaying microbial cell adherence to the epithelial cell. The protocol describes a known method for detecting a microbe. A preferred kit includes an intestinal epithelial cell. Other kits of the invention further comprise a label, such as a fluorophore or a reporter. [0110] Another monitoring method contemplated by the invention is an assay for microbial hydrophobicity. In this method, the relative or absolute hydrophobicity of a microbial cell is determined using any conventional technique. An exemplary technique involves exposure of any microbe to hydrophobic interaction chromatography, as would be known in the art. Ukuku et al., J. Food Prot. 65:1093-1099 (2002), incorporated herein by reference in its entirety. Another exemplary technique is non-polar:polar fluid partition (e.g., 1-octanol:water or xylene:water) of any microbe. See Majtan et al., Folia Microbiol (Praha) 47:445-449 (2002), incorporated herein by reference in its entirety. [0111] In one embodiment of a hydrophobicity assay for monitoring PEG administration, a stool sample is suspended in 50 mM sodium phosphate buffer (pH 7.4) containing 0.15 M NaCl. Microbes in the suspension are collected by centrifugation and resuspended in the same buffer, and the centrifugation-resuspension cycle is repeated. If feasible, the microbes are resuspended in the same buffer to an absorbancy of 0.4 at 660 nm, which will permit monitoring spectrophotometrically, without using labeled PEG. The microbial suspension is treated with xylene (2.5:1, v/v, Merck), the suspension is vigorously mixed for two minutes, and the suspension is allowed to settle for 20 minutes at room temperature. The presence of microbes in the aqueous phase is then determined, for example by spectrophotometric determination of absorbancy at 660 nm. A blank containing the sodium phosphate buffer is used to eliminate background. [0112] In obtaining microbial cells from stool samples for use in these methods, it is preferred that the HMW PEG be relatively insoluble in the fluid used to obtain the microbial suspension and any fluid used to dilute the microbial suspension. [0113] The invention further provides a kit for performing the monitoring method comprising an assay for microbial hydrophobicity, which comprises an intestinal epithelial cell and a protocol describing the determination of microbial hydrophobicity. A preferred kit includes an intestinal epithelial cell. Related kits further comprise a label, such as a fluorophore or a reporter. [0114] Still further, the invention provides a monitoring method comprising obtaining a sample of intestinal flora and detecting PA-I lectin/adhesin activity. Any technique for detecting PA-I lectin/adhesin activity known in the art may be used. For example, PA-I lectin/adhesin may be detected using an antibody (polyclonal, monoclonal, antibody fragment such as a Fab fragment, single chain, chimera, humanized or any other form of antibody known in the art) that specifically recognizes PA-I lectin/adhesin. The immunoassay takes the form of any immunoassay format known in the art, e.g., ELISA, Western, immunoprecipitation, and the like. Alternatively, one may detect a carbohydrate-binding capacity of PA-I lectin/adhesin or the intestinal epithelial barrier breaching activity of PA-I lectin/adhesin may be measured, e.g., by monitoring the trans-epithelial electrical resistance or TEER of an epithelial layer prior to, and/or during, exposure to a sample. In related kits, the invention provides a PA-I lectin/adhesin binding partner and a protocol for detecting PA-I lectin/adhesin activity (e.g., binding activity). Other kits according to the invention include any carbohydrate known to bind PA-I lectin/adhesin and a protocol for detecting PA-I lectin/adhesin activity (e.g., binding activity). [0115] Numerous modifications and variations of the present invention are possible in view of the above teachings and are within the scope of the invention. The entire disclosures of all publications cited herein are hereby incorporated by reference.
The present invention provides pharmaceutical compositions in the form of relatively high molecular weight biocompatible polymers such as polyethylene glycol, optionally supplemented with a protective polymer such as dextran and/or essential pathogen nutrients such as L-glutamine. Also provided are methods for preventing or treating gut-derived sepsis attributable to intestinal pathogens such as Pseudomonas aeruginosa by administering high molecular weight polyethylene glycol as well as methods for monitoring the administration of high molecular weight polyethylene glycol, such as in methods of preventing, ameliorating or treating microbe-induced epithelial disorders, as exemplified by gut-derived sepsis. Frequently, gut-derived sepsis arises as a complication in mammals recovering from surgical intervention or suffering from a disease or disorder, providing indications of suitable animals to receive preventative treatment. Finally, the invention provides a composition comprising infant formula and polyethylene glycol and methods for using that composition.
96,056
FIELD OF THE INVENTION The invention relates to a method and an apparatus on scannographs, in particular for computed tomographyradioscopy for interventions, and refers to adjustment of a table for the patient, fixing of its position, as well as triggering of a light-beam localiser and of a single scan after mechanical decoupling of the scannograph from the central control system. DESCRIPTION OF THE BACKGROUND ART Computed tomography has enriched medical diagnostics in an extraordinary manner and not only rendered numerous radiation-exposing X-ray examinations, such as encephalography or angiography, superfluous but also took advantage of the tomograms gained thereby for planning and checking the radiation therapy of tumors. Numerous pathological processes in the entire trunk of the body, such as carcinomata or enlarged lymph nodes, can be classified only by withdrawal of tissue and subsequently treated. Such biopsies can, inter alia, be carried out with the help of computed tomography. When doing so, the position of a needle introduced into the body is represented by executing a single sectional drawing in the plane of the needle. After corresponding preparation of the patient, i.e. after positioning of said patient and disinfection of the skin of same as well as after having locally anaesthetised the point of puncturing, the biopsy needle is, usually outside the gantry, introduced so as to lie under the surface of the skin and, thereafter, the table with the patient will be moved into the gantry for conduction of the first check scan. Control of that procedure is effected from the console of the scannograph, which console, for reasons of radiation protection, is situated outside the examination room. When a lamination is radiographed, the medical personnel are not in the examination room. After the sectional drawing has been displayed on the monitor, the patient is moved out of the gantry. After a possibly required positional correction of the needle, another radiograph is taken once the table with the patient has been moved into the gantry through the console. The entire procedure--moving of the patient out of the gantry and into the gantry again--takes up a great deal of time and, during the whole examination, the patient must remain quiet and motionless. Various solutions have been proposed, dealing with positioning of the patient resp of specific parts of the body or of tables for patients as exactly as possible, e. g.: positioning of a patient, in case of a medical panoramic radiographic facility, with the help of a sensor for determining the relative position of an object to be examined towards the radiographic facility, the determined data being compared with those of the relative position of a tomographic zone towards the radiographic facility (German Patent resp Laying-open Specification 38 08 009), a fixed device for holding the patient whereas the housing of the scannograph can be linearly displaceably) guided by means of driving and guiding facilities (German Utility Model 92 18 322), a motor-driven and computer-controlled day-bed for the patient, which day-bed can be moved into the housing of the scannograph, moving the patient synchronously with radiographing successive scans, departing from an initial position--e.g. in case of examinations of the area of the cranium (European Patent 579 036), a scannograph housing for receiving the day-bed with the patient, in which case--in order to avoid information losses between diagnosis and surgical treatment--the day-bed for the patient is, at the same time, constructed as an operating table (German Patent resp Laying-open Specification 42 02 302), physicians' or dentists' examination facilities, e.g. for radiographing the temporomandibular joint (German Patent resp Laying-open Specification 39 37 077) or for scannographing the knee after fixation of the lower leg (German Patent resp Laying-open Specification 38 09 535), scannograph with means for generating a silhouette which is represented on a monitor synchronously with the respective position of the measuring system towards the day-bed for the patient (German Patent 42 18 637, U.S. Pat. No. 5,373,543). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention is based on the object to develop a method and an apparatus by which, for computed tomography-radioscopy for interventions, exact positioning of the patient can be achieved and the number of scans for seeking the needle can be reduced. This object was solved by combining a floating table for the patient with a sectional drawing modality for biopsies under a visual ct check. The apparatus according to the invention comprises a table for the patient, which is included in a scannograph and which is provided with a handle serving for mechanically setting a random position of the table after decoupling from the central control system, and foot switches for triggering a light-beam localiser on the one hand and a single scan on the other hand. The handle newly mounted to the table for the patient enables random positioning of the table after mechanical decoupling from central control. The foot switches are installed in the examination room. They can trigger both the light-beam localiser and a single scan. The term "floating table for the patient" designates a day-bed for the patient, which, with but small mechanical effort, can freely be moved by the examining person along an axis at any time during examination. By "sectional drawing modality" an examination technique is meant which, for visualising an examined object, generates sectional drawings in a plane with a defined lamination thickness. The sectional drawing modalities include computed tomography, ultrasonics or nuclear spin resonance tomography. Installation of the handle on the table for the patient enables setting of any table position by hand during surgical treatment. The digitally indicated table position always corresponds to the real position. The light-beam localiser is triggered via an additionally installed foot switch in the examination room just like--via a further foot switch a single scan (one lamination). In order to check the position of the needle, the table is--without any control from the console--rapidly moved out of the gantry and into the gantry again so that a fresh single scan can be triggered. Surprisingly, it was found that the way of proceeding according to the invention provides, considering all the modifications--light, single scan following a pressure exerted by the foot, manually movable table with position indicator, and immediate tomogram monitoring, an examination modality by which biopsies can be conducted in more reliable a manner and which will lead to shortened examination periods. Since the patient can, by hand, be rapidly moved out of the gantry and into the gantry again--without having to leave the examination program--, the required amount of time will be considerably reduced. In order that the physician may stay in the room for inspecting the tomogram--, the latter as taken becomes visible to the examining person on a monitor standing in the gantry room. Another advantage resides in that the patient is less exposed to radiation since, due to the exact table position achieved in accordance with the invention, superfluous scans for seeking the needle will be avoided. During surgical treatment, the medical personnel will remain in the examination room so as to affect the psyche of the patient in positive manner, if need be. Apart from saving time, application of the method and apparatus according to the invention brings about multiplication of the technical possibilities and shows another new way in the field of computed tomography-radioscopy for interventions. Further advantages reside in minor exposition to radiation due to reduction of superfluous scans, in higher sensitivity, and, indirectly, in less complications as well--primarily due to the fact that the frequent manipulation, in case of needle correction, is not required any more under computed tomography-radioscopy. With conventional radioscopy, continuous projection roentgenograms are produced, not permitting any spatial allocation. When doing so, a needle is guided to its destination under constant irradiation insofar as said destination can be made out at all in the projection. The hand of the examining person is mainly situated in the direct optical path. However, movement of the table for the patient--which, on principle, is possible with most X-ray apparatuses--will not be brought about since puncturing is carried out under X-ray vision and the represented roentgenogram depicts areas of from 5 by 5 to 35 by 35 cm. Insofar, the invention is based on a principle which is different from single-scan triggering and moving the table by hand. A manually operated scannograph has not become known since such a scannograph, because of the usually required lamination examination at defined lamination distances, cannot be realised and is of no clinical relevance. The combination of a floating table with a sectional drawing modality is new. Moreover, it would make sense only for biopsies under a visual ct check. The invention shall be explained in detail on the basis of one embodiment. Embodiment The table 1 for the patient P is equipped with a handle 2 enabling the table to be taken to a random position after mechanical decoupling from central control 3. The digital indication of the table position is not affected thereby. After the patient P has been prepared in the usual way, the physician, subsequently to switching on of the light-beam localiser 4 via an additionally installed foot switch, 5 can now exactly position the table 1 within the sectional drawing modality 9. Then, a single scan (one lamination) will be triggered in the examination room via a second foot switch 6. Four seconds later, the tomogram will appear on a monitor 7; it will appear after one second, provided that all additional filters and subsequent tomogram processings are done without. The tonogram as taken becomes visible to the examining person on a monitor 7 standing in the gantry room. The physician will remain in the examination room and, during surgical treatment, can affect the psyche of the patient P in positive manner. When the position of the needle has to be checked, the table 1 can rapidly be moved out of the gantry 8 and into the gantry 8 again without any control from the console. Thereafter, a fresh single scan can be triggered. The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
A computed tomography-fluoroscopy method is invented for interventions comprising the steps of combining a floating patient table with a cross-sectional imaging modality for interventions under visual computed tomography control. A handle is installed on the patient table, which is mechanically decoupled from the central control system. During an intervention, the table is brought to a random position, and a single-scan or scan-series is triggered. A light-beam localizer is used for orientation and positioning the single-scan or scan-series.
11,077
CROSS REFERENCE TO RELATED APPLICATIONS This Application is a continuation of U.S. application Ser. No. 13/105,290 entitled “Methods and System for Simulated 3D Videoconferencing” filed May 11, 2011, which claims priority to U.S. Provisional Application Ser. No. 61/452,270 filed Mar. 14, 2011, all of which are incorporated by reference in their entirety herein. TECHNICAL FIELD The present invention relates to the field of communication, and in particular to the field of videoconferencing. BACKGROUND ART Videoconferencing enables individuals located remotely one from the other to conduct a face-to-face meeting. Videoconferencing may be executed by using audio and video telecommunications. A videoconference may be between as few as two sites (point-to-point), or between several sites (multi-point). A conference site may include a single participant (user) or several participants (users). Videoconferencing may also be used to share documents, presentations, information, and the like. Participants may take part in a videoconference via a videoconferencing endpoint (EP), for example. An endpoint (EP) may be a terminal on a network, for example. An endpoint may be capable of providing real-time, two-way, audio/visual/data communication with other terminals and/or with a multipoint control unit (MCU). An endpoint (EP) may provide information/data in different forms, including audio; audio and video; data, audio, and video; etc. The terms “terminal,” “site,” and “endpoint” may be used interchangeably. In the present disclosure, the term endpoint may be used as a representative term for above group. An endpoint may comprise a display unit (screen), upon which video images from one or more remote sites may be displayed. Example endpoints include POLYCOM® VSX® and HDX® series endpoints, each available from Polycom, Inc. (POLYCOM, VSX, and HDX are registered trademarks of Polycom, Inc.) A videoconferencing endpoint may send audio, video, and/or data from a local site to one or more remote sites, and display video and/or data received from the remote site(s) on its screen (display unit). Video images displayed on a screen at an endpoint may be displayed in an arranged layout. A layout may include one or more segments for displaying video images. A segment may be a predefined portion of a screen of a receiving endpoint that may be allocated to a video image received from one of the sites participating in the videoconferencing session. In a videoconference between two participants, a segment may cover the entire display area of the screens of the endpoints. In each site, the segment may display the video image received from the other site. An example of a video display mode in a videoconference between a local site and multiple remote sites may be a switching mode. A switching mode may be such that video/data from only one of the remote sites is displayed on the local site's screen at a time. The displayed video may be switched to video received from another site depending on the dynamics of the conference. In contrast to the switching mode, in a continuous presence (CP) conference, a conferee (participant) at a local endpoint may simultaneously observe several other conferees from different endpoints participating in the videoconference. Each site may be displayed in a different segment of the layout, which is displayed on the local screen. The segments may be the same size or of different sizes. The combinations of the sites displayed on a screen and their association to the segments of the layout may vary among the different sites that participate in the same session. Furthermore, in a continuous presence layout, a received video image from a site may be scaled, up or down, and/or cropped in order to fit its allocated segment size. It should be noted that the terms “conferee,” “user,” and “participant” may be used interchangeably. In the present disclosure, the term conferee may be used as a representative term for above group. An MCU may be used to manage a videoconference. An MCU is a conference controlling entity that is typically located in a node of a network or in a terminal that receives several channels from endpoints and, according to certain criteria, processes audio and/or visual signals and distributes them to a set of connected channels. Exemplary MCUs include the MGC-100 and RMX 2000®, available from Polycom Inc. (RMX 2000 is a registered trademark of Polycom, Inc.). Some MCUs may be composed of two logical units: a media controller (MC) and a media processor (MP). A more thorough definition of an endpoint and an MCU may be found in the International Telecommunication Union (“ITU”) standards, including the H.320, H.324, and H.323 standards. Additional information regarding the ITU standards may be found at the ITU website www.itu.int. In a CP videoconferencing session, the association between sites and segments may be dynamically changed according to the activities taking part in the conference. In some layouts, one of the segments may be allocated to a current speaker, for example. The other segments of that layout may be allocated to other sites that were selected as presented sites or presented conferees. A current speaker may be selected according to certain criteria, including having the highest audio signal strength during a certain percentage of a monitoring period. The other presented sites, may include the image of the conferee that was the previous speaker; the sites having audio energy above a certain thresholds; certain conferees required by management decisions to be visible; etc. In a conventional CP videoconference, each layout is associated with a video output port of an MCU. A conventional video output port may comprise a CP image builder and an encoder. A conventional CP image builder may obtain decoded video images of each one of the presented sites. The CP image builder may scale and/or crop the decoded video images to a required size of a segment in which the image will be presented. The CP image builder may further write the scaled image in a CP frame memory in a location that is associated with the location of the segment in the layout. When the CP frame memory is completed with all the presented images located in their associated segments, the CP image may be read from the CP frame memory by the encoder. The encoder may encode the CP image. The encoded and/or compressed CP video image may be sent toward the endpoint of the relevant conferee. A frame memory module may employ two or more frame memories, for example, a currently encoded frame memory and a next frame memory. The memory module may alternately store and output video of consecutive frames. Conventional output ports of an MCU are well known in the art and are described in a plurality of patents and patent applications. A reader who wishes to learn more about a conventional output port is invited to read U.S. Pat. No. 6,300,973, for example, the content of which is incorporated herein by reference in its entirety. A user's experience of videoconference is typically limited to one or more high-resolution two-dimensional displays. Although 3D (3-dimension) technologies have become more and more popular in other different fields, such as movies, media entertainment, etc., obstacles have prevented the 3D technology from being implemented by the videoconference industry. These obstacles include the need to wear special 3D glasses and the use of expensive cameras and displays. Creation of holograms may require special screens, cameras, and hardware that are very expensive, etc. Therefore, it is not realistic to expect conventional videoconferencing users to pay such high costs. Nor is it realistic to expect conventional videoconferencing users to sit in a videoconference wearing 3D glasses, which would be visible to other conferees. Furthermore, many companies have invested in a conventional 2D video conferencing infrastructure. Those companies would like to keep their capital investment in their current video conferencing infrastructure that does not support current existing 3D video conferencing techniques. The above-described deficiencies in videoconferencing do not limit the scope of the inventive concepts of the present disclosure in any manner. The deficiencies are presented for illustration only. SUMMARY OF INVENTION The below disclosed embodiments provide a novel system and method for manipulating a video image in videoconference such that a user may experience a 3D-like view of one or more presented sites. The disclosed exemplary embodiments do not require 3D cameras, 3D screens, 3D glasses, or hologram display hardware. On the contrary, the disclosed embodiments may utilize conventional 2D video cameras and conventional 2D video screens to create a 3D-like view of one or more presented sites. In one embodiment, a transmitting endpoint in a site may comprise two or more video cameras, each of which may record the room of the site from a different angle. The transmitting endpoint may encode each video image and send the encoded streams to an MCU. At the MCU, each of the received video streams from a plurality of conferees is transferred toward an associated input video port. In addition to the conventional components of an input video port, an input video port may comprise a conferee-point-of-view detector (CPOVD). The CPOVD may detect the angle at which the conferee looks at the screen and at which region of the screen the conferee is looking. The CPOVD may send the detected information toward a controller of the MCU. As long as the video image of a transmitting endpoint, which has two or more cameras, is embedded in the video image that is sent toward one or more receiving endpoints, the controller may periodically sample the stored information regarding the received conferee's point-of-view direction. Once a change in the viewer's point of view has been detected, the controller may determine whether to continue using the video streams from the currently chosen camera, to select a video stream received from another camera of that transmitting endpoint, etc. The viewer, in the receiving endpoint, will experience a 3D-like view of the presented sites. This experience may be affected by the number and location of the cameras in the transmitting endpoint. To enhance the experience, more cameras may be placed and along an arc wherein the center of the arc is located near to or on the centerline of the display at the transmitting site. Furthermore, the accuracy of the viewer-point-of-view detector may also affect the experience of the user. Other different techniques may be used to enhance the viewer's experience. Exemplary techniques include using a “sliding window,” for example. The sliding window imitates the effect of controlling the far end camera such as move left, right, up and down. In some embodiments, the movement of the receiving conferee's gaze may be used as a remote camera panning left or right, tilting up or down or zooming in or out. In some embodiments, the video received from the remote location may be cropped to a window that is presented on screen and slides along the video image. For example, if the conferee gaze detector indicates that the gaze of the conferee points at the most left side of the screen, the effect on the screen may resemble a panning left of the remote camera, although in this embodiment only the presented window is sliding to the left and the remote camera is not panning left. Once the conferee point of view is locked on the area in which the conferee is interested, the window may slide until it will eventually stop. In the above embodiment, the stopping point may be the point in which the conferee is staring to the center of the conferee's screen. The present disclosure is not limited to providing a 3D-like view of only one site. One or more sites may comprise a plurality of cameras. The number of segments displayed in a layout on a conferee screen as well as the conferee's screen size may affect the 3D-like experience. These and other aspects of the disclosure will be apparent in view of the attached figures and detailed description. The foregoing summary is not intended to summarize each potential embodiment or every aspect of the present invention, and other features and advantages of the present invention will become apparent upon reading the following detailed description of the embodiments with the accompanying drawings and appended claims. BRIEF DESCRIPTION OF DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an implementation of apparatus and methods consistent with the present invention and, together with the detailed description, serve to explain advantages and principles consistent with the invention. In the drawings, FIG. 1 is a block diagram illustrating relevant elements of a portion of a multimedia multipoint videoconferencing system according to one embodiment. FIGS. 2 a -2 c illustrate different instances during a video conferencing session, in which a conferee has different viewpoint in each instance. FIG. 3 is a block diagram illustrating relevant elements of portions of a transmitting site according to one embodiment. FIG. 4 is a block diagram illustrating relevant elements of an exemplary MCU, according to one embodiment. FIG. 5 is a flowchart illustrating relevant actions of a process for selecting a camera based on conferee point of view, according to one embodiment. DESCRIPTION OF EMBODIMENTS In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the invention. It will be apparent, however, to one skilled in the art that the invention may be practiced without these specific details. In other instances, structure and devices are shown in block diagram form in order to avoid obscuring the invention. References to numbers without subscripts or suffixes are understood to reference all instance of subscripts and suffixes corresponding to the referenced number. Moreover, the language used in this disclosure has been principally selected for readability and instructional purposes, and may not have been selected to delineate or circumscribe the inventive subject matter, resort to the claims being necessary to determine such inventive subject matter. Reference in the specification to “one embodiment” or to “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiments is included in at least one embodiment of the invention, and multiple references to “one embodiment” or “an embodiment” should not be understood as necessarily all referring to the same embodiment. Although some of the following description is written in terms that relate to software or firmware, embodiments may implement the features and functionality described herein in software, firmware, or hardware as desired, including any combination of software, firmware, and hardware. In the following description, the words “unit,” “element,” “module” and “logical module” may be used interchangeably. Anything designated as a unit or module may be a stand-alone unit or a specialized or integrated module. A unit or a module may be modular or have modular aspects allowing it to be easily removed and replaced with another similar unit or module. Each unit or module may be any one of, or any combination of, software, hardware, and/or firmware, ultimately resulting in one or more processors programmed to execute the functionality ascribed to the unit or module. Additionally, multiple modules of the same or different types may be implemented by a single processor. Software of a logical module may be embodied on a computer readable medium such as a read/write hard disc, CDROM, Flash memory, ROM, or other memory or storage, etc. In order to execute a certain task a software program may be loaded to an appropriate processor as needed. In the description and claims of the present disclosure, “comprise,” “include,” “have,” and conjugates thereof are used to indicate that the object or objects of the verb are not necessarily a complete listing of members, components, elements, or parts of the subject or subjects of the verb. FIG. 1 illustrates elements of an exemplary multimedia multipoint conferencing system 100 according to one embodiment. System 100 may include a network 110 , one or more multipoint control units (MCU) 120 , and a plurality of endpoints in different sites 130 a - n . Network 110 may be a packet switched network, a circuit switched network or any combination of the two, for example. The multimedia communication over the network may be based on a communication protocol, including H.320, H.323, SIP, etc. MCU 120 and endpoints 130 a - n may be adapted to operate according to various embodiments to improve the experience of a conferee looking at a CP video image of a multipoint video conference. In embodiments implementing a centralized architecture, MCU 120 may be adapted to perform the automatic display adaptation methods described herein. Alternatively, in a distributed architecture, endpoints 130 a - n with MCU 120 may be adapted to perform the automatic display adaptation methods. More information about the operation of MCU 120 and endpoints 130 a - n according to various embodiments is disclosed below. FIGS. 2 a -2 c illustrate different instances during a video conferencing session in which a conferee 204 has a different viewpoint in each instance. In FIG. 2 a , conferee 204 looks at the center along the perpendicular 210 of the two-dimensional screen 202 of the conferee's EP. In FIG. 2 b , the head of conferee 204 is rotated to the right side of the screen 202 and creates an angle 216 of +A degrees between the face (the nose) of the conferee and the perpendicular 210 to the screen. In FIG. 2 c , the head of conferee 204 is rotated to the left side of the screen 202 and creates an angle 216 of −a degrees between the face (the nose) of the conferee and the perpendicular 210 to the screen. FIG. 3 illustrates a block diagram with relevant elements of portions of a transmitting site 300 according to one embodiment. Transmitting site 300 may be a meeting room having a table 310 , a plurality of chairs 312 , and a videoconferencing endpoint 330 having a plurality of video cameras 320 , 322 , and 324 . The plurality of cameras may be located in a horizontal plane above the screen of the EP 330 along a virtual arc. Each camera captures the table 310 and the conferees along the table from a different angle simulating a different head position of a conferee that receives a video stream from the meeting room 300 . Each of the video cameras 320 , 322 , and 324 creates and delivers a stream of video images to the endpoint 330 . The endpoint 330 compresses the three video streams and sends the compressed video streams toward an MCU 120 that conducts the video conferencing session. Compressing the three video streams may be done in a single encoder that complies with the compression standard H.264 MVC, for example. Other endpoints may use three separate encoders and may send three separate compressed video streams, one for each of cameras 320 , 322 , and 324 . FIG. 4 illustrates an MCU 400 , which is capable of dynamically and automatically switching between a plurality of streams of video images. The plurality of streams received from a plurality of video cameras 320 , 322 , and 324 associated with an EP 330 located in a first site 300 . The switching at the MCU 400 may be done based on the gaze of an observer, located in a second site and receives the selected video image sent from the first site via the MCU 400 . MCU 400 may comprise a network interface module (NI) 420 , an audio module 430 , a control module (CM) 440 and a video module 450 . The control module 440 may further comprise a camera selector controller (CSC) 442 . The network interface module 420 may receive communication from a plurality of endpoints 130 a - n via network 110 . Network interface 420 may process the communication according to one or more communication standards, including H.320, H.323, SIP, etc. Network interface 420 may also process the communication according to one or more compression standards, including H.261, H.263, H.264, H.264 MVC, G.711, G.722, MPEG, etc. In addition, network interface 420 may receive and transmit control and data information to/from other MCUs and endpoints. More information concerning the communication between endpoint and the MCU over network 110 and information describing signaling, control, compression, and setting a video call may be found in the international telecommunication union (ITU) standards H.320, H.321, H.323, H.261, H.263, H.264, G.711, G.722, and MPEG etc. Network interface module 420 may multiplex/de-multiplex the different signals, media and/or “signaling and control” that are communicated between the endpoints and the MCU. The compressed audio signals may be transferred to and from the audio module 430 . The compressed video signals may be transferred to and from the video module 450 . The “control and signaling” signals may be transferred to and from control module 440 . Furthermore, if a distributed architecture is used, network interface module 420 may be capable of handling automatic and dynamic gaze related information that is transferred from the endpoints 130 a - n toward the control module 440 . In one distributed architecture embodiment the automatic and dynamic gaze detection information is sent from an EP 130 to MCU 400 . The gaze detection information may be sent from the EP 130 as a part of a predefined header of an RTP (Real-Transport Protocol) packet. NI 420 may be adapted to process the predefine header and to transfer the gaze detection information to the CM 440 . The gaze detection information may include the angle ±a ( 216 , 218 ) of the nose of the conferee from the perpendicular 210 . In another embodiment, the information about the gaze of the conferee may be expresses by the location of the conferee's nose, in pixels (W;H) along the width ‘W’ axis, and height ‘H’ axis of the video image received from that conferee's EP, for example. In some embodiments, the gaze may be expressed in number of pixels in pixels (W;H) from the top left corner of the image. In yet another distributed architecture embodiment, the EP may send information regarding the gaze of its conferee over the audio signal using dual-tone multi-frequency signaling (DTMF). In such an embodiment, the NI 420 processes the received signals and sends the compressed audio, carrying the DTMF signal toward the audio module 430 . The audio module 430 decompresses the audio signal, decodes the DTMF information, and transfers the Gaze information toward the CM 440 . In yet another distributed architecture embodiment, the EP 130 may send information regarding the gaze of its conferee via out of band connection. The out of band connection may be carried over an Internet Protocol (IP) network, for example. In such embodiment, the NI 420 may process the received IP packets, carried over an IP connection and sends the Gaze information toward the CM 440 . Audio module 430 may receive, via network interface 420 compressed audio streams from the plurality of endpoint 130 a - n . The audio module 430 may decode the compressed audio streams, analyze the decoded streams, select certain streams, and mix the selected streams. The mixed stream may be compressed and the compressed audio stream may be sent to the network interface 420 , which sends the compressed audio streams to the different endpoints 130 a - n . Audio streams that are sent to different endpoints may be different. For example, the audio stream may be formatted according to a different communication standard and according to the needs of the individual endpoint. The Audio stream may not include the voice of the user associated with the endpoint to which the audio stream is sent. However, the voice of this user may be included in all other audio streams. In some embodiments, the audio module 430 may be adapted to analyze the decoded audio signals received from the endpoints, and decodes the DTMF signals for retrieving information regarding the gaze of the conferee's whose audio signal was processed. The gaze information may be transferred to the control module 440 . In some embodiments, two or more microphones may be used in a certain site. Video module 450 may receive compressed video streams from the plurality of endpoints 130 a - n , which are sent toward the MCU 400 via network 110 and processed by network interface (NI) 420 . Video module 450 may create one or more compressed CP video images according to one or more layouts that are associated with one or more conferences currently being conducted by the MCU 400 . A video module 450 may have a plurality of input modules 451 a - c , a plurality of output modules 455 a - c and a video common interface 454 . Each input module 451 a - c may be associated with an endpoint. Each output module 455 a - c may be associated with one or more endpoints. Input module 451 a - c may include among other elements a decoder 452 and a Conferee's-Point-of-View Detector (CPOVD) 453 . CPOVD 453 may be a sub-module of input modules 451 a - c , or in an alternate embodiment, CPOVD 453 may be a sub-module of video module 450 . An input module 451 a - c may be associated with an endpoint and may process a plurality streams of compressed video images received from plurality of video cameras 320 - 324 that are connected to the associated endpoint 330 . The decoder 452 may receive the plurality of compressed video streams, which may comprise three streams for example, from an associated endpoint and decode the compressed video stream according the compression standard H.264 MVC into three decoded video data images, each decoded image received from one of the three cameras. The ITU H264 MVC standard is a multi-view-video-coding standard, which enables the transmitting endpoint to broadcast multiple video streams from the two or more cameras. Each decoded image may be stored in a decoder frame memory from which it is transferred toward one or more output modules 455 a - c via common interface 454 . The common interface 454 may be a TDM bus, packet based bus (such as an ATM bus, IP bus), serial bus, parallel bus, connection switching, shared memory, direct connection, or any variety of these. In an alternate embodiment in which H.264 MVC is not used, an input module may be associated with one of the cameras 320 - 324 of its associated endpoint 330 . Thus, endpoint 330 may be associated with three input modules 451 . The MCU receives from a plurality of endpoints a plurality of compressed video streams. Some of the endpoints may send compressed video streams received from its two or more video cameras using the ITU H.264 MVC standard, while other endpoints may send a compressed video stream received from a single video camera. In one embodiment, each of the endpoints 330 may comprise a CPOVD 453 that receives the video input data from an endpoint camera, processes the received data, and defines the direction in which the conferee is looking. The conferee point of view information may then be sent to the MCU from the endpoint. The information may be sent in-band, in association with the compressed video stream, as part of a packet's headers. Alternatively, the information may be sent out of band over a separate connection between the endpoint and the MCU, over an Internet Protocol (IP) connection, for example. In one embodiment, the decoded data stored in the frame memory, which is associated with the central camera 322 may be sampled by the CPOVD 453 . CPOVD 453 may be adapted to analyze the video image received from the central camera and to detect the gaze of the conferee that uses the associated EP 330 . A CPOVD 453 may process the decoded image; identify the nose of the conferee; and determine the location of the nose compared to the perpendicular 210 to the screen, or the center of the screen. Detecting the nose may be implemented by an image-processing algorithm that identifies the two eyes and the nose in the center. In a site that has only one camera, the images from the single camera are processed instead of the video of the central camera. In some embodiments of an MCU 400 , a central CPOVD 453 may be used. Such a central CPOVD 453 may obtain the decoded video from each one of the input video ports, in parallel or in serial. Such a CPOVD 453 may process the obtained decoded video and determine the gaze angle of the conferee. The detected gaze angle may be used for selecting the appropriate camera. In one embodiment, an MCU 400 may use a learning period for learning the properties of an organ of the conferee's face, such as a nose, an eye (left, right or both), etc. the term nose may be used as a representative term for such an organ. In addition for learning the area around the nose, the CPOVD 453 may learn the topology of the gaze (represented by the nose, for example) in relation to the video image received from the center camera and the screen of the endpoint. The learning period may begin upon receiving a request from a conferee to join the conference. During the learning period, the MCU 400 may present the self-image of the conferee, which is received from the center camera, over the entire screen of the conferee's endpoint. In addition to the self image, the MCU 400 may present above the self image three points (colored area, a circles, for example) along a virtual horizontal line starting from left to right in the middle of the height of the screen. In other embodiment, five points may be presented on the screen, one in the center of the screen, and one at the center of each quarter of the screen (i.e., the center of the top left quarter, the center of the top right quarter, the center of the bottom left and the center of the bottom right quarter). The MCU 400 , by using an interactive-video-control-human interface may place a cursor on the screen and prompt the conferee to look at the center point on the screen and to place the cursor on the conferee's nose. Prompting the conferee may be done by an Interactive Voice Response (IVR) or by presenting text instructions over the screen. After clicking on the cursor, the MCU 400 may collect information on the location of the nose and the properties in a certain area around the nose while the conferee looks at the center point. The process may be repeated for each of the colored points. In some embodiments, two or more points may be used in each side of the screen. The interactive-video-control-human interface is disclosed in U.S. Pat. No. 7,542,068, the content of which is Incorporated herein by reference in its entirety. At this point of time the CPOVD 453 has information on the location (in pixels from the top left corner of the image) of the conferee's nose in the video image received from the conferee's center camera 322 when the conferee looks at the center of the screen and at the center of each quarter of the screen. In addition, the CPOVD 453 has information on the properties of the area around the nose in each position. This information may be processed for use as filters to define the gaze of the conferee during the video session. In yet another embodiment, the CPOVD 453 may implement a gaze detector. Gaze detection methods are well known in the art of image processing. There are a plurality of articles that describe different method of gaze detection. Some of them use a wearable device such as magnetic elements, RF receivers, and or transmitters, etc., others uses a dedicated camera for tracking and capturing the user's eyes, others just run image processing algorithms that identify the user's gaze, etc. a CPOVD 453 may use a commercial gaze detector. Example commercial gaze detection systems include SMI RED systems RED, RED 250, and RED 500, manufactured by SensoMotoric Instruments GmbH (SMI) from Teltow Germany. Other gaze detection systems use the red-eye effect by using a near infrared lighting source. Gaze detection techniques are known to the art and will not be further discussed herein. Various embodiments may implement different techniques of gaze detection. Some embodiments may use near infrared (NIR) lighting and analyzing the received video image looking for the red-eye effect on the image. Other embodiments may implement image-processing methods looking for changes in the gaze direction. The information about the current gaze direction of the conferee in a receiving endpoint, or changes in the gaze directions may be utilized for controlling the video image received from a transmitting endpoint such that the transmitted image is adapted to the gaze of the receiving endpoint. In some embodiments, if two or more conferees share the same site and the same endpoint, one of them may be selected as the one to whom the gaze detector will respond. The selection of the conferee may be done automatically in one embodiment. The selection criteria that may be used may include the conferee that sits in the head of the table, the conferee that sits in the center of the group of conferees, the conferee that sits closest to the camera, etc. In other embodiments, the conferee may be selected manually during the beginning of the conference session, for example when in the learning mode. From time to time, periodically, and/or upon receiving a command from the CSC 442 , the CPOVD 453 may sample a captured frame of the decoded video. The CPOVD may analyze the sampled image and identify the direction of the conferee's gaze. The CPOVD 453 may output the gaze detected information to the CSC 442 via control line 444 . The received conferee's point of view information may be stored at the MCU controller. This information may be used for controlling a video output port that has been assigned to that received conferee. When the MCU controller determines that video image received from a transmitting endpoint having two or more cameras is to be transmitted toward the endpoint of the received conferee, then the information regarding the received conferee's point of view may be used for selecting an appropriate video stream of the video streams received from the two or more video cameras of the transmitting endpoint. In some embodiments, the CPOVD 453 may deliver parameters according to the location of the nose. The nose represents the center of the gaze of the conferee. The location may be in pixels. In some embodiments of the video module 450 , a single CPOVD 453 may be used. Such a CPOVD 453 may be a separate module external to the input module 451 a - c . In such embodiment, the CPOVD 453 may obtain from the common interface 454 a decoded video frame received from one of the input modules 451 a - c , process it, and deliver gaze information to the CSC 442 . Then, the CPOVD 453 may obtain decoded frame received from a next input module 451 a - c , process it, deliver gaze information and may continue to the following input module, looping repeatedly. In a distributed architecture, a CPOVD 453 may be located in an endpoint 330 and may process the video data generated by its central video camera 322 . More information about the operation of a CPOVD 453 is discussed below in conjunction with FIG. 5 . Among other elements, an exemplary output module 455 a - c may include an editor 456 and an encoder 458 . Editor 456 may get decoded data of selected video images from the common interface 454 to be composed into a CP image created by the output module 455 . The editor 456 may scale, crop, and place the video data of each conferee into an editor frame memory according to the location and the size of the image in the layout associated with the composed video of the CP image. Editor 456 and encoder 458 may each be considered as modules, or as sub-modules of output modules 455 a - c. When the editor frame memory is ready with all the selected conferee's images, the data in the frame memory is ready to be encoded by encoder 458 and sent toward its associated endpoint. The editor 456 may be configured to collect the decoded video images received from a plurality of endpoints (video input modules 451 a - c ), to build the frames of the CP video images based on layout instructions received from the CM 440 regarding each video image, and send the composed CP video image toward a display unit of the endpoint. Depending on the current layout that is transmitted toward the received conferee, the conferee's video output port may arrange the selected video stream in a segment of a CP video image or as a switching video image and send it toward the receiving endpoint. In some embodiments, the 3D imitation may be limited to images that are displayed in a segment bigger than a certain size, a quarter of a screen for example. Additional functions that may be included in the video module 450 are described in U.S. patent application Ser. No. 10/144,561; U.S. Pat. No. 6,100,973; and International App. Serial No. PCT/IL01/00757, the contents of which are incorporated herein by reference. In a distributed architecture, an endpoint may include an editor 456 . In such embodiment, the editor 456 may be located after a decoder of the endpoint. In addition to the operation of an editor 456 in an output module, editor 456 may be able to adapt the video image presented in at least one segment of the CP video image to the gaze of the conferee that is associated with that editor 456 and receives that CP video image. This conferee is referred to as the receiving conferee. An exemplary embodiment of an editor 456 may adapt the video image in the current speaker segment to the gaze of the receiving conferee looking at the speaker image in the CP video image. To do so, the editor 456 may obtain from CSC 442 information about which one of the three video cameras 320 - 324 of the endpoint of the current speaker fits the gaze of the receiving conferee. During a transition from one camera to another camera of the same endpoint, different techniques may be used to overcome transition digital artifacts caused by the difference between the positions of the cameras, including morphing techniques for smoothing the transition. The morphing technique may provide a perception of a smooth transition. Morphing techniques are well known in the video processing arts and have been used for more than twenty years. Other techniques that may be used include fading-in effects, fading-out effects, etc. Furthermore, in order to avoid jumping from one camera to the other and vice versa, an embodiment may have an overlap between two adjacent cameras and may use hysteresis in the decision thresholds for selecting a camera based on the receiving conferee's point of view. Consequently, the changing point from a right camera to a left camera may be other than the changing point from the left camera to the right one. In addition, some embodiments after changing the selected camera, a time delay may be implemented for a certain period, for example a few seconds, in which the selected video camera is not changed again. Control module 440 may be a logical unit that controls the operation of the MCU 400 and conducts the conference session. In addition to conventional operation of a typical MCU, MCU 400 according to various embodiments may be capable of additional functionality as result of having the control module 440 . Control module 440 may include a Camera-Selector Controller (CSC) 442 . In one embodiment, a CSC 442 may control a plurality of video output modules 455 a - c . In other embodiments, each of a plurality of CSC 442 controls an output module 455 a - c . Per each output module 455 , a CSC 442 may receive gaze information of the conferee associated with the EP that is associated with that output module 455 . The gaze information may include the view angle ±a 216 , 218 of the conferee from the perpendicular 210 to the conferee's screen. In other embodiments, the gaze information may be the coordinates (W;H, Width; Height) of the nose of the conferees in pixels along the width axis (W) and the height (H) axis of the conferee's self image received from the center camera 322 of the conferee's EP 330 , etc. In other embodiments, an MCU for media relay video conferencing (a media relay MCU or MRM) may use a distributed architecture as described herein. In such an architecture, the endpoints 330 may comprise the gaze detector and the editor. The gaze detector may process the video image received from one of the cameras 320 , 322 , and 324 of the endpoint 330 to define the gaze of the conferee and transfer the gaze information toward the CSC 442 that is located in the MRM. The editor may select one of the decoded streams from the endpoint decoder 452 that were received from a transmitting endpoint to which the gaze of the conferee pointed, according to instructions obtained from the CSC 442 , and embed the selected stream in a CP video image that may be presented on the endpoint display unit. A reader who wishes to learn more about media relay video conferencing and MRM is invited to read US Patent Application Publication No. 2010/0194847, the content of which is incorporated herein by reference. After collecting the information on the conferee's gaze and the layout that is currently presented to that conferee, the CSC 442 may determine the segment at which the conferee is looking. Then, CSC 442 may determine which camera ( 320 , 322 , or 324 ) of the endpoint 330 that is associated with this segment matches the direction of the conferee's gaze. If the conferee looks to the left side of the segment, then camera 320 may be selected. If the conferee looks to the right side of the segment, then camera 324 may be selected, and if to the center of the segment then camera 322 may be selected. Information on the selected camera may be transferred to the editor 456 of the output module 455 that is assigned to that conferee. The information may include information how to obtain the decoded data from the common interface 454 and instead of each stream to place this image in the CP video image. More information on CSC is disclosed below in conjunction with FIG. 5 . In some embodiments, a single CSC 442 may control a plurality of editors 456 . In other embodiments, a plurality of CSCs 442 each control one of the plurality of editors 456 . The CSC 442 may calculate the scaling, cropping, and movement when moving from one camera to another. Based on this information, the editor 456 starts the replacing process. In some embodiments, replacing images from two different cameras in the same room may take few frames in order to smooth the transition. An exemplary embodiment may use a fading technique in which the old image is faded while the image from the selected camera is increased. Other embodiment may use a morphing technique to provide a perception of a smooth transition, etc. FIG. 5 is a flowchart illustrating relevant actions of process 500 . Process 500 may be implemented by a CPOVD 453 for defining the gaze of the conferee that is associated with that CPOVD 453 and selecting a camera, in a second room, based on the conferee's s point of view. In this embodiment, the conferee resides at a first site, and is referred as a first conferee, while the cameras ( 320 , 322 , and 324 ) are located at a second site 300 . In one embodiment, process 500 may change cameras only if the first conferee looks at the segment of the current speaker. Other embodiments may switch between cameras even if the first conferee looks at a segment other than the segment of current speaker in the CP video image. The process may be initiated in block 502 by CSC 442 when the first conferee joins the conference. Upon initiation in block 502 , a learning period may be executed by the CPU of the CPOVD in block 504 . During the learning period in block 504 , the CPOVD 453 may learn the topology of the first site as it is reflected in a video image received from a camera in the first site. The camera may be the center camera if the endpoint in the first room has three cameras; otherwise, where only one camera exists at the first site, the camera may be the only camera used in the first site. Learning the topology may include identifying the location of the first conferee in the self-image, associating the gaze as it is expressed on the image with a location on the screen on which the conferee looks, etc. Learning the topology may be done automatically by prompting the conferee to look at a different location on the screen and determining the conferee's gaze at each time. In some embodiments, learning the topology may be performed semi-automatically, where the conferee is requested to look on a certain location on the screen and to point with a cursor on an organ on the image of the conferee's face, putting the cursor on an eye, the nose, etc. At the end of the learning period, a decision may be made in block 510 whether the conference is running. The conference may be considered as running when the video image presented over the screen of the first endpoint is received from at least one other site. If not running, process 500 waits until the conference begins to run. If in block 510 the conference is running, then information on the current presented layout on the first screen is obtained in block 512 from CSC 442 . The information may include the coordinates of the top left and bottom right of each segment, the coordinates, in pixels (Wc;Hc), of the center of each segment, the number of cameras in the site of that segment, etc. The CPOVD 453 , which is associated with the input module 451 that is assigned to the first endpoint, may obtain a decoded video stream that was received from the center camera of the first endpoint in order to detect in block 512 the gaze of the first conferee. Detecting the gaze may be done by one or more of the techniques that are described above. The gazing point on the screen of the first endpoint may be expressed in pixels (Wg;Hg) from the top left corner of the screen. Based on the coordinates of the gazing point (Wg;Hg) on the screen of the first endpoint and the obtained information on the layout present on that screen, process 500 may determine in block 512 the segment at which the first conferee is looking Based on the information obtained on that segment in block 504 , a decision is made in block 520 whether the remote site (the site that is presented in that observed segment) has a single camera. If so, process 500 waits in block 540 for a predetermined period of time. The predetermined period of time may be a configurable period between few tens of milliseconds to few seconds, for example. After the waiting period of block 540 process 500 returns to block 512 and starts a new cycle of adapting the presented image to the gaze of the conferee. If in block 520 the remote site has more than one camera, then process 500 proceeds to block 522 in which the CPOVD 453 determines, based on the detected coordinates (Wg;Hg) of the first conferee's gaze and the coordinates of the center of the relevant segment (Wc;Hc), whether the first conferee looks at the center of the segment, the left side, or the right side of the segment. In one embodiment, the decision may be made by using two values as thresholds A1 and A2 wherein the absolute value of A2 is larger than A1. The values of A1 and A2 may depend on the size of the segment, where the bigger the segment the bigger the values of A1 and A2. In order to determine in block 522 whether the first conferee looks at the center of the segment, a CPOVD 453 may calculate the value of (Wc−Wg). If the absolute value is smaller than A1, then CPOVD 453 may decide that the first conferee looks at the center of the segment. Thus, the current selected camera in the remote site is the center camera 322 . To determine whether the first conferee looks at the left side of the segment, CPOVD 453 may check if Wg<(Wc−A2). If so, then CPOVD 453 may decide that the first conferee looks at the left side of the segment and the right camera 324 may be selected to match the gaze. In order to determine whether the first conferee looks at the right side of the segment, CPOVD 453 may check if Wg>(Wc+A2). If so, then CPOVD 453 may decide that the first conferee looks at the right side of the segment. Thus, the current selected camera in the remote site is the left camera 324 . The CPOVD 453 may then determine whether there is a need to switch from the previous selected camera to the current selected camera. If in block 530 the previous selected camera is the same as the current selected camera, then there is no need to switch cameras and process 500 continues to block 540 . The decisions may be established according to various predetermined criteria, including a predefined change in the angle of the viewer's point of view, a predefined angle from which a certain camera's input is to be chosen; etc. If there is a need to switch cameras, then an instruction may be sent in block 532 to the editor module 456 to start the transition from the video stream received from the previous selected camera to the video stream received from the current selected camera. The instruction may be sent via the CSC 442 . After instructing the editor 456 , process 500 may wait in block 540 before starting a new cycle from block 512 . In one embodiment of method 500 , block 522 may further consider whether the video image of the transmitting endpoint was cropped along the width axis before being placed in the segment of the CP layout. If it was, the CSC 442 may check if the cropping area can be slightly moved in the direction that leads the Wg toward the Wc of the segment. Only after sliding the cropped image under the segment, CPOVD 453 may then determine whether there is a need to switch from the previous selected stream (camera) of the transmitting endpoint to the current selected stream (camera of the transmitting endpoint). Although the description above is written in terms of selecting a camera, one skilled in the art will recognize that a selection of a camera may be accomplished by selecting a video stream that is generated by the camera. Therefore, the terms selecting a video stream and selecting a camera may be considered as interchangeable terms. It is to be understood that the above description is intended to be illustrative, and not restrictive. The above-described apparatus, systems, and methods may be varied in many ways, including, changing the order of steps, and the exact implementation used. The described embodiments include different features, not all of which are required in all embodiments of the present disclosure. Moreover, some embodiments of the present disclosure use only some of the features or possible combinations of the features. Different combinations of features noted in the described embodiments will occur to a person skilled in the art. Furthermore, some embodiments of the present disclosure may be implemented by combination of features and elements that have been described in association to different exemplary embodiments along the discloser. The scope of the invention is limited only by the following claims and equivalents thereof.
A system and method for manipulating images in a videoconferencing session provides users with a 3-D-like view of one or more presented sites, without the need for 3-D equipment. A plurality of cameras may record a room at a transmitting endpoint, and the receiving endpoint may select one of the received video streams based upon a point of view of a conferee at the receiving endpoint. The conferee at the receiving endpoint will thus experience a 3-D-like view of the presented site.
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CROSS-REFERENCES TO RELATED APPLICATIONS This is a continuation-in-part application for the application Ser. No. 11/737,756 filed on Apr. 20, 2007, now abandoned, which is incorporated herewith by reference. FIELD OF THE INVENTION The present invention generally relates to a method and an apparatus for determining the accuracy of the location estimated for a target device in a wireless system. BACKGROUND OF THE INVENTION The wireless location determination system is widely applied to many systems, including location-sensitive content delivery, direction finding, asset tracking, emergency notification, and so on. To estimate the location of a target device, a location determining system must measure a quantity, which is at least a function of distance. This quantity can be the strength of signals transmitted from the access points (APs). In a free space, the signal strength will logarithmically decay with distance. The wireless location determining system usually uses two phases for processing. One is a training phase, and the other is a location determining phase. The training phase is an offline phase, in which the system establishes the sample points (SP) and a map, known as a radio map, capturing the AP signatures at certain points of the coverage region. In the location determining phase, i.e., on-line phase, the signal strength vector from APs is compared to the radio map to find an optimal match, such as the nearest candidate, as the estimated location of the target device. There are many methods to estimate location and determine the estimation error. U.S. Patent Publication No. 2005/0131635 disclosed a method for determining the error distance of the predicted location of a target device. This method is based on a probabilistic model 101 and the collected observations of signal value 103 to determine the location of the target device, as shown in FIG. 1 . The probabilistic model 101 shows the signal value probability distribution of a plurality of APs. The error estimate is determined by the expectation of the error distance between the actual location of the target device TD and the estimated location EL. The error distance estimation can be used to determine whether to add new SPs, or recalibrate the existing SPs. The above method depends on the location decision rule. Therefore, there is a potential problem of improper decision rule or interference. SUMMARY OF THE INVENTION The examples of the present invention provide a method for determining the confidence index of the estimated location for a target device in a wireless system, and an apparatus for implementing the method. In location determining, the motion model and the location probability distribution of the target device can be used to calculate the uncertainty of the estimated location, and further to calculate the confidence index of the estimated location. The confidence index can be further applied to evaluate the fitness of the motion model and to define searching areas in the rescue operation. After the observations of signals of the target device are received, the uncertainty of location probability distribution of the target device can be used to calculate the confidence index. In calculating the location probability distribution, the transition probability distribution of the target device moving from a location to another location is also taken into account. The meaning of the confidence index is a quantity to exclude the uncertainty of the location of the target device. The more the uncertainty is excluded, the higher the confidence index of the estimated location is. The method for determining the confidence index of the present invention includes the following steps. First, a location probability density function is determined. The location probability density function is a conditional density function p(q t |{o k } k=1 t ), where {o k } k=1 t is the received radio signals from the receiver of the target device from time 1 to time t. Then, the uncertainty of the location probability density function is calculated, and the maximum uncertainty in the current situation is also calculated. Finally, the confidence index is calculated for the current location estimate. For implementing the method, an apparatus may include a location probability model, a module for calculating the uncertainty of the location probability density function p(q t |{o k } k=1 t ) and the maximum uncertainty in the current situation, and a confidence index module for calculating the confidence index. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a conventional method for determining error distance of a predicted location for a target device. FIG. 2 a shows a flowchart illustrating the operating flow for determining the confidence index of an estimated location in a wireless system of the present invention. FIG. 2 b shows the parameters needed in calculating the location probability density function. FIG. 3 shows how a Hidden Markov Model (HMM) is applied to a location determining system. FIG. 4 shows the four probability distribution functions corresponding to the radio signals received at four different locations. FIG. 5 shows the recursive structure to calculate location probability density function. FIG. 6 a shows a pre-trained radio map. FIG. 6 b illustrating the transition probability of a target device moving to each location. FIG. 6 c shows a pre-calculated location probability density function. FIG. 6 d shows location probability density functions for different observations. FIG. 6 e shows a working example of the confidence index based on FIG. 6 d. FIG. 6 f shows another set of transition probability from SP 1 to each location and the rest remains the same as in FIG. 6 b. FIG. 6 g shows location probability density functions for different observations based on the transition probability function in FIG. 6 f. FIG. 6 h shows a working example of the confidence index based on FIG. 6 g. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As aforementioned, wireless location determining systems usually process in two phases. One is the training phase, and the other is the location determining phase. The present invention computes the confidence index when the received radio signals {o k } k=1 t from the receiver of the target device from time 1 to time t are available in the location determining phase for estimating a current location q t at time t. FIG. 2 a shows a flowchart illustrating the operating flow for determining the confidence index of the estimated location in a wireless system according to the present invention. FIG. 2 b shows parameters needed to calculate location probability density function. As shown in FIG. 2 a , the first step is to determine a location probability density function of a target device, as shown in step 201 . There are many possible examples of the location probability density functions. Without loss of generality, the following location probability density function uses posterior probability density function p(q t |{o k } k=1 t ) for description. The next step is to calculate the uncertainty U(Q t |{o k } k=1 t ) of the location probability density function p(q t |{o k } k=1 t ), and the maximum uncertainty in the current situation, as shown in step 202 . Step 203 is to calculate the confidence index R({o k } k=1 t ) based on these uncertainties. The following describes the detailed operations of steps 201 - 203 . In step 201 , the location probability density function is a conditional probability density function p(q t |{o k } k=1 t ), where {o k } k=1 t is the received radio signals obtained from the receiver of the target device from time 1 to time t. The location probability density function p(q t |{o k } k=1 t ) of the target device can be calculated by applying Hidden Markov Model (HMM) to the location tracking system. FIG. 3 shows how a Hidden Markov Model (HMM) is applied to a location determining system. As shown in FIG. 3 , the HMM includes the transition probability between two locations and the probability of observation at a specified location. The location probability can be calculated from the transition probability between two locations and the probability of observation at a specified location. When time changes from t−1 to t+1, the target device moves along three locations q t−1 , q t , and q t+1 . Notice that q t−1 is the previous location at previous time t−1, q t is the current location of the target device at time t, and q t+1 is the future location at time t+1. P(q t |q t−1 ) is the probability that the target device moves from q t−1 to q t during time t−1 to t. This transition probability can, however, be derived from exterior information such as the paths plans in a static database like the GIS system or the target device's motion model obtained real time. The motion model may contain the direction, speed and acceleration of the target device from multiple sensors or a predicted location from a Kalman filter tracking the target device. In the measurement process, the observations of the radio signal are reported. The observations are the quantity only related to the location at the corresponding time. Without loss of generality, the reported observation of radio signals by the target device forms a probability distribution, and furthermore, a conditional probability. In other words, condition probability P(o t =m t |q t =s t ) is the probability that the observation is m t when the target device is at location s t . To obtain distributions of the observed radio signals at every location, a device is needed to collect the radio signals during the training phase. The collected data are transformed to the aforementioned probability density functions and then stored in the positioning system for the use during on-line phase. FIG. 4 shows the four probability distributions PDF 1 -PDF 4 corresponding to the radio signals received at four different locations SP 1 -SP 4 . In general, the location-conditioned probabilities of observations can be viewed as independent of each other. That is, P(o t =m t , o t−1 =m t−1 |q t =s t , q t−1 =s t−1 )=P(o t =m t |q t =s t ) P(o t−1 =m t−1 |q t−1 =s t−1 ). Furthermore, the current location of the target device can be viewed as only dependent on the last location. That is, the transition model of two locations follows the Markov P(q t =s t |q t−1 =s t−1 , q t−1 =s t−2 , . . . q 0 =s 0 )=P(q t =s t |q t−1 =s t−1 ). Because it is impossible to directly obtain the locations q t−1 , q t , and q t+1 of the target device, the present invention uses a series of observations o t−1 , o t , and o t+1 to estimate the location of the target device. Therefore, the location probability density function p(q t |{o k } k=1 t ) can be obtained from the following equation: p ( q t ⁢  { o k } k = 1 t ) = p ⁡ ( q t , { o k } k = 1 t ) p ⁡ ( { o k } k = 1 t ) . Because the current observation only depends on the current location of the target device, the numerator p(q t ,{o k } k=1 t ) of location probability density function p(q t |{o k } k=1 t ) can be expressed as the following equation: p(q t ,{o k } k=1 t )=p(o t |q t )p(q t |{o k } k=1 t−1 ), where p(q t |{o k } k=1 t−1 ) is the location prediction of next time under the condition of having observations up to time t−1. The aforementioned probability density function of predicted location can further be represented in the following: p ( q t ⁢  { o k } k = 1 t - 1 ) = ∑ q t - 1 ∈ Q t - 1 ⁢ p ⁡ ( q t ⁢  q t - 1 ) ⁢ p ( q t - 1  ⁢ { o k } k = 1 t - 1 ) where p(q t |q t−1 ) is the transition probability that the target device moves from location q t−1 at previous time t−1 to possible location q t at current time t. The transition probability can be derived from the motion model and is assumed to follow HMM. According to the Bayes' theorem, the denominator p({o k } k=1 t ) of location probability density function p(q t |{o k } k=1 t ) can be obtained from the following equation: ∑ q t ∈ Q t ⁢ p ( o t ⁢  q t ) ⁢ p ⁢ ( q t  ⁢ { o k } k = 1 t - 1 ) = ∑ q t ∈ Q t ⁢ ∑ q t - 1 ∈ Q t - 1 ⁢ p ⁡ ( o t ⁢  q t ) ⁢ p ( q t  ⁢ q t - 1 ) ⁢ p ( q t - 1  ⁢ { o k } k = 1 t - 1 ) . The aforementioned calculation of location probability density function can be implemented by the recursive structure as in FIG. 5 . The star symbol (*) stands for the convolution-like operation: p ( q t ⁢  { o k } k = 1 t - 1 ) = ∑ q t - 1 ∈ Q t - 1 ⁢ p ⁡ ( q t ⁢  q t - 1 ) ⁢ p ( q t - 1  ⁢ { o k } k = 1 t - 1 ) and the cross symbol (×) stands for the arithmetical multiplication: p(q t ,{o k } k=1 t )=p(o t |q t )p(q t |{o k } k=1 t−1 ) and the normalization block implements accumulation and inverse multiplication. The motion model and the location probability distribution of the target device can be used to calculate the uncertainty of the estimated location. In step 202 , the uncertainty U(Q t |{o k } k=1 t ) of location probability density function p(q t |{o k } k=1 t ) can be the self-contained information function of location probability density function p(q t |{o k } k=1 t ), such as the average. Uncertainty U(Q t |{o k } k=1 t ) can be calculated by the following equation: U ( Q t ⁢  { o k } k = 1 t ) = H ( Q t  ⁢ { o k } k = 1 t ) = - ∑ q t ∈ Q t ⁢ p ⁡ ( q t ⁢  { o k } k = 1 t ) ⁢ log 2 ⁢ p ( q t  ⁢ { o k } k = 1 t ) , where Q t is all possible locations of the target device at time t, {o k } k=1 t are the specific observations received by the target device from time 1 to t, p(q t |{o k } k=1 t ) is the probability that the target device's location is q t at time t, given that {o k } k=1 t are received, and H(Q t |{o k } k=1 t ) is the entropy of the location probability distribution p(q t |{o k } k=1 t ). It is worth noting that H(Q t |{o k } k=1 t ) can be expressed as the following equation: H ( Q t ⁢  { o k } k = 1 t ) = ∑ q t ∈ Q t ⁢ p ⁡ ( q t , { o k } k = 1 t ) p ⁡ ( { o k } k = 1 t ) ⁢ log 2 ⁢ p ⁡ ( { o k } k = 1 t ) p ⁡ ( q t , { o k } k = 1 t ) , ⁢ where ⁢ ⁢ p ⁡ ( { o k } k = 1 t ) = ∑ q t ∈ Q t ⁢ ∑ q t - 1 ∈ Q t - 1 ⁢ p ⁢ ( o t ⁢  q t ) ⁢ p ( q t  ⁢ q t - 1 ) ⁢ p ( q t - 1  ⁢ { o k } k = 1 t - 1 ) , ⁢ and ⁢ ⁢ ⁢ p ⁡ ( q t , { o k } k = 1 t ) = ∑ q t - 1 ∈ Q t - 1 ⁢ p ⁢ ( o t ⁢  q t ) ⁢ p ( q t  ⁢ q t - 1 ) ⁢ p ( q t - 1  ⁢ { o k } k = 1 t - 1 ) . The maximum entropy of the all possible probability distributions occurs when the probabilities of possible locations are the same under the same condition, and the maximum entropy is log 2 (|Q t |), where |Q t | is the total number of all possible locations at time t and can be determined from a pre-defined size of the searching area. According to the meaning of the information entropy, the larger the entropy is, the more uncertainty the estimated location has. In other words, the prediction is less reliable. Therefore, the confidence index can be viewed as the quantity to exclude the uncertainty of the estimated location of the target device in the prediction. The more uncertainty the quantity can exclude, the higher the confidence index of the estimated location is. The present invention defines the confidence index of the estimated location of the target device as the functions of two variables. One is the current received radio signal, and the other is the maximum entropy of all possible probability distributions under the same condition. Therefore, in step 203 , the confidence index of the present invention depends on the quantity of location uncertainty of the target device that can be excluded from the location prediction of the target device. An example of the definition of the confidence index R({o k } k=1 t ) is as follows: R ⁡ ( { o k } k = 1 t ) = 1 - H ( Q t ⁢  { o k } k = 1 t ) log 2 ⁡ (  Q t  ) × 100 ⁢ % , where |Q t | is the total number of all possible locations at time t, and log 2 (|Q t |) is the maximum entropy of all possible probability distributions under the same condition. It is worth noting that the probability distribution that has the maximum entropy among all possible probability distributions indicates that the estimated location may be randomly selected, and the confidence index R({o k } k=1 t ) accordingly shall be 0%. On the contrary, if the received observation of radio signal is known, and the target device is in a certain grid/sample point with probability 1, the confidence index R({o k } k=1 t ) shall be 100%. For implementing the method with the operating flow as shown in FIG. 2 a , an apparatus may include a location probability model consisting of static geographic database, a motion model or a location prediction module to give a motion model of target device, a radio signal receiver and database that contains probability density functions of observations, a module for calculating the uncertainty U(Q t |{o k } k=1 t ) of the location probability density function p(q t |{o k } k=1 t ) and the maximum uncertainty in the current situation, and a confidence index module for calculating the confidence index R({o k } k=1 t ). The term of location probability model refers to a model that indicates a location probability density function for a target device in the wireless system, when a received radio signal from the target device is known. The following uses the four locations, SP 1 -SP 4 , as an example to describe how the uncertainty measurement is applied to the confidence index of estimated location. The known environment and the initial conditions of the wireless location determining system include the following: (a) a pre-trained radio map ( FIG. 6 a ), (b) the transition probability of the target device ( FIG. 6 b ) and (c) pre-calculated location probability density function ( FIG. 6 c ). According to step 201 of FIG. 2 a and the aforementioned description, the determined location probability density function of the target device is p(q 2 |{o k } k=1 2 ), as shown in FIG. 6 d . Finally, based on the example of the confidence index R ⁡ ( { o k } k = 1 2 ) = 1 - H ( Q 2 ⁢  { o k } k = 1 2 ) log 2 ⁡ (  Q 2  ) × 100 ⁢ % , the confidence index R({o k } k=1 2 ) can be obtained, as shown in FIG. 6 e. The results of FIG. 6 e show that the lowest confidence index is 47.31% when received observation o t is 3. In other words, the most unreliable observation is signal 3 , and the reason is that the inherited probability distribution of the observation at SP 3 has a greater variance. In the following, the use of confidence index to evaluate the motion model is illustrated. FIG. 6 f gives another set of transition probability from SP 1 to each location and the rest remain the same as in FIG. 6 b . The location probability density and the confidence index based on FIG. 6 f are shown in FIG. 6 g and 6 h , respectively. In this case, the transition probability from SP 1 to SP 4 is higher than the rest due to the prediction of the motion model tracking the target device. If the current radio signal observation is the one with highest observation probability in SP 4 according to the radio map, the location estimation will therefore have high confidence index. Moreover, if this situation continues, it indicates that the motion model in this case is suitable. On the contrary, if location estimations keep having low confidence, the tracking policies used in the motion model should be changed immediately. Thus the confidence index can be an effective index to evaluate the motion model. The confidence index can also be applied to operations of rescue and surveillance. In the on-line phase, we cannot know the error distance of a predicted location since the ground truth of the target device cannot be obtained during this time. However, to evaluate how accurate a predicted location can be by the positioning system is necessary if the provided location-based service concerns search and rescue for emergency and surveillance of clients. For instance, if an emergent call is made by a client, rescue operation will be different for different confidence levels of the estimated locations. If the estimated location has a low confidence index, say 30%, the search area for the client should start from its previous locations with high confidence index values and should cover all possible locations at the current time. On the other hand, if a target device is under surveillance, the positioning system should warn the operator when its confidence index of an estimated location down cross a pre-defined threshold or when it has low confidence index values for a long time. In summary, during the location determining, when a target device receives the radio signal, the present invention can determine the uncertainty of the estimated location based on the motion model and the location probability distribution of the target device, and further obtains the confidence index of the estimated location. The confidence index depends on the location uncertainty that can be excluded from the estimated location. The flatter the posterior location probability distribution is, the lower the confidence index is. As can be seen from the above description and examples, the present invention provides a method of evaluating and determining the accuracy of an estimated location of a target device in a wireless system by computing the confidence index of the estimated location. The higher the confidence index is, the more accurate the estimated location is. Although the present invention has been described with reference to the preferred embodiments, it will be understood that the invention is not limited to the details described thereof. Various substitutions and modifications have been suggested in the foregoing description, and others will occur to those of ordinary skill in the art. Therefore, all such substitutions and modifications are intended to be embraced within the scope of the invention as defined in the appended claims.
A method for determining the accuracy of the estimated position for a target device in a wireless system includes the computation of a confidence index. In the online location determining phase, after knowing the observations of the radio signal for a target device, the target device's probability distribution of location and its motion model are combined to calculate the position uncertainty, thereby giving the confidence index of this location estimate. The invention determines the location probability distribution, and calculates the uncertainty of the location probability distribution and the possible maximum uncertainty under the current situation. Based on these uncertainties, this invention determines the confidence index of the radio signal. The confidence may be regarded as a quantity that the location uncertainty can be excluded in the location prediction.
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CROSS-REFERENCE TO RELATED APPLICATION [0001] This application claims benefit of U.S. Provisional Patent Application No. 62/300,698, “OBTAINING AND USING TIME INFORMATION ON A SECURE ELEMENT (SE),” filed on Feb. 26, 2016, which is hereby incorporated by reference herein. FIELD [0002] The described embodiments relate to obtaining and using time information on a secure element (SE) for security purposes with respect to public-key certificates in a public key infrastructure (PKI) environment. BACKGROUND [0003] Communications of an SE, for example an embedded universal integrated circuit card (eUICC), may be authenticated using PKI techniques. Certificates used for authentication and confidentiality purposes can be generated by a trusted certificate issuer (CI). A public-key certificate may also be referred to herein simply as a certificate. [0004] A user may store a copy of a certificate, where the certificate holds the name of a given party (user identity). The public key recorded in the certificate can be used to check the signature on a message signed using a PKI private key of the given party. A user or message recipient may use an on-line protocol such as on-line certificate status protocol (OCSP) to determine if a certificate is valid. [0005] A digital signature is authentication data that binds the identity of the signer to a data part of a signed message. A certification authority (CA) is a trusted third party whose signature on a certificate vouches for the authenticity of the public key of the associated user identity. If the private key of the identified user becomes compromised, all holders of the certificate need to be notified. Notifying can be done, for example, with a certificate revocation list (CRL). Recipients of the CRL no longer trust messages signed with the corresponding public key of the identified user. [0006] Also, a public-key certificate may expire at a certain point in time. So, separate from the compromise issue, there is a need to improve recognition of expired certificates. Generally, time-variant parameters can be used in identification protocols to counteract replay attacks and to provide timeliness guarantees. SUMMARY [0007] Representative embodiments set forth herein disclose various systems and techniques for using time information in an SE to improve security in PKI environments. [0008] An SE, in some embodiments, obtains time information from an authenticated message. An SE, in some embodiments, obtains time information from a trusted interface with a device local component. The SE can store the time information for subsequent use. The time information may be in the form of actual calendar time expressed in terms of year, month, day, hour, minute and second. In some embodiments, the time information is a counter value, where a counter state determining a counter value is recognized by the SE and at least one other entity. [0009] Time information may be pushed to the SE by a CI on a periodic basis, for example. Time information may also be requested by the SE and then supplied by the CI in response to the request. In some embodiments, the SE opportunistically obtains time information by retaining time values parsed from messages primarily devoted to other purposes. [0010] Time information may correspond to a CA or to a set of CAs. In some embodiments, the time information has a global aspect and can be applied to test security materials from any CA or other entity corresponding with the SE using PKI security. [0011] After the SE obtains time information, the obtained time information can be used to replace pre-existing time information. For example, the obtained time information can be an update of the existing time information. [0012] The obtained time information can be used to check for expiration of security materials, e.g., CRLs, public keys and certificates. [0013] Time information can be used by the SE in conjunction with other certificate revocation schemes, e.g., the time information can be used when a CRL is received, when an OCSP stapling message is received, or when a server is compromised and a CI is establishing a new version number of certificates, also referred to as an epoch value. For example, the SE can trust a given server if the difference between a time in an OCSP stapling message and the time information falls within a security window, or if the given server can produce a certificate with the new epoch value. [0014] The SE can store time information in, for example, a memory of the SE operating system or in an eUICC controlling authority security domain (ECASD). [0015] This Summary is provided merely for purposes of summarizing some example embodiments so as to provide a basic understanding of some aspects of the subject matter described herein. Accordingly, it will be appreciated that the above-described features are merely examples and should not be construed to narrow the scope or spirit of the subject matter described herein in any way. Other features, aspects, and advantages of the subject matter described will become apparent from the following Detailed Description, Figures, and Claims. BRIEF DESCRIPTION OF THE DRAWINGS [0016] The included drawings are for illustrative purposes and serve only to provide examples of possible structures and arrangements for the disclosed systems and techniques for intelligently and efficiently managing calls and other communications between multiple associated user devices. These drawings in no way limit any changes in form and detail that may be made to the embodiments by one skilled in the art without departing from the spirit and scope of the embodiments. The embodiments will be readily understood by the following detailed description in conjunction with the accompanying drawings, wherein like reference numerals designate like structural elements. [0017] FIG. 1 illustrates an exemplary SE with time information in communication with a CA and a server, according to some embodiments. [0018] FIG. 2 provides exemplary logic illustrating obtaining and using time information, according to some embodiments. [0019] FIG. 3 illustrates exemplary push, pull, opportunistic, and local device sourcing approaches to obtaining time information, according to some embodiments. [0020] FIGS. 4A-4C illustrate exemplary time information embodiments, trusted and untrusted lists, and parameters and variables used in example certificate revocation schemes, according to some embodiments. [0021] FIG. 5 illustrates an exemplary PKI environment including an SE with time information, according to some embodiments. [0022] FIG. 6 illustrates an example event in the PKI environment of FIG. 5 in which the certificate of a server has become compromised or otherwise been withdrawn from use, according to some embodiments. [0023] FIG. 7 illustrates exemplary logic for obtaining time information by an SE and performing a cleanup operation, according to some embodiments. [0024] FIG. 8 illustrates exemplary logic for applying time information by an SE, according to some embodiments. [0025] FIG. 9 illustrates exemplary internal features of an SE, according to an eUICC embodiment. [0026] FIG. 10 illustrates an exemplary network system including an SE in a device, according to some embodiments. [0027] FIG. 11 illustrates an exemplary apparatus for implementation of the embodiments disclosed herein. DETAILED DESCRIPTION [0028] Representative applications of apparatuses, systems, and methods according to the presently described embodiments are provided in this section. These examples are being provided solely to add context and aid in the understanding of the described embodiments. It will thus be apparent to one skilled in the art that the presently described embodiments can be practiced without some or all of these specific details. In other instances, well known process steps have not been described in detail in order to avoid unnecessarily obscuring the presently described embodiments. Other applications are possible, such that the following examples should not be taken as limiting. [0029] Wireless devices, and mobile devices in particular, can incorporate multiple different radio access technologies (RATs) to provide connections through different wireless networks that offer different services and/or capabilities. A wireless device can include hardware and software to support a wireless personal area network (“WPAN”) according to a WPAN communication protocol, such as those standardized by the Bluetooth® special interest group (“SIG”) and/or those developed by Apple referred to as an Apple Wireless Direct Link (AWDL). The wireless device can discover compatible peripheral wireless devices and can establish connections to these peripheral wireless devices located in order to provide specific communication services through a WPAN. In some situations, the wireless device can act as a communications hub that provides access to a wireless local area network (“WLAN”) and/or to a wireless wide area network (“WWAN”) to a wide variety of services that can be supported by various applications executing on the wireless device. Thus, communication capability for an accessory wireless device, e.g., without and/or not configured for WWAN communication, can be extended using a local WPAN (or WLAN) connection to a companion wireless device that provides a WWAN connection. Alternatively, the accessory wireless device can also include wireless circuitry for a WLAN connection and can originate and/or terminate connections via a WLAN connection. Whether to use a direct connection or a relayed connection can depend on performance characteristics of one or more links of an active communication session between the accessory wireless device and a remote device. Fewer links (or hops) can provide for lower latency, and thus a direct connection can be preferred; however, unlike a legacy circuit-switched connection that provides a dedicated link, the direct connection via a WLAN can share bandwidth with other wireless devices on the same WLAN and/or with the backhaul connection from the access point that manages the WLAN. When performance on the local WLAN connection link and/or on the backhaul connection degrades, a relayed connection via a companion wireless device can be preferred. By monitoring performance of an active communication session and availability and capabilities of associated wireless devices (such as proximity to a companion wireless device), an accessory wireless device can request transfer of an active communication session between a direction connection and a relayed connection or vice versa. [0030] In accordance with various embodiments described herein, the terms “wireless communication device,” “wireless device,” “mobile device,” “mobile station,” “wireless station”, “wireless access point”, “station”, “access point” and “user equipment” (UE) may be used herein to describe one or more common consumer electronic devices that may be capable of performing procedures associated with various embodiments of the disclosure. In accordance with various implementations, any one of these consumer electronic devices may relate to: a cellular phone or a smart phone, a tablet computer, a laptop computer, a notebook computer, a personal computer, a netbook computer, a media player device, an electronic book device, a MiFi® device, a wearable computing device, as well as any other type of electronic computing device having wireless communication capability that can include communication via one or more wireless communication protocols such as used for communication on: a wireless wide area network (WWAN), a wireless metro area network (WMAN) a wireless local area network (WLAN), a wireless personal area network (WPAN), a near field communication (NFC), a cellular wireless network, a fourth generation (4G) LTE, LTE Advanced (LTE-A), and/or 5G or other present or future developed advanced cellular wireless networks. [0031] The wireless device, in some embodiments, can also operate as part of a wireless communication system, which can include a set of client devices, which can also be referred to as stations, client wireless devices, or client wireless devices, interconnected to an access point (AP), e.g., as part of a WLAN, and/or to each other, e.g., as part of a WPAN and/or an “ad hoc” wireless network, such as a Wi-Fi direct connection. In some embodiments, the client device can be any wireless device that is capable of communicating via a WLAN technology, e.g., in accordance with a wireless local area network communication protocol. In some embodiments, the WLAN technology can include a Wi-Fi (or more generically a WLAN) wireless communication subsystem or radio, the Wi-Fi radio can implement an Institute of Electrical and Electronics Engineers (IEEE) 802.11 technology, such as one or more of: IEEE 802.11a; IEEE 802.11b; IEEE 802.11g; IEEE 802.11-2007; IEEE 802.11n; IEEE 802.11-2012; IEEE 802.11ac; IEEE 802.11ax; or other present or future developed IEEE 802.11 technologies. [0032] Additionally, it should be understood that the wireless devices described herein may be configured as multi-mode wireless communication devices that are also capable of communicating via different third generation (3G) and/or second generation (2G) RATs. In these scenarios, a multi-mode wireless device or UE can be configured to prefer attachment to LTE networks offering faster data rate throughput, as compared to other 3G legacy networks offering lower data rate throughputs. For instance, in some implementations, a multi-mode wireless device or UE may be configured to fall back to a 3G legacy network, e.g., an Evolved High Speed Packet Access (HSPA+) network or a Code Division Multiple Access (CDMA) 2000 Evolution-Data Only (EV-DO) network, when LTE and LTE-A networks are otherwise unavailable. [0033] A wireless communication device may include memory resources and computational capacity to perform maintenance of its stored certificates using CRLs. A wireless communication device hosting an SE may also have a notion of actual time. An SE may be limited in memory, computational clock rate, and time information. [0034] Interest is increasing in the use of securing SE communications using PKI. Some problems or challenges with using PKI by an SE are as follows: i) checking expiration of certificates, ii) checking validity of a CRL list, iii) checking the validity of OCSP stapling messages, and iv) removing expired or compromised certificates from certificate-related storage. PKI [0035] Communications of an SE can be authenticated using PKI techniques. PKI relies on the infeasibility of a third party determining a private key of a public key-private key pair from the public key. The public key is communicated in a data structure called a certificate. A message encrypted with the private key is trusted to be from the purported signing party (i.e., authenticated) if decryption of the message with the corresponding public key is successful and the certificate holding the public key has not been revoked. Certificates [0036] A certificate is a means by which a public key can be stored and distributed over unsecured media without danger of undetectable manipulation. In practice, X.509 certificates are commonly used. X.509 is an ANSI standard which defines a certificate data structure. A public key certificate is a data structure consisting of a data part and a signature part. The data part includes a public key and a string identifying the party associated with that public key. The data part can also include a validity time period of the public key. For example, the data part can hold a published time and an expiration time. In addition, the data part can hold a serial number of the certificate or public key. The signature part consists of the digital signature of a certification authority; the signature part is the result of a function computed over (based on) the data part. [0037] A digital signature is authentication data which binds the identity of the signer to the data part. Signing transforms the data part and some secret information held by the signer into the signature. A CA is a trusted third party whose signature on the certificate vouches for the authenticity of the public key. Because the CA is trusted, the certificate allows transfer of the CA's trust in the identified party such that the certificate recipient can securely place their trust in the identified party. If the private key of the identified party becomes compromised, all holders of the certificate need to be notified so that they will no longer trust messages signed with the corresponding public key of the identified party. This notification can be done, for example, with a CRL or detected by a negative result from OCSP. [0038] OCSP is an Internet Engineering Task Force (IETF) protocol specified by RFC 6960. OCSP stapling (see IETF RFC 6066) is an extension of OCSP. OCSP stapling allows the presenter of a certificate to provide a timestamped OCSP response signed by a CA to the party seeking the certificate. An SE can use OCSP stapling as a trust verification technique in order to reduce or eliminate storage of trusted certificates (public keys) and/or CRLs. The party wishing to communicate (the certificate presenter) with the SE may supply an OCSP stapling message to the SE on an as-needed basis. Compromise or Expiry of a Certificate [0039] If a third party obtains the private key of a public key—private key pair, the security of the system is broken. This is because the third party can act as an imposter and sign messages with the private key as if the third party were the identified party associated with the public key. Harm can be limited by notifying communicating parties that the associated certificate is now revoked. Thus, there is a need to improve the security of PKI-secured communications performed by an SE since a server trusted by the SE may become compromised. Time [0040] Time-variant parameters which serve to distinguish one instance of something from another are sometimes called nonces, unique numbers, or non-repeating values. A nonce is a value used no more than once for the same purpose. Random numbers include pseudorandom numbers which are unpredictable to an adversary. A sequence number can serve as a unique number identifying a message. A sequence number can be a version number for a file. Sequence numbers are specific to a set of entities who follow a pre-defined policy for numbering. Timestamps can be used to implement time-limited access privileges. [0041] A user of a timestamp obtains a timestamp from a local clock and cryptographically binds it to a message. Upon receiving the timestamped message, a second party obtains the time from its own clock and subtracts the timestamp received. The message is valid if the timestamp difference is in an acceptable security window. The security of timestamp-based verification relies on use of a common time reference; this requires that the sender's clock and the recipient's clock be at least loosely synchronized. [0000] SE, eUICC [0042] One example of an SE is an embedded universal integrated circuit card (eUICC). A eUICC can host profiles. A profile is a combination of operator data and applications provisioned on an eUICC in a device for the purposes of providing services by an operator. A profile can contain one or more secure data used to prove identity. An eSIM is an example of a profile. An eSIM is an electronic subscriber identity module. [0043] An eUICC includes an operating system, and the operating system can include ability to provide authentication algorithms to network access applications associated with a given operator. The operating system also can include the ability to translate profile package data into an installed profile using a specific internal format of the eUICC. An ECASD provides secure storage of credentials required to support the security domains on eUICC. A controlling authority security domain (CASD) may also be referred to as a “key store” herein. SE Time Information [0044] In some embodiments provided herein, an SE stores time information in order to improve checking of secure materials. The time information is stored in a time information variable and the value of the time information variable at a given moment is a time information value. The actual time can be stored, for example in a numerical string “yyyymmddhhmmss” providing four decimal places for the year, “yyyy”, two for the month, two for the day of the month, two for the hour of the month, two for the minute of the hour and two for the second of the minute. In some embodiments, an SE may record a time information value as the value of an increasing counter. One example of an increasing counter controlled centrally may be referred to as an epoch. [0045] A CI or other CA may refresh the time information in the SE periodically. The refresh period, in some embodiments, is about one day. The refresh period is a security requirement. The refresh period, in some embodiments, is shorter than an average time between server compromise or average time between certificates expiring. The refresh period is sufficiently long to avoid unnecessary communication burden for the SE, and, for example, the CI. For example, on a daily basis, a CA or the CI may push a new time information value to the SE, in some embodiments. The SE, in some embodiments, pulls a new time information value from a CA or the CI. That is, the SE sends a message requesting a new time information value. [0046] The time information value received by an SE is signed by a CA. By implementation, time information signed by other trusted off-card entities (off-SE entities) may also be acceptable based on the SE configuration. Time information that is not under the signature of a trusted entity is not recognized or used by an SE. [0047] Distinct time information values, in some embodiments, are maintained in the SE for two or more CAs. For example, a first CA may send a first counter value to the SE and a second CA may send a second counter value to the SE. In some embodiments, a CI provides widespread time information and the SE maintains a single time information value. For example, a first CI may send an actual time value on a first day. In some embodiments, a second CI, different than the first CI, may send an actual time value on the first day or another day. [0048] In some embodiments, the time information value is updated on an opportunistic basis based on unrelated transactions between the SE and any trusted party. For example, any signed and verified time information from a CRL, OCSP, or OCSP stapling message can be used by the SE to update its time information. Since many transactions are unscheduled, these time information updates occur randomly or stochastically. The stochastic time information value update incurs no additional communication overhead because it occurs in parallel or in the background to an unrelated transaction. [0049] Time information, in some embodiments, is obtained over a trusted interface between the SE and a local component of the device. Epoch [0050] A CA may increase an epoch value; this will be reflected in subsequently issued certificates. As discussed above, an epoch value may be a counter type of time information. In some embodiments, the epoch is increased when a new certificate is issued. The SE can verify that the epoch in a received certificate is higher than that of a current certificate, before storing the new certificate. Revoking certificates in an SE can be challenging due to various SE resource constraints; i.e., processing a large revocation list may be infeasible for an SE. To avoid maintaining revocation lists, some certificates can be associated with an epoch. If a CA is compromised, the CI (which may also be referred to as a root CA) creates a unique unused epoch value and reissues certificates for all legitimate entities with the new epoch value in each new certificate. At the SE, the SE saves the expected epoch of various servers in non-volatile memory. When a received certificate contains a higher epoch, the SE may update the corresponding epoch and reject any future certificates with a lower epoch; i.e., the SE will reject rogue servers possessing certificates that have not been signed since the CA was compromised. SE Methods [0051] Maintenance of a time information variable or parameter in an SE allows the SE to perform a certificate expiration and/or publication date and/or time check. For example, if an expiration time value in a certificate is earlier than the time information value stored in the time information variable, in some embodiments, the SE may i) discard the certificate, ii) request a new certificate, iii) use the OCSP protocol, iv) use the OCSP stapling protocol, and/or v) rely on an epoch value as part of authenticating communications from the certificate holder. [0052] The SE, in some embodiments, may compare an incoming certificate or related message (e.g. OCSP stapling) time with the time information stored in the SE to ensure validity. The time checking can be done in several different ways. The purpose of the time checking is to check that the examined item (certificate, CRL, OCSP stapled message, or other secure message) is up-to-date, current, fresh, and/or not expired. The essential aspect of the time check is to measure a difference in time between the time information in the SE and a time value of some kind associated with the examined item. A thresholding measurement or acceptable difference may be indicated by use of a security window. A certificate, CRL, OCSP stapled message, or other secure message may be referred to herein as secure material. [0053] For time information of an actual (calendar) type, the difference may be computed as follows. Let TM be the time information in the SE. Let TC be general time information parsed or read from the examined item (secure material). Let TDexp be the difference taken as TDexp=TM−TCexp, where TC may be denoted TCexp, and TCexp is an expiration time. The TDexp value, a difference, will be negative if the expiration time is in the future, that is, occurs later than the SE time information, TM. Let TDpub be a difference taken as TDpub=TM−TCpub. Where TCpub is a publication time. The value of TDpub will in general be positive. In some embodiments, if TC represents an expiration time, TCexp, and TD is zero or positive, the SE discards the examined item and does not process any messages using it because the expiration time is not in the future. For example, if the examined item is a certificate for a particular user identity and TD is zero or positive, the SE discards the certificate, and optionally, requests a new certificate for the particular user identity. [0054] In some embodiments, TCpub may be the issuance time of the certificate or the CRL/OCSP published time in a response message. A positive TDpub value may be considered more reliable and a negative TDpub value may be considered unreliable in typical cases. However due to possible TM update delays, TDpub may be negative; a negative value of TDpub of small magnitude can be accepted within a security window based on configuration. It is then configurable whether TM should be updated by using TCpub as new time information based on the trust level of the source of the obtained TCpub value. [0055] The extent of the age of the examined item versus TM can be determined with the security window. Let the value of the security window be represented by a positive value TW. Determine TDexp as above. If TDexp<TW, then the time associated with the examined item, in some embodiments, is deemed to be within the security window. If TDexp is greater than or equal to TW, then the examined item is considered a security risk, and the examined item will be discarded because the expiry time was too long ago. In some embodiments, TDpub is determined as above. The expected outcome is that TDpub>0. However, there may be a lag in updating TM, such that a small negative value of TDpub would not indicate a fault. Thus, if 0<−TDpub<TW is true for TDpub<0, then the examined item is not considered a security risk solely based on the published time TCpub. The certificate may be identified as a security risk for other reasons. [0056] In general a calculated time difference is referred to herein as TD. Whether the time difference corresponds to a publication time, expiration time, or another time is determined by the nature of the time obtained from the security material. In any case, TM can be used for a security check to provide a TD to compare with an appropriate security window TW as described above. [0057] For time information of a counter type, the difference may be computed as follows. Let TMcounter be the time information in the SE. Let TCcounter_exp be the time information parsed or read from the examined item (secure material) corresponding to an expiration time. Let TDcounter_exp be the difference taken as TDcounter_exp =TMcounter−TCcounter_exp. If TCcounter_exp is a current version number or an epoch value, then this difference will be zero if the examined item is current or up-to-date. In some embodiments, if TDcounter_exp is positive, the SE discards the examined item and does not process any messages using it. For example, if the examined item is a certificate for a particular user identity and TDcounter_exp is positive, the SE discards the certificate, and optionally, requests a new certificate for the particular user identity. [0058] Corresponding calculations for a certificate publication time using counter type time information, in some embodiments, follow a similar approach. That is, TDcounter_pub=TMcounter−TCcounter_pub, and the same reasoning as applied for TCpub, TDpub, and TW above. For example, it is expected that TDcounter_pub will be positive. Small negative values of 0<−TDcounter_pub<TWcounter are not considered a security risk solely based on TCcounter_pub. [0059] The SE may use the stored time information, in some embodiments, together with revocation schemes such as CRL and OCSP. For example, upon receiving a CRL, the SE may i) immediately place on an untrusted list identities of servers whose certificates are identified in the CRL, and ii) continue to rely on the certificates of servers not identified in the CRL. In some embodiments, the SE receives an update to an epoch value from a CI, for example. The SE then, in some embodiments, does not communicate with the servers identified in the CRL until new certificates for those servers arrive at the SE with the updated epoch value. This allows smooth transition between new and old epoch update and yet allow manageable size of CRL stored on the client side. [0060] In some embodiments, an SE obtains an OCSP stapling message including a time at which the CA timestamped and signed the OCSP response. The SE may then compare the time information value stored in the SE against the signed timestamp of the OCSP stapling message (OCSP stapling timestamp). If the difference of the SE time information value and the OCSP stapling timestamp is within an acceptable window, the SE, in some embodiments, will consider the associated certificate to be trustworthy (i.e. not stale, not compromised, not revoked). [0061] Also, the SE may check the epoch in addition to checking the OCSP stapling timestamp. Depending on the security required, the SE may trust the certificate associated with the sender if either the difference of the SE time information value and the OCSP stapling timestamp is within a security window or if the epoch value associated with the received OCSP stapling message matches a current epoch value maintained by the SE. In some embodiments, the SE may require that all indications concerning the OCSP stapling message are not stale. That is, the SE may only process the message if the difference of the SE time information value and the OCSP stapling timestamp is within the security window and the epoch value associated with the received message matches a current epoch value maintained by the SE. [0062] Periodically, or after updating the timestamp information, the SE may perform a cleanup operation on the certificates and/or CRL list store in the SE. For example, after updating the time information on the SE, the SE operating system (OS) may identify information that is stale based on being too old compared to the time information value. For example, any certificate with an expiration time before an actual time stored as time information can be discarded and/or the associated server moved to an untrusted list. Any certificates which are vouched-for based on OCSP stapling can be discarded if a difference between the SE time information value and the timestamp included in the OCSP stapling message falls outside of a security window. The window may, for example, correspond to one day, one week, or one month. [0063] In this way, trusted and stored public keys and certificates that have expired can be deleted from the memory or key store of the SE. Also, when a CRL list or entries in the CRL are no longer valid, the CRL list can be corrected by recognizing servers which have obtained new certificates from, for example, a CI. In addition, an untrusted list can be updated with servers whose certificates have expired or who fail the OCSP or OCSP stapling protocol. Servers which are associated with certificates having time information or OCSP information or OCSP stapling information which falls inside of a security window when compared with the SE time information may be listed on a trusted list of servers. [0064] Embodiments will now be described with regard to the figures. Obtaining and Using Time Information, Overview [0065] FIG. 1 illustrates an exemplary system 100 for an SE 110 obtaining and using time information 102 . The time information 102 corresponds to a time information value stored in a time information variable in the SE 110 . The time information variable can be, for example, an addressed location in a memory of SE 110 . SE 110 in some embodiments possesses a public key-private key pair 106 / 104 . Exemplary stored certificates 112 and 114 are shown stored in the SE 110 . The SE 110 may host an eSIM 116 . The SE 110 may reside in a device 118 . The device 118 , in some embodiments, is a wireless communication device. In the exemplary arrangement 100 , a CA 120 sends a certificate 122 to the SE 110 . The certificate 122 is associated with an identity of a server 130 . The server 130 associated with a public key-private key pair 132 / 134 sends a message 136 signed with the public key 132 to the SE 110 . [0066] The SE 110 , in some embodiments, verifies the signature of the CA 120 on the certificate 122 . If the verification is successful, that is, authentication of the certificate using the public key of CA 120 produces a correct result, then the SE 110 parses from the message received with the certificate 122 a time information value. In some embodiments, the SE 110 then checks the stored certificates 112 and 114 to see if they have expired. [0067] The SE 110 can then determine, for example, if the time information value is for the CA 120 only (i.e., corresponds uniquely to CA 120 ) or is a widespread or quasi-global time value which is at least loosely synchronized with many CAs, CIs, and servers. Time information 102 of FIG. 1 represents, in some embodiments, several storage locations or time variables. Based on the determination, the SE 110 saves the time value as time information 102 . [0068] In some embodiments, the SE 110 verifies the signature of the CA 120 on the certificate 122 and compares an expiration time of the certificate 122 with the time information 102 . The comparison may be done, for example, by subtracting the expiration time of the certificate 122 from the value of time information 102 . For this type of comparison, the time information 102 may represent, for example, actual calendar time. If the expiration of the certificate is in the future with respect to the time information, that is the result of the subtraction is negative, then the certificate 122 is adjudged to be unexpired and valid. If the publication time of the certificate is in the future with respect to the time information, that is the result is positive but less than a fixed amount of time referred to herein as a security window, then the certificate 122 could also be adjudged to be valid. If the result is positive and not within the security window then the certificate 122 is adjudged to be stale or expired and not to be trusted. When the certificate 122 is determined to be untrusted, SE 110 will not process the message 136 because the SE 110 cannot be confident that the message 136 is indeed from the server 130 . Possibly a mischievous or adversarial or computer-hacker entity has sent certificate 122 and message 136 to SE 110 ; careful security requires that message 136 in this case not be processed. [0069] The SE 110 can request a new, updated certificate for the server 130 . The new certificate will be based on a new public key-private key pair (not on the public key-private key pair 132 / 134 ). Obtaining and Using Time Information, Exemplary Logic [0070] FIG. 2 illustrates exemplary logic 200 for obtaining and using time information. At 212 an SE receives time information in a signed message from a CA and authenticates the message at 214 . The time information is stored in the SE at 216 when the authentication is successful. The SE then performs a cleanup operation at 218 . This cleanup operation may be done whenever a new time value is obtained, or when a duration of time is estimated to have passed based on the new time information and a time of a previous cleanup operation. The duration of time may be estimated by i) storing a time value each time a cleanup is done and ii) subtracting the previous time value from the new time value. In the exemplary logic 200 , some time may pass between 218 and 220 . 220 indicates a message reception from a CA, possibly unscheduled, of a certificate for a server. At 222 , the SE checks an expiration time of the received certificate against the time value stored in the SE. If the certificate has expired (not shown), the SE will discard it. Some time may pass between 222 and 224 . At 224 , the SE receives a CRL, possibly unscheduled, from a CI. At 226 , the SE does an authentication check on the CRL. If the signature of the received CRL proves to be that of the CI, then the SE proceeds to parse out time information from the CRL or CRL message from the CI and update the stored time information. Push, Pull, Opportunistic, and Local Time Learning [0071] FIG. 3 illustrates three exemplary approaches for the SE 110 to learn or obtain time information. FIG. 3 is a message flow diagram with time advancing from top to bottom. Parties communicating with each other or communication endpoints are shown across the top of the figure. The end points of the messages are represented as solid vertical lines below the party labels. [0072] The first method of obtaining time is a push event (this portion of the drawing is annotated “PUSH”). This is indicated as Event 1 and it is initiated, for example, by a CI 302 or the CA 120 . Time information is pushed to SE 110 in a message indicated by the left-to-right arrow denoted with the number 10 (“message 10 ”). When an SE OS 310 receives the pushed time information, it performs actions denoted as Action 11 . The actions include authenticating message 10 and determining if the received time is later than the stored time. If the message 10 is authentic and the received time is later than the stored time, then the variable corresponding to time information 102 in an SE memory 312 or in an ECASD 314 is updated with the received time by message 12 . The next read of the SE memory 312 or ECASD for time information 102 will produce a value corresponding to the time information received in the message 12 . [0073] The time axis is marked with a broken wavy line before the next event, Event 2 . Event 2 corresponds to the SE initiating a request for time information with a message 20 ; this is a pull event. The CI 302 or CA 120 , for example, responds to message 20 with message 22 . Action 21 , similar to Action 11 , represents authenticating and checking the received time. Internal SE message 24 represents storing the new time information value in time information 102 . [0074] An opportunistic or stochastic method of learning time is triggered by unscheduled Event 3 . Server 130 , for example, initiates an unscheduled PKI challenge response sequence with SE 110 for some purpose unrelated to time information 102 . Possibly the server 130 is unaware of the existence of a security time feature in the SE 110 . Possibly the PKI challenge response is due to a user of the device 118 . In any case, a message 30 arrives at the SE OS 310 bearing, incidentally, time information. The SE OS 310 parses out the time information and performs action 31 , which is similar to actions 21 and 11 (authenticate, possibly check if the time is newer than the old time). If appropriate, SE OS 310 updates time information 102 using internal message 32 . After Action 31 (or before, not shown) Action 33 and messages 34 may occur corresponding to the purpose of Event 3 and message 30 from the point of view of the server 130 . [0075] The SE, in some embodiments, receives the time information via a trusted interface with a local component of the device 118 . A component of device 118 may initiate an Event 4 as shown in FIG. 3 (annotated “TRUSTED INTERFACE”). Event 4 may also be responsive to a pull request (not shown) similar to message 20 , but directed to a local component of the device 118 . A message 40 arrives at the SE OS 310 carrying time information. SE OS 310 processes the message at Action 41 . Message 42 updates time information 102 using internal message 42 . Some SE Variables [0076] FIGS. 4A-4C illustrate various time and security-related variables, parameters and values in the SE 110 . [0077] FIG. 4A provides various time information formats and types, in some embodiments. The time information of messages 10 , 22 , and 30 of FIG. 3 may be of a counter type represented as time information, counter type 412 in FIG. 4A . [0078] If a difference between a received time information value indicated as a counter type in a certificate being evaluated by the SE 110 and time information, counter type 412 is greater than a security window for counter types, the SE 110 can regard the certificate being evaluated as expired. The methods of time checking using counter type (and actual type) time information as discussed in the section “SE Methods” above may be applied in any of the embodiments described herein. [0079] Alternatively, any one of the time information of message 10 , or of the time information of message 22 , of the time information of message 30 may be an actual calendar time type as indicated by time information, actual type 414 in FIG. 4A . If a difference between a received time information value indicated as an actual type in a certificate being evaluated by the SE 110 and time information, actual type 412 is greater than a security window for actual types, the SE 110 can regard the certificate being evaluated as expired. [0080] If the time information is unique to a CA, a portion of time information 102 may be stored in a variable represented herein by time information, per CA 416 in FIG. 4A . Finally, if time information is for a set of CAs, or, for example, global or quasi-global, a portion of time information 102 may be stored in a variable represented herein by time information, per set of CAs 418 . [0081] FIG. 4B represents two summary forms of information that, in some embodiments, the SE 110 may maintain. Trusted list 432 represents a list of entities, servers, CAs, or CIs, for example, which the SE 110 trusts. For example, presence of an entity identity or user identity on trusted list 432 can indicate to the SE 110 that a certificate for that entity is stored in the SE 110 and has not been found to be expired or revoked. Untrusted list 434 can represent a list of entities, servers, CAs, or CIs, for example, which the SE 110 does not trust. For example, presence of an entity identity or user identity on untrusted list 434 can indicate to the SE 110 that no valid unexpired, or unrevoked certificate for that entity is stored in the SE 110 . SE 110 , in some embodiments, updates trusted list 432 and untrusted list 434 based on events. For example, a given entity identified on the untrusted list 434 may become a trusted entity if a trusted third party such as a CI provides a signed certificate for the given entity. [0082] FIG. 4C illustrates exemplary variables for checking certificates. Epoch 452 represents a present epoch value, like a version number, which is current or up-to-date. A certificate received by the SE 110 which includes an epoch value older than epoch 452 may be considered to be expired. The variable indicated as OCSP stapled message 454 indicates a current or up-to-date voucher message from a CA indicating that a certificate of some entity is valid. The time information 102 can be used for detecting expired certificates. [0083] FIG. 5 provides an example of a PKI environment. The double-headed arrows of FIG. 5 are not limited to particular messages but represent example connectivity. The CI 302 is shown at the top of the figure and represents a trusted third party. Trust is shared with other entities by means of their trust in CI 302 . For example, the CI 302 can provide via message exchange 524 a signed certificate to the CA 120 . Similarly, the CI 302 can provide via message exchange 554 a signed certificate to a CA 520 . The CA 120 can prove to server 130 that it is trustworthy using the certificate that the CA 120 was provided by the CI 302 . The CA 120 , may for example, provide a certificate to the server 130 including the public key 132 , represented, for example, by messages 522 . Thus there is a chain of certificates leading from the root certificate of CI 302 to the certificate of CA 120 to the certificate of server 130 . The SE 110 may, for example, obtain a certificate from the CI 302 via messages 530 at the time of manufacture. Such a certificate would include the public key 106 of the SE 110 . [0084] The server 130 , the CA 120 , the CI 302 , the CA 520 and/or the server 530 , may provide time information to the SE 102 via messages 510 , 520 , 530 , 540 , and 550 , respectively. [0085] Certificate 122 of FIG. 1 may pass in a message 520 from the CA 120 to the SE 110 , for example. The presence of certificate 122 in the SE 110 is indicated in FIG. 5 . Message 136 from the server 130 to the SE 110 may pass in a message 510 , for example. Similarly, the push, pull and opportunistic events Event 1 , Event 2 and Event 3 of FIG. 3 can occur among the entities indicated in FIG. 5 . The push and pull events can be scheduled; they are deterministic in the sense that messages can be sent purposefully at certain times to cause time information refresh. For example, a push event can be scheduled by a server, CA, or CI daily. The SE can schedule a pull event daily. The SE 110 thus maintains useful time information 102 . The time information 102 can be, for example, counter type 412 and/or actual type 414 . The time information 102 can be, for example, per CA 416 and/or per set of CAs 418 . The SE 110 may also have, for example, a value in Epoch 452 and an OCSP stapled message 454 associated with, for example, the server 530 . [0086] FIG. 6 illustrates an example situation among the entities of FIG. 5 when the PKI credentials of server 130 have been compromised as indicated by the star figure juxtaposed on server 130 . In this case, a CA or CI will produce a CRL identifying the server 130 and distribute the CRL. The server 530 has not been compromised, and so is not listed in the CRL. Based on a satisfactory check on the expiration, epoch, or publication time of the CRL, SE 110 can process the CRL and hence treat the certificate 122 as untrustworthy as explained below. [0087] In FIG. 6 , certificate 122 holding public key 132 of server 130 is now unsuitable to be part of a chain of certificates all the way to the trusted party CI 302 . Successfully decrypting, by the SE 110 , a message signed with private key 134 using public key 132 no longer proves authentication. [0088] After receiving the CRL, the SE 110 can evaluate the CRL using time information 102 . As one example time check, after authenticating the CRL, the SE 110 can determine a difference between a time value parsed from the CRL and the value of the time information 102 . If the difference indicates that the CRL time value is within a security window, the SE 110 can place confidence in the CRL and process it. Processing the CRL can include finding the certificate 122 to be untrustworthy and thus placing the identity of the server 130 on the untrusted list 432 and/or removing the identity of the server 130 from the trusted list 434 . [0089] In some embodiments, the CI 302 can initiate a migration of the PKI environment of FIG. 6 to a new epoch value after the compromise of the server 130 . This will take some time. Perhaps several days such as seven days. While the new epoch value is propagating to the various entities and new certificates are issued indicating the new epoch value, the SE 110 may, for example, evaluate the legacy certificates of entities using OCSP stapling and the time information 102 . For example, the SE 110 may possess a certificate for the server 530 with the old epoch value and the OCSP stapled message 454 may correspond to a certification of the server 530 . If the identity of the server 530 is not on the CRL and the SE 110 either has a certificate of the server 530 with the most recent epoch value before the update, or the SE 110 determines that a difference between the time of the OCSP stapled message 454 for the server 530 and the time information 102 is within a security window, then the SE 110 can continue to use the certificate it has for the server 530 ; otherwise, the SE 110 can place the identity of the server 530 on the untrusted list 434 . [0090] Alternatively, the SE 110 can trust the existing certificate of the server 530 if i) the existing certificate for the server 530 has the most recent epoch value, and ii) the difference of the time in the OCSP stapled message 454 and the time information is within the security window. The SE 110 does not trust any identity listed on the CRL until new certificates are issued for those entities or user identifiers listed on the CRL. The SE 110 , in some embodiments, trusts an entity not listed on the CRL which has the new epoch value in a new certificate issued after the CRL. Logic for Obtaining and Using Time Information [0091] FIG. 7 illustrates exemplary logic 700 for obtaining time information. At 702 an SE receives a signed message including a time information value. At 704 , the SE determines whether the message is authentic. If not, the message is ignored as indicated at 714 . If the message is authentic, at 706 the SE retrieves or parses a time information value from the message. At 708 , the SE stores the time information value in a time information variable in the SE. At 710 , the SE determines whether it is time for a cleanup of security materials on the SE. If it is time for a cleanup, at 712 the SE identifies and removes security materials such as public keys and/or certificates whose expiration times are earlier than the time indicated by the time information value. Logic for Processing a CRL Using Time Information [0092] FIG. 8 illustrates exemplary logic 800 for processing a CRL using time information at an SE. At 802 , the SE receives from a CI a CRL including a list of user identifies or serial numbers corresponding to revoked certificates. At 804 , the SE determines whether the signature on the CRL is authentic. If the signature is not authentic, the CRL is ignored as indicated at 814 . If the signature is authentic, the SE retrieves at 806 a time information variable from a time information variable in the SE. At 808 the SE computes a difference between the time information value and a time value parsed or read from the CRL. If the difference falls within a security window at 810 , the SE proceeds to process the CRL at 812 . At 812 , the SE may, for example, remove the entity names found in the CRL from a trusted list and/or add the entity names found in the CRL to an untrusted list. Some SE Details [0093] FIG. 9 illustrates some details of the SE 110 in a system 900 . In an exemplary embodiment, the SE 110 may be an eUICC. The SE OS 310 may be, for example, in communication with a mobile network operator (MNO) 910 . Device 118 can include, for example, a local component 906 in communication with the SE OS 310 over a trusted interface 916 . The device 118 can also include, in some embodiments, a user interface 104 . The SE 110 can include a profile 116 . The profile 116 can include an ISD-P 922 . An ISD-P (issuer security domain-profile) can host a unique profile within an eUICC. The ISD-P is a secure container or security domain for the hosting of the profile. The ISD-P is used for profile download and installation based on a received bound profile package. The profile 116 can also include an MNO-SD 924 . An MNO-SD is the representative on the SE 110 of an MNO providing services to an end user of the device 118 (for example, MNO 910 ). The profile 116 can also include a file system 926 and a CASD or key store 930 . Also illustrated are memory 312 and ECASD 314 . Exemplary Network System [0094] FIG. 10 illustrates an exemplary network system 1000 . The SE 110 in the device 118 can be in communication with i) an end user 1030 through interface or connection 1018 , with ii) the Internet 1040 through a wired connection 1016 , and with iii) a wireless base station 1060 through a radio connection 1066 . Wireless base station 1060 is able to communicate through the Internet 1040 as shown by connection 1050 . The CA 120 , the server 130 , and/or the CI 302 , for example, can communicate with the SE 110 through the Internet 1040 . Representative Exemplary Apparatus [0095] FIG. 11 illustrates in block diagram format an exemplary computing device 1100 that can be used to implement the various components and techniques described herein, according to some embodiments. In particular, the detailed view of the exemplary computing device 1100 illustrates various components that can be included in the device 118 , the SE 110 and the servers, CAs, and CI illustrated in one or more of FIGS. 1, 3, 4A-4C, 5-6, and 9-10 . As shown in FIG. 11 , the computing device 1100 can include a processor 1102 that represents a microprocessor or controller for controlling the overall operation of computing device 1100 . The computing device 1100 can also include a user input device 1108 that allows a user of the computing device 1100 to interact with the computing device 1100 . For example, the user input device 1108 can take a variety of forms, such as a button, keypad, dial, touch screen, audio input interface, visual/image capture input interface, input in the form of sensor data, etc. Still further, the computing device 1100 can include a display 1110 (screen display) that can be controlled by the processor 1102 to display information to the user (for example, information relating to incoming, outgoing, or active communication session). A data bus 1116 can facilitate data transfer between at least a storage device 1140 , the processor 1102 , and a controller 1113 . The controller 1113 can be used to interface with and control different equipment through an equipment control bus 1114 . The computing device 1100 can also include a network/bus interface 1111 that couples to a data link 1112 . In the case of a wireless connection, the network/bus interface 1111 can include wireless circuitry, such as a wireless transceiver and/or baseband processor. [0096] The computing device 1100 also includes a storage device 1140 , which can include a single storage or a plurality of storages (e.g., hard drives), and includes a storage management module that manages one or more partitions within the storage device 1140 . In some embodiments, storage device 1140 can include flash memory, semiconductor (solid state) memory or the like. The computing device 1100 can also include an SE 1150 . The computing device 1100 can also include a Random Access Memory (“RAM”) 1120 and a Read-Only Memory (“ROM”) 1122 . The ROM 1122 can store programs, utilities or processes to be executed in a non-volatile manner. The RAM 1120 can provide volatile data storage, and stores instructions related to the operation of the computing device 1100 . [0097] The various aspects, embodiments, implementations or features of the described embodiments can be used separately or in any combination. Various aspects of the described embodiments can be implemented by software, hardware or a combination of hardware and software. The described embodiments can also be embodied as computer readable code on a computer readable medium. The computer readable medium is any data storage device that can store data which can thereafter be read by a computer system. Examples of the computer readable medium include read-only memory, random-access memory, CD-ROMs, DVDs, magnetic tape, hard storage drives, solid state drives, and optical data storage devices. The computer readable medium can also be distributed over network-coupled computer systems so that the computer readable code is stored and executed in a distributed fashion. [0098] The foregoing description, for purposes of explanation, used specific nomenclature to provide a thorough understanding of the described embodiments. However, it will be apparent to one skilled in the art that the specific details are not required in order to practice the described embodiments. Thus, the foregoing descriptions of specific embodiments are presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the described embodiments to the precise forms disclosed. It will be apparent to one of ordinary skill in the art that many modifications and variations are possible in view of the above teachings.
A secure element (SE) with a notion of time useful for checking secure items is disclosed herein. Use of Public Key Infrastructure (PKI) with secure elements is improved by verifying secure items used by an SE. Methods of obtaining time information by the SE include push, pull, opportunistic, and local interface methods. The SE uses the time information to evaluate arriving and stored public key certificates and to discard those which fail the evaluation. The SE, in some embodiments, uses the time information in cooperation with certificate revocation lists (CRLs) and/or online certificate status protocol (OCSP) stapling procedures.
60,891
This application is a continuation of application Ser. No. 08/119,901 filed Sep. 13, 1993, now abandoned, which is a continuation of application Ser. No. 07/796,668 filed Nov. 25, 1991, now abandoned. TECHNICAL FIELD The present invention relates to an automotive interior component such as an automotive door trim and a method for fabricating the same. BACKGROUND OF THE INVENTION Typically, to the end of improving the comfort of the passenger compartment of an automobile, the grade of the material for the interior components such as automotive door trims is improved or ornamental materials such as cloth and carpet are attached to the surface of the door trims. FIGS. 14 and 15 show perspective and sectional views of an automotive door trim, and this conventional door trim 1 essentially consists of a door trim main body 4 consisting of a core member 2 formed into a desired shape, and a surface skin member 3 which is integrally attached to the surface of the resin core member 2, and an attachment member 5 which is mounted on a suitable location of the surface of the door trim main body 4 for ornamental purpose. As shown in FIG. 15, the attachment member 5 is formed by laminating an attachment pad member 5b consisting of such material as urethane foam having a suitable cushioning capability over the surface of an attachment core member 5a having a supporting capability, covering the outer surface of this assembly with an attachment surface skin member 5c made of such materials as synthetic leather and cloth, and folding back a peripheral edge of the attachment surface skin member 5c over a peripheral part of the reverse surface of the attachment core member 5a. To attach the attachment member 5 having such a structure to the door trim main body 4, pawls 6 made of steel plate are provided in the attachment core member 6 of the attachment member 5, and corresponding mounting holes 4a are provided in the door trim main body 4. The attachment member 5 is attached to the door trim main body 4 by inserting the pawls in the mounting holes 4a and bending the tips of the pawls 6. In this conventional automotive door trim 1, since the pawls 6 provided in the attachment core member 5a are inserted in the mounting holes 4a of the door trim main body 4 and the pawls 6 are bent for securing purpose, it was necessary to provide the mounting holes 4a in positions precisely corresponding to the pawls 6 of the attachment member 5, and this contributed to the increase in the cost of the product due to the complication of the fabrication steps. Further, since inserting the pawls provided in the attachment member 5 in the mounting holes 4a of the door trim main body 4 is required to be carried out without the benefit of any visual aid, the work efficiency is extremely low. The need for the step to bend the pawls presents an additional complication to the fabrication process. Furthermore, the pawls 6 are not capable of accurately joining the attachment member 5 to the door trim main body 4, and the gap which often develops between the peripheral part of the attachment member 5 and the door trim main body 4 impairs the appearance of the door trim 1. In an extreme case, the attachment member 5 may become so displaced from its proper position due to vibrations of the automobile during its motion that the attachment member 5 may be placed in an unstable condition. BRIEF SUMMARY OF THE INVENTION In view of such problems of the prior art, an object of the present invention is to provide an automotive interior component such as an automotive door trim integrally combining a main body fabricated by a mold press forming process with an attachment member which can be efficiently fabricated. A second object of the present invention is to provide such an automotive interior component which is provided with a favorable appearance owing to the accurate positioning of the attachment member. A third object of the present invention is to provide a method for efficiently fabricating such an automotive interior component. These and other objects of the present invention can be accomplished by providing an automotive interior component such as an automotive door trim comprising a main body integrally combining a resin core member and a surface skin member by a mold press forming process and an attachment member attached to a part of the main body, wherein: the attachment member is attached to the main body by way of a connecting part of the resin core member still at least in semi molten state as a result of the mold press forming process, the connecting part eventually solidifying so as to achieve a secure engagement between the resin core member and the attachment member. The connecting part may consist of an extension of the resin core member which is pushed out of openings provided in the surface skin member and adhered to the attachment member. In this case, the extension may be adhered to an attachment core member of the attachment member having a resin compatibility or to an attachment surface skin member made of fabric sheet so as to ensure a secure attachment. Alternatively, the connecting part may consist of parts of the resin core member into which engagement pawls provided in the attachment member, in particular, an attachment core member thereof are penetrated through the surface skin member. In this case, the engagement pawls may be provided with notches or openings, or may be slanted so as to ensure a secure anchoring of the engagement pawls in the resin core member of the main body. Preferably, the attachment member comprises an attachment core member consisting of metallic plate, and the engagement pawls are formed in the attachment core member by cutting out tabs from the metallic plate and bending them. In either case, solidification of the connecting parts completes the attachment of the automotive door trim. Thus, the process of mounting the attachment member is simplified, and accurate positioning of the attachment member can be achieved at the same time. BRIEF DESCRIPTION OF THE DRAWINGS Now the present invention is described in the following in terms of specific embodiments with reference to the appended drawings, in which: FIG. 1 is a perspective view showing an automotive door trim to which the present invention is applied; FIG. 2 is a sectional view taken along line II--II of FIG. 1; FIG. 3 is a sectional view showing the structure of a mold press forming device which may be used to fabricate the automotive door trim according to the method of the present invention; FIG. 4 is a sectional view showing a step of setting up and supplying the material; FIG. 5 is a sectional view showing a step of mold press forming; FIG. 6 is a sectional view similar to FIG. 2 showing a second embodiment of the present invention; FIG. 7 is a sectional view similar to FIG. 2 showing a third embodiment of the present invention; FIG. 8 is a sectional view showing the structure of a mold press forming device which may be used to fabricate the third embodiment of the automotive door trim according the present invention; FIG. 9 and 10 are views similar to FIGS. 4 and 5, respectively, showing different steps of the operation of the device shown in FIG. 8; FIG. 11 is a sectional view of the attachment member according to a fourth embodiment of the present invention; FIGS. 12 and 13 are views similar to FIG. 11 showing different embodiments of the means for preventing the disengagement of the engagement pawls from the resin core member; FIG. 14 is a perspective view showing a conventional automotive door trim; FIG. 15 is a sectional view taken along line XV--XV of FIG. 14. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to FIGS. 1 and 2, the automotive door trim 10 essentially consists of a door trim main body 20, and an attachment member 30 mounted on a suitable part of the surface of the door trim member 20. Specifically, the door trim main body 20 consists of a resin core member 21 formed into a required shape by a mold press forming, and a surface skin member 22 integrally attached over the surface of the resin core member 21. The resin core member 21 is made of composite resin material consisting of polypropylene mixed with a filler material such as talc so that a desired moldability, low cost and high mechanical strength may be achieved. The surface skin member may typically consist of a sheet such as a PVC sheet mixed with ABS resin laminated with a layer of polypropylene foam or polyethylene foam. In the attachment member 30, an attachment pad member 32 such as polyurethane foam is laminated over the surface of an attachment core member 31 such as hard board, and an attachment surface skin member 33 made of such materials as cloth and synthetic leather is placed over the outer surface of this assembly with a peripheral part of the attachment surface skin member 33 folded back onto the reverse surface of the attachment core member 31. Further, to achieve a favorable adhesion to the door trim main body 20, polyolefin film 34 is laminated over the reverse surface of the attachment core member 31. The door trim main body 20 and the attachment member 30 are securely attached to each other since the resin core member 21 and the polyolefin film 34 on the reverse surface of the attachment core member 31 are securely joined together through a favorable resin compatibility by way of a plurality of openings 23 provided in the surface skin member 22. Therefore, according to the structure of the automotive door trim 10 of the present invention, it is possible to omit the pawls for engagement which were used for mounting the attachment member by being bent in the conventional structure, and the attachment member 30 can be mounted without involving any wobbling or dislocation. FIG. 3 is a sectional view showing the structure of the device for mold press forming which can be employed for carrying out the method of the present invention, and this molding device comprises a lower die 40 for mold press forming and an upper die 50 for mold press forming which is located above the lower die and provided with a substantially same die surface. The upper die 50 can be moved vertically by a lifting device not shown in the drawings, and can be engaged with the lower die 40 defining a small gap therebetween. An extruder 41 is attached to this lower die 40 for mold press forming, and the lower die 40 is provided with gates 42 for distributing the resin material in semi molten state from the extruder 41 over the die surface of the lower die 40. An annular support frame 60 is provided between the upper and lower dies 40 and 50 for mold press forming to support the peripheral part of the surface skin member 22. The upper die 50 for mold press forming is provided with an attachment member retaining means for setting up the attachment member 30. According to the present embodiment, the retaining means consists of a plurality of needles 51 for retaining the attachment member 30, and the upper die 50 is provided with a guide wall for accurate positioning of the attachment member 30 on the die surface of the upper die 50. Now, referring to FIG. 4 and 5, the process of fabricating the automotive door trim 10 is described in the following. As shown in FIG. 4, with the upper and lower dies 40 and 50 for mold press forming opened up, the peripheral part of the surface skin member 22 is retained by the support frame 60, and is heated by a heating device not shown in the drawings. The temperature condition of this heating process may vary depending on the material. In the case of a laminated sheet consisting of a PVC sheet lined with polyethylene foam, the surface temperature of the surface skin member 22 may be in the range of 100° to 120° C. In the cases of a simple PVC sheet and a simple foamed PVC sheet, the surface temperature of the surface skin member 22 may be in the range of 80° to 100° C. Then, the attachment member 30 is placed on the upper die 50 for mold press forming as illustrated in FIG. 4. Substantially at the same time as setting up the surface skin member 22 and the attachment member 30, composite PP resin material 70 in semi molten state is distributed over the die surface of the lower die 40 for mold press forming from three gates 42 provided in suitable locations. In this material setting up step, the openings 23 provided in the surface skin member 22 are located in a region spaced inwardly 5 to 20 mm from the peripheral edge of the attachment member 30, and are each 10 mm in diameter and distributed at the pitch of 50 to 100 mm. These openings 23 may be formed either before or after the surface skin member 22 is retained by the retaining frame 60. Thereafter, the upper die 50 carrying the attachment member 30 is lowered and the upper and lower dies for mold press forming are engaged to each other leaving a prescribed clearance therebetween. The press pressure in this step is 80 kg/cm 2 and the time duration of pressure application is 40 seconds. By this mold press forming, the resin material 70 is formed into a resin core member 21 of a desired shape, and a surface skin member 22 is integrally attached to the resin core member 21 so as to form a completed door trim main body 20. During this step, the resin material 70 is exposed to the surface of the door trim main body 20 through the openings 23 provided in the surface skin member 22 and comes into contact with the attachment core member 31 of the attachment member 30 so that the resin core member 21 and the attachment member 30 may be securely bonded or adhered to each other by virtue of the resin compatibility between the polyolefin film 34 and the resin material 70. When the molded object is removed from the upper and lower dies for mold press forming by opening them up, an automotive door trim 10 as illustrated in FIGS. 1 and 2 can be obtained. In this embodiment, the polyolefin film 34 was laminated over the reverse surface of the attachment core member 31 to improve its adhesion to the resin core member 21, but it is possible to omit the polyolefin film 34 if a resin plate containing polypropylene at least partly therein is used instead of the hard board as the material for the attachment resin core member 31 whereby the overall structure may be simplified. Further, as illustrated in FIG. 6, if a fabric sheet such as cloth is used for the attachment surface skin member 33 of the attachment member, and the folded-back portion 35 along the peripheral edge of the attachment surface skin member is made larger than in the previous embodiment so that the folded-back portion 35 of the attachment surface skin member 33 may be contacted by the resin material through the openings 23 of the surface skin member 22, the door trim member 20 and the attachment member 30 are securely joined to each other by an anchoring effect owing to intrusion of the resin material 70 into the fibers of the attachment surface skin member 33. According to this embodiment, since the film for improving the adhesion to the attachment core member 31 can be omitted, and the material of the attachment core member 31 is not required to be compatible with the resin core member 31, it is possible to use an arbitrary material for the attachment core member 31. As described above, the first and second embodiments offer the following advantages: (1) Since the attachment member is securely attached to the trim main body by exposing the molten resin for forming the resin core member from the reverse surface of the trim main body through the openings provided in the surface skin member, it is possible to achieve a secure bonding compared to the conventional structure involving the bending of pawls, and the appearance of the peripheral part of the attachment member can be improved in addition to the advantage of a highly secure attachment without involving any wobbliness and dislocation of the attachment member. (2) Since the attachment member is integrally mounted during the process of mold press forming the trim main body, the step of forming holes in the trim main body can be omitted, and the fabrication process can be simplified. (3) Since the attachment member is integrally mounted during the process of mold press forming the trim main body, the cumbersome step of mounting the attachment member on the molded trim main body by bending the pawls can be omitted, and the fabrication process can be significantly simplified. FIG. 7 shows a third embodiment of the present invention which is based on a slightly different principle from that of the preceding embodiments. Referring to FIG. 7, in the attachment member 80, an attachment pad member 82 such as polyurethane foam is laminated over the surface of an attachment core member 81 made of steel plate, and an attachment surface skin member 83 made of such materials as cloth and synthetic leather is placed over the outer surface of this assembly with a peripheral part of the attachment surface skin member 83 folded back onto the reverse surface of the attachment core member 81. The attachment core member 81 is provided with a plurality of engagement pawls 84 formed as tabs which are cut out and lifted from the attachment core member 81, and these engagement pawls 84 are passed through the surface skin member 22 of the door trim main body 20 and fixedly embedded or penetrated in the resin core member 21 at their free ends. Thus, according to the automotive door trim 10 of the present invention, since the engagement pawls 84 of the attachment member 80 are fixedly anchored in the resin core member 21 of the door trim main body 20, it is possible to achieve a stable and secure attachment without involving any gap around the peripheral part of the attachment member with a favorable appearance as opposed to the conventional structure involving bending of pawls. FIG. 8 is a sectional view showing the structure of the device for mold press forming which can be employed for carrying out the method of the present invention for fabricating the automotive door trim 10 illustrated in FIG. 7, and this molding device comprises a lower die 40 for mold press forming and an upper die 50 for mold press forming which is located above the lower die and provided with a substantially same die surface. The upper die 50 can be moved vertically by a lifting device not shown in the drawings, and can be engaged with the lower die 40 defining a small gap therebetween. Between the lower die 40 and the upper die 50 for mold press forming is provided an annular support frame 60 for setting up the surface skin member 22, and the upper die 50 for mold press forming is provided with retaining means for retaining the attachment member 80. Since the attachment core member 81 of the attachment member 80 is made of steel plate, the retaining means provided in the upper die 50 consists of magnets 53 so that the attachment member 80 may be retained on the die surface by the magnetic attraction between the magnets 53 and the attachment core member 81. An extruder 41 is attached to this lower die 40 for mold press forming, and the lower die 40 is provided with passages or gates 42 for distributing the resin material in semi molten state from the extruder 41 over the die surface of the lower die 40. Now, referring to FIG. 9 and 10, the process of fabricating the automotive door trim 10 illustrated in FIG. 7 is described in the following. As shown in FIG. 9, with the upper and lower dies 40 and 50 for mold press forming opened up, the peripheral part of the surface skin member 22 is retained by the support frame 60 with the attachment member 80 placed on the die surface of the upper die 50 for mold press forming. At this time point, the surface skin member 22 is pre-heated to a prescribed temperature in the same manner as mentioned in connection with FIG. 4 and 5. The attachment core member 81 is magnetically attracted to the magnets 53 embedded in the upper die 50 for mold press forming, and the attachment core member 81 is thereby magnetically and securely attached to the die surface of the upper die 50 for mold press forming. The engagement pawls 84 lifted from the attachment core member 81 are directed downward. A prescribed amount of the semi molten resin material 70 is supplied to and distributed over the die surface of the lower die 40 for mold press forming by way of the extruder 41 and the gates 42 for supplying resin material. Thereafter, the upper die 50 for mold press forming is lowered as illustrated in FIG. 10, and the upper and lower dies 40 and 50 for mold press forming are engaged to each other leaving a prescribed clearance therebetween. The press pressure was 80 kg/cm 2 , and the time duration of pressure application was 40 seconds. The resin material 70 is formed into a desired curved shape by this mold press forming, and a surface skin member 22 is integrally attached to the surface of the resin core member 21. At this point, the engagement pawls 84 provided in the attachment core member 81 are passed through the surface skin member 22, and are forced into the resin core member 21 in semi molten state, and the eventual solidification of the resin core member 21 finally secures the engagement pawls 84 in the resin core member 21. Therefore, the integral attachment of the attachment core member 81 to the door trim main body 20 can be carried out at the same time as mold press forming the door trim main body 20, and the need for forming holes in the door trim main body and the work involved in the mounting of the engagement pawls 84 can be omitted so that the process of fabricating the door trim can be significantly reduced. Thus, the present embodiment is characterized by the securing or anchoring of the engagement pawls 84 provided in the attachment core member 81 of the attachment member 80 in the resin core member 21 of the door trim main body 20. To further improve the strength of securing the engagement pawls 84, it is possible to provide notches 85 in the engagement pawls 84 as illustrated in FIG. 11, and through holes 86 in the engagement pawls 84 as illustrated in FIG. 12 so as to achieve a favorable anchoring effect to more securely embed the engagement pawls 84 in the resin core member 21. As illustrated in FIG. 13, the engagement pawls 84 may be provided with an angle of 10 to 20 degrees with respect to the direction of mounting the attachment member so that the engagement pawls 84 may not easily come off from the resin core member 84. As an alternative embodiment, it is possible to use light weight attachment core member such as hard board instead of the attachment core member 81 made of steel plate in the previous embodiment, and, in this case, the engagement pawls 84 may be separately provided in and fixedly secured to the attachment core member 81 by any suitable known means. Thus, the embodiments illustrated in FIGS. 7 and 11 through 13 offer the following advantages in place of or in addition to the advantages of the previous embodiments: (4) Since the embodiment allows the attachment member to be attached to the trim main body more securely than the conventional structure of bending the attachment pawls by anchoring the engagement pawls provided in the attachment core member in the resin core member of the door trim main body, it is possible to prevent the attachment member from becoming wobbly, prevent the creation of a gap between the peripheral part of the attachment member and the trim main body, improve the appearance of the peripheral part, and ensure a secure attachment. Although the present invention has been described in terms of preferred embodiments thereof, it is obvious to a person skilled in the art that various alterations and modifications are possible without departing from the scope of the present invention which is set forth in the appended claims.
An automotive interior component such as an automotive door trim comprising a main body integrally combining a resin core member and a surface skin member by a mold press forming process and an attachment member attached to a part of the main body, in which the attachment member is attached to the main body by way of connecting parts of the resin core member during the process of mold press forming. The connecting part may consist of an extension of the resin core member which is pushed out of openings provided in the surface skin member and adhered to the attachment member. Alternatively, the connecting part may consist of parts of the resin core member into which engagement pawls provided in the attachment member, in particular, an attachment core member thereof are penetrated through the surface skin member. In either case, solidification of the connecting parts completes the attachment of the automotive door trim. Thus, the process of mounting the attachment member is simplified, and accurate positioning of the attachment member can be achieved.
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CROSS REFERENCE TO RELATED APPLICATION This application claims benefit of priority of U.S. Provisional Patent Application Ser. No. 61/164,888 filed on Mar. 30, 2009, and U.S. Provisional Patent Application Ser. No. 61/185,579 filed on Jun. 6, 2009, the entire disclosures of which are incorporated herein by reference. FEDERALLY-SPONSORED RESEARCH AND DEVELOPMENT This invention was made with government support under contract number DE-FG36-08G088108 awarded by the U.S. Department of Energy. The U.S. Government has certain rights in this invention. TECHNOLOGICAL FIELD This technology generally relates to systems and methods of generating hydrogen using a reactant fuel material and an aqueous solution, and more particularly, to systems and methods for generating hydrogen using sodium silicide, sodium silica gel, or multi-component mixtures when reacted with water or water solutions. BACKGROUND Fuel cells are electrochemical energy conversion devices that convert an external source fuel into electrical current. Many common fuel cells use hydrogen as the fuel and oxygen (typically from air) as an oxidant. The by-product for such a fuel cell is water, making the fuel cell a very low environmental impact device for generating power. Fuel cells compete with numerous other technologies for producing power, such as the gasoline turbine, the internal combustion engine, and the battery. A fuel cell provides a direct current (DC) voltage that can be used for numerous applications including: stationary power generation, lighting, back-up power, consumer electronics, personal mobility devices, such as electric bicycles, as well as landscaping equipment, and others. There are a wide variety of fuel cells available, each using a different chemistry to generate power. Fuel cells are usually classified according to their operating temperature and the type of electrolyte system that they utilize. One common fuel cell is the polymer exchange membrane fuel cell (PEMFC), which uses hydrogen as the fuel with oxygen (usually air) as its oxidant. It has a high power density and a low operating temperature of usually below 80° C. These fuel cells are reliable with modest packaging and system implementation requirements. The challenge of hydrogen storage and generation has limited the wide-scale adoption of PEM fuel cells. Although molecular hydrogen has a very high energy density on a mass basis, as a gas at ambient conditions it has very low energy density by volume. The techniques employed to provide hydrogen to portable applications are widespread, including high pressure and cryogenics, but they have most often focused on chemical compounds that reliably release hydrogen gas on-demand. There are presently three broadly accepted mechanisms used to store hydrogen in materials: absorption, adsorption, and chemical reaction. In absorptive hydrogen storage for fueling a fuel cell, hydrogen gas is absorbed directly at high pressure into the bulk of a specific crystalline material, such as a metal hydride. Most often, metal hydrides, like MgH 2 , NaAlH 4 , and LaNi 5 H 6 , are used to store the hydrogen gas reversibly. However, metal hydride systems suffer from poor specific energy (i.e., a low hydrogen storage to metal hydride mass ratio) and poor input/output flow characteristics. The hydrogen flow characteristics are driven by the endothermic properties of metal hydrides (the internal temperature drops when removing hydrogen and rises when recharging with hydrogen). Because of these properties, metal hydrides tend to be heavy and require complicated systems to rapidly charge and/or discharge them. For example, see U.S. Pat. No. 7,271,567 for a system designed to store and then controllably release pressurized hydrogen gas from a cartridge containing a metal hydride or some other hydrogen-based chemical fuel. This system also monitors the level of remaining hydrogen capable of being delivered to the fuel cell by measuring the temperature and/or the pressure of the metal hydride fuel itself and/or by measuring the current output of the fuel cell to estimate the amount of hydrogen consumed. In adsorption hydrogen storage for fueling a fuel cell, molecular hydrogen is associated with the chemical fuel by either physisorption or chemisorption. Chemical hydrides, like lithium hydride (LiH), lithium aluminum hydride (LiAlH4), lithium borohydride (LiBH4), sodium hydride (NaH), sodium borohydride (NaBH4), and the like, are used to store hydrogen gas non-reversibly. Chemical hydrides produce large amounts of hydrogen gas upon its reaction with water as shown below: NaBH 4 +2H 2 O→NaBO 2 +4H 2 To reliably control the reaction of chemical hydrides with water to release hydrogen gas from a fuel storage device, a catalyst must be employed along with tight control of the water's pH. Also, the chemical hydride is often embodied in a slurry of inert stabilizing liquid to protect the hydride from early release of its hydrogen gas. The chemical hydride systems shown in U.S. Pat. Nos. 7,648,786; 7,393,369; 7,083,657; 7,052,671; 6,939,529; 6,746,496; and 6,821,499, exploit at least one, but often a plurality, of the characteristics mentioned above. In chemical reaction methods for producing hydrogen for a fuel cell, often hydrogen storage and hydrogen release are catalyzed by a modest change in temperature or pressure of the chemical fuel. One example of this chemical system, which is catalyzed by temperature, is hydrogen generation from ammonia-borane by the following reaction: NH 3 BH 3 →NH 2 BH 2 +H 2 →NHBH+H 2 The first reaction releases 6.1 wt. % hydrogen and occurs at approximately 120° C., while the second reaction releases another 6.5 wt. % hydrogen and occurs at approximately 160° C. These chemical reaction methods do not use water as an initiator to produce hydrogen gas, do not require a tight control of the system pH, and often do not require a separate catalyst material. However, these chemical reaction methods are plagued with system control issues often due to the common occurrence of thermal runaway. See, for example, U.S. Pat. No. 7,682,411, for a system designed to thermally initialize hydrogen generation from ammonia-borane and to protect from thermal runaway. See, for example, U.S. Pat. Nos. 7,316,788 and 7,578,992, for chemical reaction methods that employ a catalyst and a solvent to change the thermal hydrogen release conditions. In view of the above, there is a need for an improved hydrogen generation system and method that overcomes many, or all, of the above problems or disadvantages in the prior art. SUMMARY The hydrogen generation system described below accomplishes a substantially complete reaction of reactant fuel material, such as a stabilized alkali metal material, including sodium silicide and/or sodium-silica gel, which do not contain any stored hydrogen gas or molecular hydrogen atoms. Additional reactants can include sodium borohydride (NaBH 4 ), and/or ammonia borane, and the like. Also, the system reaction employing these reactants does not require an additional catalyst chamber, and is easily start-stop controlled by the simple addition of an appropriate aqueous medium to satisfy the hydrogen demand of a fuel cell or hydrogen-drawing system. In addition, the examples below meet all of the above requirements while minimizing overall system volume and weight. One example in the present disclosure is a reactor including a reactant fuel material, which generates hydrogen when the reactant fuel material is exposed to an aqueous solution. The reactor may be a standalone hydrogen generation component which can contain the aqueous solution. Similarly, another example can include a reactor to which an aqueous solution is introduced by an external supply. The hydrogen generation may also be controlled, monitored, or processed by an external control system. The control system and reactor can operate as a standalone hydrogen generation system used to provide hydrogen to hydrogen fuel cells or for any general, laboratory, industrial, or consumer use. Likewise, the control system and reactor can be implemented in whole or in part within a complete fuel cell system supplying an end product such as a laptop computer, personal or commercial electronics products, and other devices and equipment that require a power source. One method of generating hydrogen gas includes inserting a reactant fuel material into a reactor and combining an aqueous solution with the reactant fuel material in the reactor to generate hydrogen gas. The reactant fuel material can include stabilized alkali metal materials such as silicides, including sodium silicide powder (NaSi), and sodium-silica gel (Na—SG). The stabilized alkali metal materials can also be combined with other reactive materials, including, but not limited to, ammonia-borane with, or without, catalysts, sodium borohydride mixed with, or without, catalysts, and an array of materials and material mixtures that produce hydrogen when exposed to heat or aqueous solutions. The mixture of materials and the aqueous solutions can also include additives to control the pH of the waste products, to change the solubility of the waste products, to increase the amount of hydrogen production, to increase the rate of hydrogen production, and to control the temperature of the reaction. The aqueous solution can include water, acids, bases, alcohols, and mixtures of these solutions. Examples of the aqueous solutions can include methanol, ethanol, hydrochloric acid, acetic acid, sodium hydroxide, and the like. The aqueous solutions can also include additives, such as a coreactant that increases the amount of H 2 produced, a flocculant, a corrosion inhibitor, or a thermophysical additive that changes thermophysical properties of the aqueous solution. Example flocculants include calcium hydroxide, sodium silicate, and others, while corrosion inhibitors can include phosphates, borates, and others. Further, the thermophysical additive can change the temperature range of reaction, the pressure range of the reaction, and the like. Further, the additive to the aqueous solution can include mixtures of a variety of different additives. The reactor can be a standalone, replaceable component, which enables a control system or a fuel cell system to utilize multiple reactors. The reactor may also be termed a cartridge, cylinder, can, vessel, pressure vessel, and/or enclosure. The reactor includes the reactant fuel material and either the aqueous solution inside the reactor or an inlet port, or a plurality of inlet ports, from which the aqueous solution is introduced into the reactor. The reactor can also have an output port for hydrogen gas, which may undergo additional processing (e.g., vapor condensation, purification, regulation, and the like) once it leaves the reactor and prior to being supplied to an external system, like a fuel cell. The aqueous solution may be initially stored or added by the user externally or returned from a fuel cell system into the aqueous solution input port on the reactor. The aqueous solution can be added to the reactant fuel material, including stabilized alkali metals, in the reactor via the inlet port(s) using a pump, such as a manual pump, a battery powered pump, an externally powered pump, a spring controlled pump, and the like. The aqueous solution can be stored within the reactor and separated from the reactant fuel material by a piston, bag, membrane, or other separation device. The reactor may have the hydrogen output and the aqueous solution input as part of one connection to one device or control system. The reactor may have the hydrogen output connected to one device or control system and the water input connected to a different device or control system. The reactor may have only a hydrogen output with internal controls combining the reactant fuel material with the aqueous solution. The method of generating hydrogen gas can also include filtering the generated hydrogen gas, absorbing by-products in the hydrogen gas, and/or condensing water from the generated hydrogen gas. This filtration can occur inside the reactor, inside the control system, or in both. For example, a hydrogen separation membrane can be used in either the reactor or in the control system (or in both) to filter the hydrogen, while a condenser unit can be used to condense the water from the generated hydrogen gas. Filters and condensers can act upon the generated hydrogen gas as it exits the hydrogen outlet port of the reactor. The filtered hydrogen gas and/or the condensed water can be recycled back to the reactor or to a water storage container. In generating hydrogen gas, a waste product can be created, such as sodium silicate or other reaction waste products. In one example, a control system can include a monitoring device to monitor parameters of the reaction of the reactant fuel material and the aqueous solution in the reactor. The monitoring device can monitor one or multiple parameters in or on the reactor or in an external control system. These parameters can include, but are not limited to, temperature, electrical conductivity of the reactor contents, pressure in the reactor, weight of reaction, amount of un-reacted reactant fuel material, elapsed time of reaction, amount of aqueous solution in the reactor, and a maximum amount of aqueous solution to be added to the reactor. The monitored system characteristic can then be displayed, or used in a calculation to modify the control strategy, communicate the reactor status or system status with other devices, or communicate the characteristic or a derivative characteristic to a user. An example of a user communication device is a visual display device, such as an LCD display, for example. The reaction can be controlled in association with the monitoring device using a reaction control device. Examples of reaction control devices include, but are not limited to, devices to alter temperature, electrical conductivity range, pressure, weight of reaction, as well as other environmental measures within which the combination of the reactant fuel material and the aqueous solution in the reactor proceed. For example, reaction control devices can be used to add additional reactant fuel materials to the reactor, add additional aqueous solution to the reactor, remove a waste product from the reactor, cool the reactor, heat the reactor, mix a combination of the reactant fuel materials and the aqueous solution, bleed the reactor to decrease the pressure, and to perform other control measures. Measuring reaction parameters and using reaction control devices allows the method of generating hydrogen gas to be controlled in the reactor when any of the environmental measures within the reactor is outside a respective range or by a control strategy that monitors and processes the rate of change of any of the parameters. The reactor can include a number of different filters to separate the reactants and its reaction by-products from the hydrogen gas. For example, the methods of generating clean hydrogen gas can include both separating and filtering steps. In one example, at least one of the reactant fuel materials, the aqueous solution, the hydrogen gas, and/or the reaction waste products are separated from the others. Also, the hydrogen gas can be purified using a hydrogen separation membrane, a chemical filter, a desiccant filter, a coarse media filter, a dryer filter, and/or a secondary reactor chamber. As they are used, the filters can be cleaned with a portion of the aqueous solution as the aqueous solution is inputted into the reactor. The reactor can also include structures and devices for aqueous solution distribution such as a plumbing network, nozzle arrays, flow limiters, and water distribution media such as diffusers, misters, and the like. The aqueous solution can be distributed through multiple points in the reactor in parallel, in series, or in a combination thereof. The aqueous solution distribution system can be used in whole, or in part, to react with the reactant fuel material to produce hydrogen, to purify the hydrogen stream, to clean filter media, and/or to control the waste product parameters. The reactor can include hydrogen handling components such as a safety relief mechanism such as a relief valve, burst disc, or a controlled reactor burst point. The reactor may also include an exit flow limiter to minimize, or control, the hydrogen output rate in order to supply a required fuel cell characteristic or to match the transient flow rate limitations of the filtration components. The system of generating hydrogen gas can also include a pressure transducer, a relief valve, a hydrogen-sealing check valve, a fan, a heat exchanger, and a reactor cooling source. Likewise, the system can include a recapture container for recycling fuel cell reaction waste solution and returning the recycled fuel cell reaction waste solution to the reactor. The methods of generating hydrogen can also include directing a portion of the aqueous solution to areas of the reactor to recapture the waste product resulting from the combination of the reactant fuel material and the aqueous solution. For example, a portion of the aqueous solution can be added to a secondary reactor chamber, and the generated hydrogen gas can be passed through this portioned aqueous solution. Filtering can also be performed using a liquid permeable screen to separate a waste product from un-reacted reactant fuel material and aqueous solution. These and other advantages, aspects, and features will become more apparent from the following detailed description when viewed in conjunction with the accompanying drawings. Non-limiting and non-exhaustive embodiments are described with reference to the following drawings. Accordingly, the drawings and descriptions below are to be regarded as illustrative in nature, and not as restrictive. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an example of a hydrogen generation system using a stabilized alkali metal material and an aqueous solution to provide hydrogen to a hydrogen fuel cell or a general laboratory, industrial, or consumer use. FIG. 2 illustrates an example of a hydrogen generation system with two reactors and a carry-handle accessory. FIG. 3 shows an example hydrogen gas generation system that includes a reactor, a water container, and a number of additional components FIGS. 4A-4D illustrate reactors employing multiple water dispensing nozzles at select locations. FIG. 5 schematically illustrates an example hydrogen generation system with a heat removal structure. FIG. 6 shows an example hydrogen generation system with a hydrogen outlet and water inlet at one end of the reactor in a downward orientation to mix the reaction components. FIG. 7 shows an exploded view of a hydrogen generation system with the heat removal structure shown in FIGS. 5 and 6 . FIG. 8 shows a hydrogen generation system configuration with a coarse media filter and a hydrogen filtration membrane. FIGS. 9A-9C illustrate a water feed network and a comparison of filter areas without a water feed network and those utilizing the water feed network. FIGS. 10A-10B illustrate alternative filter designs to a membrane/coarse filter system. FIGS. 11A-11B illustrate systems and techniques of waste capture and circulation. FIG. 12A illustrates an example of a reactor with multiple reaction compartments. FIG. 12B illustrates an example reactor with multiple protective insulation devices. FIG. 13 illustrates an example reactor with electrical contacts to measure changes in conductivity. FIG. 14 illustrates an example reactor with electrical contacts connected to a pressure vessel cap of the reactor. FIGS. 15A-15C shows an example lightweight, low-cost, reusable reactor in accordance with the claimed invention. FIG. 16 shows an example architecture of a low output reactor system in accordance with the claimed invention. FIG. 17 shows a detailed example of a low output reactor system in accordance with the claimed invention. FIG. 18 shows a reactor with solid reactant fuel material connected by a valve to a spring-based liquid pump system. FIG. 19 shows a graphical depiction of oscillatory hydrogen generation over time in a spring-based liquid pump system without a coupling valve FIG. 20 shows a graphical depiction of hydrogen generation pressure over time in a spring-based liquid pump system with a coupling valve. FIG. 21 shows a reactor with reactant fuel material and a spring based liquid pump system integrated within a single cartridge. FIG. 22A shows a reactor with reactant fuel material and an integrated spring based liquid pump system. FIG. 22B shows three primary sub-assemblies of an integrated cartridge with a reactor and spring based liquid pump system. FIG. 23 shows a perspective view and cross-section of an integrated cartridge with a reactor and spring based liquid pump system FIG. 24 shows an assembly view of an integrated cartridge FIG. 25 illustrates water feed distribution mechanisms. FIG. 26 shows a threaded locking mechanism to couple a separable liquid feed/reactor hydrogen generation device. FIG. 27 shows a schematic representation of a separable liquid feed/reactor hydrogen generation device. FIG. 28 shows a schematic representation of a separable liquid feed/reactor hydrogen generation device with a conical/collapsing spring FIGS. 29A-29B depict normal and compressed views of a collapsible spring to facilitate limited variability in force over travel. FIG. 30A shows a perspective view of a hydrogen generation cartridge with a spring based liquid feed and a volume exchanging system FIG. 30B shows a schematic representation of a hydrogen generation cartridge with a spring based liquid feed and a volume exchanging system. FIG. 31 shows perspective and cross-sectional views of a hydrogen generation cartridge with a volume exchanging, spring based liquid feed. FIG. 32 shows an assembly view and a cross-sectional view of a hydrogen generation cartridge with volume exchanging, spring based liquid feed. FIG. 33 shows an assembly view of an integrated cartridge filtration system example. FIG. 34 shows an assembly view of a normally closed valve to separate a reactor and a liquid feed. FIGS. 35A-B show an assembly view and a perspective view of a mating component to join a reactor and a liquid feed. DETAILED DESCRIPTION In the examples below, reference is made to hydrogen fuel cell systems, but it should be understood that the systems and methods discussed can also be implemented in any hydrogen gas generation application, such as laboratory applications, commercial or industrial applications, and consumer applications, for example. Basic Hydrogen Control System In one example, sodium silicide and/or sodium silica gel can be combined with water to generate hydrogen gas, but the developed technologies can also use other stabilized alkali metal materials, such as doped silicides and silicides that have hydrogen in association, or solid powders combined with aqueous solutions to produce hydrogen gas. Additionally, many aspects of the developed system technology can also be applied to alternative materials used in hydrogen production such as aluminum powder, or any other material, or combination of materials, that generates hydrogen when exposed to aqueous solutions. The reactant fuel materials can be free-flowing powders or materials that are compressed, molded, cut or formed into rods, cones, spheres, cylinders or other physical geometries. The materials may consist of variable powder sizes, geometric variations, material coatings, or material variations to control the reaction rate. One method for coating would be to expose the solid sodium silicide structure to humid air creating a sodium silicate barrier which is dissolvable in water. Of course other forms and geometries for the reactant fuel materials and aqueous solutions may be used with which to combine the reactant fuel materials and aqueous solutions. FIG. 1 shows an example of a hydrogen generation system 100 using a reactant fuel material and an aqueous solution to generate hydrogen gas. The generated hydrogen gas can be directed to a hydrogen fuel cell or to a general laboratory, industrial, or consumer use. The reactant fuel material 101 can be inserted into a reactor 102 . In this disclosure, the terms reactor, cartridge, and pressure vessel are used synonymously to identify a container or other receptacle in which a reactant fuel material is placed. In the example shown in FIG. 1 , a removable reactor 102 is attached to a water inlet connection 106 and a hydrogen outlet connection 108 . The connections can include, but are not limited to, normally-closed double-shut-off valves and/or normally closed check valves. The connections from the reactor 102 to the water inlet connection 106 and hydrogen outlet connection 108 can be flexible connections or can be rigid connections, depending upon the particular use. Water, or another aqueous solution, is added to the reactant fuel material, such as a stabilized alkali metal 101 to generate hydrogen gas and a by-product, such as sodium silicate. The hydrogen gas moves upward and exits the reactor 102 . Although a single reactor 102 is illustrated in FIG. 1 , it should be understood that any number of removable or fixed reactors can be used in the exemplary hydrogen gas generation systems described. For example, in FIG. 2 , two removable reactors 202 , 204 are shown. Further, the reactors can be secured in place in the system using a locking mechanism, a clip, or other similar securing device. In the example shown in FIGS. 1 and 2 , an aqueous solution, like water, is added to fill ports 110 , 210 , respectively. In another implementation, a removable water container can be used, such as water container 114 , with or without a fill port. In other examples, a reactor can be pre-filled with reactant fuel material. The aqueous solution can include additives to improve reaction efficiencies, increase hydrogen production, increase the rate of hydrogen production, reduce contaminant formation, facilitate contaminant filtration, support final hydrolysis, reduce corrosion, control the pH of the waste products, change the solubility of the waste products, and extend temperature range operation, as well as affect other reaction parameters such as the thermophysical properties of the reactants. For example, the additives can include acids, bases, alcohols, other additives, and mixtures of these additives. Examples of the additives can include methanol, ethanol, hydrochloric acid, acetic acid, sodium hydroxide, calcium hydroxide, sodium silicate, phosphates, borates, and others. Other additives can be combined with the reactant fuel material, including boron, carbon, and nitrogen to improve the hydrogen capacity, kinetics and/or to reduce reaction enthalpy. With regard to temperature range operation, salt and/or other additives can be included in the aqueous solution to reduce the freezing point of the solution. The amount of aqueous solution stored in its container can vary depending on system implementation specifics. For example, in FIG. 2 , the container can store more than a sufficient volume of aqueous solution to react multiple cartridges 202 , 204 . The system can include a condenser (not shown) to condense water from the hydrogen output stream and either return it directly to the reactor, or direct it to the water container 114 . The system can include a water inlet connection 106 for an external water source (not shown) to supply additional water to the water container 114 , or in a separate implementation directly to the reactor. In one implementation, fuel cell reaction waste water can be captured in full or in part and also contribute to the water supply to reduce the net total water requirements. For example, the sodium silicate waste product readily absorbs water, and its viscosity changes accordingly. By separating the waste product from the un-reacted reactant fuel material, the reaction can be controlled. For example, one end of the reactor can be heated or insulated to create a solubility condition where excess water exists. This water can then either be pumped back up to the stabilized alkali metal powder or allowed to react with an amount of sodium silicide configured exclusively for water usage maximization. Alternatively, at the point of reaction, the waste silicate is warm requiring little water to be in a liquid phase. At the point of reaction, a separation screen is utilized to separate the liquid waste from the unreacted reactant fuel material. Additional System Components In addition to the reactor and the aqueous solution sources, the hydrogen gas generation systems can include additional system components. For example, FIG. 3 shows an example hydrogen gas generation system 300 that includes a reactor 302 , a water container 314 , and a number of additional components. For example, water source inlet 306 allows the filling, or refilling, of water container 314 as needed. Water from water container 314 may be pumped into reactor 302 via water supply line 390 using a pump 320 , such as a peristaltic pump, a manual pump, positive displacement pumps, and other pumps. A pressure transducer 322 may be placed in line with water supply line 390 and used to regulate the amount of water pumped into the reactor 302 . For example, pressure transducer 322 may be used with a pump 320 to deliver pressure calibrated amounts of water to multiple reactors through a multiport valve 324 . Pressure transducer 322 may also be used in part to provide a fail-safe mode to prevent excess water from being pumped into the reactor 302 . In one example, the output voltage of pressure transducer 322 can be compared to a system voltage parameter using a comparator (not shown). The output of the comparator can be evaluated to determine if the voltage is in a proper operational range. When the voltage is in the operational range, additional circuitry implementing instructions from microcontroller 387 can drive pump 320 to provide water to the reactor 302 . When the voltage is outside the operational range, the pump 320 is disabled. This circuitry can use a capacitor, or other timing circuits, to create a delay in the reading of the pump to allow an instantaneously high reading during a diaphragm pump action for example. For hydrogen generation systems with multiple reactors, a supply valve 324 can be used to select which reactor receives water. The hydrogen gas generation system 300 can include a battery 388 to operate the pump 320 and/or to otherwise initiate the reaction and to operate other control electronics (shown collectively as 386 ). The hydrogen gas generation system 300 can also receive external power to either recharge the battery 388 from any external source such as a fuel cell, a wall outlet, or power from any other source. The system 300 may also include a small fuel cell system (not shown) to internally operate its internal balance-of-plant components. In one implementation, no battery is present in isolation, but rather power is obtained from a fuel cell or a fuel cell battery hybrid that is either internal to the overall system 300 or external to the hydrogen generation system 300 . In one implementation, no battery is required if the reactors are given a factory over-pressure of hydrogen, which provides enough hydrogen to start the system. Furthermore, the hydrogen generation system can be designed with a small manually operated pump (such as a syringe or the like) to start the reaction by a physical user interaction rather than an electrical start. Similar to pressure transducer 322 , a check valve 326 can be used in the reactor 302 , or in the control system, to keep hydrogen pressure in reactor 302 from pushing unallowably high pressures on control system components such as valves 324 / 361 , transducer 322 , and/or pumps 320 . For example, as the initial water enters the reactor 302 and reacts with reactant fuel material 301 in the reactor 302 , hydrogen is generated, and the hydrogen pressure in the reactor 302 builds until the hydrogen reaches a system pressure parameter value upon which the hydrogen gas is routed out of the reactor 302 and is used elsewhere. In some situations, the pressure in the reactor 302 can exceed that of the capabilities of the pump 320 and other system components. Check valve 326 can be used to prevent the pump 320 , water container 314 , and water line 390 from becoming excessively pressurized and to prevent damage to the system. Check valve 326 can be used to determine the pressure in the reactor 302 and to isolate the amount of pressure to the control system from the reactor 302 . Similarly, hydrogen output check valves 336 , 337 manage backflow in the reactor 302 . Backflow may occur when the system is used at high altitudes or when the hydrogen outputs of multiple canisters are tied to each other. Check valves and transducers in each reactor, and throughout the control system, allow for independent pressure readings of each reactor for systems that use multiple reactors. The hydrogen gas output lines 391 from each reactor 302 can include a pressure transducer 340 , located in the reactor 302 or in the control system 303 . In one implementation, the check valve 336 only allows hydrogen to flow out of the canister as opposed to air entering the canister when being connected and disconnected, or in the event that the system is inadvertently connecting high pressure from another source to a reactor. In another implementation, this check valve 336 is not required but a normally closed check valve 3430 (as shown in FIG. 34 ) is used alternatively. In one implementation, check valves are connected downstream of pressure transducers 340 which allow one reactor from back-pressuring another reactor while providing independent pressure readings of each reactor with the pressure transducers residing in the control system. In other implementations, the check valves 326 , 336 can physically reside in the reactor 302 or in the control system 303 and provide the same function. Additionally, the system can also include a pressure regulator 344 . At times, it may be desired to operate the reactor 302 at a higher pressure (e.g., 80 psi or higher). In one example, the regulator 344 can bring the pressure down to 25 psi. Alternatively, a regulator 344 with a dial, or other means of regulating pressure, can be used, which would allow a user to change the output pressure of the control system. Alternatively, an electronically controlled regulator can be used to allow a microcontroller (such as microcontroller 387 ) to set the output pressure based on the desired pressure. In a separate implementation, no regulator could be used at all, and the micro-controller could control the water flow rate and amount to control the output pressure of the reactor. Material Feeds Alternative reactant fuel material (e.g. sodium silicide)/liquid (e.g. water) mechanisms are possible. In some configurations, the reactant material can be formed, molded, or pressed into geometrical structures. For example, rods formed from stabilized alkali metal materials can be inserted into an aqueous solution at a defined rate to control the reaction. Similarly, the rod may simply be removed from the water bath, or other aqueous solution, to stop the reaction. Additionally, reactant fuel materials can also be compressed into pellets. These pellets can then be manipulated and placed into water, or other aqueous solutions, at a defined rate to effect the reaction. Aqueous Solution Feeds Water may be fed into reactor 302 in a number of different ways. For example, water can be fed into the reactor using a single water inlet 338 , or by using multiple water dispensing nozzles at select locations as shown in FIGS. 4A-4D . In simple system configurations and for small systems, a single water input will suffice. For larger systems, multiple water inputs can be used to facilitate the reaction and to aid in a reaction re-start. For example, in FIG. 4A , a water feed tube 411 extends vertically from water inlet 406 and employs multiple water dispensing nozzles 413 with which to feed water to multiple areas of the reactor 402 using a single tube 411 . Likewise in FIG. 4B , a horizontal water dispensing filter spray 415 is also used to feed water to multiple areas of the reactor 402 . In practice, a single or any number of tubes can be used. The tubes and water dispensing nozzles may be of varied sizes, and the water dispensing nozzle pattern and hole size may vary across the tube to optimize the reactor mixing conditions. For example, small tubing may be used with a number of small holes, such as holes with dimensions of 0.001″ to 0.040″ or larger in diameter, for example. Small holes can have a tendency to clog with reaction by-products when attempting to restart a reaction, while larger nozzles can cause the aqueous solution to dribble onto the reactant fuel material rather than jet or mist. When using a pump with high pressure capability, larger orifices can be used to inject water to the point of reaction. When low pressure water feed system are used, more nozzles can be used to limit the distance between the nozzle and points of reaction. Depending upon the application and the specific reactants, any of the aqueous solution delivery techniques can be selected. Additionally, the water feed tubes may be curved or spiraled as shown in FIGS. 4C and 4D . In FIGS. 4C and 4D , a spiral water feed tube 421 can be used to access multiple areas of the reactor 402 using a single tube. This spiral water feed tube 421 can have holes in a number of possible positions to maximize its coverage area and to minimize water saturation in one area of the reactor 402 with respect to another. The center post 423 can also be included for mechanical support and for heat removal. For designs that do not require such support or heat removal structures, it can be removed. Additionally, a water feed network can be integrated within the center post 423 . Other water dispersion configurations are possible as well. For example, one implementation can employ an assortment of fine holes or mesh to facilitate water transfer. In other implementations, the water feed network may not be uniform through the volume of the canister. For example, the feed network can be optimized to feed directly into the reactant fuel area. If a reactor has an excess volume for waste products or reactant foaming, the water feed network may not add water to these areas. Additionally, the water feed network can employ tubing configured to spray water on a membrane(s) used for hydrogen separation (discussed below). The tubing can include holes or it may contain additional array(s) of tube(s) or nozzles. In this manner, water is fed directly to the reactant fuel in multiple areas of the reactor 402 to facilitate its reaction with the aqueous solution. By feeding water into select locations of the reactor 402 , the water and ensuing reaction can be made to churn or mix the reactant fuel in the reactor 402 . As hydrogen is formed and rises, the hydrogen gas serves to stir the reactor materials (that is, the aqueous solution and the reactant fuel materials) enabling near complete reactivity of these reaction components. Mixing the reaction components can also be accomplished by positioning both the hydrogen outlet and water inlet on one end of the reactor with downward orientation as shown in FIG. 6 . This configuration provides a single connection plane to the hydrogen generation system. The hydrogen pickup 666 is located at the top of the reactor 602 and the pressurized gas travels to the bottom through a hydrogen tube 668 . This hydrogen tube 668 can be in or outside the reactor. Different configurations and tube geometries can also be employed. Less than complete reactivity can be employed, which may increase energy density (H 2 delivered/(mass of powder+mass of water required)) as the amount of water required is non-linear. In addition, partial reactivity can leave the waste product in a near solid state as it cools from the elevated local reaction temperature. Solid waste products can be beneficial for waste material disposal. Heat Transfer Returning to FIG. 3 , as the reaction of the reactant fuel material 301 and water progress, heat is generated inside the reactor 302 . One or more thermisters 328 can be used to measure the heat of the reactor 302 and to control a cooling system, including one or more cooling fans 360 that can be used to cool the reactor 302 . Likewise, cooling may be provided by a liquid cooling loop (not shown) using a self-contained heat management circuit, or by circulating water about the reactor 302 from the water container 314 using a separate water cooling run. Of course, thermister 328 may also control water supply valve 324 to regulate water flowing into reactor 302 to control the reaction based upon the temperature of reactor 302 , to control the amount of waste product generated, to minimize water usage, to maximize reactivity, and for other reasons. As shown in FIG. 5 , a heat removal structure 523 can be positioned in the center of the reactor 502 as well. The heat removal structure 523 may also facilitate a mechanical reactor locking mechanism by holding both ends of the reactor together when pressurized. In FIG. 5 , the bottom 572 of the reactor also serves as a heat sink and stand for the reactor 502 . While some heat is removed through the reactor walls, when these walls are clear and made from glass or plastic, these materials typically have limited thermal conductivity. In one implementation, a significant amount of heat is removed through either or both ends 562 , 572 of the reactor. One end of the reactor 502 may exclusively be a heat sink (bottom 572 ) while the other end (top cap 562 ) may contain the reactor control and connections such as hydrogen connectors 508 and water connectors 506 , relief valves 555 , electrical connections 577 , 579 such as electrical feed-thru, electrical signal processing connections, system sensing connections, and structural connections. In FIG. 5 , the entire body of the reactor 502 can be clear or translucent (e.g., made of glass or plastic), providing both a feature allowing for visual detection of the status of the reaction, an estimate of reactant fuel material consumption, as well a unique packaging and visual appearance. In another implementation, the reactor can be generally opaque with a clear viewing window with which to view the reaction. Additionally, as shown in the example of FIG. 7 , the heat sink 723 and all components are connected on one end 762 . This geometry facilitates easy connection to the hydrogen generation system with gas connections 708 , fluid connections 706 , and electrical connections 777 , while providing a direct path for heat removal by the hydrogen generation system using air cooling, liquid cooling, or any other method. Pressure Control Returning to FIG. 3 , burst relief valves, burst disks, or other controlled pressure relief points 330 can be implemented in the reactor 302 to control its pressure. For example, when the pressure in the reactor 302 reaches a predetermined system parameter, hydrogen gas could be controllably vented from the reactor 302 through a pressure relief point 330 . In one example, a flow limiter can be used to limit the hydrogen output flow, to keep the flow within an allowable range for downstream devices, and/or to keep the flow within the allowable rate for successful filtration. The flow limiter can be an orifice or a function of the check valve components. A flow limiter that limits water input to the reactor can be employed to avoid excessive instantaneous pressure generation. The hydrogen generation system 300 can be configured to operate over a range of pressures. In one implementation, a user can set the desired pressure limit, or range, using buttons, switches, or any other communications protocol (e.g., Bluetooth and the like) either directly or remotely. In one implementation, the system 300 will monitor the pressure and control the reaction accordingly to maintain that pressure in the reactor 302 within a prescribed tolerance band. The system 300 can be used for lower pressure applications (on the order of 25 psi) to facilitate user safety and operational simplicity. Many fuel cell applications operate in this pressure range. However, when necessary, sodium silicide can generate 1000's of psi for applications that require it. Hydrogen Filtration In one implementation, the reactant fuel material is sodium silicide, which is combined with an aqueous solution to form hydrogen gas and a by-product (such as sodium silicate) as the primary reaction. In practice, other by-products can be formed, such as silanes (e.g., SiH 4 ) when reacting under certain conditions. Borazine by-products can be formed when reacting mixtures with ammonia borane, and other items such as water vapor or sodium hydroxide (NaOH) particulates are also possible. In addition, aqueous solution (e.g., water), liquid waste product (e.g., silicate), and reactant fuel materials (e.g., sodium silicide) can all be present within the reactor. Multiple levels of filtration may be used to cause only hydrogen to exit at a level of purity applicable for the particular application. A hydrogen separator can be used which may serve multiple purposes. In one implementation, a separation media made of laminated Teflon (PTFE) with a pore size of about 0.45 micro-meters can be used. A wide variety of pore sizes and specific material choices are available. Implementation features include high throughput gas flow-rate, a water breakthrough pressure up to 30 psi, and ultrasonic bonding to the reactor cap. Membranes are available in a wide range of material types and thickness. Multiple membranes can be used to provide coarse and fine filtration. For example, when using sodium silicide as the reactant fuel material in the aqueous solution reaction, hydrogen bubbles can reside within a sodium silicate foam. During the reaction, this foam (or hydrogen coated sodium silicate bubbles) can coat a filtration membrane with a sodium silicate waste product. FIG. 8 shows a system configuration that uses a coarse media filter 888 to break down this foam prior to performing a finer filtration using a hydrogen filtration membrane 890 . In one implementation, a copper wire mesh is used as the coarse media filter 888 . This successfully keeps high viscosity material away from the fine filter hydrogen filtration membrane 890 . Other coarse filter media can also be used. Copper, or other materials or material coatings, can be selected to include advantageous chemical activators or absorbents for either catalyzing hydrolysis or absorbing contaminants. The fine filter membrane 890 material can also include a backing 894 between the membrane 890 and the mechanical housing 892 . This backing 894 provides mechanical support to the membrane 890 while providing paths for the hydrogen to exit the membrane 890 and enter the specific hydrogen output connections (not shown in FIG. 8 ). By providing the coarse and fine filtration at the reactor assembly, the hydrogen gas generation system capitalizes upon volume constraints. Additional filtration within the hydrogen generator system and/or fuel cell system can also be provided. For example, the hydrogen generation systems depicted in the figures can include removable filtration devices, such as a removable desiccant filter, for example. A chemical filter can also be used in the hydrogen generator system that can be serviced after a period of time. Alternatively, the filters can be constructed of a larger size such that they do not require servicing during the full product life of the reactor. For many fuel cell applications, water vapor in the hydrogen gas output stream is acceptable due to the desired humidity requirements of the fuel cell. For other uses, such as in some laboratory environments, commercial uses, and some fuel cell applications where lower humidity is dictated, water vapor in the hydrogen gas output stream may not be acceptable, and a dryer filter can be employed. The hydrogen generation systems of the claimed invention allow for a removable filter to facilitate commercial, laboratory, and fuel cell applications, for example. In addition, some fuel cell applications, such as refilling of metal hydrides, require dry hydrogen. A water absorption media and/or condenser 896 as shown in FIG. 8 can be used in these applications as well. Any use of a condenser 896 can facilitate the collection and return of water to the primary reaction to minimize water waste from the reactor 802 . The return of water to the primary reaction can be made directly to the water inlet 806 or to another connection to reactor 802 . In another implementation, the reactors can be removable or fixed, and an access door, or other access port, can be provided to add reactant fuel material and/or to remove the reaction waste once the reaction is complete. For example, an access door can be incorporated as a reactor cover, or lid, 562 as shown in FIG. 5 . Alternatively, in the implementation shown in FIG. 5 , any portion of the waste product can be stored within the reactor for later disposal or recycling. Cleaning the Filters When using sodium silicide as the reactant fuel material and water as the aqueous solution in the hydrogen gas generation systems, the primary waste product is sodium silicate, which readily absorbs water. In some reactor configurations, a significant amount of sodium silicate foam causes blockage of the filtration devices over time. The highly viscous sodium silicate can clog the filtration devices. By applying water to the sodium silicate, the viscosity changes, which allows for the sodium silicate to be washed away from the filter area. For example, in one configuration shown in FIGS. 9A-9C , a section of the water feed network (such as reference numeral 338 in FIG. 3 as one example) has a portion of the water flow directed directly onto the filtration device(s), such as coarse media filter 888 and hydrogen filtration membrane 890 shown in FIG. 8 . The water applied to the filtration devices by water spray 909 eventually drops back down to the un-reacted sodium silicide and is also reacted, but it first serves to clean the filter as part of its delivery to the reactor. Reference numeral 909 in FIG. 9A shows a stream of water aimed directly up to reach the filtration device. FIG. 9B shows a filtration device 999 b that was not cleaned during the reaction, and FIG. 9C illustrates a filtration device 999 c that was cleaned during the reaction by spraying water on the filtration device 999 c . As evident from the difference in the filter residue shown in FIGS. 9B and 9C , by applying water to the filtration device, the filter does not clog. Additional Filters Alternative filter designs to the membrane/coarse filter assembly can also be used. FIGS. 10A-10B show a number of different filter designs. For example, in FIG. 10A , a cone shaped filter 1010 can facilitate movement of the sodium silicate foam across the filter 1010 resulting in a breakdown of the bubbles 1012 . This cone-shaped filter geometry may also result in a movement of the foam to liquid collection zones in the upper corners 1014 a , 1014 b of the reactor 1002 and recirculation of the sodium silicate solution down to the base 1009 of reactor 1002 as shown by vertical arrows 1050 , 1060 pointing downward. Additional design features may be incorporated into the reactor 1002 itself to facilitate this action. Such features can include canister cooling to facilitate condensation on the reactor walls 1040 , as well as a wicking material 1071 in FIG. 10B to help move the liquid solution down the reactor walls 1040 or other appropriate areas as shown by vertical arrows 1051 , 1061 pointing downward. Multi-Chamber Reactors Even with filtration devices described above, some amount of non-hydrogen and/or non-water can escape through the coarse filter and/or membrane. FIG. 3 shows a combination chamber 355 to facilitate a process for capturing reaction waste products, such as sodium silicate. The process of using combination chamber 355 of FIG. 3 is shown schematically in FIGS. 11A-11B using multiple filters and membranes. FIGS. 11A-11B illustrate methods of waste capture and circulation. In one implementation, waste capture and circulation is performed within a disposable reactor. In FIG. 11A , hydrogen gas is generated in the larger reaction chamber 1154 by reacting water and sodium silicide 1101 , and hydrogen gas 1191 moves upward through the hydrogen membrane 1190 . Some amount of sodium silicate, water, and other reaction products may travel through or around the membrane 1190 as well. The actual flow rate of these products is much lower than the flow rate of the incoming supply water 1138 . All of these products (output hydrogen 1191 , incoming water 1138 , and reaction by-products) are combined into the smaller combination chamber 1155 . Smaller combination chamber 1155 can be supported in reactor 1102 by supports 1133 . A mesh filter 1122 can also be used to provide further incoming and outgoing filtration. The incoming water 1138 absorbs the combined reaction by-products because they are soluble in water. The water 1138 and the by-products are then pumped back into the larger reaction chamber 1154 . The output hydrogen 1191 will travel upwards to the secondary membrane 1195 , which can be of a finer pore size than membrane 1190 . Some amount of water vapor and other components may still be in the final output stream labeled “Pure Hydrogen Output” 1193 . In some operational situations, the pressure in the combination chamber 1155 and reactor chambers 1154 may equalize, and hydrogen will not flow through the membrane 1190 . To overcome the pressure equalization, the membrane/filter pressure drops, check valve pressure drops, and specific operational control methods of the water pump can be modified prior to, or during a reaction. As an example, cycling the supply pump can create pressure perturbations allowing for hydrogen to initiate or to re-initiate flow. An alternative waste product re-capturing configuration for a pump-less configuration is shown in FIG. 11B . In FIG. 11B , an over-pressure of the supplied water is used to feed water to the reactor. Architecture Using Smaller Compartments within the Reactor As outlined above, the reactors in these examples can be separated into multiple compartments. This architecture can be useful for directing water to different areas of the reaction. In one example, different areas of the reaction can be operated at different times facilitating easier restart conditions as the reaction can start much quicker when just sodium silicide as opposed to when sodium silicide and sodium silicate are present. In addition, water sprayers have been shown to be effective in controlling the reactions. Each sprayer can have a defined range of water dispersion. A sprayer with a compartment approach can work well to control the reaction. Various methods and materials to separate the compartments can be used. For example, thin tubes can be loosely inserted in the reactor compartment, a honeycomb mesh assembly can be integrated in the interior of the reactor, or a flexible membrane network can be incorporated into the reactor. Additionally, the materials used to divide the reactor can seal off the aqueous solution in one compartment from other compartments. Compartments can be configured in both horizontal and vertical directions within the reactor. The compartments can also be made of water permeable and/or hydrogen permeable materials or made of other material used for water transport via surface tension forces. FIG. 12A illustrates one implementation of such an approach where a reactant fuel material can be rolled into a cigarette-like configuration. As shown in FIG. 12A , the reactant fuel material can be wrapped in a membrane material that can distribute water all around the powder and/or permeable hydrogen. Multiple rolled compartments 1204 a , 1204 b , 1204 c , 1204 d , 1204 e , 1204 f , 1204 g , for example, can be housed within reactor 1202 . As the reactions take place in the rolled compartments 1204 a , 1204 b , 1204 c , 1204 d , 1204 e , 1204 f , 1204 g , the reactor 1202 will generate heat. Another implementation of such rolled compartments is to arrange the rolled compartments next to each other horizontally for a low profile package similar to a cigarette case. In addition to techniques discussed above, heat dissipation can be conducted through the walls 1296 of the reactor 1202 as shown in FIG. 12B . As the walls 1296 of the reactor 1202 get hot, a number of areas on the outside of the reactor 1202 can be insulated using protective pieces 1288 or other insulation devices. These insulation devices can be positioned on the outside of the reactor 1202 to enable a user to touch the reactor. Determining the Status of the Reaction After an aqueous solution is added to the reactant fuel, a reaction occurs, and hydrogen gas is generated. There are many ways to determine the status of the reaction and to verify the progress of the reaction. These techniques can include visually observing the reaction, timing the reaction, and measuring parameters of the reaction before, during, and after the reaction. For example, parameters that can be measured before, during, and after the reaction include, but are not limited to, the weight of the reactants, the temperature, the amount of aqueous solution in the reactor, the amount of reactant fuel in the reactor, the maximum amount of aqueous solution to be added to the reactor, the amount of aqueous solution added by known characterization of a pump, electrical conductivity, pressure, hydrogen output measurements either directly or indirectly by way of fuel cell current, and the like. For example, sodium silicide has minimal conductivity. However, once reacted with water, the sodium silicate readily conducts electricity at a level suitable for detection and measurement. While many different methods can be used to measure this change in conductivity, one implementation is shown in FIG. 13 , where different electrical contacts 1366 are placed on a ribbon cable 1350 inside the reactor 1302 . The electrical conductivity measurement circuit reads and compares actual resistance measurements between pads 1313 a , 1313 b , 1313 c , 1313 d , 1313 e , 1313 f and/or looks for point-to-point conductivity between pads 1313 a , 1313 b , 1313 c , 1313 d , 1313 e , 1313 f . These measurements can be made using as few as two pads or as many pads as required to provide sufficient state-of-reaction resolution. Similarly, contact probes can be placed in different locations of the reactor to perform similar readings and accomplish a similar effect. Further, in another example, a single probe can contact two electrical tips to measure the resistance at a particular point at a very specific distance in the reactor. This technique can be used in a configuration where an electrically conductive reactor is employed. In a similar implementation, a single probe, multiple probes, or conductive pads may be used, and the reactor itself can be used as a measurement ground. In one configuration, the electrical contacts are connected to the hydrogen generation system via a number of electrical contact methods, such as spring loaded contact pins, swiping pins, blade insertion devices, wireless transmission, or any other method of electrical signal transfer. One reactor example using such contacts is shown in FIG. 14 where electrical contacts 1414 connect to the pressure vessel cap 1416 of a reactor. A recessed ribbon cable 1418 connects the contacts 1414 to a microcontroller 1420 in the pressure vessel cap 1416 . The hydrogen generation system can include detection circuitry effected by programming instructions in the microcontroller 1420 to interrogate or probe the contacts 1414 , to measure the resistance, and/or to determine a short circuit and/or an open circuit. The microcontroller 1420 can include programming instructions and algorithms to interrogate the contacts 1414 , determine a signal level, and convert the signal level to a conductivity measurement and to equate the conductivity measurement to a status of reaction measurement. Of course, the microcontroller can reside on the reactor assembly (such as in the pressure vessel cap 1416 in FIG. 14 ) or in the control system 303 as shown in FIG. 3 . In another example for determining the state of the reaction, a force sensor, such as a strain gauge, can be used to measure the weight of the reactor. Over the state of the reaction, the reactor becomes heavier due to the water added to the sodium silicide. The change in weight of the reactor can be measured using a scale or other force sensor to determine the weight of reaction before, during, and after. By weighing the reactor during these periods, the status of the reaction can be determined as well as other system specific parameters such as reaction efficiency, completion percentage, a time of reaction, the amount of hydrogen gas generated from the reaction, and other parameters. The control system can adjust its pump parameters based on the state of reaction. For example, reactions can require more water to generate the same amount of hydrogen near the end of the reaction than the beginning. The microcontroller can use this system parameter to predict the reaction characteristics enabling more uniform hydrogen generation by adjusting other control measures, such as temperature ranges, pressure ranges, and the amount and speed at which the aqueous solution is added to the reaction. Displaying Reaction Status and Reaction Parameters Regardless of the measurements used to determine the status of the reaction, as shown in FIG. 2 , display devices 218 may be used to monitor and control the reaction of the reactant fuel and the aqueous solution. Display device 218 can include an LCD (liquid crystal display) or other displays to show the determined force or weight of reaction and other operating or system specific parameters. An additional example display device 318 is shown in FIG. 3 . For example, the display device 318 can display the actual weight, or use a microcontroller (such as microcontroller 387 in FIG. 3 ) to convert the actual weight to a completion percentage, a time, or to another measure related to the status of the reaction. Single Compartment Reactor Example An example lightweight, low-cost, reusable reactor 1502 is shown schematically in FIG. 15A and in detail in FIG. 15B . The thin-walled reactor 1502 is stamped and formed to include a lip 1553 around the canister cap 1555 . A separate support piece 1557 is placed on the underside of the lip 1553 . The canister cap 1555 and support piece 1557 compress the lip 1553 , facilitating a strong reactor 1502 while using a very thin walled canister that all can be disassembled and re-used. The lip 1553 facilitates a mechanical connection to secure the canister cap 1555 using a retaining ring without gluing or crimping. This provides the capability of removing the canister cap 1555 , servicing the reactor 1502 and cap 1555 , then refilling and reusing the reactor 1502 and cap 1555 . Servicing the reactor 1502 and cap 1555 can include replacing or refurbishing component pieces, such as separator membranes, filtration media, and the like. Additionally, protective methods, such as encapsulation or other methods, can be used to avoid tampering with the reactor and/or to provide reactor tampering detection. FIG. 15C shows a detailed drawing used in the manufacturing of such a thin-walled vessel including the designed over-lip 1553 . As also shown in FIG. 15B , the over-lip 1553 can be omitted if other methods are used to attach the reactor cap 1555 , such as crimp or glue-on approaches. The bottom section 1563 of the cap 1555 can be designed to minimize weight and maximize strength while providing practical connection devices (collectively shown as 1565 ) such as aqueous solution inputs, hydrogen gas inputs and outputs, electrical connection devices, and the like. As further shown in FIG. 15B and described operationally above with regard to FIG. 3 , the reactor 1502 includes both a hydrogen exit 1544 and water inlet 1591 . These connections may contain check valves and/or normally closed shut-off valves, or other devices to regulate water and hydrogen flow. An example of a normally closed shut-off valve 3434 is shown in FIG. 34 . The normally closed shut-off valve 3434 can be installed in the reactor on either the hydrogen exit 1544 and/or the water inlet 1591 as shown in FIG. 15B . A mating component 3535 shown in FIG. 35 is mounted on the control system and has an o-ring 3537 or over-molded gasket on the surface of the mating component 3535 , which touches and depresses on the surface of the normally closed shut-off valve 3434 . As the surface of mating component 3535 depresses on the valve assembly 3434 , the inner portion of shut-off valve 3434 slides to provide an open fluid channel. In the un-opened state, the spring 3430 pushes on the body of valve 3434 and causes an o-ring to seal and allow liquid to flow. An additional o-ring is used as a dynamic seal, which keeps the valve void volume to a minimum, which significantly reduces the amount of normal air added to the hydrogen gas when being connected and disconnected. The body of valve 3434 includes threads 3439 so the body may be screwed into the canister cap 1555 . The valve 3434 can be installed and held in place by many other mechanisms such as by glue, press-fit, snap-ring, and the like. The reactor shown includes integrated safety relief valves 1538 and 1588 . The safety relief valve 1538 , 1588 can be implemented in alternative methods such as a one-time controlled pressure relief burst point. In FIG. 15B , one relief valve 1538 is used to vent pressure through the filtration while another relief valve 1588 may be used to vent pressure prior to filtration. In one implementation both valves 1538 , 1588 are set to relieve at the same pressure. In another implementation, the post filter valve 1538 is set to relieve at a lower pressure than a pre-filter valve 1588 . In the event of an unattended high pressure event, the system will vent all of the high pressure hydrogen through a filtered output. The secondary valve 1588 can also serve as a backup valve in the event of a high pressure event where the filter is clogged. In another implementation, a dip tube 1543 is connected to the gas channel of the relief valve 1588 and directed to the bottom of the canister to vent the canister if stored upside down. In a version of this implementation, the dip tube 1543 can contain porous filter media at the top, bottom, or both to selectively vent hydrogen versus sodium silicate or other aqueous solution elements. The cap 1555 includes an RFID chip 1522 , such as an Atmel TK5551 RFID chip, for example. Three thin-walled tubes 1539 , 1541 , 1543 are shown within the reactor 1502 . One tube 1539 brings down water from the center of reactor 1502 and includes integrated nozzles 1549 a , 1549 b , 1549 c to direct water flow to the areas of the reactor 1502 in which the reactant fuel is present. Another tube 1541 is horizontal to the plane of top cap 1561 . This tube 1541 sweeps around the filter 1561 and sprays water across the filter 1561 to clean the filter 1561 and to further the reaction between the aqueous solution and the reactant fuel. As discussed above with regard to FIG. 3 , a check valve (not shown in FIG. 15 ) can be placed in line with the water line in the reactor 1502 . As described above, the check valve can be located in the control system, in the reactor 1502 , or in both. Water is pumped into the reactor 1502 through the previously described water network. As hydrogen exits the reactor 1502 via hydrogen exit 1591 , the hydrogen gas can be passed through a check valve (not shown in FIG. 15 ) as well. As indicated above, the hydrogen gas output check valve can also be located in the control system (shown in FIG. 3 as reference numeral 303 ), in the reactor 1502 , or in both. In systems utilizing more than a single reactor 1502 , a check valve is used for each of the hydrogen exit lines from each reactor. Also, independent pressure transducers can be used to measure each reactor pressure separately, and the independent pressure transducers are then connected to the hydrogen exit lines either in the reactors or in the control system but prior to at least one check valve or other downstream isolation mechanism. Check valves can be used to prevent one reactor from back-pressuring another. Other components, such as normally closed valves or flow control regulators, can be used to accomplish similar results. As described above with regard to FIG. 3 , hydrogen gas can pass directly out of reactor 302 . In another implementation, the hydrogen gas can first pass through a high purity contamination filter. Similarly, as shown again in FIG. 3 , the hydrogen output can be bubbled through a water tank/condenser, such as the original water tank 314 or a separate water tank. This serves to condense some amount of water vapor and to capture some amount of particulates or contaminants that may be present in the outputted hydrogen gas. After bubbling through the water tank 314 , the outputted hydrogen gas can be passed through a fine high purity filter 369 . The water tank 314 can include additives for low temperature operation or for other purposes. Additives can include a coreactant that increases the amount of H 2 produced, a flocculant, a corrosion inhibitor, or a thermophysical additive that changes thermophysical properties of the aqueous solution. For example, the thermophysical additive can change the temperature range of reaction, the pressure range of the reaction, and the like. Further, the additive to the aqueous solution can include mixtures of a variety of different additives. Some additives can facilitate less contamination in the outputted hydrogen stream, or the additive itself can serve to do hydrolysis on any developed silane (SiH 4 ) produced in the reaction. Hydrogen gas from reactor 302 can be directed to an aqueous filter 351 . A pressure transducer 340 can be used to measure and regulate the pressure of the hydrogen gas. An aqueous filter 351 is used to perform hydrolysis on any developed silane, collect particulates, and condense water from the hydrogen output stream. In the event of hydrolysis of silane, a small amount of SiO 2 and hydrogen would be generated. The produced hydrogen can be used in the hydrogen gas output 365 and the SiO 2 can be pumped into the reactor 302 with the remaining water through valves 361 , 324 . The water tank 314 can be drained and cleaned as necessary. If bubbling outputted hydrogen through water, the water tank 314 can also have a permeable membrane 367 in the top to allow hydrogen to exit at hydrogen exit port 365 , but not allow water to exit in a severe tilt or flipped upside down situation. In one implementation, the water lid 363 has a cap contact sensor 311 or other detector that notifies the micro-controller 387 once the water lid 363 is fully closed. In one implementation, the microcontroller 387 can turn off an output valve 362 before the water tank 314 to let the reactor(s) stay pressurized while more water is added. In other examples, an output valve 366 can be placed after the exit of the water tank 314 and the fine filter 367 . This output valve 366 is can be controlled by the micro-controller 387 to start the reaction and allow the pressure to build to an appropriate level to supply the outputted hydrogen gas to an end application, such as a cell phone, a laptop computer, a residential electrical grid, and the like. Another example includes a separate relief valve 368 or a bleeder valve to purge the system of any trapped air. As discussed above, a further example includes a filter 369 , such as a condenser or desiccant filter, in line with the output hydrogen line to support particular application requirements as applicable. Another example can include routing all water from reactor 302 through a secondary combination chamber 351 . Additionally, another example includes pumping input water into secondary combination chamber 351 as a direct pass on its way to the reactor 302 or with independent control to the secondary combination chamber 351 . The secondary combination chamber 351 can be coupled to the thermal control system, including thermister 328 in order to increase and/or maintain the temperature of the secondary chamber in order to facilitate hydrolysis and/or filtration, much as thermal control was provided with regard to the reactor 302 as described above. Additional Electrical Connections In both single compartment reactors and those reactors with additional compartments, additional electrical connections can be made to provide addition information to a user regarding the status of the reaction and the system specific parameters. For example in FIG. 3 , additional signal connections (either wired or wireless) can be made from reactor 302 and control system 303 to control electronics 386 to provide control devices and display devices measurement data with which to monitor and display system specific parameters. For example, one or more read/write RFID devices can be used to assess the state of the reaction by storing and reporting system specific parameters. For example, microcontroller 387 can write data indicative of the amount of water pumped into the reactor 302 to an RFID device 333 , which could be placed in a cap of reactor 302 . Based on the amount of measured water known to be inserted into the reactor 302 and with other measurements such as pressure and temperature measurements, the state-of-reaction can be determined by the system 300 . Similarly, additional RFID devices 381 , 382 , 334 can be incorporated throughout the reactor 302 and control system 303 to provide and store system information to and from microcontroller 387 . For example, each RFID device can include information such as a serial number, an amount of water inserted into the reactor, the total allowable amount of water that can be inserted into the reactor, the pressure in the reactor, the pressure in the water container and elsewhere in the system. The pressure measurements, temperature measurements, amounts of water, and other system characteristics in the RFID devices can then be used to determine the state of the reaction. Similarly, microcontroller 387 can write other system parameters, such as the water flow velocity, amount of hydrogen produced, and other parameters to RFID devices 333 , 334 , 381 , 382 and other RFID devices that can be placed in control system 303 , in reactor 302 and throughout the reaction devices. Additionally, an RFID device (not shown separately) can be integrated into the reactor 302 to provide inventory management by individually identifying the reactor 302 . This device can be used separately for inventory management, or a single device can be used in conjunction with multiple set of control functions. The RFID devices can communicate with a transponder and/or a number of transponders that can be used in multiple locations. For example, transponders can be used at a factory manufacturing reactors as part of an assembly line or as a hand-held device for quality control. Likewise, transponders can be located in mating hardware for use in the field. The mating hardware can include a hydrogen generation system, a fuel cell system, a complete power system, or other interface system. Passive Hydrogen Generation An example of a passive architecture reactor system 1600 is shown in FIG. 16 . “Passive architecture” refers to the lack of an electrical pump to initiate the reaction. Passive architecture systems are often suitable for low output systems. With this architecture, overhead operations can be minimized. For example, components of low output systems can often be combined into smaller numbers of physical packages, and other components can be eliminated altogether. For example, the fan and pump of a reactor system can be eliminated for a low-power system such as a cell phone or a cell phone recharger and other applications where low power is required and both the volume and cost must be minimized. A simplified architecture of a pump-less system for sodium silicide based (or other aqueous reactive material) hydrogen generation is shown in FIG. 16 . The water tank 1614 is initially pressurized by either connecting a pressurized source 1616 or a pump. Water is then fed through the water supply line 1690 which can also include a flow-limiter 1624 . The flow-limiter 1624 can be an active component, such as a valve, or a passive component, such as an orifice. Alternatively, gravity itself may provide the initial force to move water through the water supply line 1690 . As the initial water enters the reactor 1602 and combines with the sodium silicide 1601 , hydrogen 1634 is generated and creates hydrogen pressure, which in turn re-pressurizes the water supply 1684 via re-pressurization line 1643 . The pressure at the hydrogen output 1666 will drop as hydrogen begins to flow out of the system and back to water tank 1614 . However, the pressure at the water tank 1614 is maintained due to the check valve 1677 . This creates a pressure differential driving more water into the reactor 1602 , which then re-pressurizes the system 1600 . As the pressure increases, the total system pressure balances, which stops the water flow. Flow-limiter 1624 can be used to control the rate of water input to reactor 1602 . Otherwise, excess water could be inserted into the reactor 1602 before the hydrogen pressure has had time to develop, which could potentially lead to a positive feedback situation, and the reaction would occur prematurely. In addition, the water supply may come from either the bottom of the water tank 1614 or through another exit point (such as the top) on the tank 1614 when a water pick-up line is used (not shown in FIG. 16 ). Gravity or siphoning water feed mechanisms can also be incorporated into the system by appropriate placing of the water inlet and exits. The architecture of the low output reactor system 1600 is incorporated into a complete reactor assembly 1700 in FIG. 17 . The reactor 1702 includes reactant fuel 1701 in a reactor chamber 1722 . The reactor chamber 1722 can include membranes 1733 with which to contain the reactant fuel 1701 and provide an escape path for generated hydrogen gas. The reaction chamber 1722 can be either a rigid chamber or a flexible chamber. The reaction chamber 1722 can have membranes 1733 in multiple locations to enable the reaction chamber 1722 to be oriented in any number of directions. Surrounding the reactor chamber 1722 is the pressurized hydrogen gas 1788 within the outer hydrogen chamber 1793 , which flows out the output valve 1766 as required by the particular application. As was the case with the general low output reactor system 1600 is shown in FIG. 16 , water 1734 is supplied to reactor 1702 through a water supply line 1790 . Water 1734 can be provided to the system by water displacement pump 1716 or by an external water source through water fill port 1717 . Water re-pressurization is effected by water re-pressurization valve 1777 . In this fashion, low output reactor system 1700 can provide hydrogen gas to an end application. The reactor chamber 1722 can be fed with multiple water feed mechanisms. For example, a small pump can be integrated within the reactor 1702 to provide a fully disposable reactor with a reactor chamber, water, and pumping system. This pump can also be separated from the reactor. One example of a system with a separate pump is a spring driven system shown in FIG. 18 . FIG. 18 illustrates a spring driven reactor system 1800 with an integrated reactor chamber 1802 , water supply 1814 , and “pumping system” 1820 . The reactor 1802 can also include a water spreader (discussed below with reference to FIG. 25 ). One example spring driven reactor system incorporates a spring 1821 that pushes on a sliding piston 1831 and applies pressure to a water chamber 1841 , including water supply 1814 . Additional implementations can also be employed with different piston alternatives, such as a flexible material, elastomers, bellows, or other structures that provide movement when a differential pressure is applied across them. In the case of a spring, a small platform area 1851 can be in contact with the edge of the spring 1821 to distribute the force over a greater area. Additionally, an example of a spring driven reactor system that is fabricated into a single body package 2100 is shown schematically in FIG. 21 and pictorially in FIGS. 22A and 23 . FIGS. 22B and 24 provide exploded views of the spring driven reactor system in a single body package 2100 . Returning to FIG. 18 , as the spring 1821 develops pressure in the water chamber 1841 , water is injected into the reactor chamber 1802 . Hydrogen is generated as water contacts the reactant fuel material. As hydrogen is generated, this creates pressure in the reactor chamber 1802 , which stops the inlet of water. In this implementation, the water feed mechanism is orientation-independent. In the reactor system 1800 of FIG. 18 , the reactor chamber 1802 is not orientation-independent, because aqueous solution could block the filter 1890 , not allowing the hydrogen to pass thru when the system 1800 is upside down. To compensate for this, a reactor membrane system, such as the reactor chamber with membranes shown as reference numeral 1722 in FIG. 17 , can be implemented with multiple pickups. Additionally, a check valve 1824 can be placed between the water feed 1814 and the reactor chamber 1802 . Without such a hydrogen delivery system, hydrogen pressure pushes pack on the spring 1821 with excessive pressure, which in turn injects excessive water. The lack of a check valve could create an oscillatory system. For example, FIG. 19 shows an example pressure response over time in a system without a check valve. As shown by the graph in FIG. 19 , an oscillatory pressure response is evident when pressure equalization means, such as a check valve, is not incorporated into the system. In contrast, FIG. 20 shows an example pressure response over time in a system utilizing a check valve. The pressure response in FIG. 20 does not exhibit an oscillatory response and instead shows a steady decay associated with the spring pressure. As also shown in FIG. 20 , an initial peak at the beginning of the reaction occurs as an initial slug of water is injected into the reactor. This effect can be dampened using a water flow restrictor, or it can be increased to create a momentary transient level of high transient hydrogen generation to facilitate fuel cell stack purging. For example, in addition to the check valve 1824 , a method to slow the water flow during restarting condition can be implemented using a water flow limiter. During a restart, the instantaneous hydrogen pressure can drop to a very low value, creating an injection of water that could result in a large reaction spike. A flow limiter function can be incorporated into the water distribution function to prevent such an effect. The use of a check facilitates near constant pressure operation as determined by the spring design. Other mechanisms for the check valve feature can also be used, such as a control valve or regulator, and the like. In the passive architecture reactor systems, the water spreading and distribution can be performed using a number of techniques. For example, as shown in FIG. 25 , the water spreader 2515 can be a small diameter tube with small distribution holes 2513 . The water distribution system can also incorporate a network of holes in a silicone tube 2555 as seen inside the reactor cavity 2502 . The hole spacing, sizing, and type variability has been described above with regard to the nozzles. Additionally, the hole sizes in the silicone tube 2555 structures can provide additional flexibility. As outlined above, small holes can be subject to clogging by the generated reaction waste products, so the use of silicone tubing 2555 can allow for the pressure to create a wider hole opening up around a clog and then forcing the blockage out of the hole. Other water distribution mechanisms such as borosilicate fibers, for example, and other water wicking materials can also be used to distribute water throughout the reaction area. These water distribution techniques can be used with any type of pump or control system architecture. As shown schematically in FIG. 18 , one example of a two-part reactor system 1800 includes the reactant fuel material 1834 in one primary component or container such as reactor 1802 , and the aqueous solution is initially within another primary component or container, such as aqueous solution canister 1892 . The reactor 1802 can be disposed of or recycled once the reaction is complete, while the aqueous solution canister 1892 is reusable and refillable by a user. These two primary components 1802 , 1892 are termed a “reactor and water feed system.” In the example shown in FIG. 18 , a complete hydrogen generation system is made up of two core components: a reactant fuel reactor 1802 and an aqueous solution canister 1892 . These two separate canisters 1802 , 1892 are connected together, and interact to generate hydrogen gas. Alternatively, as discussed above, these two canisters 1802 , 1892 can simply be connected together through a water inlet valve, while a control system (e.g., fuel cell system, consumer end product, and the like) provides the mechanical rigidity to hold the canisters in place and release them accordingly. Furthermore, the entire water feed system can reside within the control system as a non-separable and/or removable component. An interface valve 1824 can reside in the reactor 1802 , in the feed system 1892 , and/or in both. When the reactor 1802 and the water feed 1892 are connected, the interface valve may not allow hydrogen pressure to deflect the spring 1821 . This can be accomplished by including features of a check valve or a controlled on/off valve in the interface valve 1824 . In a separate implementation, if the interface valve 1824 does not provide such feature, separate features can be employed to prohibit reverse movement of the spring, such as controlling the piston assembly with a screw drive or other mechanism that does not allow the water fed system to be significantly pressurized with hydrogen gas. FIGS. 22-24 show example core components in this system implementation. As shown in FIG. 22B , a metal spring 2121 is employed in the water canister 2192 to generate pressure and to provide a means for water to flow into the reactor canister. The metal spring 2121 in this example is a tapered conical extension spring, but other spring types can also be used, such as torsion, clock, inverted tapered conical, compression, and others. The spring 2121 can be mounted securely to the base 2170 of the canister 2192 , and to a plunger 2172 . Furthermore, the spring 2121 is centered to prevent plunger yaw. The plunger 2172 shown in FIG. 22B has integrated features to guide and seal as the plunger 2172 slides, but other water delivery designs can be used. For example, as discussed above, a different example can employ a flexible “bag,” which delivers water under compression to a reactor. A check valve 2162 and orifice 2164 (shown in FIG. 23 ) are incorporated into the water outlet between the water canister 2192 and powder (reactor) canister 2102 . The check valve 2162 serves to prevent hydrogen pressure from re-pressurizing the water canister 2192 , and thus prevents system instability. In other examples, the check valve 2162 can also seal upon water canister/reactor disconnection. In other examples, the check valve 2162 can also relieve pressure if excessive pressures are developed in the system. The orifice 2164 serves to limit water flow to the reactor 2102 during periods of high differential pressures between the water and reactor canisters 2102 , 2192 . As shown in FIGS. 26 and 27 , in other implementations, the reactor and water feed sub-systems are separable. For example, as shown in FIG. 26 , one example implementation employs a threaded locking mechanism 2666 to couple the two canisters 2102 , 2192 . Other locking designs can also be used such as a click to lock mechanism, or fine (10-32) internal and external threading on the water feed port. The threads of the locking mechanism do not have to seal against water or hydrogen, and O-ring or gasket type seals can be used to couple the water to reactor canister interface. The canisters in this example are both thin walled pressure vessels as described above. The reaction canister can be constructed with base corrosion resistant materials, such as nickel plated aluminum and the like. The water canister can be constructed from light metals or engineering plastics. The water canister can have a locking mechanism that prevents water flow when the canisters are disconnected or removed. The locking mechanism can be a mechanical latch that requires user intervention for water to flow. Alternatively, the reactor can contain a valve or other mechanism which stops water flow until there is user interaction. Example user interactions include a physical switch or a valve actuated by a motion of inserting the canister into fuel cell system assembly. Additionally, the spring as part of the water feed system can be configured to be outside the water as shown in the example of FIG. 27 or inside the water as shown in FIG. 28 . If the spring is located inside the water, corrosion inhibitors can be added to the aqueous solution or the spring materials can be properly selected to limit corrosion. As shown in the examples of FIGS. 29A and 29B , a number of different configurations can be used to keep a near constant water pressure the entire time of water insertion into the reactor. The springs can be selected so the actual travel distance is short in relation to the total compression distance. One method to accomplish this is by using an inverted conical spring as shown in FIGS. 29A and 29B . A long uncompressed spring 2921 can be compressed and inverted (as shown in FIG. 29B ) so that it pulls down flat while still under pressure. This enables the spring compression volume to be minimal while still providing the necessary force. Volume Considerations Some users may require configurations that are as small a volume as possible with all of the required water included within the package to minimize user complexities. In one example shown in FIGS. 30A and 30B , the reactor volume 3002 starts off small initially and grows over time as aqueous solution is depleted and added to the point(s) of reaction. The reactor volume 3002 starts off in a very compressed state. Over time, a piston 3072 or similar mechanism is used to exchange reactor volume 3002 for water feed volume 3014 . The driving force behind this can be a dynamic pumping mechanism, a spring driven mechanism, or other mechanism. In one implementation, the system is designed so that the generated hydrogen pressure does not contribute to the water delivery pressure by use of a screw-drive piston assembly, expanding gasket, or the like. In another implementation, the system is designed so that the generated hydrogen pressure does not contribute to the water delivery pressure by use of a control valve or pressure regulator as part of the water delivery system. With the spring driven mechanism shown in FIG. 30B , an inverted tapered spring 3021 is shown which allows for minimization of the water feed volume 3014 at conclusion of the reaction while still providing an acceptable force as the spring assembly can compress to be near flat while still being in an unrelaxed state. This approach uses a comparable piston (or other method), an aqueous solution distribution network, an aqueous solution flow limiter, and an integrated check valve or comparably functioned component (not shown). Mechanisms may be employed which mechanically lock the spring in place or stop aqueous solution from flowing, such as a valve or other mechanism. The aqueous solution may flow on the outside of the cartridge and can be routed through the piston geometry. Valves, regulators, or other control components can be used on the water feed line as well. Geometries and designs may be employed so that only force applied by the spring creates water displacement. For example, mechanisms such as threaded interfaces can be incorporated so that an instantaneous increase in hydrogen pressure does not translate to an instantaneous increase in water pressure. Other features such as an expanding bellows and others can be employed. Additionally, FIGS. 31-33 show a larger version of a cartridge 3100 that can be used in systems such as fuel cells for laptop computer power. Having thus described the basic concept of the invention, it will be rather apparent to those skilled in the art that the foregoing detailed disclosure is intended to be presented by way of example only, and is not limiting. Various alterations, improvements, and modifications will occur and are intended to those skilled in the art, though not expressly stated herein. These alterations, improvements, and modifications are intended to be suggested hereby, and are within the spirit and scope of the invention. Additionally, the recited order of processing elements or sequences, or the use of numbers, letters, or other designations therefore, is not intended to limit the claimed processes to any order except as can be specified in the claims. Accordingly, the invention is limited only by the following claims and equivalents thereto.
Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One system operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.
96,897
BACKGROUND AND FIELD OF THE INVENTION The present invention relates to method and apparatus for detecting the slip of a driven wheel with respect to surface with which the driven wheel is in contact. The present invention more particularly relates to a slip detecting system wherein the rotation of a driven wheel is compared with the rotation of a similar free rolling wheel also in contact with the same surface. There are a number of situations in which it is desirable to both detect and indicate slip of a driven wheel with respect to a surface against which the wheel runs. Detection of wheel slip is particularly important in connection with motor vehicles, for example, since the loss of traction accompanying the wheel slip may lead to a complete loss of control of the vehicle, resulting in property damage and/or personal injury. If the driver is aware of the slippery nature of the road surface, he can reduce the speed of the vehicle, thereby reducing the danger of loss of control. The majority of experienced drivers can detect extremely slippery road conditions early enough to prevent loss of control of the vehicle. In some situations, however, the road surface may be slippery enough to heighten the risk of high speed travel while still being modest enough to be undetectable by the motor vehicle operator. It would be desirable if some means could be provided for detecting and indicating slippery road conditions to the driver. There are other situations in which it is desirable to detect the slip of a driven wheel with respect to a surface against which the wheel runs. In agricultural equipment, for example, often heavy implements are driven by belts connected between a driven pulley and a free rolling pulley. If the implement becomes jammed, the driven wheel may begin to slip extensively with respect to the belt, thereby producing substantial friction heat and presenting a serious risk of combustion. Indeed, a number of combines have been completely lost through fires originating in this fashion. It would therefore be desirable to provide some means for detecting and indicating the presence of slip between the driven wheel (i.e., the driven pulley) and the belt. In the past, some systems have been devised for providing wheel slip detection. In one such system, a special disk containing numerous ridges or dents around its perimeter is affixed to a vehicle wheel whose slip is to be detected. A second, similar disk is affixed to a second, free rolling wheel of the vehicle. Sensors are then disposed adjacent each dented disk for detecting the rotation of the respective wheels. The sensors each provide one output pulse each time a dent passes the sensor. The rate of occurrence of the sensor pulses is therefore directly related to the speed of rotation of the wheel to which the disk is attached. Wheel slip can be detected by comparing the repetition rates of the pulses at the outputs of the two sensors. Unfortunately, dented disks are difficult and expensive to manufacture, and are likewise difficult to mount upon existing vehicles. The total cost of purchasing and installing the system tends to be so high, in fact, that ordinary drivers are unwilling to spend the money necessary to procure and mount such a system. SUMMARY OF THE INVENTION The present invention provides a system for detecting wheel slip which is substantially less expensive to construct and easier to install than prior systems. In the present system, only one sensible element (e.g., a magnet) is affixed to the driven wheel, a similar magnet being mounted on the free rolling wheel. Sensors (e.g., inductive coils) are mounted adjacent the wheels at such locations that the magnets rotate past the coils once in each revolution of the wheel. The magnets thus induce one pulse across the sensor coil for each complete revolution of the wheel to which the magnet is attached. The time interval between sucessive pulses appearing at each sensor corresponds to the time of rotation of the associated wheel, and is therefore inversely proportional to the speed of the vehicle. Wheel slip can thus be detected by comparing the time interval between pulses from the driven wheel sensor with the time interval between pulses from the free rolling wheel sensor. Since the times of occurrence of the front and rear wheel sensor pulses are usually different, the measurement of the time interval between pulses of one wheel will take place at a different time than will the measurement of the time interval between pulses of another wheel. This lack of correlation of the times of measurement is problematical, however, since the vehicle speed may change markedly during the interval between two measurements. A difference between the measured times of rotation of the driven and free rolling wheels may thus be due to acceleration of the vehicle during the time between measurements, rather than due to wheel slip. In accordance with one aspect of the present invention, the wheel slip detection process is corrected to account for vehicle acceleration. Vehicle acceleration is detected, and the detected acceleration is then used to modify either the wheel slip threshold or the wheel slip indication, itself. BRIEF DESCRIPTION OF THE DRAWINGS The foregoing and other objects and advantages of the present invention will become more readily apparent from the following detailed description, as taken in conjunction with the accompanying drawings, wherein: FIG. 1 is a schematic representation showing the manner of mounting of the rotation sensors in accordance with the present invention; FIG. 2 is a block diagram of one embodiment of the circuitry associated with the present invention; FIG. 3 is a circuit diagram of a second, and currently preferred, embodiment of the circuitry associated with the present invention; FIG. 4 is a flow chart illustrating the main program executed by the microcomputer associated with the circuitry of FIG. 3; FIG. 5 is a schematic representations of various memory locations used by the microcomputer for the storage of variable values, also showing the manner in which the data within various locations is manipulated in one branch of the flow chart of FIG. 4; FIG. 6 is a more detailed flow chart illustrating the operations performed in one part of the flow chart of FIG. 4; and, FIG. 7 is a flow chart illustrating the interrupt servicing routine performed by the microcomputer in the FIG. 3 embodiment. DETAILED DESCRIPTION FIG. 1 illustrates the manner in which the sensing elements may be attached to a standard passenger vehicle. FIG. 1 is more specifically a representation of the rear suspension of a 1981 Volkswagen Jetta, however the sensor elements can of course be mounted in an entirely equivalent fashion on the suspension of virtually any wheeled vehicle currently in use today. In FIG. 1, a rubber tire 10 is mounted on a metal wheel or rim 12. The wheel or rim 12 is bolted to a brake/bearing assembly 14. The brake/bearing assembly is secured to a support beam 16, which is in turn affixed to the frame of a vehicle through suitable shock insulating components including a shock absorber 18. The rotation sensor includes a magnet 20 and a magnetic coil 22. The magnet 20 is attached to the perimeter lip of the wheel 12 by a suitable adhesive (e.g., epoxy cement, double-faced contact tape, etc.), and the magnetic coil 22 is suspended over the perimeter of the wheel by a bracket 24. The bracket 24 is fastened to the shock absorber 18 by a conventional U-bolt 28. The coil 22 will preferably be positioned immediately adjacent the path of rotation of the magnet 20, however the exact axial spacing between the coil 22 and the path of magnet 20 is not critical. The sensor will operate properly with axial spacings as great as an inch. The sensor coil and magnet are inexpensive, and can be mounted in the illustrated positions with little difficulty, and without removing the tire and wheel. The positioning of the magnet upon the perimeter lip of the wheel 12 is not critical. The position of the sensor coil 22 relative to the rotational path of the magnet 20 can readily be adjusted by sliding the U-bolt 28 up and down on the shock absorber 18, and by rotating the U-bolt and mounting bracket 24 around the shock absorber. Moreover, the mounting stud projecting from the sensor coil 22 is carried in an elongated slot in the bracket 24, and can be slid back and forth within the slot to obtain optimum adjustment of the position of the sensor coil 22. In other systems, wherein plural sensible elements are disposed around the perimeter of the wheel, the spacing of the elements is quite important. In such systems, the interval between pulses is dependent not only upon the rotational speed of the wheel, but also upon the spacing between the two sensible elements which produce those pulses. The spacing between the various sensible elements therefore should be the same, or otherwise it would not be known whether a change from one time interval to the next were due to a change in the velocity of the vehicle or to a nonuniformity in the spacing between the various sensible elements. In the present system, this problem does not arise. Since there is a single magnet mounted on the wheel, each pulse appearing at the output of the sensor coil 22 is caused by the passage on the same point on the wheel. It is therefore known that the interval between pulses in each case corresponds to the exact same degree of rotation (i.e., one full turn) of the wheel 10. A similar magnet and coil are mounted to a front wheel of the vehicle. Preferably, the sensors on the front and rear of the car are mounted on the same side of the vehicle. Thus, for example, the sensors could be mounted on the front right and rear right wheels of the car. The vehicle to which the sensors are attached may be either a front wheel drive, or rear wheel drive car. For the purposes of the discussion which follows, however, it will be presumed that the vehicle to which the sensors are attached is a front wheel drive car. The front wheel is thus a driven wheel and the rear wheel is the free rolling wheel. The two ends of each sensor coil 22 are connected to electronic circuitry through electrical cables 26 (FIG. 1). The electronic circuitry (not shown in FIG. 1), determines, and warns of, wheel slip by measuring and comparing the time intervals between consecutive sensor pulses. FIG. 2 is a simplified schematic of one embodiment of electronic circuitry which could be utilized in conjunction with the sensors to provide the slip warning. In FIG. 2 and the figures which follow, various system elements and firmware steps refer to certain variable names used to identify system variables. The table which follows identifies the variables, and is included for reference purposes. TABLE I______________________________________MCNTR Main counterRTROT (N) Rear wheel time of rotation (new)RTROT (N-1) Rear wheel time of rotation (old)RT (N) MCNTR value at rear wheel pulse (new)RT (N-1) MCNTR value at rear wheel pulse (old)FTROT (N) Front wheel time of rotation (new)FTROT (N-1) Front wheel time of rotation (old)FT (N) MCNTR value at front wheel pulse (new)FT (N-1) MCNTR value at front wheel pulse (old)ACC Wheel accelerationSLIP Difference in rotation times of wheelsFCNTR Front wheel low speed counterRCNTR Rear wheel low speed counterTHRESH Slip warning thresholdFLAGS Various system flags______________________________________ In FIG. 2, the rear and front wheel sensors are indicated at 50 and 52. The sensors 50 and 52 of FIG. 2 each include a sensor coil and suitable signal conditioning circuitry for conditioning the output signal pulses provided by the coils in response to each passage of an associated magnet. Each sensor 50 and 52 therefore provides a singular, well defined pulse each time its associated magnet passes by. The circuitry of FIG. 2 generally includes a clock circuit 46 for generating a two-byte digital word which indicates and changes with the current time, and a time interval processing circuit 48 responsive to the output of the clock circuit 46 and the sensor outputs for measuring and comparing the rotation times of the front and rear wheels. The processing circuit 48 includes five digital registers, each capable of storing one digital word. The output line of rear sensor 50 is connected to the "load" input of three of the digital registers 54, 56 and 58, and the output of the front sensor 52 is similarly connected to the "load" input of the remaining two digital registers 60 and 62. Each time a pulse occurs on the "load" input of one of the five registers, that register latches and thus stores the digital word being provided in parallel to its input. The stored number is continuously provided at the register output. The parallel input of register 56 is taken from the parallel output of register 54, hence register 56 will store the value previously contained in register 54 upon the occurrence of a sensor pulse. Similarly, the parallel input of register 62 is taken from the parallel output of register 60, hence register 62 will respond to each sensor pulse by storing the value previously contained in register 60. The inputs to registers 54 and 60, on the other hand, are both connected to the parallel output of the clock circuit 46. In FIG. 1, clock circuit 46 is comprised of a free running counter 64. Free running counter 64 is periodically incremented by pulses provided by a clock oscillator 66. Clock oscillator 66 provides clock pulses at a fixed frequency which is substantially greater than the highest expected frequency of pulses at the output of either of the sensors 50 or 52, whereby the counter 64 will increment through at least several hundred different values between each pair of consecutive sensor output pulses. Each time a sensor pulse occurs, the current count contained within the counter 64 is loaded into a respective register 54 or 60. Register 54, therefore, may be considered to contain a number RT(N) identifying the time of occurrence of the most recent rear wheel sensor pulse. At the same time that the current count contained within counter 64 is loaded into register 54, the value previously stored within register 54 is loaded into register 56. Register 56 therefore contains the counter reading RT(N-1) at the time of occurrence of the rear wheel sensor pulse just prior to the most recent pulse. The difference between the numbers stored in registers 54 and 56 represents the number of pulses of clock 66 which had transpired between the two rear wheel sensor pulses, and therefore is directly related to the most recent time of rotation RTROT(N) of the rear wheel. A digital subtractor circuit 68 is connected to the outputs of the two registers 54 and 56, and develops the difference signal corresponding to the time of rotation of the rear tire. Registers 60 and 62 contain similar information relating to the front wheel, and have their outputs connected to a subtractor circuit 70. The output of subtractor circuit 70 is a digital word representative of the time of rotation FTROT(N) of the front wheel. The outputs of the two subtractor circuits 68 and 70 are subtracted from one another in a third digital subtractor circuit 72. The resulting difference signal corresponds to the difference in rotation times of the front and rear wheels, and therefore corresponds with the degree of wheel slip. A subtractor circuit 74 subtracts a reference signal from the slip signal, and provides an output signal which will be negative as long a the reference signal is greater in magnitude than the slip signal. The output of the subtractor circuit 74 is applied to a warning circuit 76. Warning circuit 76 provides a warning indication if the output signal provided by the subtractor circuit 74 becomes greater than zero. Thus, whenever the slip signal represented at the output of subtractor 72 becomes greater than the reference signal, a warning indication will be provided to the vehicle operator. The timing relationship between the various values stored in the four registers 54, 56, 60 and 62 is represented in the graph associated with FIG. 2. In the graph, the signal from sensor 52 is designated as signal "F" (front) and the signal from sensor 50 is designated as signal "R" (rear). Pulse C of signal R is the most recent pulse, and its time of occurrence RT(N) is stored in register 54. The times of occurrence of the other rear and front wheel pulses are indicated on the graph. From the graph, it can be seen that the front and rear wheel pulses do not occur at the same time. In fact, the phase relationship between the front and rear wheel pulses will change, due primarily to wheel slip. Since the front and rear wheel pulses are not aligned in time, however, the times of wheel rotation RTROT and FTROT are measured over different time intervals. In the example illustrated in the graph of FIG. 2, for example, the front wheel time of rotation FTROT(N) actually was measured over approximately the same time interval over which the previous rear wheel time of rotation RTROT(N-1) was measured. If vehicle speed has changed, however, RTROT(N) will be different than RTROT(N-1). Thus, in the example, FTROT(N) should more properly be compared with RTROT(N-1) since those measurements were more closely aligned in time. At another time, however, the timing relationship between front and rear wheel pulses may be such that FTROT(N) is measured over an interval nearly coincident with RTROT(N). In that circumstance FTROT(N) should be compared with RTROT(N) instead of RTROT(N-1). It can be concluded, however, that in the absence of slip FTROT(N) should have a value somewhere between the values of RTROT(N) and RTROT(N-1). If RTROT(N) is equal to RTROT(N-1), there is no uncertainty in the expected no-slip value of FTROT(N). If RTROT(N) and RTROT(N-1) are different, however, an uncertainty is added as to the correct no-slip value of FTROT(N). The uncertainty is directly related to the difference between RTROT(N) and RTROT(N-1), and is thus directly related to change in vehicle velocity (i.e., vehicle acceleration). This uncertainty is accounted for in the FIG. 2 embodiment by adding the vehicle acceleration to the alarm warning reference level. Acceleration is determined by subtracting the present time of rotation of the wheel from the immediately preceding time of rotation for the same wheel. The immediately preceding time of rotation is stored in a register 58 having its parallel input lines connected to the output of subtractor 68. Register 58 is loaded by the same output pulses of sensor 50 which load registers 54 and 56. Thus, with each pulse, the contents of register 54 are loaded into register 56, and the output signal of subtractor 68 is loaded into register 58. Subtractor circuit 78 subtracts the output of subtractor circuit 68 (i.e., the most recent time of rotation of the rear wheel) from the output of register 58 (i.e., the time of rotation of the rear wheel immediately preceding the current time of rotation) to thereby provide an acceleration signal. The acceleration signal appearing at the output of signal subtractor 78 is used to modify a threshold signal provided by threshold circuit 80. Threshold circuit 80 provides a threshold signal which preferably will have a value dependent upon the most recent time of rotation of the free rolling (rear) wheel of the vehicle. If a fixed threshold signal were instead provided, the threshold would seem higher at high speeds than at low speeds because the total time of rotation of a tire diminishes with increasing vehicle speed. Thus a fixed threshold would be a greater precentage of the total time of rotation at low speeds than at high speeds. A suitable threshold value can be derived by dividing down the signal at the output of subtractor 68. In the embodiment shown in FIG. 2, the threshold signal comprises the higher ordered bits of the digital word appearing at the output of subtractor 68. The four lowest ordered bits are discarded, thus effectively dividing the signal at the output of subtractor 68 by a factor of 16. The resulting threshold signal corresponds to a fixed percentage (approximately 6%) of the output of the signal subtractor 68. An adder circuit 84 additively combines the acceleration signal at the output of subtractor 78 with the threshold signal provided by threshold circuit 80. The result of the addition process is a reference signal which is essentially a fixed percentage of the rotation time of the free rolling wheel, but which is increased by the amount of acceleration of the free rolling tire to account for changes in the speed of the vehicle during the interval between successive rotation time measurements. Thus, during the portion of the time in which the vehicle is accelerating or decelerating, the threshold is increased or reduced by an amount dependent upon the amount of acceleration or deceleration. It will be noted that the relationships shown in the graph associated with FIG. 2 no longer apply once the next front wheel pulse (C') arrives. After C', FTROT(N) is moved up to the interval between B' and C', and hence it should be compared against RTROT(N) and RTROT(N+1). RTROT(N+1) cannot yet be determined, however, since the next rear wheel pulse has not yet been received. The circuit of FIG. 2 solves this problem by disabling the output of subtractor 74 until the next rear wheel pulse arrives. In FIG. 2, a set/reset flip-flop 86 is controlled by the front and rear wheel sensor pulses. The output of the flip-flop, in turn, controls a solid state switch 88 located between subtractor 74 and warning circuit 76. Flip-flop 86 is reset by each rear wheel pulse and set by each front wheel pulse, hence the switch 88 is only closed for the interval after a rear wheel pulse and before a front wheel pulse. Thus, the warning circuit 76 is connected to the subtractor 74 only when FTROT(N) falls between RTROT(N) and RTROT(N-1), as illustrated in the graph associated with FIG. 2. Warning circuit 76 includes a conventional attack/release circuit for sustaining a warning initiated by the intermittent closure of switch 88. In the next embodiment (FIG. 3), the problem is solved somewhat differently. Thus, the FIG. 3 embodiment functions such that, after a rear wheel pulse, wheel slip is compared against a threshold adjusted in accordance with rear wheel acceleration, but after a front wheel pulse, wheel slip is compared against a threshold adjusted in accordance with front wheel acceleration. FIG. 3 is a circuit schematic of a second, presently preferred embodiment of a circuit for use in the wheel slip detector in accordance with the present invention. The circuit consists of little more than a single chip microcomputer 100, two sensor coil signal processing circuits 102 and 104, a sensitivity switch 106, and an indicating buzzer 108 and two indicator lamps 110 and 112. The various registers shown in the FIG. 2 embodiment are also used in the FIG. 3 embodiment, but are represented by various data storage locations within the microcomputer 100. The loading of the data into the registers and the processing of the data within the registers by subtraction, addition, etc., however, are all accomplished through firmware permanently resident within the microcomputer 100. The firmware will be described hereinafter with reference to FIGS. 4-7. The microcomputer 100 may take any conventional form, but in the embodiment described comprises a model 8748 single chip microcomputer, manufactured and sold by Intel Corporation of Santa Clara, Calif. A detailed description of the contents of the 8748 microcomputer, its various hardware and software functions, and a complete description of its instruction set is contained within the Intel Microcontroller Handbook, first published by Intel Corporation in 1983. The heart of the microcomputer 100 is a microprocessor 120. The microprocessor 120 communicates with the remainer of the elements of the microcomputer through a system bus including a conventional data bus, address and control bus. Instructions for operation of the microprocessor (known as "firmware") are stored within a read only memory (ROM) 124. Working storage of variable values is provided by 64 bytes of random access memory (RAM) 126. Both ROM 124 and RAM 126 are connected to the microprocessor 120 through the system bus. In a conventional and well known fashion, the microprocessor executes the program stored in the read only memory by first addressing the first location within the read only memory, executing that instruction, and then proceeding on to the next instruction. The microprocessor proceeds to read and execute instructions in sequence from the read only memory 124, jumping out of sequence only when a particular instruction directs the microprocessor to continue program execution at some other address within the read only memory. A timer 128 is included in the microcomputer. The timer is essentially just a free running counter, and is incremented by a clock signal derived from the clock (not shown) which operates the microprocessor 120. The timer 128 is loaded with an initial count by the microprocessor 120, and thereafter increments the count periodically in accordance with the clock signal. When the timer overflows, it places an interrupt signal on the interrupt line 130, thereby advising the microprocessor that the selected interval of time has elapsed. The length of time necessary for the timer 128 to overflow is directly related to its initial value, and is therefore directly programmable by the microprocessor 120. Three ports 132, 134, and 136 provide interfaces between the system bus and devices external to the microcomputer 100. Port 132 includes output lines which are essential bidirectional, hence some lines of the port may be used as inputs, while others are simultaneously used as outputs. In the embodiment of FIG. 3, two of the lines leading to port 132 are taken from the outputs of the sensor signal processors 102 and 104, whereas the third is taken from the sensitivity switch 106. Three other lines from the port 132 are applied to the driver transistors 140, 142, and 144 respectively associated with the buzzer 108 and indicator lamps 112 and 110. The microprocessor 120 can read both the sensor output signals and the sensitivity switch position by reading port 132. Similarly, the microprocessor 120 can control the states of the driving transistors 140, 142 and 144 by writing data into the port 132. Ports 134 and 136 of the microcomputer 100 are hard wired with data input values used to access a lookup table and thereby retrieve a threshold value for use in the processng of the wheel slip information. Thus, the sensitivity of the wheel slip detector may be changed by reconnecting the input lines to the ports 134 and 136 in a different manner. This will be described in greater detail hereinafter with respect to FIG. 6. In FIG. 3, the sensor coil 146 associated with the rear (free rolling) wheel is connected to a signal processing circuit 102. In the signal processing circuit 102, each end of the sensor coil 146 is connected to a corresponding input of a signal comparator circuit 148. One end of the coil 146 is connected to the inverting input of comparator 148 through a resistor 150, and the other end of the coil 146 is connected to the noninverting input of the comparator through a similar resistor 152. Comparator 148 provides an output signal which is high (i.e., approximately equal to the positive supply voltage) when the signal on its noninverting input is greater than the signal on its inverting input. The comparator output signal is low (approximately equal to signal ground), however, whenever the signal on its inverting input is greater than the signal on its noninverting input. A positive feedback resistor 154 is connected between the output of signal comparator 148 and its noninverting input so as to provide the switching characteristics of the comparator whith some degree of hysteresis. A capacitor 156 is connected across the two inputs to the signal comparator to suppress noise on the comparator inputs. The signal coil 146 is connected to the inputs of the signal comparator 148 in such a fashion that, each time the magnet passes the coil, the signal on the noninverting input of the signal comparator goes positive relative to the signal of the inverting input, after which it goes negative relative to the input on the inverting input. When the input signal provided by the coil 146 goes positive, the output of signal comparator 148 is forced high. When shortly thereafter the input signal goes negative, however, the output of the signal comparator 148 is forced to return to a low signal level. Thus, the output of signal comparator 148 is normally low, but switches high for a brief period of time each time the magnet passes the coil 146. The input lines to the signal comparator 148 are protected by signal clipping circuits 158 and 160. The clipping circuit 158 includes two diodes and a resistor, all connected in parallel between one end of the coil 146 and a reference voltage V ref . The diodes are connected anti-parallel to one another. Signal clipping circuit 160 is similar to signal clipping circuit 158, although the three parallel elements are instead connected between the other lead of the coil 146 and the reference voltage V ref . The purpose of the signal clipping circuits 158 and 160 is to protect the signal comparator 148 by preventing the input signals on the two input lines from rising to levels which could damage the comparator. This form of signal protection is desirable since the output of the coil 146 could otherwise reach quite high levels at high vehicle speeds. The signal clipping circuits, however, prevent the signals on the input lines to the signal comparator from deviating from the reference voltage V ref by more than approximately 0.7 volt. The reference voltage V ref is established by a voltage divider (not shown) connected between the positive supply rail and ground. The signal processing circuit 104 associated with the front inductive coil 162 is similar to signal processing circuit 102. Thus, signal processing circuit 104 provides an output which is normally low, but which switches high briefly whenever the magnet on the front wheel passes the inductive coil 162. Slip warning buzzer 108 is controlled by an output of port 132 through a driver transistor 140. In the embodiment shown in FIG. 3, the driver transistor 140 has its collector-emitter current path connected across the supply voltage in series with the buzzer 108, a manual switch 170, and a current limiting resistor 172. A free wheeling diode 174 is connected across the coil 108. Normally, the switch 170 is closed such that power is supplied to the buzzer 108 whenever the transistor 140 is turned on. The switch 170 may be manually opened by the operator to disable the audible warning, however. The two indicator lamps 110 and 112 are similarly controlled by outputs of the port 132 through driving transistors 142 and 144. The indicator lamps 110 and 112, however, do not require or include free wheeling diodes, disabling switches, or current limiting resistors. The sensitivity switch 106 comprises a single pole double-throw manual switch having one contact connected to the positive supply rail and the other contact connected to ground. The microcomputer 100 responds to the position of the switch 106 by establishing either a high or a low threshold level. Thus, the operator can manually control the threshold point at which the indicator buzzer and lamps are actuated by selecting the corresponding position of the switch 106. The firmware associated with the microprocessor 120 in FIG. 3 includes two major components: a main program (FIG. 4), and an interrupt servicing routine (FIG. 7). The main program performs the bulk of the processing required to generate the slip warning signal. The microprocessor continuously cycles through the main program, but is interrupted every 160 microseconds during the execution of the main program by the interrupt signal generated by the timer 128. Each time the microprocessor 120 is interrupted by the timer 128, it suspends execution of the main program shown in FIG. 4 and jumps to the interrupt servicing routine shown in FIG. 7. The functions performed by the microprocessor during the interrupt servicing routine will be described in detail hereinafter with reference to FIG. 7. Generally, however, the functions may be divided into two categories: (1) If the system is in what is known as a low speed or "LS" mode, the microprocessor executes a branch of the interrupt servicing routine wherein the microprocessor examines the interval between successive pulses provided by the sensors 146 and 162, switching the system to the high speed mode if the interval is less than an amount corresponding to a vehicle speed of 25 kilometers per hours. (2) If the system is in the high speed (HS) mode, the microprocessor executes a branch of the interrupt servicing routine wherein (a) a main counter MCNTR, similar in function to the counter 64 of FIG. 2, is incremented, (b) the value of a variable FT(N) is set equal to the current value of MCNTR if a pulse is detected by the front sensor 162, and (c) a variable RT(N) is set equal to the current value of MCNTR if a pulse is detected by the rear sensor. As long as the vehicle is traveling in excess of 25 kilometers per hour, the interrupt servicing routine will thus spend the majority of its time searching for front and rear sensor pulses, and will record the value of the main counter MCNTR at the time of each. Since the interrupt servicing routine occurs so frequently, however, most often the interrupt servicing routine will not detect either a front or rear wheel pulse, hence no value will be recorded. Even at highway speeds of 100 kilometers per hour, approximately 70 milliseconds is still required for a wheel to complete one full revolution. During that 70 millisecond interval, approximately 500 interrupts will occur and be processed. Thus, the main counter MCNTR will be incremented at least several hundreds of times during the time interval between consecutive pulses from the same rotation sensor. FIG. 4 is a flow chart of the main program executed by the microprocessor 120. When power is applied to the system, a reset circuit 180 applies a pulse to the reset input of the microprocessor, causing it to begin programmed operation at a pre-established address within the read only memory. The reset address corresponds to the start location of FIG. 4. Following the reset, the microprocessor performs the usual initialization routines 200, establishing the initial values of the various working registers of the microprocessor, performing initial housekeeping functions such as diagnostic procedures, and enabling the interrupt input to the microprocessor. The microprocessor also operates the buzzer and indicator lights momentarily to assure the operator that the system has begun operating normally, and initializes the system mode flag to the low speed mode. In the next step 204, the operating registers corresponding to the registers shown in FIG. 2 (RT(N) RT(N-1), FT(N), FT(N-1), and other registers used in intermediate stages of processing) are reset to prepare for entry into the main processing loop. The beginning of the main processing loop is identified by the label MLOOP, and begins with step 206. In step 206, the microprocessor checks the timer to make sure that it is operating and that the interrupt input to the microprocessor is enabled. This is largely a precautionary step whose function is to restart the timer in the unlikely event that noise within the system causes it to spontaneously become disabled. In the next step 208, the microprocessor tests the internal mode flag to determine whether the system is operating in the high speed (HS) or low speed (LS) mode. (The system will be in the HS mode when the vehicle is cruising at normal highway speeds, and will be in the LS mode otherwise.) If the system is in the low speed mode, the microcomputer proceeds on to step 210. In step 210, a "two turns" counter is reset. The "two turns" counter is used in another part of the main loop, described hereinafter, to insure that wheel slip is not calculated until data has been acquired for two full revolutions of the vehicle wheels after the system has switched to the high speed mode of operation. After step 210, the microprocessor jumps back to step 204. As long as the system remains in the low speed mode, it will continue to cycle through the steps 204, 206, 208 and 210. If the vehicle speeds up, however, the system will be switched to a high speed mode of operation during servicing of one of the timer interrupts. Thus, at some point the microprocessor will reach step 208, and will find that the system has been switched to the high speed mode. At that point, program flow will jump to step 212. In step 212, an internal front sensor pulse flag is checked to determine whether there has been a pulse from the front sensor since the last time that the microprocessor passed through step 212. If there has been no front pulse, the microprocessor proceeds on to step 214, where a similar check for a rear wheel sensor pulse is performed. If there has also been no rear wheel sensor pulse, the microprocessor continues on with step 216, thereafter returning to the point in the program (step 206) identified by the label MLOOP. Step 216 is included to cause the buzzer 108 and indicator lights 110 and 112 to rapidly switch on and off when the slip warning flag is high. In step 216, the value of one of the middle ordered bits of the current value of MCNTR is read and applied to the driver transistors 142 and 144 through port 132. Since the MCNTR bit toggles on and off periodically as MCNTR continues to count, the lights will similarly blink on and off. The same bit value is stored as a "beep" flag, used in step 620 of the interrupt servicing routine of FIG. 7 to control the buzzer 108. The front and rear wheel sensor pulse flags are set by the interrupt servicing routine. Each time the microprocessor is interrupted by the timer 128, it checks for a front or a rear sensor pulse. If a pulse is found, the current MCNTR value is stored as either RT(N) or FT(N), as appropriate, and the corresponding sensor pulse flag is set to indicate that new pulse data is available for processing by the main loop. When, in examining the sensor pulse flags in steps 212 or 214, it is found that a front or a rear pulse has occurred since the last time that steps 212 or 214 of the program were executed, the microprocessor jumps to the data processing branches of the main program. FIG. 5 is a schematic illustration of the fashion in which data is stored and manipulated by the microprocessor during the front wheel pulse processing branch (steps 250-264 and step 400) of the main loop. In FIG. 5, each rectangular block represents a storage location within the random access memory 126 of FIG. 3. Each of the illustrated storage locations is two bytes wide, and stores a value of a corresponding system variable. (The variables are listed, above, in Table I.) The circled arithmatic signs represent the arithmatic data manipulations performed by the firmware routine, and the arrows pointing to and from the circled arithmatic signs identify the sources of the information used in the arithmatic operation and the destination of the results of the arithmatic process. The circled numbers in FIG. 5 represent the order in which the various steps are performed during the execution of the main loop. FIG. 5 will not be separately described, but should be consulted in considering the following description of the pulse processing branches of the main loop of FIG. 4. In the main program of FIG. 4, the microprocessor jumps to step 250 if it is determined in step 212 that a pulse has been received from the front sensor. In step 250, the "front pulse" flag is cleared. Succeeding passes through program step 212 will therefore not be diverted to step 250 until such time as the next front pulse occurs. Also in step 250, the current value of the "front wheel time of rotation" variable FTROT(N) is loaded into the memory location used for the old value of the same variable (FTROT(N-1)). A new front wheel time of rotation is then calculated by subtracting the value of the main counter at the time of the preceeding front wheel pulse (FT(N-1)) from the value of the main counter at the time of the most recent front wheel pulse (FT(N)). The result of the subtraction process is loaded into the memory location for the variable representing the most recent front wheel time of rotation (FTROT(N)). Then, the current value of the variable FT(N) is loaded into the memory location storing the previous value of the same variable, FT(N-1), thereby freeing the FT(N) memory location to be loaded with new data upon the occurrence of the next front sensor pulse. In step 252, the microprocessor examines the value of the "two turns" counter. If the two turns counter contains a value less than 2, the microprocessor increments the turns counter in step 254, and returns to the main loop at the point labelled MLOOP. As stated previously, the purpose of the "two turns" counter (and steps 252 and 254) is to insure that at least two full revolutions of the vehicle tires have been completed before wheel slip is calculated. Only then will all of the systems variables have acquired meaningful values. If it is determined in step 252 that two full turns of the vehicle tires have been completed since the system last switched to the high speed mode of operation, program flow proceeds to step 256. In step 256, the current front wheel time of rotation FTROT(N) is compared with a constant representative of a speed of 35 kilometers per hour. If the current value of FTROT(N) is less than the limit, then the speed of the vehicle is greater than the limit of 35 miles per hour and program execution proceeds on to step 258. In step 258, front wheel acceleration is calculated by subtracting the previous front wheel time of rotation from the current front wheel time of rotation. The resulting acceleration signal is then loaded into the memory location designated to contain the acceleration variable. A threshold value is also calculated in step 258. The steps involved in the calculation of the threshold value are shown in FIG. 6, and will be described hereinafter with reference to that Figure. If it is determined in step 256 that the speed of the front wheel of the vehicle is less than 35 kilometers per hour, program execution jumps to steps 260, 262 and 264. Steps 260, 262 and 264 are included to determine whether the system should be switched into the low speed or "LS" mode of operation. In step 260, the current time of rotation of the front wheel (FTROT(N)) is compared with a limit corresponding to a vehicle speed of 20 kilometers per hour. If the time of rotation is less than the limit, then the speed of the vehicle is greater than 20 kilometers per hour. In this event, the microprocessor remains in the high speed mode, but returns to the point in the program labelled MLOOP. If the speed of the front wheel is below 20 kilometers per hour, however, program execution proceeds on to step 262. In step 262, the current rear wheel time of rotation RTROT(N) is compared against the same 20 kilometer per hour limit used in step 260. If the rear wheel time of rotation is less than the limit, then the speed of the rear wheel is in excess of 20 kilometers per hour. In this event, the system again remains in the high speed mode of operation, but again returns to the point in the main program designated by the label MLOOP. If, however, it is determined in step 262 that the speed of the rear wheel is also less than 20 kilometers per hour, program execution proceeds on to step 264. In step 264 the system is switched to the low speed (LS) mode, and the main counter MCNTR is reset. Thereafter, program execution continues at the point in the main program designated by the label MLOOP. Thus, steps 256, 260, and 262 function to place the system in the low speed mode of operation only when both the front and rear wheels of the vehicle are traveling at a rate of speed below 20 kilometers per hour. In all other circumstances the system remains in the high speed mode of operation, although certain portions of the signal processing are bypassed if the speed of the vehicle is between 20 and 35 kilometers per hour. The sequence of steps 350-364 which are executed if a rear wheel pulse is detected are essentially the same as steps 252-264, except that rear wheel variables are used instead of front wheel values. The purpose of both sequences of steps is to derive a new value of acceleration (rear wheel acceleration in one case, front wheel acceleration in the other), a new value of current time of rotation for the respective tire, and a new threshold value. Having acquired this information in either step 258 or 358, the microprocessor jumps to step 400. In step 400, reached through either step 258 or 358, the difference in rotation times of the front and rear tires is determined by subtracting RTROT(N) from FTROT(N). The difference is stored as a variable SLIP. A wheel slip reference value is then calculated by adding together the threshold signal THRESH and the acceleration signal ACC. The difference (DIFF) between the variable SLIP and the reference value is calculated and used to determine whether wheel slip is excessive. If the DIFF value calculated in step 400 is greater than zero, the audible and visual alarms are turned on by setting the slip warning flag. If the DIFF value is less than zero, however, meaning that wheel slip is less than the sum of the threshold and acceleration values, then both alarms are instead turned off by resetting the slip warning flag. Program flow then returns to the main program at label MLOOP. As stated previously, the threshold against which the difference in rotation times of the front and rear wheels is compared is calculated in each pass through either step 258 or 358. There are, of course, numerous different procedures which could be employed to calculate the threshold in steps 258 or 358. For example, the time of rotation of the free rolling wheel could merely be divided by an appropriate factor of two (i.e., be shifted right) as described previously with respect to FIG. 2. Preferably, however, a procedure such as that shown in FIG. 6 is instead employed. In the procedure of FIG. 6, one of thirty-two different linear relationships between time of rotation and threshold will be selected, dependent upon three different factors: (1) the position of the sensitivity switch 106 of FIG. 3, (2) whether the speed of the vehicle is above or below a selected breakpoint, and (3) the sensitivity select words hard wired into the inputs ports 134 and 136 of FIG. 3. In essence, the digital number applied to the input port 134 of FIG. 3 selects two "high sensitivity" linear relationships between time of rotation and threshold (from a set of 16 available relationships), one for vehicle speeds above the breakpoint and another for speeds below the breakpoint. Similarly, the digital number applied to the input port 136 selects two "low sensitivity" linear relationships between time of rotation and threshold from among a different set of 16 available relationships. One of the four different linear relationships thus identified is then chosen in accordance with the position of the sensitivity switch (high or low sensitivity) and the decision as to whether the vehicle speed is above or below the breakpoint. A specific threshold value is then calculated from the chosen linear relationship. In step 502, the three different criterion for selecting a linear relationship between time of rotation and threshold are examined. The sensitivity switch 106 is read by reading port 132, the time of rotation of the respective wheel (the front wheel when executing step 258 and the rear wheel when executing step 358) is compared with the breakpoint corresponding, for example, to a vehicle speed of 100 kilometers per hour, and the curve numbers are read from ports 134 and 136. These values are then used to address a ROM look-up table containing the slope and offset (Y-axis intercept) values defining a specific linear relationship between time of rotation and threshold. The remaining steps 506, 508, and 510 calculate the threshold from those values by solving the equation: TROT(N)=OFFSET+THRESH*SLOPE for the threshold value THRESH. In step 506, the threshold variable is given an initial value of zero, and a temporary variable M is given an initial value equal to OFFSET. In step 508, the value of SLOPE is added to the variable M, and the current value of THRESH is incremented. In step 510, the variable M is compared with the time of rotation of the corresponding wheel (again, the front wheel in step 258 and the rear wheel in step 358). If the present value of the variable M is less than the time of rotation, program execution returns to step 508, wherein the threshold is incremented further and the temporary variable M is advanced by an amount equal to the variable SLOPE. The program will continue to cycle through steps 508 and 510 until such time as the temporary variable M does become greater than the time of rotation of the corresponding wheel. At that time the threshold variable THRESH has assumed the correct value, and program execution continues on with step 400. FIG. 7 is a flow chart of the interrupt servicing routine performed by the microprocessor 120 each time its execution of the main program loop is interrupted by the timer 128. The interrupt is issued by the timer each time it overflows. When an interrupt first occurs, the microprocessor suspends execution of the main program loop, and jumps to the interrupt servicing routine at step 602. In step 602, the interrupt timer is reloaded with an initial value, and is then restarted to begin counting up from that initial value. The initial value is selected such that the timer will count for approximately 160 microseconds, for example, before generating the next interrupt signal. The timer will thus overflow at equal intervals of approximately 160 microseconds in the example being described. In the next step 604, the microprocessor reads the outputs of the signal processing circuits 102 and 104 of FIG. 3 by reading the port 132. The states of the output signals of circuits 102 and 104 are compared with the states of the same signals at the time of the last interrupt. If either output signal has changed from a low to a high level in the interim, the sensor pulse flag for that wheel is set. The flag is not set, however, if the sensor output signal is now low, or if it is high now but was also high at the time of the last interrupt. The current states of the outputs of signal processing circuits 102 and 104 are then stored for use the next time the interrupting servicing routine is performed. In step 606, the mode flag is examined to determine whether the system is currently operating in the low speed mode or the high speed mode. If the system is currently operating in the low speed mode, program execution branches to the series of steps 626-648. The principal purpose of steps 626-648 is to determine whether or not the system should be switched to the high speed mode of operation. That branch will be described hereinafter. If it is determined in step 606 that the system is currently operating in the high speed mode, however, program execution continues with step 608. In step 608, the two-byte value of the variable MCNTR is incremented. Because of step 608, the main counter will be incremented once each 160 microseconds during normal, high speed mode operation. In step 610, the front and rear wheel pulse flags used by the main program in steps 212 and 214 are set in accordance with the results of step 604. If there has been a front pulse (tested in step 612), the current value of the main counter MCNTR is stored (step 614) in the memory location for the variable FT(N), representing the time of occurrence of the most recent front wheel pulse. Similarly, if there has been a rear wheel pulse (step 616), the current value of the main counter MCNTR is stored (step 618) in the memory location containing the variable RT(N), representing the time of occurrence of the most recent rear wheel pulse. In step 620, the microprocessor examines the flag indicating whether the slip warning is currently being given. If the slip warning is not being given, the microprocessor proceeds on to step 622, wherein the bit B O controlling the audible alarm is reset and the reset bit is loaded into the appropriate bit position of port 132. If the slip warning is currently being given, however, (having been set in step 400, FIG. 4) the microprocessor jumps to step 624. In step 624 the current value of the bit B O is toggled, and the toggled bit is loaded into port 132. In other words, if the bit B O currently has a value of zero, then it is set to a value of one, whereas if it currently has a value of one, then it is reset to a value of zero. Because of step 624, the bit B O will be periodically turned on and off, causing an AC signal to be applied to the buzzer 108 of FIG. 3. After steps 622 and 624, program flow returns to the execution of the main program at the point of interruption. The program branch including steps 626-648 is executed whenever it is determined in step 606 that the system is operating in the low speed mode of operation. In step 626, the microprocessor tests to determine whether a front pulse has occurred. Program flow continues on to step 628 if a front pulse has not occurred. In step 628 it is determined whether a rear pulse has occurred. If no rear pulse has occurred, program flow proceeds on to step 630-636. Steps 630-636 deal with the incrementing of two counters which are used by the program only during the low speed mode of operation. One of the counters FCNTR (front wheel counter) is used to measure the time between pulses for the front wheel, whereas the other counter RCNTR (rear wheel counter) is used to measure the time between pulses for the rear wheel. The main counter is not used to measure times of rotation at low speeds since at low speeds it is possible for the main counter to overflow once, twice, or even more times between consecutive sets of pulses. It is thus difficult to obtain an unambiguous reading from the main counter as to the actual time interval between successive pulses. The front counter FCNTR is incremented in step 632 if it is determined in step 630 that the front counter value has not yet reached the terminal count of L1 (corresponding to a vehicle speed of 25 km/hr). Similarly, the rear counter RCNTR is incremented in step 636 if it is determined in step 634 that the rear counter has also not reached the terminal count limit of L1. The decision step 630 and 634 cause bypassing of the counter incrementing steps when each counter reaches its terminal count value of L1. This eliminates the problem of counter overflow which would otherwise exist when the vehicle is traveling at very low speeds, or is stopped. After steps 634 and 636, the microprocessor leaves the interrupt servicing routine, returning to the main program at the point of interruption. If it is determined back in step 626 that a front wheel pulse has occurred, however, the microprocessor proceeds to step 630, wherein the current value of the front counter FCNTR is compared with the terminal limit of L1. If the value of FCNTR is less than L1, meaning that the speed of the vehicle is in excess of 25 kilometers per hour, the microprocessor proceeds on to step 640. In step 640 the system mode flag is changed to place the system in the high speed mode. In the succeeding step 642, the front counter FCNTR value is reset to zero. If it is determined in step 638 that the front counter value is not less than the terminal count of L1, however, then the program bypasses step 640, thereby remaining in the low speed mode, and proceeds directly to step 642 and the resetting of the front counter. A sequence of steps similar to steps 630-642 is performed if it is determined in step 628 that a rear wheel pulse has occurred. More particularly, the current value of the rear wheel counter RCNTR is compared with the 25 kilometer per hour limit L1 in step 644. If the RCNTR value is less than L1, the system is switched to the high speed mode of operation in step 646. Thereafter, the rear counter is reset in step 648. If the rear counter value is not less than the terminal count of L1, however, the program flow bypasses step 646, proceeding directly to step 648 and the resetting of the rear counter RCNTR. Again, the program leaves the interrupt servicing routine following the execution of step 642 or 648, returning to the main program at the point of interruption. A wheel slip detector has thus been described which is both inexpensive and easy to mount on a vehicle, and yet which provides a reliable indication of excessive wheel slip, even in the presence of vehicle acceleration. Although the invention has been described with respect to a preferred embodiment, it will be appreciated that various rearrangements and alterations of parts may be made without departing from the spirit and scope of the present invention, as defined in the appended claims.
Apparatus is disclosed for detecting wheel slip of a driven wheel with respect to a surface. A magnet is fastened to the wheel and a sensor coil is fixedly mounted adjacent the path of rotation of the magnet. The sensor generates one electrical pulse each time the associated magnet rotates past it. Thus, the time of rotation of the wheel corresponds to the time interval between the pulses provided by the coil. The rotation time of the driven wheel is compared against the rotation time of a similarly equipped free rolling wheel to detect wheel slip. A wheel slip indication is given if the difference in wheel rotation times is greater than a selected limit. Acceleration of the wheels may interfere with the wheel slip detection, because the rotation times of the driven and free rolling wheels are not measured at precisely the same time. To account for this, acceleration over the rotation time measurement interval is itself measured and used to increase the allowable difference in wheel rotation times before a slip indication is given.
58,704
FIELD OF THE INVENTION The present invention relates to a thermal transfer printing method and intermediate sheets used therefor. More particularly, it relates to an improvement of a thermal transfer printing method, which makes it possible to print on plain paper, and intermediate sheets which are used for the method. BACKGROUND OF THE INVENTION Thermal transfer printing is a method wherein a thermal ink film is heaped on an image receive sheet and heated by a thermal head to print images directly onto a receive sheet. When a sublimable dye is employed in this method, it is known to the art that the obtained image properties are very good like photographs. The photograph-like image, however, is not obtained when the receive sheet is plain paper, because the plain paper has rough surface and it is difficult to fix the image on it. In order to obtain the photograph-like image, it is necessary that particular paper sheets have a printing layer onto which the sublimable dye is easily fixed. It is, however, desired to form the photographical image on plain paper. In order to satisfy this desire, it is proposed that the images are preliminarily transferred on an intermediate sheet having a printing layer and then only the printing layer is transferred onto a receive sheet (see U.S. Pat. No. 4,923,848). In this process, the intermediate sheet and the thermal ink film are sandwiched between the thermal head and a platen roller under a certain pressure, and thermal printing is conducted. Among the thermal transfer printing, the method employing the sublimable dye requires energy several times larger than the conventional hot melt type thermal transfer printing process. It is therefore required that the printing layer on the intermediate sheet be anchored on the substrate of the intermediate sheet even after such higher energy printing. Since the sublimable thermal transfer printing is generally applied for full color printing, the heating step with the thermal head should be conducted at least three times, after which the printing layer is required to be anchored on the substrate of the intermediate sheet. Contrary to this step, the printing layer is adhered onto the receive sheet by heat or pressure and then the substrate of the intermediate sheet is necessary to be peeled off in the next step. It is therefore required that the printing layer of the intermediate sheet have two properties which are in conflict with each other. Especially in the sublimable dye, if the color layer of the ink film and the printing layer have high heat resistance, printing sensitivity significantly lowers. Both layers should be prepared from a material having lower heat resistance, and therefore easily gives rise to problems of heat fusion between the printing layer and the color layer of the ink film or between the printing layer and the substrate of the intermediate sheet. It is proposed that the printing layer is prepared from saturated polyester resin. However, since the substrate to be covered with the printing layer is generally formed from polyester, the adhesion power between the polyester printing layer and the polyester substrate is quite strong and therefore difficult to peel the substrate off after attaching the printing layer onto the receive sheet. It is also considered that a releasing layer is disposed between the printing layer and the substrate. The releasing layer in turn allows the printing layer to transfer onto the thermal ink film during heat printing with the thermal head. In order to promote to adhering the printing layer onto the receive sheet or to inhibit transferring the printing layer onto the color layer of the ink film, it is proposed that an adhesive layer is disposed either between the printing layer and the substrate of the intermediate layer or on the surface of the printing layer. Since the adhesive layer is thermoplastic at ambient temperature, the printed images in the printing layer often bleed into the adhesive layer. The adhesive layer also has adhesive properties to everything and may give rise to mechanical operation and treatment problems. SUMMARY OF THE INVENTION In the intermediate sheet, the printing layer is very important and should have some properties which are in conflict with each other. The printing layer is formed from a material which is easily dyed with a sublimable dye, but which hardly-adheres with the thermal ink film. The printing layer also adheres on the substrate of the intermediate sheet during thermal printing, but should adhere to the receive sheet and is easily peeled off from the substrate. The present invention, accordingly, is directed to a thermal transfer printing process comprising: heating a thermal ink film with a printing head to print dye transferring images onto an intermediate sheet which comprises a substrate and a printing layer thereon, heaping an image receive sheet on said printing layer, and transferring said printing layer onto the image receive sheet by pressure or heat; an improvement residing in that said printing layer is formed from polyvinyl acetal. The present invention also provides an intermediate sheet for the above thermal transfer printing process comprising a substrate and a printing layer on said substrate wherein said printing layer is formed from polyvinyl acetal. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view illustrating the thermal transfer printing process of the present invention. FIG. 2 is a sectional view of the thermal ink film. FIGS. 3-6 are sectional views which show several embodiments of the intermediate sheet of the present invention. DETAILED DESCRIPTION OF THE INVENTION FIG. 1 is a schematic view which illustrates the thermal transfer printing process of the present invention. FIG. 1, of course, is not to be construed as limiting the present invention to its detailed system, in number of rollers, platen rollers, printing heads and the like. A thermal ink film 1 is heaped with an intermediate sheet 2 so that a color layer 9 of the thermal ink film 1 is faced with a printing layer 11 of the intermediate sheet 2, and then sandwiched between a printing head 4 and a platen roller 5 under a certain pressure. Printing informations are sent to the printing head 4 from an information processing system which is not shown in FIG. 1, and then printed on the printing layer 11. The traveling speeds of the thermal ink film i and the intermediate sheet 2 may be the same or different. In case of obtaining full color images, for example, the process of the above mentioned process is repeated with the thermal ink film which has cyan, magenta and yellow color layer. Also, a plural of printing heads may be used for the full color images. The printing head is not limited as long as the color dye in the color layer 9 is sublimated or diffused onto the printing layer 11. Examples of the printing heads are a thermal head, an electrode head, a light head and the like. Subsequently, the intermediate sheet 2 is heaped with an image receive sheet 3 so that the printing layer 11 is faced with the surface of the receive sheet 3, and pressed or heated to transfer or adhere the printing layer 11 onto the image receive sheet 3. The substrate 10 of the the intermediate sheet 2 may be peeled off simultaneously with the transferring or afterward. Heating or pressing may be provided by passing the intermediate sheet 2 and the image receive sheet 3 between mediums of which at least one is heated or between mediums which are pressed with each other. Heating may be carried out by a light source which has a high radiant heat. In FIG..1, two heat rollers 6 and 7 are employed. The heat rollers may be rubber covered rollers, plastic rollers, metal rollers and the like. The heating or pressing method is not limited as long as the printing layer is transferred onto the image receive sheet, but preferred is a combination of rollers of which at least one is a heat roller. More preferred is a combination of a resilient roller (rubber covered roller) and a metal roller, or a combination of two resilient rollers. A temperature of heating is not limited, but generally is within the range of room temperature to 300° C. An amount of pressure is not limited, but generally is less than 10 8 pa. FIG. 2 shows a schematic sectional view of the thermal ink film 1 which is employed in the present invention. The thermal ink film 1 is at least composed of a substrate 8 and the color layer 9. The substrate 8 can be formed from a material which is known to the art, including a polymer film, a surface treated polymer film, an electroconductive film and the like. Examples of the polymer films are polyolefin, polyamide, polyester, polyimide, polyether, cellulose, poly(parabanic acid), polyoxadiazole, polystyrene, fluorine-containing film and the like. Preferred are polyethylene terephthalate, polyethylene naphthalate, alamide, triacetyl cellulose, poly(parabanic acid), polysulfone, polypropylene, cellophane, moistureproof cellophane and polyethylene. It is preferred that at least one side of the substrate is covered with a heat resistance layer, a lubricant layer (or a lubricant electroconductive layer) and a lubricant heat resistance layer (or a lubricant heat resistance electroconductive layer) to enhance heat resistance and traveling stability of the thermal ink film. Examples of the electroconductive films are a polymer film containing electroconductive particles (e.g. carbon black or metal powder), a polymer film on which an electroconductive layer is formed, a polymer film on which an electroconductive vapor deposition layer is formed, and the like. It is also preferred that an anchor coat is present between the color layer and substrate 8 to prevent the color layer 9 from peeling off. The color layer 9 is mainly composed of a dyestuff and a binder. The dyestuff is not limited, including a disperse dye, a basic dye, a color former and the like. The binder includes acryl resins, styrene resins, urethane resins, polyester resins, polyvinyl acetal resins, vinyl acetate resins, chlorinated resins, amide resins, cellulose resins and the like. Examples of the cellulose resins are methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, nitrocellulose, acetic cellulose and the like. Preferred binders are acrylonitrile-styrene copolymer, polystyrene, styrene-acryl copolymer, saturated polyester, polyester-urethane, vinyl chloride resin, chlorinated vinylchloride resin, vinyl chloride-vinyl acetate copolymer (which is further copolymerized with vinyl alcohol,. maleic acid and the like), vinyl chloride-acrylate copolymer (of which acrylate may be a mixture), vinyl acetate resin, rubber chloride, chlorinated polypropylene, polycarbonate and cellulose resins, because printing sensitivity is high and they effectively prevent the color layer from fusing. The copolymer may be prepared from three monomers. The binder may also be polyvinyl acetals, such as polyvinyl formal, acetoacetalized polyvinyl alcohol, propionacetalized polyvinyl alcohol, polyvinyl butyral and the like. It is preferred that the binder has a glass transition temperature of 40° to 150° C. and an average polymerization degree of 200 to 2,700. The color layer may further contain fluorine-containing moisture curable resins or siloxane-containing moisture curable resins to prevent heat fusing. The fluorine-containing moisture curable resins or siloxane-containing moisture curable resins include moisture curable resins which contain hydrolyzable silyl groups (see Japanese Patent Application Ser. No. 144241/1988); and moisture curable resins which contain hydrolyzable isocyanate groups into which fluorine or silicon is introduced. The fluorine-containing moisture curable resins include fluorine-containing polymer having hydrolyzable silyl groups, for example moisture curable resins as described in Japanese Kokai Publication 558/1987, especially fluorine-containing acryl silicon resin; or fluorine-containing polyurethane resin having hydrolyzable isocyanate group at terminals or side chains. The siloxane-containing moisture curable resins include siloxane-containing vinyl polymers having hydrolyzable silyl groups, especially siloxane-containing acryl silicon resins; or siloxane-containing polyurethane resins having hydrolyzable isocyanate groups at terminals or side chains. The fluorine-containing moisture curable resins or siloxane-containing moisture curable resins may be modified with urethane resins. Examples of the fluorine-containing acryl silicon resins are fluorine-containing acryl silicon resins available from Sanyo Chemical Industries Ltd. as F-2A. Examples of the siloxane-containing acryl silicon resins are siloxane-containing acryl silicon resin available from Sanyo Chemical Industries Ltd. as F-6A. Examples of the siloxane-containing moisture curable resins having hydrolyzable isocyanate groups are siloxane-containing moisture curable resins available from Sinko Technical Research CO., LTD. as SAT-300P. The color layer 9 may further contain a reaction promoter for the moisture curable resin, if necessary. Examples of the reaction promoters are titanares (e.g. alkyl titanate), amines (e.g. dibutylamine-2-hexoate), organic tin compounds (e.g. tin octylate, dibutyltin dilaurate, dibutyltin maleate), acidic compounds and catalysts as described in Japanese Kokai Publication 19361/1983. An amount of the reaction promoter is within the range of 0.001 to 100% by weight based on the amount of the resin. The color layer 9 may also contain a storage stabilizer in case where the moisture curable resin is used as a coating composition. Examples of the storage stabilizers are as described in Japanese Kokai Publication 51724/1985 and 147511/1982. The color layer 9 is composed of plural layers. Also, a lubricating layer or another layer may be formed on the color layer. The uppermost layer may preferably contain the fluorine-containing moisture curable resins, siloxane-containing moisture curable resins, or the other silicon or fluorine materials or antistatic agents. FIGS. 3-6 are sectional views which show several embodiments of the intermediate sheet of the present invention. The intermediate sheet 2 is mainly composed of the substrate 10 and the printing layer 11. The substrate is not limited, including paper having a smooth surface, a polymer film and an electroconductive film. The polymer film and the electroconductive is the same as mentioned above for the substrate 8 of the thermal ink film. On the substrate 10, various coatings as described in the explanation of the substrate 8 (e.g. heat resistance layer and the like) may be disposed. The substrate 10 preferably has a thickness of 2 to 100 micrometer. The printing layer 11 is mainly prepared from polyvinyl acetal. The polyvinyl acetal is a resin which is prepared by reacting polyvinyl alcohols with aldehydes (e.g. formaldehyde, acetoaldehyde, propionaldehyde, butyraldehyde and the like). Typical examples of the polyvinyl acetals are polyvinyl formal, acetoacetalized polyvinyl alcohol, propionacetalized polyvinyl alcohol, polyvinyl butyral and the like. The polyvinyl acetal has superior dyeing ability for a disperse dye, because it has polar groups which are acetal constructions. The acetal construction has a hydrogen atom or an alkylidene group. It is preferred that the polyvinyl acetal has a high acetalization degree and the alkylidene group has 3 carbon atoms or more., because such polyvinyl acetal effectively prevents heat fusion. Also, the polyvinyl acetal having high acetalization degree and an alkylidene group having at least three carbon atoms has a low glass transition Temperature, thus resulting in high printing sensitivity. Since the polyvinyl acetal has poor adhesive properties with polyester film, it is easily removable from the polyester substrate. However, when printing the printing images on the printing layer, the printing layer is heated more than the glass transition temperature and softened so as to adhere to the polyester film. Even in the softened condition, the polyvinyl acetal has insufficient adhesion to adhere to the thermal ink film. It is believed that this is the reason why the polyvinyl acetal remains on the substrate 10 when printing. Once printing has finished, the polyvinyl acetal layer contains dye and lowers its softening point in comparison with that not containing dye. Accordingly, when the polyvinyl acetal layer 11 is contacted with the image receive sheet 3, it is easily adhered onto the sheet 3. If the image receive sheet 3 is plain paper, the polyvinyl acetal is coiled with the paper matrix to promote the transferring. This is the reason why the polyvinyl acetal layer is stuck on the substrate 10 when printing by the printing head and transferred onto the image receive sheet 3 during the next transferring step. The polyvinyl acetal preferably has an average polymerization degree of 2,700 or less, more preferably less than 1,500. It is also preferred that the polyvinyl acetal has a flow softening point of 250° C. or less, more preferably 200° C. or less. The flow softening point (or flow beginning temperature) is determined by a flow tester (temperature rise rate=6° C./min, extruding pressure=9.8×106 Pa, die=1 mm (pore diameter)×10 mm). The polyvinyl acetal which satisfies the range mentioned above has good printing sensitivity and good transferability to the image receive sheet. Since the polyvinyl acetal which has a higher acetalization degree exhibits a higher heat fusion prevention properties, it is desired that the acetalization degree is 50 mol % or more. It is most preferred that the polyvinyl acetal is polyvinyl butyral which has a butyralization degree of 50 mol % or more, because it has excellent heat fusion preventive properties and printing sensitivity. Suitable polyvinyl butyral is commercially available from Sekisui Chemical Co., Ltd. as BL-1 (butyralization degree=63±3 mol %, flow softening point=105° C.), BL-2 (-butyralization degree=63±3 mol %, flow softening point=120° C.), BH-S (butyralization degree=70 mol % or more, flow softening point=160° C.), BM-S (butyralization degree=70 mol % or more, flow softening point=150° C.), BL-S (butyralization degree=70 mol % or more, flow softening point=110° C.), BH-3 (butyralization degree=65±3 mol %, flow softening point=205° C.) BM-2 (butyralization degree=68±3 mol % flow softening point=140° C.), BM-1 (butyralization degree=65±3 mol % flow softening point=130° C.), BM-5(butyralization degree=65±3 mol % flow softening point=160° C.) and the like. The polyvinyl acetal may be reacted with phenol resin, epoxy resin, melamine resin, isocyanate compound or dialdehyde compound to form a crosslinked structure. The polyvinyl acetal has no stickiness at an ambient temperature and therefore has no bleeding and is easily treated. In addition to the main components, the printing layer may also contain fluorine-containing moisture curable resins or siloxane-containing moisture curable resins to prevent heat fusion. Examples of the fluorine-containing moisture curable resins or siloxane-containing moisture curable resins are the same as mentioned in the thermal ink film. The addition of the fluorine-containing moisture curable resins or siloxane-containing moisture curable resins is very preferred, because the heat fusion between the thermal ink film and the printing layer would not occur. The printing layer may further contain other resins, such as acryl resins, urethane resins, polyester resins, vinyl acetate resins, chlorinated resins, styrene resins, cellulose resins and the like. Preferred are acrylonitrile-styrene copolymer resin, polystyrene, styrene-acryl copolymer resin, saturated polyester, polyester-urethane, vinyl chloride resin, chlorinated vinyl resin, rubber chloride, chlorinated polypropylene, polycarbonate, vinyl chloride-vinyl acetate resin, vinyl chloride-acrylic ester copolymer and vinyl acetate resin. If necessary, either a polymer material layer 28 or a releasing layer 27 or both are disposed between the substrate 10 and the printing layer 11 (see FIGS. 4-6). The polymer material layer is prepared from thermoplastic resins or curable resins by means of heat, light or electron beam. The polymer material includes acryl resins, urethane resins, amide resins, ester resins, cellulose resins, styrene resins and the like. Preferred polymer materials are polyvinyl alcohol, polyvinyl alcohol derivatives, cellulose derivatives, modified starch, starch derivatives, chlorinated resin and polycarbonate, because they have good solvent resistance to aromatic hydrocarbons or ketones which are used for the printing layer and have poor adhesive properties with polyester films which are typically used for the substrate 10. Examples of the polyvinyl alcohol derivatives are polyvinyl acetal and the like. Examples of the cellulose derivatives are methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, nitrocellulose, acetic cellulose and the like. Examples of the processed starches are oxide starch, enzyme-treated starch and the like. Examples of the starch derivatives are hydroxyethyl starch, carboxymethyl starch, cyanoethylated starch and the like. Examples of the chlorinated resins are rubber chloride, chlorinated polyethylene, chlorinated polypropylenee and the like. These polymers are not sticky at an ambient temperature and have no bleeding properties. The polymer material preferably has a glass transition temperature of more than 50° C. in view of the reliability of the printed images. In order to coil the polymer material into the paper matrix, the polymer material preferably has an average polymerization degree of 200 to 2,700, more preferably 200 to 1,500 or a flow softening point of 80 to 250° C., more preferably 80 to 200° C. The polymer material may further contain the fluorine-containing moisture curable resins or siloxane-containing moisture curable resins to prevent heat fusion. The releasing layer 27 mainly contains a releasing agent or a combination of the releasing agent and a polymer binder. The releasing agent includes the fluorine-containing moisture curable resins, siloxane-containing moisture curable resins, other silicone releasing agents and fluorine releasing agents. The fluorine-containing moisture curable resins or siloxane-containing moisture curable resins are the same as mentioned above. Typical examples of the other silicone releasing agents are dimethylsilicone oil, phenylsilicone oil, fluorine-containing silicone oil, modified silicone oil (e.g. modified with SiH, silanol, alkoxy, epoxy, amino, carboxyl, alcohol, mercapt, vinyl, polyether, fluorine, higher fatty acid, carnauba, amide or alkylallyl), silicone rubber, silicone resin, silicone emulsion and the like. Typical examples of the other fluorine releasing agents are fluorine resins (e.g. polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), fluorine rubbers (e.g. vinylidene fluoride-hexafluoropropylene rubber), fluorine surfactants, fluoride carbons, fluorine rubber latex and the like. The releasing agent also includes fatty acid esters, waxes and oils. The polymer binder can be the polymer listed in the polymer material layer 28. The releasing layer 27 and the polymer material layer 28 may contain antistatic agents. The printing layer 11 is required to have writing properties and therefore may contain micro particles, such as synthetic amorphous silica, titanium oxide, calcium carbonate, alumina; or transparent micro particles. I t may further contain a ultraviolet absorber, an antioxidant and a fluorescent agent. The polymer material layer 28 is preferably transparent, because this layer is transferred onto the image receive sheet 3 together with the printing layer 11. The polymer material layer 28 may contain micro particles, such as synthetic amorphous silica, titanium oxide, calcium carbonate, alumina; or transparent micro particles to impart writing properties. It may further contain a ultraviolet absorber, an antioxidant and a fluorescent agent, because this layer functions as a protective layer for the printed images. The polymer material layer 28, if necessary, may contain an agent to develop color of the dye in the thermal ink film. The color layer 9, the printing layer 11 or the polymer material layer 28 may contain one or more releasing agents. The releasing agent is the silicone or fluorine releasing agent as described in the releasing layer 27. The image receive sheet 3 is not limited in material, quality and shape, including non-coated paper, coated paper, film, sheet, synthetic paper, continuous sheet or cut sheet. The image printed in the receive sheet 3 is a mirror image to the image printed on the printing layer 11, because the printing layer 11 is transferred onto the receive sheet 3. Accordingly, the informations to be sent to the printing head should take into consideration this mirror image. According to the present invention, printing photographic images can be possible on various kind of paper, such as plain paper, transparent film for OHP, bond paper, coated paper and non-coated paper. The process of the present invention is very simple and easily treated. EXAMPLES The present invention is illustrated by the following Examples which, however, are not to be construed as limiting the present invention to their details. EXAMPLE 1 Preparation of a Thermal Ink Film A polyethylene terephthalate (hereinafter "PET") film with 4 micrometer thickness, which had a lubricant heat resistance layer on one side and an anchor layer on the other side, was coated by a wire bar with a paint prepared from the following ingredients on the anchor layer side to form a color layer with about 1 micrometer. ______________________________________Ingredients Parts by weight______________________________________Azo disperse dye 2.8Acrylonitrile-styrene copolymer 4Amide-modified silicone oil 0.04Toluene 252-Butanone 25______________________________________ Preparation of an Intermediate Sheet A PET film with 9 micrometer thickness was coated by a wire bar with a paint prepared from the following ingredients. ______________________________________Ingredients Parts by weight______________________________________Polyvinyl butyral resin*.sup.1 4Siloxane acryl silicon resin*.sup.2 0.23D-n-butyltin dilaurate 0.0012Toluene 182-Butanone 18______________________________________ *.sup.1 Available from Sekisui Chemical Co., Ltd. as BLS having a polymerization degree of 350. *.sup.2 Available from Sanyo Chemical Industries, Ltd. as F6A-4 having 54 wt % active ingredients. The coated film was dried and then heated at 100° C. for 30 minutes to form a color layer having about 2 micrometer. The resulting intermediate sheet was heaped with the thermal ink film so that the color layer was faced with the printing layer, and then sandwiched between a thermal head and a platen roller under a pressure of about 3 Kg. Printing was conducted by the following conditions; ______________________________________Printing rate 33.3 ms/linePrinting pulse width 2-8 msMaximum printing energy 6 J/cm.sup.2______________________________________ After printing, the intermediate sheet was removed from the thermal ink film and gradation patterns were printed on the printing layer without any heat fusion. Subsequently, a plain paper (wood free paper) was heaped on the printing layer and passed at about 180° C. between a rubber covered metal roller and a metal roller under a pressure of about 5 Kg. The PET substrate sheet was removed to find that the printed printing layer was adhered on the plain paper. The printed image had a reflective printing density of 1.6 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 2 Preparation of a Thermal Ink Film A polyethylene terephthalate (hereinafter "PET") film with 4 micrometer thickness, which had a lubricant heat resistance layer on one side and an anchor layer on the other side, was coated by a wire bar with a paint prepared from the following ingredients on the anchor layer side to form a color layer with about 1 micrometer. ______________________________________Ingredients Parts by weight______________________________________Azo disperse dye 2.8Polyvinyl butyral resin*.sup.3 4Amide-modified silicone oil 0.04Toluene 252-Butanone 25______________________________________ *.sup.3 Available from Sekisui Chemical Co., Ltd. as BHS. Preparation of an Intermediate Sheet A PET film with 9 micrometer thickness was coated by a wire bar with a paint prepared from the following ingredients. ______________________________________Ingredients Parts by weight______________________________________Polyvinyl butyral resin*.sup.1 4Fluorine containing acryl 0.83silicon resin*.sup.4D-n-butyltin dilaurate 0.004Toluene 182-Butanone 18______________________________________ *.sup.1 Available from Sekisui Chemical Co., Ltd. as BLS having a polymerization degree of 350. *.sup.4 Available from Sanyo Chemical Industries, Ltd. as F2A having 48 w % active ingredients. The coated film was dried and then heated at 100° C. for 30 minutes to form a color layer having about 2 micrometer. Printing was conducted as generally described in Example 1. After printing, the intermediate sheet was removed from the thermal ink film and gradation patterns were printed on the printing layer without any heat fusion. Subsequently, a plain paper was heaped on the printing layer and transferred as generally described in Example 1, with the exception that a pressure between rollers was about 50 Kg. The PET substrate sheet was removed to find that the printed printing layer was adhered on the plain paper. The printed image had a reflective printing density of 1.7 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 3 Printing and transferring were conducted as generally described in Example 1 with the exception that the receive sheet was changed to an OHP film. The substrate sheet of the intermediate sheet was removed to find that the printed printing layer was adhered on the OHP film. The printed image had a reflective printing density of 0.88 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 4 Printing and transferring were conducted as generally described in Example 1 with the exception that the receive sheet was changed to a bond paper (cotton 100%). The substrate sheet of the intermediate sheet was removed to find that the printed printing layer was adhered on the bond. The printed image had a reflective printing density of 1.58 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 5 Preparation of a Thermal Ink Film A polyethylene terephthalate (hereinafter "PET") film with 4 micrometer thickness, which had a lubricant heat resistance layer on one side and an anchor layer on the other side, was coated by a wire bar with a paint prepared from the following ingredients on the anchor layer side and heated at 60° C. for one hour to form a color layer with about 1 micrometer. ______________________________________Ingredients Parts by weight______________________________________Azo disperse dye 2.8Acrylonitrile styrene 4copolymer resinSiloxane containing acryl 0.5silicon resin solution*.sup.5 -Di-n-butyltin dilaurate 0.005Toluene 252-Butanone 25______________________________________ *.sup.5 Available from Sanyo Chemical Industries Ltd. as F6A having 54 wt % active ingredients. Preparation of an Intermediate Sheet A PET film with 9 micrometer thickness was coated by a wire bar with a paint prepared from the following ingredients. ______________________________________Ingredients Parts by weight______________________________________Polyvinyl butyral resin*.sup.6 4Toluene 182-Butanone 18______________________________________ *.sup.6 Available from Sekisui Chemical Co., Ltd. as BMS having a polymerization degree of about 850. The coated film was dried to form a color layer having about 2 micrometer. Printing was conducted as generally described in Example 1. After printing, the intermediate sheet was removed from the thermal ink film and gradation patterns were printed on the printing layer without any heat fusion. Subsequently, a plain paper was heaped on the printing layer and transferred as generally described in Example 1, with the exception that a temperature between rollers was about 200° C. The PET substrate sheet was removed to find that the printed printing layer was adhered on the plain paper. The printed image had a reflective printing density of 1.5 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 6 A PET film with 6 micrometer thickness was coated with a paint which contained 5 parts by weight of a polyvinyl butyral resin (available from Sekisui Chemical Industries Ltd., as BX-1 having about 1,700 polymerization degree and about 225° C. flow softening point), 50 parts by weight of toluene and 50 parts by weight of 2-butanone, to form a polymer material layer having a thickness of about 1.5 micrometer. On this polymer material layer, a paint from the following ingredients was coated with a wire bar. ______________________________________Ingredients Parts by weight______________________________________Polyvinyl butyral resin*.sup.6 4Fluorine containing acryl 0.24silicon resin solution*.sup.4Di-n-butyltin dilaurate 0.002Toluene 202-Butanone 20______________________________________ The coated film was dried and heated at 100° C. for 30 minutes to form a printing layer having about one micrometer. During forming the printing layer, the polymer material layer was hardly changed with the solvent in the paint of the printing layer. Printing was conducted as generally described in Example 1, using the thermal ink film of Example 1. After printing, the intermediate sheet was removed from the thermal ink film and gradation patterns were printed on the printing layer without any heat fusion. Subsequently, a plain paper was heaped on the printing layer and transferred as generally described in Example 1, with the exception that a temperature between rollers was about 200° C. The PET substrate sheet was removed to find that the printed printing layer was adhered together with the polymer material layer on the plain paper. The printed image had a reflective printing density of 1.5 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 7 A PET film with 6 micrometer thickness was coated with a paint which contained 5 parts by weight of a polyvinyl alcohol (available from Kuraray Co., Ltd. as PVA-105) and 95 parts by weight of water, to form a polymer material layer having a thickness of about 2 micrometer. On this polymer material layer, the paint for the printing layer of Example 6 was coated to form an intermediate sheet. During forming the printing layer, the polymer material layer was hardly changed with the solvent in the paint of the printing layer. Printing and transferring were conducted as generally described in Example 6 to form a high quality printing on a plain paper. The printed image had a reflective printing density of 1.5 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 8 A PET film with 6 micrometer thickness was coated with a paint which contained 5 parts by weight of an acetoacetalized polyvinyl alcohol (available from Sekisui Chemical Industries Ltd. as KS-5, having 2,400 polymerization degree), 50 parts by weight of toluene and 50 parts by weight of 2-butanone, to form a polymer material layer having a thickness of about 2 micrometer. On this polymer material layer, the paint for the printing layer of Example 6 was coated to form an intermediate sheet. During forming the printing layer, the polymer material layer was hardly changed with the solvent in the paint of the printing layer. Printing and transferring were conducted as generally described in Example 6 to form a high quality printing on a plain paper. The printed image had a reflective printing density of 1.5 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 9 A PET film wish 6 micrometer thickness was coated with a paint which contained 4 parts by weight of hydroxyethyl cellulose and 96 parts by weight of water, to form a polymer material layer having a thickness of about 2 micrometer. On this polymer material layer, the paint for the printing layer of Example 6 was coated to form an intermediate sheet. During forming the printing layer, the polymer material layer was hardly changed with the solvent in the paint of the printing layer. Printing and transferring were conducted as generally described in Example 6 to form a high quality printing on a plain paper. The printed image had a reflective printing density of 1.5 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 10 A PET film with 6 micrometer thickness was coated with a paint which contained 4 parts by weight of carboxymethyl starch, 0.02 parts by weight of polyether-modified silicone oil and 96 parts by weight of water, to form a polymer material layer having a thickness of about 2 micrometer. On this polymer material layer, the paint for the printing layer of Example 6 was coated to form an intermediate sheet. During forming the printing layer, the polymer material layer was hardly changed with the solvent in the paint of the printing layer. Printing and transferring were conducted as generally described in Example 6 to form a high quality printing on a plain paper. The printed image had a reflective printing density of 1.5 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 11 A thermal ink film was prepared as generally described in Example 5, with the exception that a vinyl chloride-vinyl acetate copolymer-resin (glass transition temperature=70° C., average polymerization degree=420) was employed instead of the acrylonitrile-styrene copolymer resin. Then, a PET film with 6 micrometer thickness was coated with a paint which contained 10 parts by weight of a chlorinated polypropylene (available from Asahi Denka Kogyo K.K. as CP-100), 0.03 parts by weight of polyether-modified silicone oil, 50 parts by weight of toluene and 50 parts by weight of 2-butanone, no form a polymer material layer having a thickness of about 2 micrometer. On this polymer material layer, the paint for the printing layer of Example 6 was coated to form an intermediate sheet. During forming the printing layer, the polymer material layer was hardly changed with the solvent in the paint of the printing layer. Printing and transferring were conducted as generally described in Example 6 to form a high quality printing on a plain paper. The printed image had a reflective printing density of 1.7 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 12 A thermal ink film was prepared as generally described in Example 5, with the exception that a vinyl chloride-acrylic ester copolymer-resin (available from Sekisui Chemical Co., Ltd., as S-LEC E-C110, glass transition temperature=about 65° C., average polymerization degree=about 380) was employed instead of the acrylonitrile-styrene copolymer resin. Then, a PET film with 6 micrometer thickness was coated with a paint which contained 10 parts by weight of polycarbonate and 90 parts by weight of toluene, to form a polymer material layer having a thickness of about 2 micrometer. On this polymer material layer, the paint for the printing layer of Example 6 was coated to form an intermediate sheet. During forming the printing layer, the polymer material layer was hardly changed with the solvent in the paint of the printing layer. Printing and transferring were conducted as generally described in Example 6 to form a high quality printing on a plain paper. The printed image had a reflective printing density of 1.67 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 13 A PET film with 9 micrometer thickness was coated by a wire bar with a paint which contained 10 parts by weight of a silicone releasing agent (available from Toray Dow Corning Silicone Co., Ltd. as PRX 305 Dispersion) and 10 parts by weight of toluene, and heated at 100° C. for one hour to form a silicone rubber releasing layer having a thickness of about 5 micrometer. On this layer, a paint from the following ingredients was coated with a wire bar. ______________________________________Ingredients Parts by weight______________________________________Polyvinyl butyral resin*.sup.1 4Fluorine containing acryl 0.75silicon resin solution*.sup.4Di-n-butyltin dilaurate 0.004Toluene 182-Butanone 18______________________________________ The coated film was dried and heated at 100° C. for 30 minutes to form a printing layer having about one micrometer. During forming the printing layer, the polymer material layer was hardly changed with the solvent in the paint of the printing layer. Printing was conducted as generally described in Example 2, using the thermal ink film of Example 1. After printing, the intermediate sheet was removed from the thermal ink film and gradation patterns were printed on the printing layer without any heat fusion. Subsequently, a plain paper was heaped on the printing layer and transferred as generally described in Example 1, with the exception that a temperature between rollers was about 180° C. The PET substrate sheet coated releasing layer was removed to find that the printed printing layer was adhered on the plain paper. The printed image had a reflective printing density of 1.6 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 14 A PET film with 6 micrometer thickness was coated by a wire bar with a paint which contained 10 parts by weight of a silicone coating agent (available from Toray Dow Corning Silicone Co., Ltd. as SE9157RTV) and 15 parts by weight of toluene, and heated at 100° C. for one hour to form a silicone rubber releasing layer having a thickness of about 5 micrometer. On this layer, a paint from the following ingredients was coated with a wire bar to form a polymer material layer having about 1.5 micrometer thickness. ______________________________________Ingredients Parts by weight______________________________________Polyvinyl butyral resin*.sup.7 5Toluene 502-Butanone 50______________________________________ *.sup.7 Available from Sekisui Chemical Co., Ltd. as BL2 having about 450 polymerization degree. A paint from the following ingredients was further coated thereon with a wire bar. ______________________________________Ingredients Parts by weight______________________________________Polyvinyl butyral resin*.sup.3 4Fluorine containing acryl 0.67silicon resin solution*.sup.4Di-n-butyltin dilaurate 0.003Toluene 202-Butanone 20______________________________________ The coated film was dried and heated at 100° C. for 30 minutes to form a printing layer having about one micrometer. During forming the printing layer, the polymer material layer was hardly changed with the solvent in the paint of the printing layer. Printing was conducted as generally described in Example 2, using the thermal ink film of Example 1. After printing, the intermediate sheet was removed from the thermal ink film and gradation patterns were printed on the printing layer without any heat fusion. Subsequently, a plain paper was heaped on the printing layer and transferred as generally described in Example 1, with the exception that a temperature between rollers was about 210° C. The PET substrate sheet coated releasing layer was removed to find that the printed printing layer was adhered together with the polymer material on the plain paper. The printed image had a reflective printing density of 1.6 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 15 A PET film with 9 micrometer thickness was coated by a wire bar with a paint which contained the following ingredients; ______________________________________Ingredients Parts by weight______________________________________Polyvinyl butyral resin*.sup.1 4Fluorine containing acryl 0.83silicon resin solution*.sup.4Di-n-butyltin dilaurate 0.001Toluene 182-Butanone 18______________________________________ and heated at 100° C. for 30 minutes to form a polymer material layer with about 2 micrometer. On this layer, a paint containing the following ingredients was coated with a wire bar. ______________________________________Ingredients Parts by weight______________________________________Polyvinyl butyral resin*.sup.1 5Toluene 182-Butanone 18______________________________________ It was then heated at 100° C. for 30 minutes to form a printing layer with about 2 micrometer. Printing was conducted as generally described in Example 5, using the thermal ink film of Example 1. After printing, the intermediate sheet was removed from the thermal ink film and gradation patterns were printed on the printing layer without any heat fusion. Subsequently, a plain paper was heaped on the printing layer and transferred as generally described in Example 1, with the exception that a temperature between rollers was about 180° C. The PET substrate sheet was removed to find that the printed printing layer was adhered together with the polymer material on the plain paper sheet. The printed image had a reflective printing density of 1.6 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 16 A PET film with 9 micrometer thickness was coated by a wire bar with a paint which contained the following ingredients; ______________________________________Ingredients Parts by weight______________________________________Epoxy acrylate resin 10Sensitizer*.sup.8 0.5Fluorine containing acryl 1.0silicon resin solution*.sup.4Di-n-butyltin dilaurate 0.001Ethyl acetate 90______________________________________ *.sup.8 Available from CIBAGEIGY (Japan) Limited as Irgacure 184. and exposed to a 4 KW high pressure mercury lamp to cure, thus forming a one micrometer releasing layer. On this layer, the printing layer paint of Example 15 was coated to form an intermediate sheet. Printing was conducted as generally described in Example 1, using the thermal ink film of Example 5. After printing, the intermediate sheet was removed from the thermal ink film and gradation patterns were printed on the printing layer without any heat fusion. Subsequently, a plain paper was heaped on the printing layer and transferred as generally described in Example 1, with the exception that a temperature between rollers was about 180° C. The PET substrate sheet was removed to find that the printed printing layer was adhered on the plain paper sheet. The printed image had a reflective printing density of 1.6 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 17 A thermal ink film was prepared as generally described in Example 2, with the exception that a saturated polyester (available from Toyoho Co., Ltd., as VYLON RV200, glass transition temperature=about 67° C.) was employed instead of the polyvinyl butyral resin. Printing was conducted as generally described in Example 1, using the above obtained thermal ink film and the intermediate sheet of Example 2, to form a high quality printing without heat fusion of the ink film. It was then combined with a plain paper and transferring was conducted between two heat rollers as generally described in Example 1. After transferring, the substrate film of the intermediate sheet was removed from the plain paper to find that the printing layer was transferred onto the paper. The printed image had a reflective printing density of 1.85 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed. EXAMPLE 18 A thermal ink film was prepared as generally described in Example 2, with the exception that a vinyl acetate resin having an average polymerization degree of 530 was employed instead of the polyvinyl butyral resin. Printing was conducted as generally described in Example 1, using the above obtained thermal ink film and the intermediate sheet of Example 2, to form a high quality printing without heat fusion of the ink film. It was then combined with a plain paper and transferring was conducted between two heat rollers as generally described in Example 1. After transferring, the substrate film of the intermediate sheet was removed from the plain paper to find that the printing layer was transferred onto the paper. The printed image had a reflective printing density of 1.85 at a pulse width 8 ms and was a high quality image having uniform dots from the lower printing density to the higher printing density. The printed image was left at 60° C. and 60% relative humidity for 200 hours, but no bleeding was observed.
The present invention is directed to a thermal transfer printing process comprising: heating a thermal ink film with a printing head to print dye transferring images onto an intermediate sheet which comprises a substrate and a printing layer thereon, heaping an image receive sheet on said printing layer, and transferring said printing layer onto an image receive sheet by pressure or heat; The improvement residing in that said printing layer is formed from polyvinyl acetal. The present invention also provides an intermediate sheet for the above thermal transfer printing process comprising a substrate and a printing layer on said substrate wherein said printing layer is formed from polyvinyl acetal.
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FIELD OF THE INVENTION AND RELATED ART The present invention relates to a controlling apparatus, an image heating apparatus, and an image forming apparatus. In the filed of an image forming apparatus which uses an electrophotographic image forming method or the like, it has been a common practice to form an image on a sheet of recording paper with the use of toner, and fix the toner image to the sheet of recording paper with the use of a fixing apparatus (image heating apparatus), more concretely, a pair of rotational components, that is, a fixation roller and a pressure roller. The contact between the peripheral surface of a fixation roller and a sheet of recording paper tends to create numerous minute peaks and valleys across the peripheral surface of the fixation roller. More concretely, as a fixation roller repeatedly comes into contact with sheets of recording paper, the portions of the peripheral surface of the fixation roller, which correspond in position to the edges of the sheet of recording medium, in terms of the recording paper conveyance direction, become recessive compared to the rest of the peripheral surface of the fixation roller. In other words, they sustain numerous minute scars (which hereafter may be referred to as “paper edge scars, or simply, edge scars”). As the number of times the fixation roller comes into contact with sheets of recording paper increases, these recesses tend to leave their impression across the toner image on the sheet of recording paper. This property of the peripheral surface of the fixation roller may be referred to as “surface texture transferability”, hereafter. In recent years, there have been made a substantial amount of improvement in the field of a fixation roller, in particular, in terms of the smoothness of its peripheral surface, being thereby increased in “surface texture transferability”. Therefore, from the standpoint of forming a highly glossy image of high quality, it has become increasingly important for a fixation roller to be reliably maintained at a desired level in terms of surface condition. There have been available the following documents which are related to means for maintaining a fixation roller in terms of surface properties to prevent a fixing apparatus from yielding an image which is nonuniform in gloss. In the case of Japanese Laid-open Patent Application 2008-40365, in order to prevent the fixing device from outputting images which are nonuniform in gloss, a rotational abrasive component, the peripheral surface of which is covered with abrasive particles which are in a range of #1000-#4000 in particles size, is used to give the peripheral surface of the fixation roller fine scars, in order to make inconspicuous the minute scratches made by sheets of recording paper across the peripheral surface of the fixation roller. Further, the fixing device disclosed in Japanese Laid-open Patent Application 2008-40365159 is structured so that when the fixation roller is not abraded, the rotational abrasive component is kept separated from the fixation roller, in order to minimize the amount by which offset toner adheres to the rotational abrasive component, and also, that as no less than a preset number of sheet of recording paper are conveyed, for fixation, through the fixing device, the rotational abrasive component is automatically placed in contact with the fixation roller to abrade the peripheral surface of the fixation roller. As the inventors of the present invention, their colleagues, etc., studied a case in which a fixing device is also provided with a rotational abrasive component for its pressure roller, it was found that the following problems would possibly occur. First, the primary reason why a pressure roller also has to be abraded is that the paper dust from recording paper cumulatively adheres to the peripheral surface of the pressure roller. As paper dust accumulates on the peripheral surface of a pressure roller, it is possible that while an image forming apparatus is operated in the two-sided image forming operation, the paper dust will transfer onto the image on the first surface of a sheet of recording medium, and therefore, the image on the first surface of a sheet of recording paper will be reduced in image quality. On the other hand, paper dust is unlikely to accumulate on the peripheral surface of the fixation roller (portion of peripheral surface of fixation roller, which is actually used for fixation), because when the fixation roller comes into contact with a sheet of recording paper, there is a toner image between the fixation roller and the sheet. On the other hand, certain portions of the peripheral surface of a fixation are made to recess by their contact with the side (lateral) edges of a sheet of recording paper, as described above. Therefore, it is desired that the peripheral surface of a fixation roller also is periodically abraded. As described above, the reason why a fixation roller is to be abraded across its peripheral surface is different from the reason why a pressure roller is to be abraded across its peripheral surface. Thus, a fixation and a pressure roller are inevitably different in the timing with which they are to be abraded (although it is possible that they will become the same in abrasion timing every so often). If a fixing device is structured, based on the above described background information, so that both the fixation roller and pressure roller of a fixing device are unconditionally abraded in response to a command from a user, it is possible for the following problems to occur. For example, if a fixing device is forced to perform an abrading operation in spite of the fact that the pressure roller has just been abraded, the pressure roller will be excessively abraded, which results in unnecessary reduction in the length of service of the pressure roller 51 . This problem applies to the fixation roller as well. SUMMARY OF THE INVENTION According to an aspect of the present invention, there is provided a controlling apparatus for controlling an image heating apparatus, said image heating apparatus including first and second rotatable members for heating therebetween a toner image on a sheet, a first rubbing rotatable member for rubbing said first rotatable member, and a second rubbing rotatable member for rubbing said second rotatable member, said controlling apparatus comprising a counter configured to count a number of heated sheets; a first executing portion configured to execute rubbing by said first rubbing rotatable member in accordance with an output of said counter; a second executing portion configured to execute rubbing by said second rubbing rotatable member in accordance with an output of said counter; an acquiring portion execution instructions of an operation in an image glossiness property improving mode provided by an operator; and a determination portion configured to determine which rotatable member or rotatable members of said first rotatable member and said second rotatable member is to be rubbed in accordance with an output of said counter, when said acquiring portion acquires the execution instructions. According to another aspect of the present invention, there is provided an image heating apparatus comprising first and second rotatable members configured to heat therebetween a toner image on a sheet; a first rubbing configured to rub said first rotatable member; a second rubbing rotatable member configured to rub said second rotatable member; a counter configured to count a number of heated sheets; a first executing portion configured to execute rubbing by said first rubbing rotatable member in accordance with an output of said counter; a second executing portion configured to execute rubbing by said second rubbing rotatable member in accordance with an output of said counter; an acquiring portion execution instructions of an operation in an image glossiness property improving mode provided by an operator; and a determination portion configured to determine which rotatable member or rotatable members of said first rotatable member and said second rotatable member is to be rubbed in accordance with an output of said counter, when said acquiring portion acquires the execution instructions. According to a further aspect of the present invention, there is provided an image forming apparatus comprising an image forming station configured to form a toner image on a sheet; first and second rotatable members configured to heat therebetween the toner image formed by said image forming station on the sheet; a first rubbing configured to rub said first rotatable member; a second rubbing rotatable member configured to rub said second rotatable member; a counter configured to count a number of heated sheets; a first executing portion configured to execute rubbing by said first rubbing rotatable member in accordance with an output of said counter; a second executing portion configured to execute rubbing by said second rubbing rotatable member in accordance with an output of said counter; an operating portion configured to instruct, by an operator, execution of an operation in a mode for improving a glossiness property of the image; and a determination portion configured to determine which rotatable member or rotatable members of said first rotatable member and said second rotatable member is to be rubbed in accordance with an output of said counter, when execution of the operation in the mode is instructed by said operating portion. Further features of the present invention will become apparent from the following description of exemplary embodiments (with reference to the attached drawings). BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart of the control sequence which is to be carried out when an image forming apparatus equipped with an apparatus for controlling a fixing device is in the user mode (manual mode). FIG. 2 is a sectional view of an image forming apparatus equipped with a controlling apparatus (device) for controlling its fixing device, which shows the general structure of the image forming apparatus. FIG. 3 is a sectional view of the fixing device while the fixing device 5 is not being made, by the controlling device, to carry out an operation for refreshing its fixation roller, nor an operation for refreshing its pressure roller. FIG. 4 is a sectional view of the fixing device while the fixing device is being made, by the controlling device, to carrying out an operation for refreshing its fixation roller. FIG. 5 is a sectional view of the fixing device while the fixing device is being made by the controlling device to carrying out an operation for refreshing its pressure roller. FIG. 6 is a sectional view of the fixing device while the fixing device is being made by the controlling device to carrying out both an operation for refreshing its fixation roller and an operation for refreshing its pressure roller at the same time. FIG. 7 is an enlarged sectional view of a part of the peripheral portion of the refresh roller of the fixing device. FIG. 8 is an enlarged view of one of the paper edge scars of the fixation roller of the fixing device, which is for describing the paper edge scar in detail. FIG. 9 is an enlarged view of a portion of the peripheral surface of the pressure roller of the fixing device, which is covered with paper dust. FIG. 10 is an enlarged view of the separation claw scars on the pressure roller of the fixing device. FIG. 11 is a graph for showing the relationship among the surface roughness of the refresh rollers, the number of sheets of recording paper conveyed through the fixing device, and the amount of refresh roller contamination. FIG. 12 is a flowchart of the control sequence which the fixing device is made to carry out by the control device, when the image forming apparatus is in the automatic mode. FIG. 13 is a block diagram of the control device for controlling the fixing device. FIG. 14 is a drawing of the control panel of the image forming apparatus equipped with the control device for controlling its fixing device. FIG. 15 is a drawing of the control panel of the image forming apparatus equipped with the controlling device for controlling its fixing device, when the display of the control panel is showing the user mode screen. FIG. 16 is a drawing of the control panel of the image forming apparatus equipped with the controlling device for controlling its fixing device, when the display of the control panel is showing the maintenance mode screen. DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention is concretely described with reference to some of the most preferable embodiments of the present invention. However, these embodiments are not intended to limit the present invention in scope. <<Embodiment 1>> (Image Forming Apparatus) FIG. 2 is a sectional view of the image forming apparatus equipped with a controlling apparatus (device) for controlling the fixing apparatus (device) in this embodiment. It shows the general structure of the apparatus. The image forming apparatus 100 is a full-color laser beam printer, which uses an electrophotographic image forming method. There are disposed in tandem the first, second, third, and fourth image forming sections Pa-Pd, in the main assemble of the apparatus. In the image forming sections Pa-Pd, monochromatic toner images, which are different in color, are formed one for one, through processes of forming a latent image, developing the latent image, and transferring the developed latent image. The image forming sections Pa-Pd have drum-shaped electrophotographic photosensitive components, more specifically, photosensitive drums 3 a - 3 d as their own image bearing components, respectively. The photosensitive drums 3 a - 3 d are rotationally driven in the direction indicated by arrow marks R 1 in FIG. 2 , at a preset peripheral velocity. It is on these photosensitive drums 3 a - 3 d that monochromatic toner images, different in color, are formed one for one. There is disposed next to the photosensitive drums 3 a - 3 d , an intermediary transfer belt 130 , as an intermediary transferring component. As the toner images, different in color, are formed on the photosensitive drums 3 a - 3 d , one for one, they are transferred (primary transfer) onto the intermediary transfer belt 130 , in the primary transfer sections N 1 a -N 1 d , respectively. Then, they are transferred (secondary transfer) onto a sheet P of recording paper, in the secondary transfer section N 2 . After the transfer of the toner images onto the sheet P of recording paper, the sheet P is conveyed to a fixing apparatus (device) 9 , in which the sheet P and the toner images thereon are subjected to heat and pressure. Thus, the toner images become fixed to the sheet P. Thereafter, the sheet P is discharged, as a print, from the main assembly of the apparatus. The image forming sections Pa-Pd are also provided with charge rollers 2 a - 2 d as charging means, and developing devices 1 a - 1 d as developing means, which are disposed in the adjacencies of the photosensitive drums 3 a - 3 d , respectively. Also disposed in the adjacencies of the photosensitive drums 3 a - 3 d are primary transfer rollers 24 a - 24 d as primary transferring means, and cleaners 4 a - 4 d as cleaning means. Further, there are disposed above the photosensitive drums 3 a - 3 d , laser scanners La-Ld, as exposing means, which are equipped with a light source and a polygonal mirror. The photosensitive drums 3 a - 3 d are roughly uniformly charged by the charge rollers 2 a - 2 d , respectively. Then, the charged portion of each photosensitive drum 3 is exposed by the laser scanner L (La, Lb, Lc or Ld). A beam of laser light emitted by the light source is deflected by a rotating polygon mirror in a manner of scanning the charged portion of the photosensitive drum 3 , is changed in direction by a reflection mirror, and is focused by an f-θ lens onto the generatrix of the photosensitive drum 3 ( 3 a , 3 b , 3 c or 3 d ). Consequently, four electrostatic images (latent images), which correspond to the image formation signals, are effected on the photosensitive drums 3 a - 3 d , one for one. The developing devices 1 a - 1 d contain a preset amount of yellow, magenta, cyan, and black toners, as developer), respectively. They are replenished with toner, as necessary, by replenishing devices 117 a - 117 d , respectively. They develop the latent images on the photosensitive drums 3 a - 3 d into visible images, more specifically, yellow, magenta, cyan and black toner images, respectively. The intermediary transfer belt 130 is being rotationally driven, in the direction indicated by an arrow mark A, at the same peripheral velocity as the photosensitive drums 3 a - 3 d . In an operation for forming a full-color image, for example, first, a yellow toner image (image of first color) is formed on the photosensitive drum 3 a . This yellow toner image is transferred (primary transfer) onto the outward surface of the intermediary transfer belt 130 (with reference to loop which belt forms), while the yellow toner image is conveyed through the nip (primary transfer nip) N 1 a , which is the area of contact between the photosensitive drum 3 a and intermediary transfer belt 130 . While the yellow toner image is conveyed through the primary transfer nip N 1 a , the primary transfer bias is applied to the intermediary transfer belt 130 by way of the primary transfer roller 24 a . Thus, the yellow toner image on the photosensitive drum 3 a is transferred onto the intermediary transfer belt 130 by the combination of the electric field generated by the primary transfer bias, and the pressure in the primary transfer nip N 1 a . Similarly, the magenta toner image (toner image of second color), cyan toner image (toner image of third color), and black toner image (toner image of fourth color) are sequentially transferred in layers onto the intermediary transfer belt 130 . Consequently, a full-color image, which reflects the image formation signals, are synthetically formed. The secondary transfer section is provided with the secondary transfer roller 11 as a secondary transferring means which is supported by a pair of bearings, in parallel to the intermediary transfer belt 130 , and also, in contact with the downwardly facing portion of the outward surface of the intermediary transfer belt 130 . To the secondary transfer roller 11 , a preset secondary transfer bias is applied by a secondary transfer bias power source. Meanwhile, sheets P of recording paper are conveyed to the secondary transfer section by a recording paper supplying means. More specifically, the sheets P are conveyed one by one to the secondary transfer nip from a sheet feeder cassette 10 , by way of a pair of registration rollers 12 , an upstream transfer guide (unshown), etc., with such a timing that each sheet P of recording paper arrives at a preset point in time, at the secondary transfer nip, which is the area of contact between the intermediary transfer belt 130 and secondary transfer roller 11 . While the sheet P is conveyed through the secondary transfer nip, the secondary transfer bias is applied to the secondary transfer roller 11 from a secondary transfer bias power source. Thus, the synthetic full-color toner image, which is made up of the four monochromatic toner images, different in color, which were transferred in layers onto the intermediary transfer belt 130 , is transferred (secondary transfer) onto the sheet P or recording paper. By the way, the toner (transfer residual toner) which is remaining on the photosensitive drums 3 a - 3 d after the completion of the primary transfer, is removed and recovered by the cleaners 4 a - 4 d . That is, the photosensitive drums 3 a - 3 d are cleaned so that they can be used for the formation of the next latent images. As for the transfer residual toner, and other contaminants, remaining on the intermediary transfer belt 130 , they are wiped way by a cleaning web (unwoven cloth) which is placed in contact with the surface of the intermediary transfer belt 130 . After the transfer of the toner images onto the sheet P of recording paper, in the second transfer section, the sheet P is introduced into a fixing device 9 , which will be described later in detail. In the fixing device 9 , heat and pressure are applied to the sheet P and toner image(s) thereon. Consequently, the toner image(s) becomes fixed to the sheet P. (Image Heating Apparatus, and Controlling Apparatus for Image Heating Apparatus) In this embodiment, the controlling apparatus (device) for controlling the fixing device as an image heating device is provided with an automatic mode and a user mode (manual mode), which will be described later. The controlling device may be a part of an image forming apparatus, like the one in this embodiment, or a part of a fixing device, like the one with which a fixing device is provided in a case where the fixing device is independent from the image forming apparatus. FIG. 3 is a sectional view of the fixing device 9 , while it is not in the state in which it can perform neither an operation for refreshing the fixation roller, nor an operation for refreshing the pressure roller. It shows the structure of the fixing device 9 . The fixing device 9 has a fixation roller (thermally fixing component) 40 , which is a rotational heating component (first rotational component) for heating the image on a sheet P of recording paper. The fixing device 9 has also a pressure roller (pneumatic fixing component) 41 , which is a rotational pressure applying component (second rotational component). It is pressed upon the fixation roller 40 to form a nip (fixation nip). As a sheet P of recording paper, on which a toner image is present, is conveyed through the fixation nip, remaining pinched between the pressure roller 41 and fixation roller 40 , while the fixation roller 40 is heated by a heat source 40 a disposed in the hollow of the fixation roller 40 , the toner image becomes fixed to the sheet P. Further, the fixing device 9 is provided with a fixation roller refreshing system 50 , which can be placed in contact with, or separated from, the fixation roller 40 . It is also provided with a pressure roller refreshing system 60 , which can be placed in contact with, or separated from, the pressure roller 41 . 1. Fixation Roller Referring to FIG. 3 , the fixation roller 40 is made up of a metallic core (sustratative layer) 40 b , an elastic layer 40 c , and a parting layer 40 d . The elastic layer 40 c is formed of rubber, on the peripheral surface of the metallic core 40 b . The parting layer 40 d is the surface layer of the fixation roller 40 . It covers the elastic layer 40 c . More concretely, in this embodiment, the metallic core 40 b is a piece of hollow aluminum tube which is 68 mm in external diameter. The elastic layer 40 c is formed of silicone rubber, and is 20° in rubber hardness (JIS-A: under 1 kg of weight), and is 1.0 mm in thickness. The parting layer 40 d , which covers the outward surface of the elastic layer 40 c , is formed of fluorinated resin, and is 50 μm in thickness. Thus, the fixation roller 40 is 70 mm in external diameter. The fixation roller 40 is rotatably supported by a pair of supporting components located at the lengthwise ends of the metallic core 40 b (in terms of direction parallel to rotational axis of metallic core 40 b ). It is rotationally driven by an unshown motor as a driving means, in the direction indicated by an arrow mark in FIG. 3 . The material for the parting layer is a piece of tube made of fluorinated resin, such as PFA resin (copolymer of tetrafluoroethylene resin and perfluoroalkoxylethylene), PTFE (tetrafluoroethylene), or the like, which is excellent in parting properties. The material for the parting layer of the fixation roller 40 in this embodiment is a piece of PFA resin tube. The parting layer 40 d , which is the surface layer of the fixation roller 40 is desired to be no less than 30 μm, and no more than 100 μm, in thickness. The fixation roller 40 internally holds a halogen heater 40 a as its heat source. Its temperature is kept by a combination of a temperature sensor 42 a and a temperature control circuit, within a range of 150-180° C., in which toner is fixable to a sheet P of recording paper. This target temperature has to be varied according to recording paper type. By the way, in this embodiment, the peripheral velocity of the fixation roller 40 was set to 220 mm/sec. This peripheral velocity of the fixation roller 40 is equivalent to the process speed (image outputting speed) of the image forming apparatus 100 . 2. Surface Condition of Fixation Roller At this time, the changes in the surface condition of the fixation roller 40 , which are caused by a sheet P of recording medium as the sheet P is conveyed through the fixing device 9 , are described. Hereafter, the portions of the peripheral surface of the fixation roller 40 , which the side edges (lateral edges) of a sheet P of recording paper contact, are referred to as paper edge portions. As the problem that the peripheral surface of the fixation roller 40 is gradually roughened by the side edges (lateral edges) of a sheet of recording paper was examined by the inventors of the present invention, the following became evident. That is, as a substantial number of sheets P of recording paper are conveyed through the fixing device 9 in such a manner that the sheets always contact the same portion of the fixation roller 40 in terms of the lengthwise direction of the fixation roller 40 , the peripheral surface of the fixation roller 40 becomes nonuniform in surface roughness, as will be described next. That is, referring to FIG. 8 , the paper path portion (I), out-of-paper-path portions (II), and paper edge portions (III), or the borderline between the paper path portion (I) and out-of-paper-path portion (II), of the peripheral surface of the fixation roller 40 , become different in surface roughness. When the fixation roller 40 is in the new condition, the peripheral surface of the fixation roller 40 , which is the outward surface of the parting layer formed of fluorinated resin or the like, is in the mirror-like condition; the surface roughness Rz (JIS: ten point average roughness) is roughly in a range of 0.1 μm-0.3 μm. In comparison, as a substantial number of sheets P of recording paper are conveyed through the fixing device 9 , the portion of the peripheral surface of the fixation roller 40 , which corresponds in position to the recording paper path (portion which comes into contact with recording paper) is gradually eroded by being attacked by the fibers, internal and external additives of the recording paper. Thus, the surface roughness of this portion of the fixation roller 40 gradually increases to roughly 0.5 μm-1.0 μm. The out-of-paper-path portions (II) of the peripheral surface 40 d of the fixation roller 40 contact the peripheral surface 41 d of the pressure roller 41 which opposes the fixation roller 40 . Thus, the surface roughness Rz of the out-of-paper-path portions (II) of the peripheral surface of the fixation roller 40 settles to a value in a range of 0.4 μm-0.7 μm. Thus, the peripheral surface of the fixation roller 40 is made nonuniform in surface condition, in terms of the lengthwise direction of the fixation roller 40 , by the conveyance of sheets P of recording paper through the fixing device 9 , as described above. Next, the relationship between the condition of the peripheral surface of the fixation roller 40 and the nonuniformity in gloss of an image outputted from the fixation roller 40 is described. In order to fix an unfixed toner image to a sheet P of recording paper, the fixing device 9 applies pressure and heat to the sheet P and the unfixed toner image thereon. During this process, the surface condition (presence of numerous minute peaks and valleys) of the peripheral surface of the fixing device 9 is transferred onto the surface of the toner image as the sheet P is conveyed through the fixing device 9 . Thus, the surface condition of the peripheral surface of the fixation roller 40 , more specifically, the nonuniformity of the peripheral surface of the fixation roller 40 , makes the toner image on a sheet P of recording paper nonuniform in surface condition while the sheet P is conveyed through the fixing device 9 . Consequently, the image forming apparatus 100 outputs images which are nonuniform in gloss ( FIG. 8 ). Generally speaking, with regards to surface gloss, if a surface is capable of highly accurately reflecting an optical image, the surface is recognized as highly glossy, whereas if a surface is incapable of highly accurately reflecting an optical image, it is recognized as low in gloss or not glossy. For example, in a case where an image such as a silver-salt photographic image is seen under florescent illumination, not only is the light from the florescent bulb reflected by the image surface, but also, the shape of the florescent bulb can be seen in the image surface. In such a case, the image is thought to be highly glossy, whether consciously or unconsciously. This means that the surface of the photographic image is in the mirror-like condition, that is, being virtually free of visible peaks and valleys. On the other hand, if a surface is low in gloss, the opposites can be said. That is, in the case of an image which is low in gloss, the minute peaks and valleys which its surface has are relatively large. Therefore, as the light from a florescent bulb hits the surface, it is randomly reflected, and therefore, the shape of the florescent bulb is not recognizable in the surface of the image. That is, there is a correlation between the surface condition (presence of minute peaks and valleys) of an image, and the glossiness of the image. Therefore, if a fixation roller having deteriorated in surface condition is used to fix an image to highly glossy recording medium, such as coated paper, which is used to yield high quality images, an image forming apparatus (fixing device) is likely to output images which are nonuniform in gloss. For example, an image forming apparatus (fixing device) is likely to output images which have unwanted lines which are low in gloss and correspond in position to the paper edge portions of the fixation roller 40 , images which are nonuniform in gloss because of the difference in gloss between its portion corresponding to the paper-path portion of the fixation roller, and its portions corresponding to the out-of-sheet-path portions of the fixation roller, and the like images. Hereafter, the difference in gloss between a portion of an image, which corresponds in position to the paper edge portion (III) of the fixation roller 40 , and the portion of the image, which corresponds in position to the sheet-path portion (I) of the fixation roller, is referred to as a paper edge scar, and so is the difference in gloss between the portion of an image, which corresponds in position to the paper edge portion (III) of the fixation roller. In comparison, the difference in gloss between the portion of an image, which corresponds in position to the paper-path portion (I) of the fixation roller, and the portion of the image, which corresponds in position to the out-of-sheet-path portion (II) of the fixation roller is referred to as gloss nonuniformity. The sheet edge portion (III) is roughly 1-2 mm in width. That is, it is very narrow. Therefore, the difference in gloss between the portion of an image, which corresponds in position to the paper-path (I) of the peripheral surface of the fixation roller 40 , and the portion of the image, which corresponds in position to the out-of-paper-path portions (II) of the fixation roller 40 , is more conspicuous than the paper edge scars, regardless of severity in roughness of the sheet edge portions of the fixation roller. 3. Fixation Roller Refreshing System At this time, the fixation roller refreshing system 50 is described. Referring to FIG. 4 , a refreshing roller (abrading roller) 52 , which is an abrading component (first rotational abrading component), is made up of a metallic (stainless steel SUS 304) core 53 which is 12 mm in external diameter, and an abrasive layer (surface layer) 55 which covers the peripheral surface of the metallic core 53 . More concretely, the abrasive layer 55 is formed by forming an adhesive layer (intermediary layer) 54 on the peripheral surface of the metallic core 53 , and then, densely adhering abrasive particles, as abrasive material, to the adhesive layer 54 (peripheral surface of the metallic core 53 . FIG. 7 is an enlarged schematic sectional view of the refreshing roller 52 . As the abrasive 55 of which the abrasive layer 33 (surface layer) of the refreshing roller 52 is formed, minute particles of one of the following substances, and their mixtures, can be listed. More specifically, minute particles of aluminum oxide, aluminum hydroxide, silicon oxide, cerium oxide, titanium oxide, zirconia, lithium silicate, silicon nitride, iron oxide, chrome oxide, antimony oxide, diamond, etc., may be listed. In this embodiment, alumina (aluminum oxide) (which is referred to as Alundum or Morundum) was used as the abrasive 55 . Alumina-based abrasive is the most widely used abrasive. It is substantially higher in hardness than the fixation roller 40 . Further, its edges are acute-angled. Therefore, it is excellent in terms of abrasiveness. Thus, it is suitable as the abrasive 55 for this embodiment. The alumina-based abrasive used for this embodiment was no less than 5 μm and no more than 20 μm in particles size. Thus, the abrasive layer 33 is such a layer that is no less than 5 μm and no more than 20 μm in thickness. This range (5 μm and no more than 20 μm in thickness) was a range in which the refreshing roller 52 can effectively refresh the fixation roller 40 in surface condition, while keeping the fixation roller 40 satisfactory in surface properties. The refreshing roller 52 is rotatably supported by a pair of supporting components located at the lengthwise (parallel to rotational axis of roller) ends of the metallic core 53 . Referring to FIG. 4 , the refreshing roller 52 is rotationally drivable by a motor 54 as a driving means. Further, the supporting components located at the lengthwise ends, one for one, of the refreshing roller 52 are kept under the pressure generated by a pair of compression springs (unshown) as pressure applying means. Therefore, the refreshing roller 52 is pressed upon the pressure roller 41 by a preset amount of pressure. Therefore, an abrading nip, which has a preset width in terms of the rotational direction of the refreshing roller 52 and fixation roller 40 , is formed between the refreshing roller 52 and fixation roller 40 . The refreshing roller 52 may be rotated either in such a direction that makes the refreshing roller 52 and fixation roller 40 the same, or opposite, in the direction in which their peripheral surface moves in the area of contact (abrading section) between the refreshing roller 52 and fixation roller 40 . Further, the refreshing roller 52 is disposed so that it can be placed in contact with, or separated from, the fixation roller 40 by a refreshing roller positioning mechanism. 4. Pressure Roller Referring to FIG. 3 , the pressure roller 41 is made up of a metallic core (sustrative layer) 41 b , an elastic layer 41 c , and a parting layer 41 d . The elastic layer 41 c is formed of rubber, on the peripheral surface of the metallic core 41 b . The parting layer 41 d is the surface layer of the pressure roller 41 , and covers the elastic layer 41 c . More concretely, in this embodiment, the metallic core 41 b is a piece of hollow aluminum tube which is 48 mm in external diameter. The elastic layer 41 c is formed of silicone rubber and is 20° in rubber hardness (JIS-A: under 1 kg of weight), and is 2.0 mm in thickness. The parting layer 41 d , which covers the outward surface of the elastic layer 41 c , is formed of fluorinated resin, and is 50 μm in thickness. Thus, the pressure roller 41 is 50 mm in external diameter. The pressure roller 41 is rotatably supported by a pair of supporting components located at the lengthwise (direction parallel to axial line of metallic core) ends of the metallic core 40 b. The pair of pressure roller supporting components located at the lengthwise ends of the pressure roller 41 are kept pressed by a pair of compression springs (unshown), as pressure applying means, one for one. Thus, the pressure roller 41 remains pressed upon the fixation roller 40 by a preset amount of pressure. Therefore, a fixation nip, which has a preset width in terms of the direction in which the peripheral surface of the fixation roller 40 and that of the pressure roller 41 move, is formed between the fixation roller 40 and pressure roller 41 . In this embodiment, the total amount of pressure by which the pressure roller 41 is kept pressed upon the fixation roller 40 is 800 N. The pressure roller 41 internally holds a halogen heater 41 a as a heat source. Its temperature is kept by a combination of a temperature sensor 42 b and a temperature control circuit, within a range of 90-110° C., which does not make the first and second surfaces of a sheet P of recording paper different in gloss in the two-sided mode, and also, the pressure roller 41 does not substantially reduce the fixation roller 40 in temperature. If the temperature of the pressure roller 41 substantially exceeds its target level, the pressure roller 41 is cooled by an unshown cooling fan or the like to reduce the temperature of the pressure roller 41 to the target level. This target temperature level is varied according to recording paper type, or the like factor. 5. Surface Condition of Pressure Roller At this time, the changes in the surface condition of the fixation roller 40 , which are caused by a sheet P of recording medium as the sheet P is conveyed through the fixing device 9 , are described. There is a problem that as the fixing device 9 increases in the cumulative number of times sheets P of recording medium were conveyed through the fixing device 9 , the peripheral surface of the pressure roller 41 is gradually roughened by the contaminants such as paper dust. Thus, the inventors of the present invention studied the adhesion of paper dust to the pressure roller 41 . As a result, the following became evident. By the way, the frequency with which the pressure roller 41 comes into contact with the toner image on a sheet P of recording medium is less than the frequency with which the fixation roller 40 does. Therefore, it may be said that the pressure roller 41 is smaller than the fixation roller 40 , in terms of the effect they have upon the above described paper edge scars, which results in the formation of images which are nonuniform in gloss. Each time a sheet P of recording paper moves through the fixation nip, calcium carbonate, and the like, which are ingredients of the paper dust which originates from the sheet P, adhere to the surface layer of the pressure roller 41 , although by an extremely small amount. The surface layer of the pressure roller 41 , which is formed of fluorinated resin, is excellent in parting properties. Normally, therefore, it is unlikely that the paper accumulates on the peripheral surface of the pressure roller 41 . However, the temperature of the pressure roller 41 is kept relatively low as described above. In the case of the fixation roller 40 , there is a toner image between the fixation roller 40 and a sheet P of recording paper. Therefore, it may be said that the amount by which paper dust ingredients adhere to the fixation roller 40 will be very small. As the amount of the paper dust having adhered to the peripheral surface of the pressure roller 41 exceeds a certain value, the pressure roller 41 substantially loses its parting properties. Consequently, the paper dust begins to acceleratedly accumulate on the peripheral surface of the pressure roller 41 . FIG. 9 is an enlarged view of the paper edge portions of the peripheral surface of the fixation roller 40 and those of the pressure roller 41 , and their adjacencies, It shows the paper dust on the pressure roller 41 . More specifically, after a substantial amount of paper dust adhered to this portion of the pressure roller 41 , a sheet of glossy paper (coated paper) was used to form a monochromatic black toner image on both the first and second surfaces the sheet. Then, the glossiness of the toner image on the first surface was measured. Then, the obtained values were plotted along the points of measurement of the fixation roller 40 . As is evident from FIG. 9 , as a given point of the peripheral surface of the pressure roller 41 reduces in surface roughness due to the paper dust adhesion, it reduces in fixation performance (ability to conduct heat to toner). Thus, the point of the resultant image, which corresponds to the given point, is significantly less in gloss. 6. Separation Claw Mechanism Next, a separation claw mechanism 70 , which is a sheet separating unit, is described. Referring to FIG. 5 , the fixing device 9 is provided with multiple separation claws 71 , which are disposed in the adjacencies of the pressure roller 41 , being aligned in tandem in the lengthwise direction of the pressure roller 41 , as shown in FIG. 10 . The separation claws 71 prevent a sheet P of recording paper from wrapping around the pressure roller 41 , by being placed in contact with the peripheral surface of the pressure roller 41 , when the sheet P is discharged from the fixation nip while remaining in contact with the pressure roller 41 . A sheet P of recording paper, which is high in rigidity, is less likely to wrap around the pressure roller 41 at the sheet exit of the fixation nip. Therefore, when the sheets P of recording paper which are used for an image forming operation is higher in rigidity than a certain value, it is unnecessary for the separation claws 71 to be placed in contact with the pressure roller 41 . Thus, the fixing device 9 is structured so that the separation claws 7 can be placed in contact with, or separated from, the peripheral surface of the pressure roller 41 . It is impossible to accurately obtain the rigidity of a sheet of recording paper. In this embodiment, therefore, whether the separation claws 71 need to be placed in contact with, or kept separated from, the peripheral surface of the pressure roller 41 , is determined based on whether or not the recording paper is coated paper, and/or based on the basis weight of the recording paper. Further, in a case where a toner image is present on the surface of a sheet P of recording medium, which is facing the pressure roller 41 , as when the image forming apparatus 100 is in the two-sided image forming mode, the adhesiveness of the toner image comes into play. Therefore, it is more likely for the sheet P to wrap around the peripheral surface of the pressure roller 41 . Thus, when the image forming apparatus 100 is in the two-sided mode which makes it likely for a toner image to be on the surface of a sheet P of recording medium, which is facing the pressure roller 41 , the separation claws 71 are placed in contact with, or kept separated from, the peripheral surface of the pressure roller 41 , based on Table 1 (which shows, in numerical value, conditions in which separation claws are to be placed in contact with, or kept separated, from pressure roller), in which “ordinary paper” includes high quality paper with no coating, recycled paper, and the like, and “other” includes all the other categories of sheet of recording medium such as a sheet of plastic film for an overhead projector which does not belong to the “coated paper” category. TABLE 1 ON/OFF Separation Claw ON OFF Kinds of sheets 1st 2nd 1st 2nd Plain paper - 105 gsm - 105 gsm 106 gsm - 106 gsm - Coated paper - 105 gsm - 128 gsm 106 gsm - 129 gsm - Other - 128 gsm - 135 gsm 129 gsm - 136 gsm - 7. Pressure Roller Refreshing Mechanism Next, a system 60 for refreshing the pressure roller 41 is described. Referring to FIG. 5 , a refreshing roller 62 (roughening roller) which is an abrading component (second rotational abrading component) is made up of a metallic (stainless steel SUS 304) core 53 which is 12 mm in external diameter, and an abrasive layer (surface layer) 33 which covers the peripheral surface of the metallic core 53 . More concretely, the abrasive layer 33 was formed by forming an adhesive layer (intermediary layer) 54 on the peripheral surface of the metallic core 53 , and then, densely adhering abrasive particles, as abrasive material, to the adhesive layer 54 (peripheral surface of the metallic core 53 . FIG. 7 is an enlarged schematic sectional view of the refreshing roller 62 . As the abrasive 55 of which abrasive layer 33 (surface layer) of the refreshing roller 62 is formed, minute particles of the following substances, and their mixtures, can be listed. More specifically, minute particles of aluminum oxide, aluminum hydroxide, silicon oxide, cerium oxide, titanium oxide, zirconia, lithium silicate, silicon nitride, iron oxide, chrome oxide, antimony oxide, diamond, etc., may be listed. In this embodiment, alumina (aluminum oxide) (which is referred to as Alundum or Morundum) was used as the abrasive 55 . Alumina-based abrasive is the most widely used abrasive. It is substantially higher in hardness than the pressure roller 41 . Further, its edges are acutely angled. Therefore, it is excellent in terms of abrasiveness. Thus, it is suitable as the abrasive 55 for this embodiment. The alumina-based abrasive used for this embodiment was no less than 5 μm and no more than 20 μm in particles size. Thus, the abrasive layer 33 is such a layer that is no less than 5 μm and no more than 20 μm in thickness. This range (5 μm and no more than 20 μm in thickness) was in a range in which refreshing roller 61 can effectively refresh the pressure roller 41 in surface condition, while keeping the pressure roller 41 satisfactory in surface properties. The refreshing roller 62 is rotatably supported by a pair of supporting components located at the lengthwise (parallel to rotational axis of refreshing roller) ends of the metallic core 53 . Referring to FIG. 6 , the refreshing roller 62 is rotationally drivable by a motor 54 as a driving means. Further, the supporting components located at the lengthwise ends, one for one, of the refreshing roller 62 are under the pressure generated by a pair of compression springs (unshown) as pressure applying means. Therefore, the refreshing roller 62 is pressed upon the pressure roller 41 by a preset amount of pressure. Therefore, an abrading nip, which has a preset width in terms of the rotational direction of the refreshing roller 62 and pressure roller 41 , is formed between the refreshing roller 62 and pressure roller 41 . The refreshing roller 62 may be rotated either in such a direction that makes the refreshing roller 62 and pressure roller 41 the same, or opposite, in the direction in which their peripheral surface moves in the area of contact (abrading section) between the refreshing roller 62 and pressure roller 41 . Further, the refreshing roller 62 is disposed so that it can be placed in contact with, or separated from, the pressure roller 41 by a refreshing roller positioning mechanism 61 . 8. Difference Between Fixation Roller 40 and Pressure Roller 41 in Terms of Surface Layer Condition As described above, the fixation roller 40 and pressure roller 41 are different from each other in the reason why their surface layer changes in condition. The fixation roller 40 is higher in a target temperature level for their temperature control. That is, the fixation roller 40 melts toner to fix the toner to a sheet of recording paper. Therefore, the changes in the surface roughness of the fixation roller 40 is more likely to affect the gloss which the image on the sheet P will be given while the sheet P is conveyed through the fixation nip, than those of the pressure roller 41 . In other words, if paper edges scars are made by the pressure roller 41 , they are likely to be inconspicuous, but if they are made by the fixation roller 40 , they are likely to be recognized as nonuniformity in gloss. Further in the case of a fixing device such as the one in this embodiment which is for forming high quality images which are highly glossy, the fixing device 9 is operated without placing the separating components in contact with the fixation roller 40 . In such a case, the accumulation of paper dust on the pressure roller 41 , and the pressure roller scars attributable to the separation claws are the primary factors which affect the nonuniformity in image gloss. The amount by which paper dust is generated by each sheet P of recording medium is extremely small. It is unlikely for paper dust to adhere to the peripheral surface of the fixation roller 40 , while it is used for toner image fixation. In comparison, the peripheral surface of the pressure roller 41 comes into contact with the surface of each sheet P of recording paper, which does not have a toner image. Therefore, it is likely for paper dust to adhere to the peripheral surface of the pressure roller 41 . If paper dust collects on the peripheral surface of the pressure roller 41 , the surface layer of the pressure roller 41 reduces in parting properties, even if the paper dust layer is very thin. Thus, once a paper dust layer is formed on the peripheral surface of the pressure roller 41 , it becomes easier for paper dust, toner, etc., to adhere to the peripheral surface of the pressure roller 41 . Therefore, when the image forming apparatus 100 is operated in the two-sided mode, the paper dust on the peripheral surface of the pressure roller 41 transfers onto the image on the first surface of a sheet P of recording medium, possibly reducing the image in quality. As described above, the fixation roller 40 and pressure roller 41 are different from each other in the reason why their peripheral surface changes in condition. Therefore, the fixation roller 40 and pressure roller 41 are made different in the timing with which their peripheral surface (surface layer) is abraded (refreshed). That is, the operation for refreshing (abrading) the fixation roller 40 and that for refreshing (abrading) the pressure roller 41 are independently controlled from each other. 9. Refreshing Operation In this embodiment, three types of nonuniformity in the texture of the peripheral surface of the fixation roller 40 and pressure roller 41 are eliminated with the use of the refreshing rollers 52 and 62 . The first nonuniformity is attributable to the transfer of the scars, which the peripheral surface of the fixation roller 40 sustained as the peripheral surface of the fixation roller 40 came into contact with the side (lateral) edges of a sheet P of recording paper, onto the image surface. The second nonuniformity is attributable to the transfer of the scars which the peripheral surface of the pressure roller 41 is made to sustain by the separation claws 71 , as the pressure roller 41 was rotated while the separation claws 71 were in contact with the peripheral surface of the pressure roller 41 , onto the image. The third nonuniformity is attributable to the deterioration of the surface properties of the pressure roller 41 , which was caused by the paper dust, etc., having adhered to the peripheral surface of the pressure roller 41 while sheets P of recording paper are conveyed through the fixation nip. In order to prevent the image forming apparatus 100 from outputting images which suffer from one or more of the abovementioned three types of nonuniformity, the fixation roller refreshing system 50 and pressure roller refreshing system 60 are controlled by the controlling device for controlling the fixing device 9 . More specifically, the fixation roller 40 and pressure roller 41 are abraded by the refreshing rollers 52 and 62 , respectively, to cover the entirety of the peripheral surface of fixation roller 40 and the entirety of the peripheral surface of the pressure roller 41 , in terms of their lengthwise direction, to virtually eliminate the distance between the adjacent peak and valley, in terms of the direction parallel to the radius direction of the two rollers 40 and 41 . Further, the minute amount of paper dust and the like contaminants having adhered to the surface layer of the pressure roller 41 are scraped away. This is how the image forming apparatus 100 is prevented from outputting images which suffer from streaks which are lower in gloss than their adjacencies, and the difference in gloss between the portion of the image, which corresponds in position to the recording paper path portion of the fixation roller 40 and/or pressure roller 41 , and the portions of the image, which correspond in position to the out-of-paper-path portions of the fixation roller 40 and/or pressure roller 41 . Further, after the peripheral surface of the fixation roller 40 and that of the pressure roller 41 are given numerous minute scratches by the refreshing rollers 52 and 62 , the impression of the preexisting scars and scratches of the peripheral surface of the fixation roller 40 and those on the pressure roller 41 , on the surface of the fixed image are unrecognizable. More concretely, the fixation roller 40 and pressure roller 41 , the surface layer, that is, the parting layer, of which is formed of fluorinated resin or the like substance, is roughly 0.1 μm-0.3 μm in surface roughness Rz, across their out-of-paper-path portions, and roughly 0.5 μm-2.0 μm in surface roughness across their paper-path portion. In comparison, the portions of the peripheral surface of the pressure roller 41 , which was made to deteriorate in surface properties, by their contact with the paper edges, separation claws, and also, the adhesion of paper dust thereto, are roughly 1.0-4.0 μm in surface roughness Rz. Therefore, the fixation roller 40 and pressure roller 41 were refreshed by the refresh rollers 52 and 62 so that their peripheral surface becomes no less than 0.5 μm and no more than 2.0 μm in surface roughness Rz. By the way, the instrument used for measuring the surface roughness Rz of the two rollers 40 and 41 was a surface roughness gauge SE-3400 (product of Kosaka Laboratory Co., Ltd.). The condition under which the surface roughness of the two rollers 40 and 41 was measured was 0.5 mm/s in speed, 0.8 mm in cutoff, and 2.5 mm in measurement length. It is unnecessary for the refresh rollers 52 and 62 to continuously rub (abrade) the fixation roller 40 and pressure roller 41 , respectively, throughout a given image forming operation. For example, the fixing device 9 may be equipped with a sheet counter so that a refreshing (abrading) operation will be automatically and periodically performed for every preset number of sheets P of recording paper. Also, the control panel of the image forming apparatus 100 may be provided with a button for making the apparatus to start operating in the user mode, in order to enable a user to make the apparatus to perform a refreshing operation as the image nonuniformity becomes noticeable. Therefore, the fixing device 9 in this embodiment is provided with a mechanism for placing the refreshing rollers 52 and 62 in contact with, or keep the refreshing rollers 52 and 62 separated from, the fixation roller 40 and pressure roller 41 , respectively. Referring to FIGS. 3 and 4 , the operation of the mechanism 51 , which is for placing the refreshing roller 52 in contact with, or separating and keeping separated the refreshing roller 52 from, the fixation roller 40 , is controlled by the controller 53 (controlling means) of the fixation roller refreshing system 50 . Further, the controller 53 controls the operation of the motor 54 which transmits rotational driving force to the refreshing roller 52 in order to rotate the refreshing roller 52 for a preset length of time. Next, referring to FIGS. 3 and 5 , the pressure roller refreshing system 60 uses the controller 53 (controlling means) to activate the mechanism 61 for placing the refreshing roller 6 in contact with, or separating and keeping separated from, the pressure roller 41 . Further, the controller 63 controls the operation of the motor 64 which transmits rotational driving force to the refreshing roller 63 , in order to rotate the refreshing roller 63 for a preset length of time. As described above, in this embodiment, the fixing device 9 is structured so that its fixation roller refreshing roller 52 can be placed in contact with, or separated, and kept separated, from, the fixation roller 40 , and also, so that its pressure roller refreshing roller 63 can be placed in contact with, or separated, and kept separated, from, the pressure roller 41 . Thus, the fixation roller 40 and pressure roller 41 can be improved in peripheral surface properties by the placement of the two refreshing rollers 52 and 62 in contact with the fixation roller 40 and pressure roller 41 , respectively, for a desired length of time, with a desired timing, with the use of the fixation roller refreshing system 50 and pressure roller refreshing system 60 , when the two rollers 52 and 62 are on standby, that is, when they are remaining separated from the fixation roller 40 and pressure roller 41 , respectively. By the way, in this embodiment, the motors 54 and 64 were provided as means for transmitting rotational driving force to the refreshing rollers 52 and 62 , respectively. However, the fixing device 9 may be structured so that the rotational driving force is transmitted from the pressure roller 41 by way of a driving gear. 10. Surface Contamination of Refreshing Roller FIG. 11 shows the changes in surface roughness Rz of the surface layer of the refreshing rollers 52 and 62 , which occurs when the refreshing operation was carried out for five seconds for every 500 sheets of recording paper while sheets of recording paper of size A4, on each of which a monochromatic halftone image, which is roughly 0.5 in image data density, is present were conveyed through the fixation nip. “Fixing component-during printing” refers to a case in which an operation for refreshing the fixation roller 40 was carried out without interrupting the on-going image forming operation. “Fixing component-on standby” refers to a case in which the operation for refreshing the fixation roller 40 was carried out while the image forming apparatus 100 was kept on standby (printing operation was interrupted). “Pressing component-during printing” refers to a case in which an operation for refreshing the pressure roller 41 was carried out without interrupting the on-going printing operation. “Pressing component-on standby” refers to a case in which the operation for refreshing the pressure roller 41 was carried out while the image forming apparatus 100 was kept on standby (printing operation was interrupted). As the surface layer of the refreshing roller reduces in its surface roughness, it reduces in its refreshing performance as well. Thus, in order to improve (restore) the refreshing rollers 52 and 62 in the surface condition of their surface layer, the refreshing rollers 52 and 62 have to be resurfaced so that their surface roughness Rz becomes no less than 7-8 μm. This has been found out through experiments. With reference to these values, in the case of the refreshing roller 62 for the pressure roller 41 , whether the pressure roller refreshing operation was carried out without interrupting the on-going printing operation, or while the image forming apparatus 100 was on standby, made hardly any difference. In comparison, in the case of the refreshing roller 52 for the fixation roller 40 , when the refreshing operation was carried out without interrupting the on-going printing operation, the surface roughness of the fixation roller 40 fell below the referential values, as slightly less than 100,000 sheets of recording paper were conveyed through the fixing device 9 . This is less by ⅓ than when the refreshing operation was carried out while the image forming apparatus 100 was kept on standby. This reduction in surface roughness is attributable to the phenomenon that the peripheral surface of the refreshing roller 52 is packed with the toner having offset to the peripheral surface of the fixation roller 40 , paper dust, and the like contaminants. Moreover, after the refreshing roller 52 reduced in surface roughness, the peripheral surface of the refreshing roller 52 had the same color as the toner. Thus, the following are evident from these results. That is, in a case where the operation for refreshing the refreshing roller 52 is carried out without interrupting the on-going printing operation, contaminants adhere to the peripheral surface of the refreshing roller 52 . Therefore, the fixation roller 40 reduces in the surface roughness. Thus, in a case where the operation for refreshing the fixation roller 40 without interrupting the on-going printing operation, the fixation roller 40 reduces in surface roughness faster than in the case where the operation is carried out while the image forming apparatus 100 is kept on standby. In other words, it is evident that it is desirable that the operation for refreshing the fixation roller 40 is carried out after the on-going printing operation ends, or temporarily interrupted. That is, it is evident that it is desirable that the operation for refreshing the fixation roller 40 is carried out after the on-going job (printing operation) in which sheets of recording paper are conveyed through the nip (fixation nip) is interrupted. By the way, instead of interrupting the job in which sheets of recording paper are conveyed through the nip (fixation nip), the operation for refreshing the fixation roller 40 may be carried out between two jobs which are to be sequentially carried out. In comparison, as for the operation for refreshing the pressure roller 41 , whether it is carried out without interruption of the on-going printing operation, or while the image forming apparatus 100 is kept on standby, had little to do with the effectiveness of the pressure roller refreshing operation. That is, even if the operation for refreshing the pressure roller 41 is carried out without the interruption of the on-going printing operation, there will be no problem. The reason why the peripheral surface of the pressure roller 41 is not contaminated during a printing operation is thought to be as follows. That is, as the toner on a sheet of recording paper is heated in the fixation nip which the fixation roller 40 and pressure roller 41 form, it melts, and then, is fixed to the sheet P. During this process, most of the toner is fixed to the sheet P. However, it is possible that a small amount of the toner will offset onto the fixation roller 40 . This phenomenon is referred to as “hot offset”. Regarding this “hot offset”, the higher in temperature the fixation roller 40 , with which toner comes into contact, the more likely for the surface of each toner particle to be excessively melted, and therefore, the smaller the adhesive force between adjacent two toner particles. Therefore, the more likely for the toner to offset onto the fixation roller 40 . On the other hand, in the case of the pressure roller 41 , when the image forming apparatus 100 is in the one-sided mode, the surface of a sheet P of recording paper, on which an image is not present, comes into contact with the pressure roller 41 . Therefore, “hot offset” does not occur. Further, in a case where the image forming apparatus 100 is in the two-sided mode, the surface (first surface) of a sheet P of recording medium, on which a fixed toner image is present, comes into contact with the pressure roller 41 . However, the target temperature level for the pressure roller 41 is very low compared to that for the fixation roller 40 . In addition, the toner image on the first surface of the sheet P melted and solidified while it was fixed. Therefore, it is unlikely for toner to hot-offset onto the pressure roller 41 . 11. Refreshment Sequence (Automatic Mode) FIG. 13 is a block diagram of the system for refreshing the fixation roller 40 and/or pressure roller 41 , which can be set to an automatic mode or a user (manual) mode, which will be described later. Each signal is process by the CPU 81 as a part of a control system (controlling means), to control the aforementioned motors and heaters. This CPU 81 functions also as an obtaining portion for obtaining a command (signal) for making the image forming apparatus 100 (fixing device 9 ) operate in the mode for improving the image forming apparatus 100 in terms of image glossiness. First, the refreshment sequence carried out in the automatic mode is described, with reference to the flowchart for the automatic mode, with the use of the flowchart in FIG. 12 , and Table (which contains threshold values for deciding whether or not refreshment sequence is to be carried out). Here, the automatic mode is different from the user mode in that in the user mode, each time a refresh key, with which the control panel, as inputting means, is provided, is pressed (touched), the CPU 81 decides which refreshment sequence is to be carried out, and makes the fixing device 9 carry out the selected refreshment sequence, whereas in the automatic mode, each time the CPU 81 , which functions also as an executing portion, decides whether or not the fixation roller refreshing operation and/or pressure roller refreshing operation is to be carried out, each time the value in the counter which functions as a part of computing portion, reaches the threshold value. Then, the CPU 81 makes the image forming apparatus 100 (fixing device 9 ) carry out one or both of the refreshment sequences. Incidentally, the calculating portion is equipped with three counters. TABLE 2 Execution duration threshold per one Fixing Width counter 3000 60 sec roller sheets Pressing Passed sheet 500 sheets 10 sec roller counter Claw-on time 300 sec 10 sec counter Referring to FIG. 12 , steps ( 1 )-( 7 ) make up the refreshment sequence for nullifying the paper edge scars of the fixation roller 40 , and steps ( 1 ), ( 8 ), ( 9 ) and ( 13 )-( 15 ) make up the refreshment sequence for scraping away paper dust, and the like contaminants, from the pressure roller 41 . Further, steps ( 10 )-( 15 ) make up the refreshment sequence for nullifying the separation claw scars which are attributable to the contact between the pressure roller 41 and separation claws 71 . As a printing operation is started, whether or not a sheet P of recording paper has moved through the fixing device 9 is detected, in step ( 1 ). Then, the number of times a sheet P of recording paper moved through the fixing device 9 is counted by the counter 100 ( FIG. 13 ) in step ( 2 ). This counter 100 is controlled in such a manner that the value by which the value in the counter 100 is increased is varied based on the width (length in terms of recording paper conveyance direction) of the sheet P. More concretely, if a sheet P of recording paper is of size A4 (210 mm), the value in the counter 100 is increased by +1, and if a sheet P of recording paper is of size A3 (420 mm), which is equivalent to two sheets of size A4, the value in the counter 100 is increased by +2. Then, if the value in one of the counters 100 exceeds a threshold value, step ( 4 ) is taken to initiate the fixation roller refreshment sequence. If the value is no more than the threshold value, steps ( 1 )-( 3 ) are repeated as long as the on-going printing operation continues. After the completion of step ( 1 ), step ( 8 ) also is carried out, independently from the above described steps (sequences), for the following reason. That is, step ( 8 ) is for dealing with the roller contamination by paper dust. Thus, the number of times sheets P of recording paper which have just been heated for image fixation move through the fixing device 9 was counted regardless of sheet width (size). As in step ( 2 ), a value equivalent to the count of sheets of size A4 is added to the value in the counter 100 . If the value in the counter 100 is no less than the threshold value, in step ( 9 ), step ( 13 ) is taken. Incidentally, steps ( 4 )-( 7 ) may be taken as they are taken from step ( 3 ). In this case, however, the on-going print job has to be interrupted, which results in the reduction in productivity of the printer. Therefore, the operation for refreshing the pressure roller 41 is desired to be carried out without interruption of the on-going printing operation as long as it is possible. Step ( 10 ) also is independently carried out right after the starting of a printing operation, for the following reason. That is, this step is for dealing with the separation claw scars. The reason why this step is carried out regardless of the number of times sheets P of recording paper were conveyed through the fixing device 9 is that the extent of the scars attributable to the contact between the pressure roller 41 and separation claws 71 is related to how long the pressure roller 41 rotated in contact with the separation claws. That is, in a case where the pressure roller 41 remains constant in peripheral velocity, the length the separation claws 71 moved along the peripheral surface of the pressure roller 41 in contact with the peripheral surface of the pressure roller 41 , is proportional to the progression of the deterioration (separation claw scars) of the peripheral surface of the pressure roller 41 . The separation claws 71 come into contact with the pressure roller 41 before a sheet P of recording paper is discharged from the fixation nip. Then, they remain in contact with the pressure roller 41 until the sheet P moves out of the fixation nip. In this case, there is not the so-called proportional relationship between the number of sheets of recording paper having moved through the fixation nip and the length of time the separations claw 71 were in contact with the pressure roller 41 . Instead, the extent of separation claw scar is affected by the length of time (distance) it takes for sequentially conveyed two sheets P of recording paper to move through the fixation nip, and/or the number of prints (images) to be formed in a given printing job. Further, in some cases, it is only when the leading edge of a sheet P of recording paper comes out of the fixation nip that the separation claws 71 are required to be in contact with the pressure roller 41 , although it depends on the structure of a given fixing device. In such a case, the length of time the separation claws 71 are required to be in contact with the pressure roller 41 is relatively shorter, with reference to the number of sheets P of recording paper having moved through the fixation nip. A counter which is based purely on the number of sheets P of recording paper having moved through the fixation nip may be employed. However, controlling the refreshing operation based on the length of time the pressure roller 41 rotated while the separation claws 71 were in contact with the pressure roller 41 is more precise than otherwise. This is why the value in a duration counter is increased only by the length of time the pressure roller 41 rotates while the separation claws 71 are in contact with the pressure roller 41 , in step ( 11 ). Then, if the value in the duration counter is no less than the threshold value in step ( 12 ), step ( 13 ) and thereafter are taken to carry out the refreshing operation while images are being formed, as they are taken from step ( 9 ). Next, the sequence made up of steps ( 4 )-( 7 ), and the sequence made of steps ( 13 )-( 15 ), are described. Steps ( 4 )-( 7 ) are such steps that are to be carried out after the on-going printing is interrupted. In step ( 4 ), the length of time the fixation roller 40 is to be refreshed (abraded) is calculated based on the value in each counter. The objective of the fixation roller refreshing operation is to deal with the paper edge scars. Therefore, the length of time the fixation roller 40 is to be refreshed is set based on the condition of the portion of the peripheral surface of the fixation roller 40 which have the severest paper edge scars. In this embodiment, the threshold value is 3,000. Therefore, the fixation roller refreshing operation is carried out for 60 seconds. Next, the length of time the pressure roller 41 is to be refreshed is calculated in step ( 5 ). In a case where the on-going printing operation is interrupted for the fixation roller refreshing operation, the pressure roller refreshing operation may be carried out at the same time, because carrying out the pressure roller refreshing operation at the same time as the fixation roller refreshing operation does not have an additional effect upon productivity. Of course, it is not mandatory that the pressure roller 41 is refreshed with the above described timing. That is, the pressure roller 41 may be refreshed without interrupting the on-going printing operation. However, there are cases in which the pressure roller refreshing operation cannot be carried out during a printing operation, for example, such cases as where printing operations for outputting only a small number of prints (images) are carried out one after another. This is why the pressure roller refreshing operation is to be carried out whenever it can be. As soon as the length of time the fixation roller 40 is to be refreshed, and the length of time the pressure roller 41 is to be refreshed, are calculated, the on-going printing operation is interrupted in step ( 6 ). Then, as soon as the sheet P of recording paper in the fixing device 9 comes out of the fixing device 9 , the fixation roller refreshing operation and pressure roller refreshing operation are carried out in step ( 7 ). In comparison, in the case of the sequence comprising steps ( 13 )-( 15 ), the refreshing operations are carried out without interrupting the on-going printing operation. More specifically, in step 13 ), the length of time necessary for the pressure roller refreshing operation is calculated based on the value in the sheet counter and duration counter. Then, in step ( 14 ), it is permitted to carry out the pressure roller refreshing operation. Then, the pressure roller refreshing operation is carried out in step ( 15 ). 12. User Mode In this embodiment, a user mode is provided in addition to an automatic mode, in order to allow a user to perform a refreshing operation whenever the user notices that the image forming apparatus 100 began to output images which are nonuniform in gloss. FIG. 14 is a drawing of the control panel 150 of the image forming apparatus 100 . A referential code 151 stands for a print start button for commanding the image forming apparatus 100 to start a printing operation; 152 , a reset bottom for resetting the image forming apparatus 100 to the initial mode; 153 , a numerical input section (ten key section) for inputting numerical values such as the number of prints to be formed; 154 , a clear button for clearing the numerical input section of the inputted numerical value; 155 , a stop button for interrupting the on-going printing operation; 156 , a touch panel for setting various operational modes, and also, for showing the print condition; and a referential code 157 is a user mode button for selecting the user mode. As a user presses the user mode button 157 , mode section bars are displayed on the touch panel 156 , as shown in FIG. 14 . As the user selects a refresh mode bar, for example, on the touch panel 156 of the control panel, the screen displayed on the touch panel 156 turns into a refresh UI (user interface) screen, as shown in FIG. 15 . Then, as the user touches the refresh key 106 , a signal for the command for making the image forming apparatus 100 (fixing device 9 ) operate in the mode for improving the apparatus (device) in image gloss is inputted into the CPU 81 . As soon as the CPU 81 receives this signal, it makes the image forming apparatus 100 (fixing device 9 ) carry out the refreshing operations, which will be described later. By the way, if the user wants to go back from the refresh UI screen to the user mode, the user is to touch a cancel button 161 . 13. Refreshing Operation (Abrading Operation) in User Mode Next, referring to the flowchart in FIG. 1 , the operational sequence carried out when the image forming apparatus 100 (fixing device 9 ) is in the user mode is described. While the refresh UI screen is on the touch panel 156 in step ( 1 ), it is allowed to perform the refreshing operations, as long as the image forming apparatus 100 is on standby, in step ( 2 ). Next, as the refresh key 160 as a command obtaining section (inputting means) for obtaining the command for making the image forming apparatus 100 operate in the mode for improving the image forming apparatus 100 in image gloss is pressed, in step ( 3 ), the following sequences, and/steps, are carried out. That is, the CPU 81 ( FIG. 13 ), which functions also as a decision making section, confirms (obtains) the value in the refresh counter, in order to decide whether or not the fixation roller 40 and/pressure roller 41 is to be refreshed, in step ( 4 ). Here, the refresh counter is the sheet counter 100 , the value in which is compared with the threshold value to decide whether or not the fixation roller 40 is to be refreshed in the above described first roller refreshment sequence (automatic mode). It is also the sheet counter, the value in which is compared with the threshold value to decide whether or not the pressure roller refreshing operation is to be carried out in the roller refreshing second operation. Further, it is the duration counter, the value in which is compared with the threshold value to decide whether or not the pressure roller refreshing operation is to be carried out in the roller refreshing third sequence. If the values in all the refresh counters are no more than 10% of the threshold values when the refresh key 160 was pressed, in step ( 5 ), the fixation roller 40 and pressure roller 41 are refreshed for the shortest length of times in Table 3. That is, the fixation roller 40 and pressure roller 41 are refreshed for 5 seconds and 2 seconds, respectively. Here, the reason why both rollers 40 and 41 are refreshed (abraded) is that it is not clear that which of the fixation roller 40 and pressure roller 41 is to be refreshed, and also, it is thought that there is a connection between carrying out both the fixation roller refreshing operation and pressure roller refreshing operation, instead of not carrying out, and the improvement in fixation. Thereafter, in step ( 6 ), the refresh key 160 on the refresh UI screen is dimmed, and the operation in the refresh mode is ended in step ( 7 ). Once the refresh key 160 is dimmed, it does not occur that the image forming apparatus 100 is operated in the refresh mode, regardless of how many times and how hard the user touches the refresh key 160 , since the image forming operation has been interrupted. That is, the refreshing operations are not going to be carried out until the user mode button 157 is pressed again. If an image forming operation is carried out after the completion of the operation in the refresh mode, the refresh mode key 160 is highlighted again to allow the user to input a command for making the image forming apparatus 100 operate in the refresh mode. On the other hand, as the refresh key 160 is pressed, the value in the refresh counter is confirmed in step. If the value in one of the refresh counters is no less than the threshold value, it is decided whether or not the fixation roller 40 and pressure roller 41 are to be refreshed in step ( 4 ). That is, the sequence for deciding whether or not the value in the refresh counter for the fixation roller 40 is no more than 10% of the threshold value is decided in step ( 8 ), and the sequence for deciding whether or not the value in the refresh counter for the pressure roller 41 is no more than 10% of the threshold value, are carried out in step ( 9 ). If the value in the refresh counter for the fixation roller 40 is no more than 10% of the threshold value, the fixation roller refreshing operation is prohibited, and only the pressure roller is refreshed (abraded). On the other hand, the value in the refresh counter for the pressure roller refreshing operation is no more than 10% of the threshold value for the pressure roller refreshing operation, only the fixation roller refreshing operation is carried out; the pressure roller refreshing operation is prohibited. The reason why only one of the two rollers 40 and 41 is prevented from being refreshed is that it is clear that which is to be refreshed, the fixation roller 40 or pressure roller 41 , and therefore, only the roller to be refreshed is refreshed to prevent the other roller from reduced in service life, by being subjected to a refreshing operation. On the other hand, if the values in the refresh counter for the fixation roller 40 and the value in the refresh counter for the pressure roller 41 are no less than the threshold values, both the fixation roller refreshing (abrading) operation, and the pressure roller refreshing (abrading) operation, are carried out. The lengths of time these refreshing operations are to be carried out are given in Table 3. That is, when the refresh key 160 is pressed, if value in the sheet counter based on sheet width is between 300 and 3000, the fixation roller 40 is abraded for a length of time between 5 to 60 seconds, based on the value in the counter. Further, when the refresh key 160 is pressed, if the value in the sheet counter is between 50-500, or the length of time the separation claws were in contact with the pressure roller 41 is between 30 seconds to 300 seconds, the pressure roller refreshing operation is carried out for a length of time (second) between 2 seconds to 10 seconds, based on the value in the counter. By the way, regarding the length of time (in second) the refreshing operation is to be carried, the length may be set in a manner of stair steps so that the greater the value in the counter, the longer the refreshing operation is to be carried out. TABLE 3 <Threshold: less than 10%> Execution duration threshold per one Fixing Width counter 300 5 sec roller sheets Pressing Passed sheet 50 sheets 2 sec roller counter Claw-on time 30 sec 2 sec counter <Threshold: not less than 10%> Execution duration threshold per one Fixing Width counter - 3000 - 60 sec roller sheets Pressing Passed sheet - 500 - 10 sec roller counter sheets Claw-on time - 300 sec - 10 sec counter After the completion of the refreshing operations, the refresh counter for the roller for which the refreshing (abrading) operation was carried out is set to zero. That is, in a case where the rotational component for which the abrading operation is carried out is the fixation roller 40 , the paper width counter is reset to zero. On the other hand, in a case where the rotational component for which the abrading operation is carried out is pressure roller 41 , the sheet counter and separation claw contact time counter are reset to zero. Then, the highlighted refresh key 160 of the refresh UI screen is dimmed (darkened) in step ( 6 ), and the operation in refresh mode is ended in step ( 7 ). As described above, in the user mode, the CPU 81 decides which, or both, of the fixation roller 40 and pressure roller 41 is to be refreshed. Then, it automatically decides (sets) the length of abrading time, so that the length of abrading time matches the extent to which the roller(s) is to be abraded. Thus, all that is necessary for the fixation roller 40 and/or pressure roller 41 to be optimally refreshed is for a user to press the refresh key 160 . Thus, it does not occur that a wrong roller is selected to be refreshed, and also, the refreshing operation can be simply and accurately carried out. 14. Maintenance Mode In this embodiment, the image forming apparatus 100 is provided with a maintenance mode in order to enable a maintenance engineer to operate the image forming apparatus 100 in the maintenance mode, which is for testing and maintaining the image forming apparatus 100 . Referring to FIG. 16( a ) , as a maintenance engineer inputs his or her password with the use of the numerical input section 153 , the maintenance mode is highlighted on the touch screen. A maintenance engineer is to examine the surface condition of the surface layer of the fixation roller 40 as well as the pressure roller 41 , to find out which refreshing operation is to be carried out. Then, the engineer is to press the button, on the screen 170 , which indicates the roller to be refreshed, to refresh the roller. In this embodiment, the length of time each refreshing operation is to be carried out was set to the minimum length of time in Table 3. Then, the engineer is to repeat the refreshing operation while examining the images outputted by the image forming apparatus 100 , in order to improve each roller in surface condition. In a case where the value in one of the counters will have reached refresh rollers 52 and/or 62 will have reached the preset value for roller replacement, the button which represents the roller to be replaced, will be dimmed, as shown in FIG. 16( b ) . As described above, the image forming apparatus 100 in this embodiment is provided with the maintenance mode in order to enable a maintenance engineer to perform the refreshing operations. Thus, the fixation roller 40 and pressure roller 41 can be maintained at a satisfactory level in terms of the surface condition of their surface layer. Further, it can be easily decided whether the refreshing rollers 52 and 62 need to be replaced. (Effects of Present Embodiment) According to present invention, all that is necessary for a user to do to decide whether or not the surface layer of the fixation roller 40 and/or pressure roller 41 needs to be refreshed is for the user to select the user mode and press a single button, that is, the button for automatically deciding which, or both, of the fixation roller 40 and pressure roller 41 need to be refreshed. Therefore, it is possible to prevent the problem that the surface layer of the fixation roller 40 and/or pressure roller 41 is excessively abraded due to the error in the selection of the roller(s) to be refreshed, and/or excessive refreshing of the roller(s). (Modifications) In the foregoing, one of the preferable embodiments of the present invention was described. However, the preceding embodiment is not intended to limit the present invention in scope. That is, the present invention is also applicable to various modified version of the image forming apparatus, and fixing device, in the preceding embodiment, within the scope of the present invention. (Modification 1) In the preceding embodiment described above, the user mode, which is to be selected by a user, is provided, in addition to the automatic mode which does not require an instruction from a user. However, the preceding embodiment is not intended to limit the present invention in terms of the user mode. For example, the present invention is also applicable to an image forming apparatus and its fixing device structured so that as a user inputs an instruction, with the use of the UI screen or PC screen, to make the apparatus carry out a refreshing operation, the apparatus automatically decides which roller is to be refreshed, and carries out the refreshing operation for the selected roller. For example, in a case where an image forming apparatus is a printer which does not have a control panel, a refresh mode command transmitted from a host computer is inputted into the CPU 81 of the image forming apparatus, provided that the printer is in connection to the host computer (PC), wirelessly or through LAN cable. The operational sequences hereafter are the same as those in the above-described embodiment. Regarding the mode (refresh mode) for improving an image forming apparatus in image gloss, it may be for restoring the image forming apparatus by 80%-90%, in image gloss, relative to the initial condition, instead of restoring (refreshing) to 100%. That is, all that is necessary here is that operating an image forming apparatus in the refresh mode improves the apparatus in image gloss. While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions. This application claims priority from Japanese Patent Application No. 215387/2013 filed Oct. 16, 2013, which is hereby incorporated by reference.
A controller for controlling an image heating device which includes first and second rollers for heating therebetween a toner image on a sheet, a first rubbing roller for rubbing the first roller, and a second rubbing roller for rubbing the second roller, said controller including a counter configured to count a number of heated sheets; a first executing portion configured to execute rubbing by the first rubbing roller in accordance with an output of the counter; a second executing portion configured to execute rubbing by the second rubbing roller in accordance with an output of the counter; an acquiring portion execution instructions of an image glossiness improving mode operation provided by an operator; and a determination portion configured to determine which roller or rollers of the first second rollers is to be rubbed in accordance with an output of the counter, when the acquiring portion acquires the execution instructions.
96,967
FIELD OF THE INVENTION This application claims priority to Great Britain Application No. 1020130.9 filled Nov. 26, 2010 the disclosure of which is hereby incorporated by reference, BACKGOUND The present invention relates to an inhalation device for oral or nasal delivery of medicament in powdered form. More specifically, the invention relates to an inhaler having a housing to receive a strip having a plurality of blisters spaced along the length of the strip, each blister having a puncturable lid and containing a dose of medicament for inhalation by a user. The invention also relates to an inhaler containing a strip of blisters each having a puncturable lid and containing a dose of medicament for inhalation by a user of the device according to the invention. Oral or nasal delivery of a medicament using an inhalation device is a particularly attractive method of drug administration as these devices are relatively easy for a patient to use discreetly and in public. As well as delivering medicament to treat local diseases of the airway and other respiratory problems, they have more recently also been used to deliver drugs to the bloodstream via the lungs, thereby avoiding the need for hypodermic injections. It is common for dry powder formulations to be pre-packaged in individual doses, usually in the form of capsules or blisters which each contain a single dose of the powder which has been accurately and consistently measured. A blister is generally cold formed from a ductile foil laminate or a plastics material and includes a puncturable lid which is permanently heat-sealed around the periphery of the blister during manufacture and after the dose has been introduced into the blister. A foil blister is preferred over capsules as each dose is protected from the ingress of water and penetration of gases such as oxygen in addition to being shielded from light and UV radiation all of which can have a detrimental effect on the delivery characteristics of the inhaler if a dose becomes exposed to them. Therefore, a blister offers excellent environmental protection to each individual drug dose. Inhalation devices that receive a blister pack comprising a number of blisters each of which contain a pre-metered and individually packaged dose of the drug to be delivered are known. Actuation of the device causes a mechanism to breach or rupture a blister, such as by puncturing it or peeling the lid off, so that when the patient inhales, air is drawn through the blister entraining the dose therein that is then carried out of the blister through the device and via the patient's airway down into the lungs. Pressurized air or gas or other propellants may also be used to carry the dose out of the blister. Alternatively, the mechanism that punctures or opens the blister may push or eject the dose out of the blister into a receptacle from which the dose may subsequently be inhaled. It is advantageous for the inhaler to be capable of holding a number of doses to enable it to be used repeatedly over a period of time without the requirement to open and/or insert a blister into the device each time it is used. Therefore, many conventional devices include means for storing a number of blisters each containing an individual dose of medicament. When a dose is to be inhaled, an indexing mechanism moves a previously emptied blister away from the opening mechanism so that a fresh one is moved into a position ready to be opened for inhalation of its contents. An inhaler of the type described above is known from the Applicant's own co-pending international application that has been published as WO2005/037353 A1. According to one embodiment described and claimed in WO 2005/037353 A1, and illustrated in FIGS. 1 and 2 of the accompanying drawings, an inhaler 1 has a housing 2 containing a coiled strip of blisters 3 . An indexing mechanism 4 comprising a single actuating lever 5 unwinds the coil 3 one blister at a time so that they pass over a blister locator chassis 6 and successively through a blister piercing station 7 , when the actuator 5 is pivoted in a direction indicated by arrow “A” in FIG. 2 . The blister 3 a located at the blister piercing station 7 on each movement of the actuator 5 is pierced on the return stroke of the actuator 5 (in the direction indicated by arrow “B” in FIG. 2 ) by piercing elements 8 on the actuator 5 itself so that, when a user inhales through a mouthpiece 9 , an airflow is generated within the blister 3 a to entrain the dose contained therein and carry it out of the blister 3 a via the mouthpiece 9 and into the user's airway. The device known from WO2005/037353 A1 has already been modified so as provide a fully integrated device, i.e. one in which the used blisters are retained within its housing so that a user never has to come into direct contact with the blister strip. In one modified embodiment, known from the Applicant's own previous application that has now been published as WO09/007,352 A1, there is provided a flexible and resilient spiral element mounted within the housing of the device into which the used portion of the blister strip is directed so that, as the strip is gradually used up, the spiral expands as more and more of the strip is fed or pushed into it between its coils. The inhaler of the present invention, in its preferred form, is also a fully integrated device that retains the used blisters, although in a preferred embodiment it has a wall to separate the interior of the housing into used and unused blister compartments. The wall is preferably rigid and slideably mounted so that the size of the unused and used blister compartments changes relative to each other as the number of blisters that are used increases and the number of unused blisters decreases. The aforementioned document also describes an embodiment in which used blisters are crushed between the blister strip drive or indexing wheel and the inner surface of the casing of the device, which is also a feature of the inhaler of the present invention. As crushing takes place as the used strip passes around the blister strip drive member, a curl or curved form is imparted to the strip which helps it to coil up within the chamber. The inhaler of the invention may also incorporate a blister strip drive mechanism or indexing mechanism that forms the subject of the Applicant's own previous international application that has now published as WO2009/092652 A1. The disclosures of WO2005/037353 A1, WO09/007,352 A1 and WO2009/092652 A1 are all incorporated herein by reference. SUMMARY OF THE INVENTION The present invention seeks to provide another inhalation device of the type disclosed in the above-mentioned applications, and which also has a relatively simple construction, is robust, straightforward to manufacture and easy for the patient to use. According to the invention, there is provided an inhaler comprising a housing to receive a strip having a plurality of blisters, each blister having a puncturable lid and containing a dose of medicament for inhalation by a user, a mouthpiece mounted to the housing and through which a dose of medicament is inhaled by a user, a blister piercing member mounted for rotation about a first axis and an actuating mechanism including an actuating lever mounted for rotation about a second axis to sequentially move each blister into alignment with the blister piercing member, wherein the actuating lever cooperates with the blister piercing member so that the blister piercing member pivots about said first axis in response to rotation of the actuating member from an initial position about the second axis to puncture the lid of an aligned blister so an airflow through the blister is generated to entrain the dose contained therein and carry it, via the mouthpiece, into the user's airway when a user inhales through the mouthpiece. In a preferred embodiment, the blister piercing member is fixed to the mouthpiece and the mouthpiece is pivotally mounted to the housing so that the mouthpiece pivots, together with the blister piercing member, about said first axis in response to rotation of the actuating lever about the second axis. In another embodiment, the blister piercing member is pivotally mounted to the mouthpiece for rotation about said first axis so that the blister piercing member pivots about said first axis relative to the mouthpiece, in response to operation of the actuating lever. Preferably, the actuating lever is pivotable in the same direction about the second axis to sequentially move each blister into alignment with a blister piercing member and to cause rotation of the blister piercing member about the first axis so that the blister piercing member punctures the lid of an aligned blister. The actuating mechanism may be configured such that rotation of the actuating lever about the second axis through a first portion of its stroke moves a blister into alignment with a blister piercing member and, further rotation of the actuating lever about the second axis in the same direction, during a second portion of its stroke, causes rotation of the blister piercing member about the first axis so that the blister piercing member punctures the lid of an aligned blister. The actuating mechanism may include a blister strip drive wheel and the actuating lever may be engaged with said blister strip drive wheel during rotation of the actuating lever to rotate said blister strip drive wheel and drive said strip. In a preferred embodiment, the actuating mechanism is configured such that the actuating lever and blister strip drive wheel disengage at the end of the first portion of the stroke so that the blister strip drive wheel remains substantially stationary during rotation of the actuating lever through said second portion of its stroke. Preferably, the actuating mechanism comprises a drive coupling member rotatable in response to rotation of the actuating lever to rotate the blister strip drive wheel, the blister strip drive wheel being rotatably mounted on said drive coupling member, wherein the actuating mechanism includes means to control rotation of the blister strip drive wheel relative to rotation of the drive coupling member so that the blister strip drive wheel rotates together with the drive coupling member during the first portion of the stroke of the actuating lever but not during the second portion of the stroke of the actuating lever. In a preferred embodiment, the means for controlling rotation of the blister strip drive wheel is also configured to inhibit rotation of the blister strip drive wheel when the actuating lever is rotated in the opposite direction. The drive coupling member may include a drive gear rotatable together with the drive coupling member and the actuating lever can include a drive gear segment that drivingly engages with the drive gear member so that the drive gear rotates in response to rotation of the actuating lever to rotate the drive coupling to member. Preferably, the means to control rotation of the blister strip drive wheel includes cooperating elements on the drive coupling member and on the housing. In an embodiment where the mouthpiece is pivotally mounted together with the blister piercing element, one of the actuating lever and the mouthpiece can have a drive cam element and the other of the actuating lever and the mouthpiece can have a drive cam surface. The drive cam element cooperates with the drive cam surface so that the mouthpiece pivots about said first axis in response to rotation of the actuating member about the second axis to puncture the lid of an aligned blister. The cam groove may have an arcuately shaped region having an axis that corresponds to the second axis about which the actuating lever rotates such that, during said initial rotation of the actuating lever through its first portion of its stroke, the drive cam element slides along said arcuately shaped region of the cam groove without causing rotation of the mouthpiece about the first axis. In this embodiment, the cam groove can have a second region shaped such that, during further rotation of the actuating lever through its second portion of its stroke, cooperation between the drive cam element and the second region of the cam groove causes the mouthpiece to rotate at the same time as the actuating lever so that the blister piercing element punctures the lid of an aligned blister. Alternatively, in the embodiment where the blister piercing element is pivotally mounted to a fixed housing, one of the actuating lever and the blister piercing member can have a drive cam element and the other of the actuating lever and the blister piercing member can have a drive cam surface. The drive cam element cooperates with the drive cam surface so that the blister piercing element pivots about said first axis in response to rotation of the actuating member about the second axis to puncture the lid of an aligned blister. The cam groove can have an arcuately shaped region having an axis that corresponds to the second axis about which the actuating lever rotates such that, during said initial rotation of the actuating lever through its first portion of its stroke, the drive cam element slides along said arcuately shaped region of the cam groove without causing rotation of the blister piercing member about the first axis. The cam groove may have a second region shaped such that, during further rotation of the actuating lever through its second portion of its stroke, cooperation between the drive cam element and the second region of the cam groove causes the blister piercing element to rotate together with the actuating so that the blister piercing element punctures the lid of an aligned blister. In any of the embodiments, the inhaler may comprise a cap and a coupling pivotally mounting the cap to the housing for rotation about a third axis, the cap covering the mouthpiece in a closed position. The housing preferably comprises a shell and the actuating lever is mounted for rotation about the second axis on the shell and includes a mounting plate that extends within a space between the shell and the cap. In one embodiment, the actuating lever comprises a button extending from said plate and protruding out of said space to enable actuation of the actuating lever by a user. Preferably, the actuating lever comprises an arcuately shaped opening extending about the second axis, the coupling that pivotally mounts the cap to the housing extending through said opening so that the coupling travels along the arcuately shaped opening as the actuating lever pivots about the second axis. The cap and actuating lever may include cooperating means configured such that, when the cap is rotated from its open position back into its closed position in which it covers the mouthpiece, the actuating lever is rotated rotate back into its initial position. Preferably, the cooperating means comprises a wall on the actuating lever and a drive member depending from the cap towards the actuating lever, said wall and drive member being positioned between the second and third axes such that the drive member engages the wall when the cap is rotated in a direction back into its closed position to rotate the actuating member about the second axis back into its initial position. In any embodiment, the inhaler may include a detent mechanism such as a cantilevered arm on the actuating lever and a pawl on the shell, the arm being resiliently deformed by said pawl as the actuating lever reaches the end of the second portion of its stroke, to hold the actuating lever in position until the cap is closed. The cantilevered arm preferably includes a kinked portion that snaps over the pawl when the actuating lever is rotated towards the end portion of its stroke. In a preferred embodiment, a wall is slideably mounted in the housing to divide it into unused and used blister compartments. The wall preferably comprises a baffle extending between opposing housing walls and an elongate foot extending substantially at right-angles to the baffle and being slideably received within a recess in a surface of a wall of the housing. The baffle is preferably attached to a central region of the foot. In a preferred embodiment, the foot is widest at its ends remote from the baffle such that only the ends of said foot contact the walls of said recess in the housing. According to another aspect of the invention, there is provided an inhaler comprising a housing to receive a strip having a plurality of blisters, each blister having a puncturable lid and containing a dose of medicament for inhalation by a user, a mouthpiece pivotally mounted to the housing and through which a dose of medicament is inhaled by a user and an actuating mechanism including a lever operable to sequentially move each blister into alignment with a blister piercing member depending from the mouthpiece said actuating lever also being operable to cause the mouthpiece to pivot so that the blister piercing member punctures the lid of an aligned blister so that, when a user inhales through the mouthpiece, an airflow through the blister is generated to entrain the dose contained therein and carry it, via the mouthpiece, into the user's airway. A cap is preferably pivotally mounted to the housing that covers the mouthpiece in a closed position. The cap may extend over the actuating lever in a closed position. In one embodiment, the actuating lever is pivotally mounted to the housing and the actuating mechanism is configured such that the actuating lever is pivotable to sequentially move each blister into alignment with a blister piercing member and also pivotable to cause rotation of the mouthpiece so that the blister piercing member punctures the lid of an aligned blister. The actuating lever is preferably pivotable in the same direction to sequentially move each blister into alignment with a blister piercing member and to cause rotation of the mouthpiece so that the blister piercing member punctures the lid of an aligned blister. The actuating mechanism may be configured such that an initial rotation of the actuating lever through a first portion of its stroke moves a blister into alignment with a blister piercing member and, further rotation of the actuating lever causes rotation of the mouthpiece so that the blister piercing member punctures the lid of an aligned blister. In a preferred embodiment, the actuating mechanism is configured such that movement of the strip stops between said initial and further rotation of the actuating lever. The actuating mechanism preferably includes a blister strip drive wheel around which a blister strip received in the housing is fed, said blister strip drive wheel being rotatable in response to rotation of the actuating lever to drive said strip. In one embodiment, wherein the blister strip drive member comprises a plurality of spokes extending from a hub, the spokes being spaced from each other such that a spoke locates between blister cavities as a blister strip passes around the blister strip drive member to engage and drive a strip as the blister strip drive member rotates, the blister strip drive member being positioned relative to a wall such that the distance between the hub and said wall is less than the height of a blister cavity such that onward rotation of the wheel causes a blister cavity to be at least partially squashed or sandwiched between the hub and said wall. The inhaler preferably includes a drive coupling member rotatable in response to rotation of the actuating lever, the blister strip drive wheel being rotatably mounted on said drive coupling member, the drive coupling member and the housing including means to control rotation of the blister strip drive member relative to rotation of the drive coupling member so that the blister strip drive wheel rotates together with the drive coupling member during part of the rotation of the drive coupling member in the same direction. In one embodiment, the means for controlling rotation is configured so that the blister strip drive wheel rotates together with the drive coupling member during part of the rotation of the drive coupling member in the same direction and the blister strip drive wheel does not rotate at all when the drive coupling member rotates in the opposite direction. The drive coupling member may include a drive gear member and the actuating lever includes a drive gear segment that drivingly engages with the drive gear member so that the drive gear member rotates in response to rotation of the actuating lever. The drive coupling member and the drive gear member may be integrally formed as one component. Preferably, the actuating lever includes a mouthpiece drive cam element that cooperates with a cam groove formed in the mouthpiece. The cam groove in the mouthpiece can have an arcuately shaped region such that, during said initial rotation of the actuating lever through its first portion of its stroke, the drive cam element slides along the cam groove with substantially no rotation of the mouthpiece. The cam groove may also have a second region shaped such that, during further rotation of the actuating lever beyond the first portion of its stroke, cooperation between the drive cam element and the cam groove causes the mouthpiece to rotate together with the actuating lever to pull the blister piercing element depending therefrom into the lid of an aligned blister. The cap and the actuating lever may be configured such that, when the cap is rotated from an open position back into its closed position, the cap cooperates with the actuating lever to cause it to rotate back into its initial position. Rotation of the actuating lever back into its initial position in response to rotation of the cap may also cause the drive cam element to slide back along the cam groove and lift the mouthpiece back into its original position in which the blister piercing element is removed from the aligned blister. In a preferred embodiment, the cap includes a drive pin that cooperates with the actuating lever during closure of the cap so that the actuating lever is also rotated back to its initial position. The actuating lever may have a hole therethrough and the drive pin extends from the cap into said hole, the drive pin engaging with the sidewall of said hole when the cap is rotated from its open into its closed position. In one embodiment, the housing comprises a shell that defines a chamber to receive a blister strip, the blister strip drive wheel being received in the shell, the shell having opposing end walls spaced from each other by a side wall, the drive coupling member extending through a hole in one of said opposing end walls such that the drive gear is disposed on the outside of the shell. The actuating member may comprise a plate extending between an actuating button and the gear segment, said plate extending across a surface of an end wall on the outside of the shell. The actuator can be pivotally mounted to a hub upstanding from said surface. The actuating member may also comprise a second plate that extends parallel and spaced from the first plate, the shell being received between said plates and said second plate being pivotally mounted to a hub upstanding from the surface of said opposite end wall of the shell. In one embodiment, the mouthpiece has a peripheral wall that extends across the surface of the outside of the shell. The actuating lever may include an actuating button that extends between said plates and across the side wall of the shell. The cap can have parallel side wall sections spaced from each other by an intermediate section, the side wall sections each extending across a corresponding end wall of the shell, one of said side wall sections of the cover enclosing the first and second plates of the actuating lever and at least a portion of the side wall of the mouthpiece. The intermediate section may extend across the side wall of the shell and covers the mouthpiece in a closed position. In one embodiment, a boss upstands from opposite surfaces of the shell each of which locate in a recess in a corresponding side wall section of the cap to pivotally mount the cap to the shell. BRIEF DESCRIPTION OF THE DRAWINGS Embodiments of the invention will now be described, by way of example only, with reference to FIGS. 3 to 16 of the accompanying drawings, in which: FIGS. 1 and 2 are side views of a conventional inhalation device to show how a strip is driven to sequentially move blisters into alignment with a blister piercing element by movement of an actuator from the position shown in FIG. 1 to the position shown in FIG. 2 which drives an indexing wheel. A piercing head on the actuator pierces the lid of an aligned blister when the actuator is returned to its normal position, as shown in FIG. 1 ; FIGS. 3 a to 3 e is a sequence of drawings to show the general function and operation of the inhaler according to the invention; FIG. 4 is a side elevation of an inhalation device according to an embodiment of the invention; FIG. 5 is the side elevation of FIG. 4 , but with the cap removed so that the internal components can be seen; FIG. 6 is the side elevation of FIG. 5 after removal of one-half of the shell forming the housing of the inhaler; FIG. 7 is an exploded perspective view showing the individual components of the inhaler according to the invention. FIG. 8 is a partial perspective view of the blister strip indexing mechanism for use in the inhaler of the invention; FIG. 9 is a partial perspective view of the blister strip indexing mechanism shown in FIG. 8 following partial rotation of the actuating lever into an intermediate position from its home position; FIG. 10 is the same view as shown in FIG. 9 , but without the optional cantilevered chassis arm; FIG. 11 is a partial perspective view of the blister strip indexing mechanism shown in FIGS. 8 to 10 , after the actuating lever has been rotated to a point at which drive between the drive coupling and the actuator has disengaged; FIG. 12 is a partial perspective view of the opposite side of the indexing mechanism shown in FIGS. 9 to 11 ; FIG. 13 a is a perspective view of the drive coupling used in the indexing mechanism of the inhaler shown in FIGS. 9 to 12 ; FIG. 13 b is a side view of the drive coupling illustrated in FIG. 13 a in which the flexible flange portion has been deflected in a direction “T” towards the shaft or, towards an indexing wheel mounted on that shaft. FIG. 14 is a partial view of the inhaler according to the invention showing the form and position of the indexing wheel that may be used in order to crush used blisters as they pass around the indexing wheel; FIG. 15 is an exploded perspective view showing the individual components of the inhaler according to another embodiment of the invention; and FIG. 16 is a cross-sectional side view of the inhaler shown in FIG. 15 . DETAILED DESCRIPTION Referring now to FIGS. 3 a to 3 e of the accompanying drawings, there is shown an inhaler 10 having a housing 11 formed from two shell portions 11 a , 11 b (see FIGS. 6 and 7 ), a cap 12 pivotally mounted to the housing 11 for rotation about an axis marked “C” (see FIGS. 5 to 7 ) from a closed position as shown in FIG. 4 in which the cap 12 covers and protects a mouthpiece 13 to a fully open position, as shown in FIGS. 3( b ) to 3 ( d ) and in a direction indicated by arrow “R” in FIG. 3( a ), in which the mouthpiece 13 is exposed to enable a user to inhale a dose of medicament through the mouthpiece 13 . It should be noted that the cap is ‘passive’ in the sense that it can be opened and closed freely without performing the function of indexing of the blister strip or causing a blister piercing member 15 depending from the mouthpiece 13 to pierce the lid of an aligned blister. The cap 12 is rotated into its fully open position in the direction of arrow “R”. An actuating lever 14 is revealed as soon as the cap 12 is rotated out of its closed position. The user then applies pressure to the actuating lever 14 , so that it rotates in the direction indicated by arrow “S” in FIG. 3( b ). During initial rotation of the actuating lever 14 through a first portion of its stroke into the position as it is shown in FIG. 3( b ), the strip is indexed so as to move an unused blister into alignment with the blister piercing member 15 . When the actuating member is rotated through a second portion of its stroke beyond the position shown in FIG. 3( b ) and after having completed the first portion of its stroke, in the direction of arrow “T” in FIG. 3( c ), the strip remains stationary but the mouthpiece 13 is now pivoted so that the blister piercing member 15 pierces the lid of the previously aligned blister. Although reference is made to a blister piercing member 15 , it will be appreciated that multiple openings are formed in the lid of the blister so that air can be drawn into the blister through one or some of those openings and flow out of the blister together with an entrained dose of medicament, through one or more other openings and via the mouthpiece into a patient's airway. Once the actuating lever is in the position shown in FIG. 3( c ), the user now inhales through the mouthpiece 13 , as shown by arrows indicated by “U” in FIG. 3( d ). After inhalation, the user rotates the cap in the opposite direction, i.e. in the direction indicated by “V” in FIG. 3( e ). During this movement, the cap 12 engages with the actuating lever 14 so that the actuating lever 14 also returns to its initial position as shown in FIG. 3( a ), the strip remaining stationary during this return movement of the actuating lever 14 . As mentioned above, the cap 12 is passive, although it does perform the function of re-setting the actuating member back to its original position in the event that the actuating lever is depressed prior to closing the cap. As previously mentioned, the inhaler of the invention has an indexing mechanism that has previously been described with reference to WO2009/092652 A1. This aspect of the inhaler of the invention will now be described in detail with reference to FIGS. 8 to 13 a . Although the drawings show a slightly different arrangement, in which an actuator 54 takes the place of a drive gear 16 attached to the drive coupling member 57 in the present invention, the principle remains the same as the actuator 54 and the drive gear are both rotated to index the strip. Therefore, rotation of the drive gear 16 performs the same function as rotation of the actuator 54 referred to in the description of FIGS. 8 to 13 a below. Referring now to FIG. 8 , there is shown a partial perspective view of an inhalation device 50 comprising an indexing mechanism 51 . The indexing mechanism 51 includes an indexing wheel 55 comprising four vanes 55 a , 55 b , 55 c , 55 d , each having an enlarged head portion 56 a , 56 b , 56 c , 56 d . As is clear from reference to FIGS. 1 and 2 , once a blister strip (not shown in FIGS. 8 to 14 ) has passed over the blister locating chassis 53 , it passes around the indexing wheel 55 . A blister locates in the space between two vanes 55 a , 55 b , 55 c , 55 d so that, as the indexing wheel 55 rotates in response to rotation of the actuator 54 , a vane 55 a , 55 b , 55 c , 55 d engages a blister located between the vanes 55 a , 55 b , 55 c , 55 d so as to drive the strip around the indexing wheel 55 to sequentially move each blister forward by a sufficient distance to move a fresh blister into alignment with a blister piercing element. The indexing mechanism 51 includes a drive coupling member 57 (most clearly shown in FIGS. 13 a and 13 b ) for selectively or temporarily coupling the actuator 54 to the indexing wheel 55 so that, when coupled, the indexing wheel 55 rotates in response to rotation of the actuator 54 to index the strip. The drive coupling member 57 comprises a shaft 58 defining an axis of rotation “A” (see FIGS. 13 a and 13 b ) on which the indexing wheel 55 is rotatably received so that it can rotate freely about the shaft 58 about said axis of rotation “A”. The actuator 54 is fixedly attached to the drive coupling member 57 (the gear drive would also be fixedly attached to the drive coupling member 57 ) so that the drive coupling member 57 rotates together with the actuator 54 at all times. In the embodiment illustrated and described with reference to FIGS. 8 to 12 , the actuator 54 , drive coupling member 57 and indexing wheel 55 are all mounted coaxially for rotation about the same axis “A”. However, it will be appreciated that in the embodiment of FIG. 7 , the mouthpiece 13 and actuating lever 14 are not coaxially mounted with Axis ‘A’. The drive coupling member 57 has a circular flange 59 that extends radially from one end of the shaft 58 . A portion 60 of the flange is cut-away (see arcuate opening 61 in FIG. 8 ) over an angle of approximately 180 degrees where the flange 59 joins the shaft 58 so that this portion 60 of the flange 59 is not directly attached to the shaft 58 but only to the remaining portion of the flange 59 at each of its ends 60 a , 60 b . As a result, this portion 60 of the flange 59 is flexible relative to the rest of the flange 59 and can be deflected out of the plane of the flange 59 that extends at right angles to the axis of the shaft, in an axial direction (indicated by “T” and “S”, in FIG. 13 b ) either towards or away from the shaft 58 or, more importantly, towards or away from the indexing wheel 55 which is mounted on the shaft 58 , when force is applied to it. This flexible flange portion 60 hinges about an axis B which intersects the axis A of the shaft 58 and actuator 54 but extends at right angles to it. The drive coupling member 57 , or at least the flange 59 , is made from a resilient material so that when the deflected flexible flange portion 60 is released, it returns to its neutral, unstressed position, in which it lies coplanar with the remaining fixed portion of the flange 59 . The flexible flange portion 60 has an integrally formed flange deflecting dog 62 projecting radially from its circumferential edge. The flange deflecting dog 62 has first and second angled engaging faces 63 , 64 on opposite sides. When the drive coupling member 57 is rotated in response to rotation of the actuator 54 in one direction, one of the first or second angled engaging faces 53 , 54 cooperate with a fixed formation 65 on the housing 52 to cause the flexible flange portion 60 to deflect in a first direction. When the drive coupling member 57 is rotated in the opposite direction, the other angled engaging face cooperates with the formation 65 on the housing 52 to cause the flexible flange portion 60 to deflect in a second, opposite direction, as will be explained in more detail below. The flexible flange portion 60 also has an arcuately shaped indexing wheel drive dog 66 that upstands in an axial direction from its surface towards the indexing wheel 55 in the same direction as the shaft 58 and extends partially around the circumference of the flexible flange portion 60 . As will now be explained in more detail below, an end face 66 a (see FIG. 13 a ) of the indexing wheel drive dog 66 engages a vane 55 a , 55 b , 55 c , 55 d of the indexing wheel 55 when the flexible flange portion 60 has been deflected in a first direction, as indicated by arrow “T” in FIG. 13 b (the flange portion 60 is shown in its deflected position in FIG. 13 b ), so that the indexing wheel 55 is driven together with the drive coupling member 57 . As mentioned above, the flange deflecting dog 62 engages a formation 65 on the housing 52 when the drive coupling member rotates in response to rotation of the actuator 54 so as to flex the deflectable portion 60 of the flange 59 . This formation 65 comprises first and second arcuately shaped tracks or paths 67 , 68 positioned one above the other or spaced from each other in the axial direction. The surface of the innermost track 67 is visible in FIG. 8 . The lower or outermost track 68 is located beneath it and is visible in FIG. 12 . The ends of the tracks 67 a , 68 a have angled faces for reasons that will become apparent. When the actuator 54 (or the drive gear) is rotated in a first direction, the drive coupling member 57 rotates together with it and the first outwardly facing angled surface 63 on the flange deflecting dog 62 contacts the angled face 67 a of the innermost track 67 . Further rotation of the drive coupling member 57 causes the flange deflecting dog 62 to ride up onto the surface of the innermost track 67 thereby deflecting the flexible flange portion 60 inwardly, i.e. in a direction into the housing 62 or towards the shaft 58 and the indexing wheel 55 . When the flexible flange portion 60 has been deflected inwardly in the direction of arrow T, further rotation of the drive coupling member 57 causes the indexing wheel drive dog 66 to engage a vane, which as shown in FIG. 8 is vane 55 c , of the indexing wheel 55 so that the indexing wheel 55 rotates together with the drive coupling member 57 and drive to the indexing wheel 55 is engaged. When the end of the innermost track 67 has been reached, the flange deflecting dog 62 falls off the surface of the track 67 and the resilience of the flexible flange portion 60 causes it to return to its original unstressed or neutral position. When the drive coupling member 57 is rotated further, the indexing wheel drive dog 66 no longer engages with the vane 55 c of the indexing wheel 55 and instead passes beneath it so the indexing wheel 55 remains stationary. Therefore, drive to the indexing wheel 55 is disengaged, despite continued rotation of the actuator 54 in the same direction. When the actuator 54 is rotated back in the opposite direction towards its home position, the second inwardly facing angled surface 64 of the flange deflecting dog 62 now contacts the lower or outermost track 68 so that the flange deflecting dog 62 now rides onto the surface of that second track 68 , thereby causing the flexible flange portion 60 to deflect outwardly or in the opposite direction to the direction in which it was previously deflected. Engagement of the flange deflecting dog 62 with the outermost track 68 so as to deflect the flange portion 60 in the opposite direction, enables the drive coupling member 57 to rotate in the opposite direction without any drive to the indexing wheel 55 . It will be appreciated that, if the flange portion 60 was not deflected in the opposite direction, the flange deflecting dog 62 would simply engage against the end of the formation 65 in the housing 62 when rotated back in the opposite direction, thereby preventing rotation in the opposite direction or, the flange deflecting dog 62 would travel back over the innermost track 67 deflecting the flexible flange portion 60 in the same direction causing the opposite end 66 b of the indexing wheel drive dog 66 to engage with a vane 65 b of the indexing wheel 65 thereby driving the indexing wheel 65 backwards rather than leaving it stationary with no drive engaged. Therefore, it is necessary to ensure that the flexible flange portion 60 is deflected in the opposite direction so that there is no drive to the indexing wheel during rotation of the coupling member 67 in the opposite direction. When the drive deflecting dog 62 reaches the end of the outermost track 68 , the flexible flange portion 60 returns to its original unstressed or neutral position, due to its resilience. It will be appreciated that the extent of rotation of the indexing wheel 55 relative to the extent of rotation of the actuator 54 may be controlled by altering the circumferential length of the inner and outer tracks 67 , 68 . If the tracks are made longer, the flexible flange portion 60 will be deflected for a greater proportion of the angle through which the actuator 54 is rotated and so the indexing wheel drive dog 66 will be engaged with the indexing wheel 55 to rotate the indexing wheel 55 throughout that angle. If required, the tracks 67 , 68 could be made sufficiently long so that the indexing wheel 55 rotates during rotation of the actuator 54 through its entire angle of movement in one direction. Alternatively, the tracks 67 , 68 could be made shorter to reduce the angle through which the actuator 54 and indexing wheel 55 rotate together. Ideally, the track length can be selected so that the indexing wheel 55 is rotated through a sufficient angle to move the next, unused blister, into alignment with the blister piercing element. The further rotation of the actuator 54 (the gear drive) causes the mouthpiece to rotate so that the blister piercing member pierces the lid of a blister that has just been moved into alignment with the blister piercing element. It will be appreciated that the indexing mechanism 51 is designed to enable a stroke to be aborted when the actuator 54 or cap has been rotated through an angle which is sufficient to cause initial indexing of the strip but which is not such that the drive to the indexing wheel 55 has disengaged, i.e. a position in which the flange drive dog 62 has not reached the end of the innermost track 67 . If the stroke is aborted and the actuator 54 returned to its original position before drive to the indexing wheel 55 has disengaged (or the drive gear rotated back to its initial position), the strip will be driven backwards into its original position as a rear surface 66 b of the indexing wheel drive dog 66 will engage a preceding vane 55 b to drive the indexing wheel 55 in the opposite direction. The indexing mechanism 51 also includes optional means for locking the indexing wheel 55 to prevent its rotation between indexing steps and means for temporarily releasing that lock to allow rotation of the indexing wheel 55 when driven by the indexing wheel drive dog 66 . The lock also improves positional accuracy of the strip and, more specifically, the next blister to be pierced. This locking arrangement will now be described in more detail below, although it should be noted that the locking mechanism can be omitted altogether. The blister location chassis 53 may optionally comprise a resiliently flexible cantilever arm 70 that extends from the body 53 of the chassis towards the indexing wheel 55 . The free end of the cantilever arm 70 has an enlarged head portion 71 comprising a letterbox shaped slot, window or opening 72 in which the head 56 c of a vane 55 c of the indexing wheel 55 is located. The opening 72 is dimensioned such that the head 56 c of the vane 55 c (as shown in FIG. 8 ) is a snug fit therein so that rotation of the indexing wheel 55 is prevented. In the normal or home position of the actuator 54 , the head 56 c of a vane 55 c is located in said opening 72 in the cantilever arm 70 of the chassis 53 so that rotation of the indexing wheel 55 is prevented. When the actuator 54 is rotated and the flange drive dog 62 engages the innermost track 67 so as to deflect the flexible portion of the flange 60 inwardly towards the indexing wheel 55 , the indexing wheel drive dog 66 initially engages with a protrusion 71 a extending from an inner side of the enlarged head 71 on the cantilever arm 70 of the chassis 53 so that the cantilever arm 70 is deflected outwardly, away from the indexing wheel 55 , to free the head 56 c of the vane 55 c from the slot 72 , thereby unlocking the indexing wheel 55 . Only once the indexing wheel 55 has been released by the indexing wheel drive dog 66 pushing the cantilever arm 70 away from the indexing wheel 55 does the indexing wheel drive dog 66 subsequently engage a vane 55 c of the indexing wheel 55 so that further rotation of the drive coupling member 57 rotates the indexing wheel 55 . Prior to the flange drive dog 62 falling off the end of the innermost track 67 and the flexible flange portion 60 returning to its undeflected state due to its resilience, the indexing wheel drive dog 66 no longer pushes against the cantilever arm 70 and so the cantilever arm 70 is free to move back towards the indexing wheel 55 . As the cantilever arm 70 is free to move back just prior to rotation of the indexing wheel 55 being completed, the cantilever arm is prevented from moving all the way back by the head 56 b of a following vane 55 b which contacts the cantilever arm 70 . During further rotation of the indexing wheel, the head 56 b slides across the cantilever arm and then drops into the opening 72 thereby allowing the cantilever arm 70 to move all the way back and locking the indexing wheel 55 in position prior to any further rotation of the drive coupling member 57 in response to continued rotation of the actuator 54 . On the return stroke of the actuator 54 , it will be appreciated that deflection of the flexible flange portion 60 in the opposite direction, i.e. in a direction away from the indexing wheel, also ensures that the indexing wheel drive dog 66 clears the chassis arm 70 and so the indexing wheel 55 is not unlocked, thereby preventing any rotation of the indexing wheel 55 during the return stroke. The blister strip drive member or indexing wheel 15 of the invention may take a slightly different form to that described with reference to FIGS. 8 to 13 b , although the principle still remains the same. In particular, the indexing wheel 15 may be used to squeeze the used blister cavities as they pass around it, thereby at least partially crushing them. This is achieved by enlarging the axle or hub 18 of the indexing wheel so that the distance (X in FIG. 14 ) between the hub and the casing or wall of the device 11 , or a component fixed to the casing 11 , is less than the maximum height of a blister cavity. As the blister cavities are entrained between the spokes 17 a of the indexing wheel 17 , onward rotation of the wheel 17 causes the cavities to be at least partially squashed or sandwiched between the enlarged hub 18 of the indexing wheel 17 and the casing 11 of the device. The advantage of at least partially crushing the empty blister cavities is that they then take up less space when coiled within the used blister chamber of the device as the coiled strip has a smaller diameter. Furthermore, a natural curvature is imparted to the strip, both as a result of being fed around the blister drive wheel and also as a result of the crushing of the blister cavities. This encourages the used portion of the strip to coil more readily. It is also apparent that, when the blister cavities have been crushed, the cavity is more resilient to denting at the point at which the spoke of the blister drive wheel contacts the strip, i.e. at the root where the blister cavity meets the remainder of the strip. Therefore, a more positive and precise drive of the strip is achieved when the blisters have been crushed. As mentioned above, the drive coupling member 57 of the inhaler of the present invention is modified in that the drive gear 16 is attached thereto in place of the actuator 54 so that the drive coupling member 57 rotates in response to rotation of the drive gear 16 . It is also envisaged that the drive gear 16 may be moulded integrally with the drive coupling member 57 . It will be apparent from FIG. 7 , that the drive coupling member 57 extends into an opening 19 in a side wall of the shell 11 b of the housing 11 and the drive gear 16 is coupled thereto so that it is disposed on the outside surface of said side wall, only the drive coupling member 57 , the blister strip drive wheel 17 and the blister strip itself, being received within the housing between the shell portions 11 a , 11 b. The actuating lever 14 has a first plate-like portion 20 that extends across the outside surface of the shell lib and has a hole 21 therein to receive a boss 22 upstanding from said surface, to pivotally mount the actuating lever 14 to the shell 11 for rotation about a second axis (A-A in FIGS. 7 and 15 ). The actuating lever 14 may also have a second plate-like portion 23 that is parallel to and spaced from the first portion 20 by an actuating button 24 . The second plate-like portion extends across the opposite surface of the shell 11 a and also has a hole 25 to engage with a corresponding boss upstanding from said opposite surface so as to pivotally couple the actuating member 14 to the shell 11 with the actuating button extending between the plates 20 , 23 and opposite surfaces of the shell portions 11 a , 11 b. The first plate 20 has a further aperture 26 therein and the cap 12 is pivotally mounted to the outer shell portion 11 b by a coupling such as a boss 80 upstanding from a surface of the shell portion 11 b that locates in a corresponding recess (not shown in FIG. 7 , but see hole 92 in FIG. 15 ) in the cap 12 , for rotation of the cap 12 about a third axis. The boss 80 extends through the aperture 26 in the actuating member 14 . The aperture 26 is arcuately-shaped and has the second axis as its centre so that, when the actuating lever 14 is rotated about the second axis, the boss 80 travels within the aperture 26 without engaging the actuating member 14 , and so the cap 12 remains stationary. The actuately-shaped aperture 26 acts as a clearance hole for the pivotal attachment of the cap 12 to the shell 11 b and so as to allow rotation of the actuating lever 14 about the second axis. A drive member (not shown) extends from an inner surface of the cap 12 . The drive member is located between, and spaced from, each of the second and third axes and extends towards the actuating lever 14 and the actuating lever 14 includes a wall 27 for engagement by said drive member when the cap 12 is rotated it about its third axis back towards its closed position and after the actuating member 14 has been rotated about its second axis. The drive member and wall 27 meet at a location between the second and third axes so that, upon further rotation of the cap 12 back towards its closed position, the drive member pushes against the wall 27 . Pressure of the drive member against the wall 27 causes the actuating member 14 to rotate back into its original position, together with the cap 12 into its closed position. The cap 12 and actuating lever 14 are configured so that, when the cap 12 is in its closed position and the actuating lever 14 has returned to its initial position, the cap 12 overlies the actuating button 24 which is pressed by a user to operate the device. This prevents a user from attempting to operate the device by rotating the actuating member 14 prior to opening the cap 12 . The actuating member 14 has a gear segment 28 that drivingly meshes with the gear drive 16 so that rotation of the actuating member 14 also causes rotation of the gear drive 16 and selective rotation of the blister strip drive member relative to the gear drive 16 whilst the actuating member 14 is rotated through the initial portion of its stroke, due to the indexing mechanism described above, so that the blister strip is initially driven to move the next blister into alignment with the blister piercing member 15 . During further rotation of the actuating member 14 through the second portion of its stroke, the blister strip is prevented from moving as the drive coupling member 57 is de-coupled from the blister strip drive wheel 17 . During rotation through the second portion of its stroke, the blister piercing member 15 carried by the mouthpiece 13 is rotated so that it pierces the aligned, and now stationary, blister. A cam drive member (not shown) extends from the first plate 20 towards the second plate 23 . The cam drive member is received in a cam groove or slot 29 formed in a peripheral wall 30 depending from the mouthpiece 13 . As is apparent from FIG. 7 , the cam groove or slot 29 has an arcuate portion 29 a followed by a leg portion 29 b at one end. It will be appreciated that the slot 29 may alternatively be provided in the actuating lever 14 and the cam drive member may extend from the mouthpiece 13 to achieve the same function. During initial rotation of the actuating member 14 through the first portion of its stroke, the cam drive member slides along the arcuate portion 29 of the cam slot 29 without causing any movement of the mouthpiece 13 , as the arcuate portion 29 a of the cam slot 29 has the second axis as its radius. However, during subsequent rotation of the actuating member 14 , the cam member reaches the leg portion 29 b of the cam slot 29 and engages the side walls of the cam groove 29 so as to cause the mouthpiece 13 to rotate about a first axis B-B together with the actuating member 14 thereby pulling the blister piercing member 15 , depending from the mouthpiece 13 , into the aligned blister. Although reference is made to a pivoting mouthpiece 13 , it will also be appreciated that, in an alternative embodiment, the blister piercing member 15 may be pivotally attached to a mouthpiece 13 or mounted in a support or module that is pivotally attached to the mouthpiece 13 . In these embodiments, the mouthpiece 13 itself remains stationary so that, in response to operation of the actuating member 14 , the blister piercing member 15 pivots relative to the stationary mouthpiece 13 to puncture the lid of an aligned blister. During rotation of the cap 12 from its open to its closed position, rotation of the actuating member 14 due to rotation of the cap 12 also causes rotation of the mouthpiece back to its original position as the cam member travels back along the cam slot 29 b. As shown in FIG. 7 , a spiral element 31 is also optionally mounted within the housing 11 into which the used portion of the strip is fed. Although a region is provided within the housing 11 to receive the used portion of the strip, it will be appreciated that the invention is also applicable to other inhalation devices (not shown) in which used blisters are not retained within the housing 11 but pass out through an opening (not shown) in the wall of the housing 11 for periodic detachment by a user. Although piercing of an aligned blister only occurs after movement of the strip has stopped, it is envisaged that the mechanism could be configured so that de-coupling of the blister strip drive wheel 17 and the drive coupling member 57 only occurs after the blister piercing element 15 has pierced, or begun to pierce, the lid of a blister so that the piercing element is drawn across and through the lid of the blister as it enters it. This creates a larger hole relative to the size of hole created when the strip is stationary prior to being puncturing by the blister piercing element. A larger hole can advantageously ensure that all the drug dose is entrained and removed from the blister. A modified embodiment is shown in FIGS. 15 and 16 . This embodiment is similar to the previous embodiment and functions in the same way but additionally includes a detent mechanism for holding the actuating lever 81 at the end of its stroke so that a small force must be applied to it to overcome the hold placed on it by the detent mechanism and allow the actuating lever 81 to return to its initial position. The detent mechanism includes a cantilever 82 that extends from the actuating lever 81 and has a kinked region 82 a which engages with a pawl 83 on the shell portion 84 b as the actuating lever 81 approaches the end of the second portion of its stroke, so that the cantilever 82 is resiliently deformed and as it rides over the kinked region 82 a and springs back to its original shape once the pawl 83 has cleared the kinked region 82 a . When the actuating lever 81 is rotated back towards its initial position, sufficient force must initially be applied to the actuating lever 81 so that the cantilever 82 is deformed by the pawl 83 and rides back over it. In addition to providing a slight resistance to initial movement of the actuating lever 81 , it also generates an audible ‘click’ as the end of the second portion of the stroke of the actuating lever 81 is reached and so provides an audible signal to the user that the end of the travel of the actuating lever 81 has been reached. This embodiment also includes a rigid dividing wall 85 that separates the interior of the housing into an unused and used blister chamber 86 , 87 (see FIG. 16 ). The wall 85 is slideably mounted within the shell portion 84 a of the housing so that, as more of the blisters are used, the force of the used coil of blisters in the used blister chamber 86 presses against the wall 85 and pushes it in the direction indicated by arrow ‘P’ in FIG. 16 , to enlarge the space for the used blisters and reduce the space previously occupied by the unused blisters. The sliding wall 85 comprises an elongate foot 88 which is attached to and integrally formed with a baffle 89 that divides the compartment. An approximate central region 88 a of the foot 88 is attached to the baffle 89 so that it extends in opposite directions on either side of the baffle 89 . The foot 88 is slideably received in a recess 90 formed in a wall of the housing and is wider at its ends 88 b than in its centre 88 a where it joins the baffle 89 so that contact with the walls of the recess 90 is primarily made with the wider ends 88 b of the foot 88 . A deeper, narrower recess 91 may extend deeper into the wall within the first recess 90 to receive a strengthening rib (not shown) depending from the underside of the foot 88 . Many modifications and variations of the invention falling within the terms of the following claims will be apparent to those skilled in the art and the foregoing description should be regarded as a description of the preferred embodiments of the invention only. For example, although reference is made to a “mouthpiece”, the invention is also applicable to devices in which the dose is inhaled through the nasal passages. Therefore, for the purposes of this specification, the term “mouthpiece” should also be construed so as to include within its scope a tube which is inserted into the nasal passages of a patient for inhalation therethrough. Furthermore, although the blister piercing member 15 is described as being attached to the mouthpiece so that the mouthpiece 13 and the blister piercing member rotate together, it is also envisaged that the mouthpiece itself could remain stationary and the blister piercing element 15 could be pivotally mounted to the mouthpiece 13 so that the blister piercing member 15 rotates relative to the mouthpiece 15 to pierce the lid of an aligned blister. In another embodiment, the cap and the actuating member could be combined into a single component so that rotation of the cap also causes indexing of the strip and piercing of an aligned blister. It will be appreciated that the inhaler of the invention may be either a passive or active device. In a passive device, the dose is entrained in a flow of air caused when the user inhales through the mouthpiece. However, in an active device, the inhaler would include means for generating a pressurised flow of gas or air through the blister to entrain the dose and carry it out of the blister through the mouthpiece and into the user's airway. In one embodiment, the inhaler may be provided with a source of pressurised gas or air within the housing.
An inhaler comprising a housing to receive a strip having a plurality of blisters is disclosed. Each blister has a puncturable lid and contains a dose of medicament for inhalation by a user. A mouthpiece is pivotally mounted to the housing through which a dose of medicament is inhaled by a user. The inhaler also has an actuating mechanism including a lever operable to sequentially move each blister into alignment with a blister piercing member depending from the mouthpiece. The actuating lever is also operable to cause the mouthpiece to pivot so that the blister piercing member punctures the lid of an aligned blister so that, when a user inhales through the mouthpiece, an airflow through the blister is generated to entrain the dose contained therein and carry it, via the mouthpiece, into the user's airway.
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CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation of U.S. patent application Ser. No. 13/741,332 filed Jan. 14, 2013, entitled, “MULTIMEDIA COMMUNICATION SYSTEM AND METHOD”, which is a continuation and claims the benefit of priority under 35 U.S.C. §120 of U.S. patent application Ser. No. 13/004,862 filed on Jan. 11, 2011, entitled, “MULTIMEDIA COMMUNICATION SYSTEM AND METHOD” which is a continuation and claims the benefit of priority under 35 U.S.C. §120 of U.S. patent application Ser. No. 11/404,509, filed Apr. 13, 2006, entitled “MULTIMEDIA COMMUNICATION SYSTEM AND METHOD”, which claims priority under 35 U.S.C. §119 to U.S. Provisional Application Ser. No. 60/671,170, filed Apr. 13, 2005, entitled “MULTIMEDIA COMMUNICATION SYSTEM AND METHOD”, which the disclosure of which is incorporated herein by reference. BACKGROUND [0002] In today's internet age, development of a communication piece such as a presentation, banner advertisement, website or brochure, whether static or dynamically employing multimedia, is usually contracted out to a professional graphic designer. Such professional is typically part of a professional agency, such as an advertisement agency, which are usually cost-prohibitive for small enterprises (i.e. sole proprietor or small business), and can be unnecessarily costly for larger enterprises. These agents or agencies consume large amounts of resources, in time and/or money particularly, for creating a media-rich communication, such as a website, an e-mail campaign, a banner advertisement, or other communication. Accordingly, a system and method which automates the process of creating and distributing professional quality, media-rich communications is needed. SUMMARY [0003] This document discloses systems and methods for creating, editing, sharing and distributing high-quality, media-rich web-based communications, also known as “engines” or “creative works.” The communications can be created in a layered fashion that integrates text, colors, background patterns, images, sound, music, and/or video. Other media can also be used. The systems and methods can be used to generate, edit, broadcast, and track electronic presentations, brochures, advertisements (such as banner advertisements on highly trafficked media websites), announcements, and interactive web pages. [0004] In one aspect, a method and apparatus are provided for dividing the work of creating a multimedia file for a communication into a logical step-by-step, start-to-finish process that requires no programming intervention. In a specific exemplary embodiment, the multimedia file is based on Flash, an authoring software developed by Macromedia for vector graphics-based animation programs with full-screen navigation interfaces, graphic illustrations, and simple interactivity in an antialiased, resizable file format that is small enough to stream across any type of Internet connection and play while downloading. Other multimedia software and/or protocols can be used. [0005] In particular embodiments, a system and method are provided for creating and/or delivering multimedia files via a SaaS model, and for loading media assets into an advertising engine online. In other embodiments, a system and method are provided for automatically creating and hosting data-specific communications for use as websites, presentations, advertisements, brochures and the like, for use with various communication media, systems and networks. The data-specific communications include, without limitation, data related to software programs, web services, proprietary data from third party databases, persons, locations, keywords, companies and combinations thereof. [0006] In another aspect, a method and system are provided for automatically extracting and formatting multimedia code, such as Flash or other actionscript code, for use as a template that can be edited via a user interface without the intervention of a programmer, and for providing editorial control of multimedia files, keyword and content specific files or websites by a master user controlling the editorial rights of one to N number of sub-users within the system. [0007] In yet other aspects, a method and apparatus are provided for online creation and editing of multimedia files compiled from a set of data; for creation, editing and distribution of multimedia files created from a wide variety of content including video, audio, images, text, raw data, Flash™ programs, software programs, web services or other media-rich content; and for auto-determining the “content” to be included in a communication based on answers to a series of prompts or interview questions and/or other meta data. [0008] In yet other aspects, a method and apparatus is provided for auto-determining the “look and feel” of a communication based on a series of interview questions and/or other meta data, and for combining data, content, and “look and feel” to create unique communications. Other systems and methods are provided for converting unique communications to multiple formats and media, such as a website, a multimedia file, a printed medium, a video, etc. [0009] The details of one or more embodiments are set forth in the accompanying drawings and the description below. Other features and advantages will be apparent from the description and drawings, and from the claims. BRIEF DESCRIPTION OF THE DRAWINGS [0010] These and other aspects will now be described in detail with reference to the following drawings. [0011] FIG. 1 illustrates a multimedia communication system. [0012] FIG. 2 illustrates a method for creating a template includes creating one or more communication templates. [0013] FIG. 3 illustrates a method 300 for template customization and media asset usage. [0014] FIG. 4 illustrates a method 400 for distributing and tracking communications. [0015] FIG. 5 illustrates sharing by users of media assets with other users. [0016] FIGS. 6-16 are block diagrams depicting a general system and method for creating, distributing and tracking multimedia and hypermedia-based communications. [0017] Like reference symbols in the various drawings indicate like elements. DETAILED DESCRIPTION [0018] The systems and methods described herein relate to software as a service (SaaS), a software distribution model in which applications are hosted by a service provider and made available to users over a network such as the Internet. The systems and methods include the use of templates and a thin client interface to create multimedia communications. Low-level functionality of the multimedia communication system is accessed through a set of function calls and easily understood pre-built components for populating the template. Furthermore, an API provides a user access to the full scope of a programming language which allows for template scalability without the need for in-depth knowledge of the programming or authoring language to produce highly functional, professional template-based communications. Additionally, the systems provide sample source files to encourage reverse engineering. [0019] FIG. 1 illustrates a multimedia communication system 100 for creating, storing and distributing multimedia communications (hereafter, “communications”) such as, for example, content-rich e-mails, presentations, websites and segments of websites. The communication system 100 includes a communication builder engine 102 that interacts with a client user interface 104 over a network 106 . The client user interface 104 can be a window in a browser application that runs on a personal computer. The network 106 is preferably the Internet, but can be any type of network, particularly as used in a client/server configuration. [0020] The communication builder engine 102 includes a project builder 108 for generating a project viewer 118 via which a user can view and assemble various media components or assets into an integrated communication. The communication builder engine 102 further includes a media repository 110 for storing communication project templates, media assets, communication project metadata, and any other data resources used for creating, storing and distributing completed communication projects. The completed communication projects are accessed from the media repository 110 and distributed to selected recipients by a distribution program 112 . The distribution program 112 controls the format and communication protocols for distributing the communications. [0021] The communication builder engine 102 further includes a sharing program 114 , which prompts a user to provide distribution parameters such as a type of communication (e-mail, website, etc.), a number and type of recipients, and communication medium by which the communication needs to be sent. The sharing program 114 can also report to the sending user certain qualitative and quantitative data such as transmission results, responses received from recipients, etc. [0022] A communication is a collection of slides. The number of slides for any given communication project can range from 0 to N. The slide types that are available to any given communication project are dependant on the class of the communication, and are defined in the class XML file, and define a template class. The template class is chosen based on a number of user inputs. For example, one template class is chosen based on the responses to an interview/query process operated by the user of the system prior to creating the communication. This allows the system to only offer slide types that are relevant to the user's responses to the interview and/or query process. [0023] Slides are a grouping of design layers, design elements, and content containers. The design layers are predefined and remain static. However, they are able to accommodate any design arrangement of content deemed necessary by the template designer. In an exemplary embodiment, the slide layers include background, main, foreground, and navigation. There is one core design file for each layer except for the main layer and they are as follows: background.fla, slideTypen.fla, foreground.fla, and nay.fla. The number of slideTypen.fla core files that exist depend on the number of slide types that are defined for the given class. For example, one particular class has five slide types defined in its XML class file. Therefore there are five main core design files (slideType0.fla, slideType1.fla, slideType2.fla, slideType3.fla, and slideType4.fla). [0024] A class is a unique collection of slide type(s). The number of slide types in any given class can range from 1 to N. Classes are used to organize communication types by the quantity and type of content displayed on each slide in the class. For example, a template class can have five unique slide types, with each slide type containing no more than a certain number of content containers. In an embodiment, the slide type contains no more than five content containers, although more than five content containers can be used. However, instead of adding the new slide type to a template class, for example, a new class can be created to accommodate the new slide type(s). A class is defined, and a sufficient number of slide types are provided for the user to achieve their design goals, but the total number of slide types are limited as so not to overload the user with too many choices. The system manages and controls the creation and maintenance of all classes. [0025] A slide type is a unique collection of media container(s). The number of containers for any given slide type can range from 1 to N. Slide types are used to organize the quantity and type of content that will be displayed on any given slide. In an exemplary embodiment, a number of standard container types can be used when creating a slide type. A text container includes text components and is used for displaying HTML formatted text, a image container includes image components and is used to display images and .swf files, and a video container includes video components and is used to display streaming video. An audio container includes audio components and is used to provide streaming audio or audio clips. The user is responsible for the layout of the containers that appear on a slide. The quantities and types of containers for a given slide type are defined in the class XML file. Other than following the naming convention defined in the XML class file for the containers, the system is flexible and allows the user to use the containers in any design arrangement they choose. Each content type component, or media asset, can be represented in a palette of related content types, for selection by a user and incorporation into a communication. [0026] The project viewer, such as the project viewer 118 shown in FIG. 1 , is an application that renders or “serializes” the communication project slides and content, and provides them with functionality. When the project viewer is launched, it is passed a data structure and associated software programs called the project object. The project object contains the information necessary for the communication project to render and playback as configured by the end user. Slides are represented in the project object as elements in an array. Once the project object is loaded and interpreted, the project viewer determines a load sequence for the communication project content. The project object is agnostic as to the type of file it is rendering and is, therefore, able to produce a wide variety of communications such as websites, dynamically created websites, Flash™ banner ads, presentations, brochures, advertisements on third party websites, and/or the like. [0027] The content loads in the specific design layer (i.e. background, foreground, etc.) assigned by the end user. As each layer loads in the load sequence, the project viewer then loads the content into the containers in that layer. Once the sequence has finished executing, the communication project will begin playback. Communication project playback has two states: auto-play on and auto-play off. [0028] In one embodiment, if auto-play is on, the project viewer determines the duration property of the current slide. If the value of that property is greater than zero, the project viewer waits for that value in seconds before automatically advancing to the next available slide in the communication project. If the value of that property equals zero, the slide viewer stops on the slide until the user navigates to a different slide. If auto-play is off, users must use the slide navigation controls to view a different slide. [0029] The project viewer also provides the conduit for the exchange of information and/or commands between the different design layers, or between the project viewer itself and a specific layer, referred to herein as the Slide Layer Interface. This interface not only enables the basic “built-in” functionality between the layers, their containers, and the project viewer, but also allows for much greater programming control for advanced developers. This is because the Slide Layer Interface is basically a collection of pointers. In an embodiment, this interface allows the direct use of AS 1.0 as the command language. This will enable the creation of highly functional and complex core files able to achieve all customization needs that fit within the programming scope of AS 1.0, the specification for which is incorporated by reference herein. [0030] Any content that loads on the main layer will change from slide type to slide type. Any content that loads on the background, foreground, or navigation layers typically remains constant and does not change between slides. That content is referred to as “universal content,” and typically consists of header logos, communication titles, headlines, etc. Mechanisms allow slide layers to communicate with each other as well as load any type of content on any layer. All of the complex programming needed to govern content loading, playback, and functionality has been incorporated into the project viewer and container components. [0031] The system includes a number of core design files. One such file is “background.fla.” This file is loaded in the bottom-most position in the project viewer. Any content or design elements that needs to appear behind other content or design elements should be placed in this core file. The background.fla file has a number of native functions: initTemplateObject( ): This function is called after the first frame is fully loaded. This function creates the templateObject object which is used by the project viewer. setValues( ): This function is called after ieController has been assembled and distributed to the various layers. Color information is retrieved from the ieController object and stored in local variables (color1Value, color2Value, color3Value). These values can be used to dynamically color shape elements (i.e. movie-clips) used in the template. This function is also used to distribute any image, .swf, video, or HTML text content to their proper movie clips for the currently selected slide. startPlayback( ): This function is called by the project viewer after this .swf has been fully loaded and initialized. [0035] Another core design file is “foreground.fla”. This file is loaded just under the top-most position (nay.fla) in the project viewer. Any content or design elements that need to appear above other content or design elements (except the navigation controls) are placed in this core file. Native functions of “foreground.fla” include: initTemplateObject( ): This function is called after the first frame is fully loaded. This function creates the templateObject object which is used by the project viewer. setValues( ): This function is called after ieController has been assembled and distributed to the various layers. Color information is retrieved from the ieController object and stored in local variables (color1Value, color2Value, color3Value). These values can be used to dynamically color shape elements (i.e. movie-clips) used in the template. This function is also used to distribute any image, .swf, video, or HTML text content to their proper movie clips for the currently selected slide. startPlayback( ): This function is called by the project viewer after this .swf has been fully loaded and initialized. [0039] Another core design file is “intro.fla”. This file loads prior to any other core file. No other core files will render until this file is done executing. It is located on layer above the nay.fla file. Native functions of this file include: initTemplateObject( ): This function is called after the first frame is fully loaded. This function creates the templateObject object which is used by the project viewer. setValues( ): This function is called after ieController has been assembled and distributed to the various layers. Color information is retrieved from the ieController object and stored in local variables (color1Value, color2Value, color3Value). These values can be used to dynamically color shape elements (i.e. movie-clips) used in the template. This function is also used to distribute any image, .swf, video, or HTML text content to their proper movie clips for the currently selected slide. [0042] A “slideTypen.fla” core design file loads above the background file and below the foreground file. Main slide content typically appears in this file. Its functions include: initTemplateObject( ): This function is called after the first frame is fully loaded. This function creates the templateObject object which is used by the project viewer. setValues( ): This function is called after ieController has been assembled and distributed to the various layers. Color information is retrieved from the ieController object and stored in local variables (color1Value, color2Value, color3Value). These values can be used to dynamically color shape elements (i.e. movie-clips) used in the template. This function is also used to distribute any image, .swf, video, or HTML text content to their proper movie clips for the currently selected slide. startPlaybackO: This function is called by the project viewer after this .swf has been fully loaded and initialized. [0046] A “nay.fla” core design file loads above the foreground file and includes the navigation controls. The visibility of the navigation controls is determined by the end user. Toggling the visibility to false causes the project viewer to skip the loading of this file. Its native functions include: initTemplateObject( ): This function is called after the first frame is fully loaded. This function creates the templateObject object which is used by the project viewer. setValues( ): This function is called after ieController has been assembled and distributed to the various layers. Color information is retrieved from the ieController object and stored in local variables (color1Value, color2Value, color3Value). These values can be used to dynamically color shape elements (i.e. movie-clips) used in the template. This function is also used to distribute any image, .swf, video, or HTML text content to their proper movie clips for the currently selected slide. buildNavigation( ): This function is called by the navPane clip after it is fully loaded on the time line and after the ieNavXML XML object is created and placed on this time line. The ieNavXML XML object is created inside the project viewer based on the tree structure of the slides (i.e. how they are organized in the tree hierarchy). Main options are represented by Parent nodes in the XML object. Menu items are Children of the particular Parent node. changeSlide(optionNumber, itemNumber): This function is called when an item is clicked in the navigation menu controls. Options are grouped by main options and sub options. The first main option is indexed at zero and all first sub-options are also zero-indexed. When a menu item is clicked, it simply passes the main option it is located at as the optionNumber parameter. The value of the itemNumber parameter is same as the menu item's position in the list of sub-options. For example: The third sub-option “About Our Company” of the second main option “About Us” would make the call to changeSlide( )—changeSlide(1, 2). [0051] A configuration file “containerData.xml” defines the class. It is provided only as a reference as to how containers are declared within a slide type, and how slide types are declared within the class. This file is used by the project viewer application and the project builder application for determining available slide types and locating the containers within the slide. [0052] Container Components [0053] Working examples of container components are provided in a “Source.fla” folder to illustrate how the container components are integrated into the template design. In these examples is shown a fully functional template so that a deep understanding of how the components work is not necessary. Once the user is comfortable with the core design files and how the components operate, the system provides different ways to apply design style changes to the components. [0054] Image Component [0055] The image component is a multimedia module that is used inside the core design files to load and display images and/or .swf files. One such multimedia module is based on a Macromedia Flash MX® component, which in turn is based on AS 1.0. The user integrates and positions this component into their design. Once finished, the component will be able to load and display any image or .swf content that the end user assigns to it. The image component is easy to integrate into any graphic layout or animation schema, and does not restrict the user from using Flash™ animation or other visual effects. The image component is used only in edit mode. [0056] From the main timeline inside a core template file (for example: a five slide class, foreground.swf), this component can be found at the frame labeled “staticView”, inside of a movie clip named foreground GaphicA. The module initLayout( ) is used to initialize the component and prepare it to begin loading image or .swf content. Properties include: [0057] container Width: sets the width of the display pane. [0058] containerHeight: sets the height of the display pane. [0059] containerPath: is a component, such as a Flash™ component, as defined in the XML class file. [0060] slideLayer: defines the layer in which this component is located. Valid values can include “foreground”, “background”, and/or “communication”. [0061] Video Component [0062] The video component is used inside the core design files to load and display .flv video. In an embodiment, the video component is a Macromedia Flash MX® component based on AS 1.0. The template designer integrates and positions this component into their design. Once finished, the component will be able to load and display any .flv content that the end user assigns to it. The video component is also easy to integrate into any graphic layout or animation schema, and does not restrict the user from using Flash™ animation or other visual effects. The video component is used only in playback mode. [0063] In order to use the video component, from the main timeline inside a core template file (for example: five slide class, foreground .swf), the video component can be found inside of a movie clip named imageContainer1.videoContent. The video component includes the following methods: initLayout( )—used to initialize the component and prepare it to begin playing a video stream; and initVideoPane(videoURL, bufferTime, videoVolume)—used to start the video stream. The properties of the video component include: [0064] containerWidth: sets the width of the video pane. [0065] containerHeight: sets the height of the video pane. [0066] controllerXPos: sets the x-position of the playback controller. A value of −1 aligns the left edge of the controller with the left edge of the video pane. [0067] controllerYPos: sets the y-position of the playback controller, where a value of −1 aligns the top edge of the controller with the bottom edge of the video pane. [0068] controller Width: sets the width of the playback controller, where value of −1 causes the controller to adopt the width of the video pane. [0069] callback: a function that gets called when the video buffer is full. [0070] autoSizePane: that forces sizing, alignment, and position of the video pane and the playback controller. [0071] controlBarHeight: sets the height of the playback controller. [0072] Text Component [0073] The text component is used inside the core design files to load and display HTML formatted text. In an embodiment, the text component is a Macromedia Flash MX® component based on AS 1.0. The user integrates and positions this component into their design, and then names the component according to the class XML file. Once finished, the component will be able to load and display any HTML text content that the end user assigns to it. The text component is needed only in edit mode. During playback, specific text content is manually assigned to a Flash™ text field by the user. [0074] The text component can be found, from the main timeline inside a core template file (for example: five slide classes, foreground .swf), at the frame labeled “staticView”, inside of the movie clips named foregroundTextA and foregroundTextB. [0075] The function call “initLayout( )” is used to initialize the component and prepare it to begin displaying HTML text. Properties of the text component include: [0076] container Width: sets the width of the text pane. [0077] containerHeight: Sets the height of the text pane. [0078] containerPath: The Flash path of the component as defined in the XML class file. [0079] headline: a Boolean property that sets the display state of the component. Text components set to the headline state are able to use a custom movie clip to display the text content. This allows the user to use custom fonts and text styles and disable text formatting from the user. [0080] staticHeadline: The name of the linked clip in the library to use to display the text content. [0081] slideLayer: The layer in which this component is located. Valid values are “foreground”, “background”, and “communication”. [0082] Custom Components [0083] Custom components are designed and implemented by the user or template designer, and can be used just like the standard components for integration into the communication project. Custom components pass a configuration object to the slide viewer which allows the user to configure any properties of the component. This object is a basic name/value structure that represents a hash of the property/value pairs. This hash is then be dynamically integrated into the system and assigned to the slide on which it is located. This schema allows user/developers to create and introduce powerful components that can handle tasks such as xml feeds (such as data from the Google Adwords or Overture system, or other proprietary data feeds from proprietary databases, conferencing/chatting, or web services), along with many other applications. [0084] Custom components can include voiceover narration (i.e. digital voice files), personal audio files, special images and/or graphics such as logos, and videos that a user provides to the system for storing in the media repository, [0085] View Modes [0086] The user builds their layout in the core design files. The project viewer is able to open and render these files in a layered manner so that the content “stacks” according to the layer on which it is located. For example, content on the background layer appears below content in the foreground layer. In one embodiment, there are two project viewers. In a preferred exemplary embodiment, the two project viewers are substantially identical. One of the project viewers is provided for live playback of the communication project, while the other is embedded within the communication project builder and is needed to render the core files to the end user so that the user can edit desired content in the containers. In an alternative embodiment, another project viewer is provided to render out or “serialize” completed communication files into a variety of third party formats such as .swf, .pdf, xml, html, txt, or any other format. [0087] Accordingly, all of the core files can support two states: a playback state and an edit state. These states are designated within each core file by a frame label. When loaded into the builder, the project viewer immediately sends the playhead inside the core files to the frame labeled “staticView”. Otherwise, the playhead is positioned at the first frame and stopped until the communication project is ready to play. [0088] Live View [0089] “Live View” describes the full playback of a communication project. During live view, all functionality, design, and animation are active and visible to the end user. It is the finished product as configured by the user. [0090] Edit View [0091] “Edit View” is experienced within the project builder and, in some instances, the “Live View” where a user contributes edits or comments to a communication. Though functionality and design remain intact, animations are disabled. This “display” view offers the users context within the design so content can be configured and assigned to containers. [0092] Groups [0093] “Groups” is an application that enables groups of users to create, edit, share and distribute communications created by the system according to a set of business rules. For example, a group of 25 users can utilize the system to communicate a uniform message, yet still retain the autonomous controls to customize each communications piece according to the rules set up by the Administrator. Each Group contains a defined set of roles and abilities. These abilities are set by a system administrator, and then utilized by the users in that Group. [0094] In one embodiment, a user can purchase access to a group of other users, called a “Team account.” In the Team account, one administrator has the right to share communications with the other users; in effect, creating communications for them and giving them limited rights to edit the communication. In another embodiment, a user can purchase access to an enterprise group of users which can be N number of users and M number of administrators. This functionality gives the enterprise the ability to uniformly use the same communication, but tailor it to a specific market, segment, opportunity or the like. [0095] Sharing [0096] “Sharing” is an application that enables administrators and users to set up a system, whereby administrative users can create and share communications with N number of users in up to N accounts or physical locations. Several types of sharing exist, each having a set of advantages. In one example, three types of sharing include: Live Sharing, Linked Sharing, and Smart Sharing. Live Sharing maintains a link between the communications in use so that an administrator can make changes to a communication, so that changes to the communication are updated in real time. That is, there is no time delay between the time the edit is made and the time the edit is published live to the communication. [0097] Linked Sharing allows an administrator to make changes to a “main” communication and up to N “derivative” communications such that changes to the main communication are disseminated to each derivative communication in real time. Accordingly, there is no time delay between when an edit is made and the time the edit is published live to each relevant communication. [0098] Smart Sharing allows several Administrators to make changes to several “main” communication and up to N “derivative” communications, such that changes to the main communication are disseminated to each derivative communication in real time. Thus, there is no time delay between the time an edit is made and the time the edit is published live to each derivative communication. However, in Smart Sharing, business rules are applied so that an organizational hierarchy can be created to manage the flow of the main and derivative communications. Business rules of Smart Sharing are also applied to allow for deletion of derivative communications from the system without affecting other derivative communications in the linked chain. This allows for the consistent and rapid dissemination of information across a broad range of users, and is particularly useful for a corporate salesforce or regional advertisers in maintaining a consistent communications message. Example [0099] The following describes an example of the functionality of the system and method described herein, as used by a user. [0100] A membership account includes online access to all the functions for editing, distributing, and tracking your communications. A variety of selectable options are offered based on a user's individual needs. The number of communications in an account is based on the membership level purchased. A user may edit communications as often as desired, and as many copies as desired can be saved to a storage device, such as a computer hard drive. To access the account (and associated communications), a user must first login from a homepage, i.e. www.impactengine.com. The user then must specify a user name and password that was used to sign up. To change account information, a user can select a “My Account” link from a main navigation bar, shown in the screen shots as being located on the left side of a page, and then select a “Make Changes” control to make a change. [0101] Edit Process [0102] There is no limit to how often a communication can be updated. Accordingly, recipients and viewers can always see the most up-to-date information. To edit a communication, a user first enters “Edit Mode” by selecting the “Edit” button next to the name of the selected communication. The “Edit” button is located in a communication Control Panel on the “MyHome” page, preferably at the top of the page. [0103] Once in Edit Mode, a user will see a new navigation menu above, and can click on the appropriate tab and make any changes in the forms provided. When finished, the user selects the “finish” button and the communication will be updated. The communication is pre-filled with default text, however all fields can be updated with whatever information chosen. Graphics may be uploaded in “Edit Mode” by selecting the “Upload” button to access and upload images. The steps to be followed can be displayed to upload images from your hard drive. Each membership includes an amount of disk space memory, i.e. up to a gigabyte of disk space, in which images are stored. [0104] Distribute [0105] Once a communication is created, a user may use it in a variety of ways including: as a website, as a printed communication, as an email, or as a communication stored on a hard disk, CD-rom or other media device. All features are available from the main navigation inside a user account. An email function can be accessed by selecting the “Show” button next to the name of the communication to be sent. The “Show” button is located in the communication Control Panel on the home page. The user is provided a form to complete, and the communication will be sent to the designated e-mail recipients. Each recipient is sent a standard email with a graphic “view” link at the bottom. This link launches the communication directly from a designated website. There are no attachments or downloads needed. The body, title, and “from” name of the message can be customized. [0106] The email interface allows a user to send a communication to one or more recipients at a time. In an embodiment, the number of recipients is limited to a particular number, i.e. six recipients. A user may send as many emails as desired. Spamming of any kind is forbidden in conjunction with an account. [0107] CD-ROM cards that include the communication can also be created. CD-ROM cards play in standard tray loading CD-ROM drives on Windows and Macintosh computers. The communication will automatically launch for maximum impact. [0108] A communication can also be used as a user's home page. To execute this functionality, a user can click on the “My Websites” from inside the account to generate a website based on the communications that are chosen. Then, the Domain Name Service (DNS) settings are automatically set up with the system's servers, and the website is available by typing in any URL (i.e. www.mywebsite.com). This function is used as the core to use any communication created by the communication builder engine system as a dynamically created site for use with private web sites such as Google, Overture, eBay, Amazon and the like. [0109] A communication can also be added to an existing web page by clicking on the “Show” from inside the account to generate HTML or the actionscript (“objectembed”) code to directly embed the file into the page. This HTML can be placed anywhere on a web page. [0110] In accordance with the above description, and as shown in FIGS. 2-5 , a communication method includes a number of steps for creating, storing and distributing multimedia communications. As shown in FIG. 2 , a method 200 for creating a template includes creating one or more communication templates, at 202 . The templates are typically created by designers and represent general structures and arrangements of multimedia communications that are suitable for distribution to a number of different recipients via a number of different transmission mechanisms. In a preferred embodiment, the templates are created in Flash™ actionscript using a proprietary application programming interface (API) for being loaded into the media repository. [0111] At 204 , media assets are provided for general use by any user. The media assets include media components such as text, font type, audio clips, video clips, images or graphics, Flash™ animation files, etc. At 206 , media assets for private use are received by the communication builder engine and system. These private media assets can include proprietary logos, images, sound files, or the like. At 208 , the project template(s), general use media assets, and private use media assets are loaded and stored into the media repository, for future access by the user. Private media assets can be accessed only by the user (or authorized agent thereof) that provided them. [0112] FIG. 3 illustrates a method 300 for template customization and media asset usage. At 302 , the communication builder engine interviews the user to determine the templates and/or media assets that will be appropriate for that user. For instance, a real estate agent user may indicate a need to utilize stock images of houses, as opposed to images of only people in social settings. Likewise, the type, profession, or characteristics of the user can be used to tailor the types of templates and/or media assets that will be available for access by that user, so as to not overburden the user with choices, but also to intelligently provide the user with the most pertinent and efficient communication creation system possible. [0113] At 304 , the communication builder engine provides the appropriate templates and/or media assets to the user, as determined by the interview or by user input data, for being customized into a communication by the user. At 306 , the customized communication project(s) are received from the user and compiled into a format suitable for transmission. At 308 , the compiled communications are stored as projects in the media repository, for access by the distribution and sharing programs. [0114] FIG. 4 illustrates a method 400 for distributing and tracking communications. At 402 , the communication builder engine receives a selection of completed communication projects that have been stored in the media repository. At 404 , the communication builder engine receives from the user a selection of distribution mechanisms by which the communications will be transmitted. The distribution mechanism include, without limitation, websites, e-mail systems, CD-ROM, DVD, or via an offline copy (i.e. hardcopy or print). At 406 , the selected communications are distributed to the selected distribution mechanisms for transmission or sending to the selected recipients. [0115] FIG. 5 illustrates sharing by users of media assets with other users that may be affiliated by employer, by contract or other arrangement. At 502 , the communication builder engine receives a selection of completed communication projects that can be shared among one or more other users. At 504 , the one or more other users are identified and received by the communication builder engine. At 506 , the sharing program of the communication builder engine processes the selections, and at 508 the processed selections and associated communication projects and/or media assets are made available to the selected one or more other users. [0116] Embodiments of the invention and all of the functional operations described in this specification can be implemented in digital electronic circuitry, or in computer software, firmware, or hardware, including the structures disclosed in this specification and their structural equivalents, or in combinations of them. Embodiments of the invention can be implemented as one or more computer program products, i.e., one or more modules of computer program instructions encoded on a computer readable medium, e.g., a machine readable storage device, a machine readable storage medium, a memory device, or a machine-readable propagated signal, for execution by, or to control the operation of, data processing apparatus. [0117] The term “data processing apparatus” encompasses all apparatus, devices, and machines for processing data, including by way of example a programmable processor, a computer, or multiple processors or computers. The apparatus can include, in addition to hardware, code that creates an execution environment for the computer program in question, e.g., code that constitutes processor firmware, a protocol stack, a database management system, an operating system, or a combination of them. A propagated signal is an artificially generated signal, e.g., a machine-generated electrical, optical, or electromagnetic signal, that is generated to encode information for transmission to suitable receiver apparatus. [0118] A computer program (also referred to as a program, software, an application, a software application, a script, or code) can be written in any form of programming language, including compiled or interpreted languages, and it can be deployed in any form, including as a stand alone program or as a module, component, subroutine, or other unit suitable for use in a computing environment. A computer program does not necessarily correspond to a file in a file system. A program can be stored in a portion of a file that holds other programs or data (e.g., one or more scripts stored in a markup language document), in a single file dedicated to the program in question, or in multiple coordinated files (e.g., files that store one or more modules, sub programs, or portions of code). A computer program can be deployed to be executed on one computer or on multiple computers that are located at one site or distributed across multiple sites and interconnected by a communication network. [0119] The processes and logic flows described in this specification can be performed by one or more programmable processors executing one or more computer programs to perform functions by operating on input data and generating output. The processes and logic flows can also be performed by, and apparatus can also be implemented as, special purpose logic circuitry, e.g., an FPGA (field programmable gate array) or an ASIC (application specific integrated circuit). [0120] Processors suitable for the execution of a computer program include, by way of example, both general and special purpose microprocessors, and any one or more processors of any kind of digital computer. Generally, a processor will receive instructions and data from a read only memory or a random access memory or both. The essential elements of a computer are a processor for executing instructions and one or more memory devices for storing instructions and data. Generally, a computer will also include, or be operatively coupled to, a communication interface to receive data from or transfer data to, or both, one or more mass storage devices for storing data, e.g., magnetic, magneto optical disks, or optical disks. [0121] Moreover, a computer can be embedded in another device, e.g., a mobile telephone, a personal digital assistant (PDA), a mobile audio player, a Global Positioning System (GPS) receiver, to name just a few. Information carriers suitable for embodying computer program instructions and data include all forms of non volatile memory, including by way of example semiconductor memory devices, e.g., EPROM, EEPROM, and flash memory devices; magnetic disks, e.g., internal hard disks or removable disks; magneto optical disks; and CD ROM and DVD-ROM disks. The processor and the memory can be supplemented by, or incorporated in, special purpose logic circuitry. [0122] To provide for interaction with a user, embodiments of the invention can be implemented on a computer having a display device, e.g., a CRT (cathode ray tube) or LCD (liquid crystal display) monitor, for displaying information to the user and a keyboard and a pointing device, e.g., a mouse or a trackball, by which the user can provide input to the computer. Other kinds of devices can be used to provide for interaction with a user as well; for example, feedback provided to the user can be any form of sensory feedback, e.g., visual feedback, auditory feedback, or tactile feedback; and input from the user can be received in any form, including acoustic, speech, or tactile input. [0123] Embodiments of the invention can be implemented in a computing system that includes a back end component, e.g., as a data server, or that includes a middleware component, e.g., an application server, or that includes a front end component, e.g., a client computer having a graphical user interface or a Web browser through which a user can interact with an implementation of the invention, or any combination of such back end, middleware, or front end components. The components of the system can be interconnected by any form or medium of digital data communication, e.g., a communication network. Examples of communication networks include a local area network (“LAN”) and a wide area network (“WAN”), e.g., the Internet. [0124] The computing system can include clients and servers. A client and server are generally remote from each other and typically interact through a communication network. The relationship of client and server arises by virtue of computer programs running on the respective computers and having a client-server relationship to each other. [0125] Certain features which, for clarity, are described in this specification in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features which, for brevity, are described in the context of a single embodiment, may also be provided in multiple embodiments separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination. [0126] Particular embodiments of the invention have been described. Other embodiments are within the scope of the following claims. For example, the steps recited in the claims can be performed in a different order and still achieve desirable results. In addition, embodiments of the invention are not limited to database architectures that are relational; for example, the invention can be implemented to provide indexing and archiving methods and systems for databases built on models other than the relational model, e.g., navigational databases or object oriented databases, and for databases having records with complex attribute structures, e.g., object oriented programming objects or markup language documents. The processes described may be implemented by applications specifically performing archiving and retrieval functions or embedded within other applications.
Systems and methods are disclosed for creating, editing, sharing and distributing high-quality, media-rich web-based communications. The communications are created in a layered fashion that integrates user-selected text, colors, background patterns, images, sound, music, video, or other media. The systems and methods are used to generate, edit, broadcast, and track electronic presentations, brochures, advertisements (such as banner advertisements on highly trafficked media websites), announcements, and interactive web pages, without the need for the user to understand complex programming languages.
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BACKGROUND OF THE INVENTION 1. Field of Invention The present disclosure relates in general to a method and system for analyzing a core sample from a wellbore. More specifically, the present disclosure relates to a trailer and chassis design that isolates a core scanning system from shock and vibration. 2. Description of Prior Art Various techniques are currently in use for identifying the presence of hydrocarbons in subterranean formations. Some techniques employ devices that emit a signal from a seismic source, and receive reflections of the signal on surface. Others involve disposing logging devices downhole in a wellbore intersecting the subterranean formation, and interrogating the formation from within the wellbore. Example downhole exploration devices include seismic tools that can transmit and receive seismic signals, or ones that simply receive a seismic signal generated at surface. Other devices collect and sample fluid from within the formation, or from within the wellbore. Nuclear tools are also employed that direct radiation into the formation, and receive radiation that scatters from the formation. Analyzing the scattered radiation can provide information about fluids residing in the formation adjacent the wellbore, the type of fluid, and information about other materials next to the wellbore, such as gravel pack. Logging downhole also is sometimes done while the wellbore itself is being drilled. The logging devices are usually either integral with a drill bit used during drilling, or on a drill string that rotates the drill bit. The logging devices typically are either nuclear, seismic, can in some instances optical devices. In some instances, a core is taken from the wellbore and analyzed after being retrieved to the surface. Analyzing the core generally provides information about the porosity and/or permeability of the rock formation adjacent the wellbore. Cores are generally elongated cylindrical members and obtained with a coring tool having an open barrel for receiving and retaining the core sample. SUMMARY OF THE INVENTION Disclosed herein is an example of a system for analyzing a core sample which includes a chassis, a core sample imaging device on the chassis, wheels coupled to the chassis, and a suspension system for absorbing shock and vibration that comprises an air bag assembly mounted in a path of force transmission between the wheels and the chassis. The system may further include a leg that telescopes from the chassis into supporting force against a surface on which the wheels are in contact. This example may further have an air bag assembly in the leg for absorbing shock and vibration. In an alternative, the system further includes a dolly assembly coupled to and supporting an end of the chassis, wherein the dolly assembly has a base that couples to the chassis, wheels coupled to the base, and an airbag system mounted on the base and in a path of vibrational force between the wheels and the chassis and that is for absorbing shock and vibration. Optionally further included with this example is a frame that extends forward from the base and has a pivoting coupling that selectively couples to a tractor rig, wherein the pivoting coupling isolates shock and vibration in the tractor rig from the chassis and from the core sample imaging device. A trailer may alternatively be provided on the chassis for housing the core sample imaging device. In this embodiment, the chassis, trailer, and core sample imaging device define a mobile unit. Further in this embodiment, the mobile unit has an offset center of gravity. The suspension system can isolate vibration acceleration up to about 4.0 G forces during transit and isolates vibrational forces having a frequency of between about 10 Hz to about 15 Hz. The system may optionally further include multiple mobile enclosures on the chassis that are coupled with a connector, so that coupling between mobile enclosures stiffens the chassis. Another embodiment of a system for analyzing a core sample includes a chassis, a trailer mounted onto the chassis that forms an enclosure, a core sample imaging device supported on the chassis and housed within the enclosure, wheels coupled to the chassis for providing mobility of the trailer thereby defining a mobile unit, a telescoping leg having an end mounted to the chassis, and a system of air bags provided between the wheels and the chassis and in the telescoping leg. The system of air bags can attenuate shock and vibration experienced by the wheels thereby isolating the chassis and the core sample imaging device from the shock and vibration. In an example, the system of air bags resists axial movement between the chassis and the wheels, so that when the mobile unit is accelerated, the chassis is restrained in a generally level orientation. The system can further include a dolly assembly coupled to and supporting an end of the chassis, and a frame that extends forward from the base and has a pivoting coupling that selectively couples to a tractor rig. In one embodiment, the dolly assembly is made up of a base that couples to the chassis, wheels coupled to the base, and an airbag system mounted on the base and in a path of vibrational force between the wheels and the chassis and that is for absorbing shock and vibration, and wherein the pivoting coupling isolates shock and vibration in the tractor rig from the chassis and from the core sample imaging device. Also provided herein is a method of isolating forces from a core sample analysis system which includes mounting a core sample imaging device supported on a chassis, coupling the chassis to a series of wheels, and isolating the core sample imaging device from shock and vibration experienced by the wheels by disposing air bags between the wheels and the chassis. The method may further include strategically sizing the air bags so that the air bags isolate the chassis from vibrational forces of up to about 4.0 G forces that are experienced by the wheels. In an embodiment the method also includes strategically disposing the air bags so that the chassis remains substantially level when the chassis is accelerated during transportation. The chassis can be transported by coupling the chassis to a dolly having wheels, a base, and a frame that connects to a tractor rig with a pivoting connection. In an embodiment, the pivoting connection attenuations vibration experienced by the tractor rig from being transferred to the dolly or the chassis. The method may further include providing a telescoping leg on a lower side of the chassis, and providing an air bag in the telescoping leg for attenuation vibration propagating within a surface on which the wheels are in contact. BRIEF DESCRIPTION OF DRAWINGS Some of the features and benefits of the present invention having been stated, others will become apparent as the description proceeds when taken in conjunction with the accompanying drawings, in which: FIG. 1 is a plan partial sectional view of an example of a system for analyzing a core sample. FIG. 2 is an overhead view of an example of a cabinet for shielding radiation and conditioning a scanning unit for a core sample. FIG. 3 is an axial sectional view of the cabinet of FIG. 2 and taken along lines 3 - 3 . FIG. 4 is a perspective view of the cabinet of FIG. 2 . FIG. 5 is a perspective view of the cabinet of FIG. 2 in partial phantom view and an example scanning unit in the cabinet. FIG. 6 is a side view of an example of a chassis for supporting a mobile enclosure. FIGS. 7A and 7B are overhead and side views of an example of a dolly coupled to the chassis of FIG. 6 . FIG. 8 is a side view of an example of a leg for supporting the chassis of FIG. 6 . FIG. 9 is a graphical illustration of vibration isolation provided by an example of a suspension system provided with the chassis of FIG. 6 . FIGS. 10 A and B are graphical illustrations of vibration absorbed by the chassis of FIG. 6 while being transported. While the invention will be described in connection with the preferred embodiments, it will be understood that it is not intended to limit the invention to that embodiment. On the contrary, it is intended to cover all alternatives, modifications, and equivalents, as may be included within the spirit and scope of the invention as defined by the appended claims. DETAILED DESCRIPTION OF INVENTION The method and system of the present disclosure will now be described more fully hereinafter with reference to the accompanying drawings in which embodiments are shown. The method and system of the present disclosure may be in many different forms and should not be construed as limited to the illustrated embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey its scope to those skilled in the art. Like numbers refer to like elements throughout. In an embodiment, usage of the term “about” includes, but is not necessarily limited to, +/−5% of the cited magnitude. In an embodiment, usage of the term “substantially” includes, but is not necessarily limited to, +/−5% of the cited magnitude. It is to be further understood that the scope of the present disclosure is not limited to the exact details of construction, operation, exact materials, or embodiments shown and described, as modifications and equivalents will be apparent to one skilled in the art. In the drawings and specification, them have been disclosed illustrative embodiments and, although specific terms are employed, they are used in a generic and descriptive sense only and not for the purpose of limitation. Shown in a plan partial sectional view in FIG. 1 is one example of a core analysis system 10 , which includes first, second and third mobile enclosures. In the example of FIG. 1 , the first mobile enclosure is a scan trailer 12 , the second mobile enclosure is a handling trailer 14 , and the third mobile enclosure is an analysis trailer 16 . In one example, each of the enclosures may be part of a tractor trailer and which are movable by a tractor trailer. Schematically illustrated in the scan trailer 12 is a scan system 18 , and substantially all of which is housed within a cabinet 19 . In the illustrated example, cabinet 19 is specially designed to shield any radiation within, generated, inherent, or otherwise, from making its way to outside of the cabinet 19 . Thus, cabinet 19 is in compliance with 21 C.F.R. 1020.40. Further shown in cabinet 19 is a scan source 20 , which in one embodiment includes a device for emitting radiation, such as but not limited to an X-ray, microwave, millimeter wave, etc. A scan receiver 22 is also shown provided within cabinet 19 and combined with scan source 20 , in one example, forms a Computed Tomography (CT) scanner. An elongate and cylindrical core sample 24 is shown axially inserted within scan system 18 . Core sample 24 is disposed into scan system 18 through a loading assembly 26 , which is shown coupled to one end of the scan system 18 and projecting through an opening in a side wall of handling trailer 14 . In an example, core sample 24 is taken from a subterranean formation below system 10 , and is retrieved via a wellbore 27 shown adjacent system 10 . Thus the wellbore 27 intersects the subterranean formation. Embodiments exist where the system 10 is “onsite” in the field and where the distance between the wellbore 27 to system 10 can range from less than one hundred yards up to five miles, and any distance between. Accordingly, real time analysis while drilling the wellbore 27 can take place within the system 10 . Feedback from the analysis can be used by the drilling operator to make adjustments or changes to the drilling operation. A hatch assembly 28 is schematically illustrated which provides the coupling interface between trailers 12 , 14 and includes scaling around the loading assembly 26 . While in scan system 18 , core sample 24 rests on a core carrier 30 . In an example, core carrier 30 is fabricated from a material transparent to X-Rays, and can support the load of the core sample 24 with minimum deflection to maintain the resolution of a stationary scanner. Core carrier 30 is part of a manipulator system 31 , which further includes a manipulator arm 32 that telescopingly moves along a manipulator base 34 . As shown, an end of manipulator arm 32 distal from manipulator base 34 couples onto an end of core carrier 30 , so that core carrier is basically cantilevered on an end of the manipulator arm 32 . Manipulator arm 32 is shown in an extended position over manipulator base 34 . Manipulator arm 32 axially moves with respect to manipulator base 34 via a motor 36 shown having a shaft 38 that couples to manipulator arm 32 . In one example, motor 36 is a linear direct current motor. A gear (not shown) on an end of shaft 38 distal from motor 36 engages a gear rack 40 that is provided on manipulator arm 32 . Accordingly, selectively operating motor 36 urges manipulator arm 32 , core carrier 30 and core sample 24 in an axial direction with respect to scan source 20 . Moving manipulator arm 32 into a retracted position onto manipulator base 34 positions the entire length of core sample 24 in scan system 18 , so that all of core sample 24 may be analyzed by the scan system 18 . In one example, the scan source 20 and scan receiver 22 orbit around the core sample 24 and so that when in combination of axial movement of core sample 24 within system 18 , a helical scan is taken of core sample 24 . Further optionally, motor 36 , or additional motors not shown, may manipulate and selectively move manipulator arm vertically and/or laterally to thereby better position core sample 24 into a designated orientation and/or spatial position during the scanning process. Further shown in FIG. 1 are a series of work surfaces 42 provided within handling trailer 14 . In one example of operation, before or after core sample 24 is scanned, it may be broken into sections for further analysis and analyzed on surfaces 42 . Examples of the surfaces 42 include a crusher, sample divider, and mortar grinder. Additional analysis may take place within analysis trailer 16 . Schematically illustrated within analysis trailer 16 are a variety of analysis equipment such as, but not limited to, scanners and spectrometers. One such analysis equipment is a nanotom 44 , which can include a scanning system for scanning the internals of core sample 24 , or parts of the core sample. Further analysis equipment in the analysis trailer 16 may be a laser induced spectroscope 46 , a Raman spectroscope 48 , and near infrared spectroscope 49 . It will be understood that alternate embodiments may include more trailers or fewer trailers. For example, an appropriately sized scan system 18 may allow loading assembly 26 to be in scan trailer 12 without projecting through an opening in the trailer and without a hatch assembly 28 . A further embodiment may provide work surfaces 42 in the same trailer as the analysis equipment, or the analysis equipment may be contained in handling trailer 14 . In yet a further embodiment, scan system 18 , loading assembly 26 , work surfaces 42 and analysis equipment (e.g., nanotom 44 , spectroscopes 46 , 48 , 49 , or others) are all contained in one trailer. Referring now to FIG. 2 , shown in an overhead view is an example of the scan system 18 and an upper surface of cabinet 19 . Further illustrated in this example is a conditioning vent 50 on an upper end of the cabinet 19 , where conditioning vent 50 provides a path for airflow and that is used in conditioning the inside of the cabinet 19 , while blocking the leakage of any radiation from cabinet 19 . An advantage of the conditioning vent 50 is that conditioned air at proper temperature and humidity may be injected into the inside of cabinet 19 so that the sensitive devices housed within the cabinet 19 may be maintained in proper operating conditions to ensure normal operating functionality. In an example, operational conditions require maintaining a substantially constant temperature within the cabinet 19 . In one embodiment, the temperature variation in the cabinet 19 is kept of within 2 degrees C. of a designated temperature. An advantage of the device described herein is that the temperature in the cabinet 19 can be maintained within the designated range in spite of substantial air replacement. Air replacement in the cabinet 19 , due to the loading mechanism operation, maintains temperature uniformity across the scanner frame and rotary element. In one example, the volumetric rate of air replacement is at least about 4 m 3 /min. A power distribution panel 52 is shown provided at an aft end of cabinet 19 , and which includes buses (not shown) and other devices for distributing power through cabinet 19 into scan system 18 . A control panel 54 is shown adjacent power distribution panel 52 and includes hardware and software for managing control of the operation of the systems house within cabinet 19 . Projecting outward past the forward end of cabinet 19 is the loading assembly 26 in an open configuration. In the illustrated example, the loading assembly 26 includes a loading cover 56 and loading basin 58 , where the loading cover 56 is shown swung open from a loading basin 58 . As shown the core sample 24 has been inserted into open loading assembly 26 and onto the core carrier 30 . As will be described in more detail below, safety features are included with the system that prevent operation of the manipulator system 31 when the loading assembly 26 is in the open position of FIG. 2 . FIG. 3 shows an example of the cabinet 19 in a sectional view and taken along lines 3 - 3 of FIG. 2 . This view which is taken along the axial portion of manipulator system 31 shows one example of a wiring track 60 ; which has cross members for organizing the control and power wires needed for use in the scan system 18 and as the manipulator arm 32 axially moves with respect to manipulator base 34 . Wiring track 60 maintains the wires in a designated location and position with use of wiring track 60 during operation of the manipulator system 31 . Further in the example of FIG. 3 is a shroud 62 shown mounted on an upper end of manipulator system 31 and which covers a portion of the upper end and shields components within the manipulator system 31 . Manipulator base 34 (and thus manipulator arm 32 ) is supported on a vertical mounting pedestal 64 , which has a generally rectangular cross section along its axis, and has a lower end mounted on the floor of cabinet 19 . Shown housed within shroud 62 is a wiring bus 66 which extends axially along the manipulator assembly. FIG. 4 provides in perspective view of one example of the cabinet 19 and having hinged panel 68 along its outer surface. As indicated above, the structure of cabinet 19 is in compliance with 21 C.F.R. 1020.40. Thus proper protective shielding and interlocking is provided in the panel 68 and along the hinged interface. An additional safety feature is a door assembly 70 which includes a barrier (not shown) that slides axially across the opening shown at the base of the loading assembly 26 and in a forward wall of cabinet 19 . The barrier thus provides a radiation shield from the inside to the outside of cabinet 19 while still allowing core sample loading in compliance with 21 C.F.R. §1020.40. An example of the manipulator assembly within cabinet 19 is illustrated in perspective view in FIG. 5 , and where cabinet 19 is shown in a partial phantom view. In this embodiment, a rearward end of manipulator base 34 is supported on a rearward end of cabinet 19 ; manipulator base 34 extends axially away from the rearward wall of cabinet 19 with the manipulator arm 32 axially sliding on manipulator base 34 . Motor 36 is shown oriented generally perpendicular to an axis of manipulator arm 32 and manipulator base 34 , and couples to manipulator arm 32 by shaft 38 . Further illustrated is how the core carrier 30 couples to a mounting plate 72 ; where mounting plate 72 is a generally circular and planar member that mounts on a forward end of manipulator arm 32 . In one embodiment, this member along with an extended tunnel provides the seal that inhibits excessive air flow during the loading process. Axial movement, as shown by the double headed arrow A, of core sample 24 is accomplished via motor 36 . X, Y, and Z axes are illustrated to define an example coordinate system for the purposes of reference herein. While not limited to this coordinate system, the axes depict axial movement of any object, such as the core sample 24 , to be along the Z axis, vertical movement to be along the Y axis, and lateral movement to be along the X axis. As indicated above, operation of motor 36 can move core sample 24 along all of these axes. Further shown in FIG. 5 are curved supports 74 , 76 that circumscribe manipulator arm 32 and provide a mounting surface for scan source 20 and scan receiver 22 . The combination of the support 74 , 76 define a gantry 78 that when rotated puts the scan source 20 and scan receiver 22 at an orbiting rotation around the core sample 24 and provides the scanning capabilities of the scan system 18 . As indicated above, the air replacement capabilities provided with cabinet 19 maintains a substantially constant temperature across the gantry 78 . Referring back to FIG. 4 , an interlock connector 80 is shown provided on the loading cover 56 and loading basin 58 . The interlock connectors 80 thus may recognize when the cover 56 is in the open position of FIG. 4 and in combination with controller 82 may prevent operation of the manipulator assembly. However, the control system associated with the scan system 18 that allows for motion of the manipulator assembly when the cover 56 is in the closed position and interlock connectors are adjacent one another. Shown in a side view in FIG. 6 is an example of the scan trailer 12 mounted on a chassis 84 . Wheels 86 are provided on the chassis 84 for facilitating transportation of the chassis 84 having the scan trailer 12 A suspension system 87 is provided between the wheels 86 and chassis 84 , that in one example includes a series of airbags (not shown) for isolating vibration experienced in the wheels 86 from the chassis 84 . Further provided with the chassis 84 is a leg 88 , which can telescope axially and into supporting contact with a surface 90 on which the chassis 84 is resting. Example surfaces 90 include bare ground, a pad, a road, or other parking surface. Shown extending laterally away from an end of the chassis 84 is an example of a dolly 91 , which provides rolling support for a forward portion of the chassis 84 . Included with the dolly 91 is a hitch assembly 92 for coupling the chassis 84 to a tractor rig 93 that can selectively pull the chassis 84 (and mounted scan trailer 12 ) to a designated location. In an alternate embodiment, multiple mobile enclosures (or trailers) are provided on a single chassis 84 . A connector (not shown) may adjoin adjacent mobile enclosures, which also helps to stiffen the chassis 84 and reduce its deflection while in transit. An example of a connector is found in U.S. Pat. Nos. 4,599,829 and 5,454,673, which are incorporated by reference herein in their entireties. More specifically, the suspension system 84 , with airbags, can be strategically disposed between the wheels 86 and the chassis 84 so that during transportation of the scan trailer 12 , the sensitive scanning equipment housed within the scan trailer 12 is not damaged. Further, airbags can also be selectively disposed within the leg 88 , so that when the chassis 84 is stationary and leg 88 is extended to support the chassis 84 , the chassis 84 , and thus the scan trailer 12 , can continue to be isolated from shock/vibration that may be transmitted from the surface 90 to the leg 88 . Seismic sources in this instance may emanate from typical wellbore operations, such as hydraulic fracturing. Advantages of the device disclosed herein include the ability to provide isolation from vibration up to 4.0 g due on/off road transport and through the truck. In one example, these vibrational forces are mitigated down to 0.3 g. A further advantage is to provide isolation from low frequency around the 10 Hz-15 Hz range for suitable operation of scan system 18 and other laboratory analytical equipment in the trailers 12 , 14 , 16 . This isolation can occur while stationary or during transit. The system can also provide leveling while in transit against acceleration, deceleration and turns to prevent tipping over of the off center of gravity loads. In an alternative, the hitch assembly 92 is removable, which can minimize the spacing requirement on site and for container alignment. In another alternative, the air ride suspension and trailer/suspension/tire integration can be variable. Low frequency vibration at the natural frequency of the trailer while stationary at the drilling site can be mitigated. In one embodiment a site leveling, stabilizing and isolation system is included, which provides support to ensure the equipment is leveled for suitable core loading despite the severely uneven center of gravity. A separate air bag leveling system can optionally be included to balance the off center of gravity during transit incidents such as body dive, acceleration/deceleration. An additional optional airbag isolation system can be provided below the turntable (not shown) which provides vibration isolation of the containerized equipment from the truck vibration. Referring now to FIGS. 7A and 7B , shown respectively in plan and side views is an example of the dolly 91 ( FIG. 6 ). The hitch assembly 92 includes a frame 94 that has an end mounted to a base 95 of the dolly 91 . The hitch assembly 92 further includes a pintle ring 96 on an end of the frame 94 distal from the base 95 . A pintle hook 98 ( FIG. 78 ) attached to an end of the tractor rig 93 selectively mates with the pintle ring 96 to couple together the tractor 93 and chassis 84 ( FIG. 6 ). The pintle hook 98 and pintle ring 96 selectively transfer an axial force between the two, but can pivot with respect to one another to form a pivoting type connection. An advantage of the dolly 91 and pintle coupling is that the pivoting type connection between the pintle hook 98 and ring 96 attenuate vibrational forces that might otherwise be transferred in a more rigid or fixed coupling. Thus a reduced amount of vibrational forces are transferred from the tractor 93 to the chassis 84 . As such, the scan system 18 ( FIG. 1 ) can be isolated from vibrational forces transmitted by the tractor 93 . Further illustrated in FIGS. 7A and 7B are wheels 10 that mount on an axle 102 that extends through the base 95 of the dolly 91 . Air bags 106 are shown mounted to the base 95 for attenuating vibration experienced by the wheels 100 that may otherwise be transmitted from the wheels 100 , thereby isolating the chassis 84 from vibrational forces generated as the wheels 100 travel along the surface 90 . Moreover, the air bags 106 , in conjunction with other air bags coupled with the chassis 84 , can maintain the chassis 84 level, even when the trailer 12 is being accelerated/decelerated, thus preventing “body dive” and other types of tipping that an unsupported trailer could experience. FIG. 8 shows in elevational side view an example of a leg 88 attached to a lower end of the chassis 84 and which provides support for the chassis 84 . In the example of FIG. 8 , the leg 88 includes an upper portion with an end that connects to a lower end of the chassis 84 , and a lower portion 110 that inserts into an end of upper portion 108 distal from chassis 84 and that selectively telescopes with respect to the upper portion 108 thereby making both the length of the leg 88 and the elevation of the chassis 84 adjustable. A pin 112 is optionally provided for locking together the upper and lower portions 108 , 110 and setting a length of the leg 88 . Further included in the example of FIG. 8 is an air bag assembly 114 for isolating the chassis 84 from vibrational forces that might be propagating to or along the surface 90 . Example vibrational forces that propagate to/along the surface include those generated by vehicles that may be proximate the chassis 84 , as well as from downhole activities, e.g. hydraulic fracturing, formation drilling, perforating, logging, and the like. The air bag assembly 114 thus also isolates the scan system 18 (shown in dashed outline above the chassis 84 ) from vibrational forces propagating to/along the surface 90 . The example air bag assembly 114 includes a membrane 116 , which in an example is formed from an elastomeric material that in one embodiment is filled with a fluid (e.g. air, nitrogen, water). Alternatively, membrane 116 could be a substantially solid member, where example materials include an elastomeric material or other vibrational attenuating substance. An upper plate 118 is shown mounted on a lower end of lower portion 110 and rests on an upper portion of membrane 116 . Lower plate 120 is shown generally coaxial with upper plate 118 and on a side of membrane opposite upper plate 118 . Upper and lower plate 118 , 120 as shown are generally transverse to an axis A X of the leg 88 . Graphically depicted in the example of FIG. 9 is a plot 122 having a line 124 representing values of vibrational transmissibility (ordinate) across the suspension system 87 with respect to values frequency (abscissa). In the illustrated embodiment, vibration frequencies of interest range from about 10 Hz to about 15 Hz. At these respective frequencies, and as illustrated by line 124 , the suspension system 87 (with airbags) provides about 94 to about 96% vibration mitigation. Such mitigation enables the scan system 18 , and other associated analytical equipment, to provide accurate readings during use, such as when located at or adjacent a drilling rig (not shown). FIGS. 10A and 1011 are graphical illustrations of plots 126 , 128 with lines 130 , 132 that represent amounts of vibration absorbed by the chassis 84 ( FIG. 6 ) over time while being transported on a paved surface, such a road formed from asphalt or concrete. The units of the vibration are in gravitational force (G-force) (ordinate) and seconds (abscissa). Plot 126 reflects the vibration the chassis 84 would experience on the example paved surface without the air suspension system 87 . Plot represents vibrational forces experienced by the chassis 84 equipped with the suspension system 87 having the air bags (not shown). Clearly illustrated in FIGS. 10A and 10B is that the chassis 84 having the suspension system 87 described herein is subjected to vibrational amounts of less than 0.3 G forces. In contrast, without the suspension system 87 , as shown in FIG. 10A , vibrational forces exerted onto the chassis 84 are up to 3 G forces. Accordingly, a 90% reduction of vibrational forces is experienced with the chassis 84 having the suspension system 87 , which is unexpected. The present invention described herein, therefore, is well adapted to carry out the objects and attain the ends and advantages mentioned, as well as others inherent therein. While a presently preferred embodiment of the invention has been given for purposes of disclosure, numerous changes exist in the details of procedures for accomplishing the desired results. Features of the system described herein provide appropriate trailer height, leveling and trailer dimensions suitable for preparing and loading core samples as well as testing in mobile CT scanning and laboratory analytical equipment on a container whose center of gravity is offset. The present system also provides sufficient spacing between trailers through a modified equipment hitch and tongue design and provide isolation from vibration up to 4 g from transportation (on or off a paved surface), or through the trailer rig. Further, while stationary, the scanning systems provided herein are isolated from low frequency vibrations (e.g. from about 10 hz to about 15 hz) by the above described isolation systems. Moreover, the suspension system associated with the chassis 84 maintains the chassis 84 in a level orientation while being transported, even during episodes of acceleration, deceleration, and directional changes, which limits acceleration forces experienced by the scanning equipment and also maintains the chassis 84 in a stable orientation. These and other similar modifications will readily suggest themselves to those skilled in the art, and are intended to be encompassed within the spirit of the present invention disclosed herein and the scope of the appended claims.
A chassis that supports a scanning system that images core samples from a wellbore. The chassis provides a mounting base for the scanning system for transportation of the scanning system, and also while the scanning system is in use and stationary. A suspension system mounts between the chassis and wheels that facilitate transportation of the chassis. The suspension system isolates the scanning system from shock and vibration encountered by the wheels while transporting the chassis and scanning system. In an example the chassis is a trailer, and which is pulled by a tractor. Legs can telescope downward from the chassis and against the surface on which the chassis is disposed. Airbags are strategically located within the chassis that absorb the vibration and thereby isolate the scanning system from the shock and vibration. Locations of the airbags include paths of force transmission between the wheels and the trailer.
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FIELD OF THE INVENTION The present invention relates to the field of plant breeding and, more specifically, to the development of onion variety DULCIANA (or NUN 01206 ON or NUN 1206. BACKGROUND OF THE INVENTION Onions belong to the lily family, Amaryllidaceae , and the genus, Allium. Alliums comprise a group of perennial herbs having bulbous, onion-scented underground leaves, including such commonly cultivated crops as garlic, chives, and shallots. It also includes ornamental species grown for their flowers. Onions are an important vegetable world-wide, ranking second among all vegetables in economic importance with an estimated value of $6 billion dollars annually. The onion is also one of the oldest cultivated vegetables in history. The common garden onions are in the species Allium cepa . Onions are classified in numerous ways, by basic use, flavor, color, shape of the bulb, and day length. Onions come in white, yellow, and red colors. The bulb may be rounded, flattened, or torpedo shaped. Commercial onions include “storage onions”, “fresh onions”, “pearl or mini onions”, and “green onions”. “Fresh onions” tend to have a lighter color with a thin skin, a milder, sweeter flavor, and must be eaten fresh as they do not store well. These onions are available in red, yellow, and white colors. Storage onions are available from harvest, which is at the beginning of August, and are stored and available throughout the winter months up to about March. Storage onions have a darker skin that is thicker than that of a fresh onion. They are also known for intense, pungent flavor, higher percentage of solids and desirable cooking characteristics. These onions are also available in red, yellow and white colors. Not all long day length type (long day type) onions are suitable for storage. A true storage onion is one that can be harvested in late summer or fall, and stored, under proper conditions, until the spring, when the fresh onion crop is again available. “Spanish onion”, “Spanish onions”, or “Spanish type” are terms applied to various long-day onions, generally yellow, though some white, and generally varieties that are large and globe-shaped. Spanish onion is commonly applied to various long day type onions of the type grown in western states of the United States (California, Idaho, Oregon, Washington, Colorado) with a bulb size averaging 300-700 grams (g) (typically over 3 inches up to 4 inches but also up to 5 inches in diameter for bulbs classified as “colossal”). Onion varieties initiate bulbing when both the temperature and a minimum number of daylight hours reach certain levels. When onions are first planted, they initially develop their vegetative growth, with no sign of bulb formation until the proper day length for that onion variety triggers the signal to the plant to stop producing above ground vegetative growth and start forming a bulb. Onions are thus sensitive to the hours of daylight and darkness they receive, and for most varieties it is only when the specific combination of daylight and darkness is reached, that the bulb starts to form. Onions are therefore classified by the degree of day length that will initiate bulb formation. Onions are described as short-, intermediate-, and long-day length types. Short day means that bulbing will initiate at 11 to 12 hours of daylight. Intermediate day is used for onions bulbing at 12 to about 14 hours of daylight. Long day onions require about 14 or more hours of daylight for bulb formation to start. Growers producing onions in more northerly climates plant long-day length onions. Daylight length varies greatly with latitude, and at higher latitudes long-day onions will produce sufficient top growth before the day length triggers bulbing to produce a large bulb. A short-day onion grown in the North (higher latitudes) will bulb too early and produce relatively small bulbs. Short day onions are preferred for southern areas such as southern Texas, southern California and Mexico. If a long day type onion is planted in such a short day climate, it may never experience enough day length to trigger the bulbing process. Onions are also classified on flavor, with the common designations of sweet, mild, and pungent. The flavor of the onion is a result of both the type of onion and the growing conditions. For instance, soils containing a high amount of sulfur result in more pungent flavored onions. Sweetness in onions is caused by the sugars glucose, fructose and sucrose. Onions also contain polymers of fructose called fructans. Onion cultivars differ quite markedly in the relative amounts of sucrose, glucose, fructose and fructans which they contain. They also differ in sugars according to length of storage and location in the bulb. Short day cultivars, which are poor storers, tend to have higher levels of sucrose, fructose and glucose, but hardly any of the fructans. In contrast, long day type cultivars and intermediate storage cultivars such as Pukekohe Longkeeper have less sucrose, glucose and fructose and higher amounts of fructans. Short day varieties do not keep well in storage conditions, and the pungency of short day varieties can climb considerably during storage. Present production in North America and Europe allows harvest of short day onions from mild winter regions from November through April. Long day onions are available fresh in the late summer and as storage onions from September through March, or even year round, have not been available in low pungency varieties (with the exception of U.S. patent application Ser. No. 12/861,740 which is based on U.S. patent application Ser. No. 12/020,360). Sweet onions must be imported from the southern hemisphere to fill the gap in sweet onion production (November-February). In the United States, regions like Georgia and Texas produce short day onions from March to June, while low pungency onions available from November to February are short day onions, produced in the southern hemisphere. The use of a type of onion is depending on a customer's preference for taste, aroma, appearance and color of an onion. There is thus a need for new short day onions with new appearance and color properties. SUMMARY OF THE INVENTION In one aspect, the present invention provides an onion plant of the variety designated DULCIANA. Parts of the onion plant of the present invention are also provided, for example, including a leaf, pollen, an ovule, a bulb and a cell of the plant. The invention also concerns seed of onion variety DULCIANA. The onion seed of the invention may be provided as an essentially homogeneous population of onion seed. Therefore, seed of the invention may be defined as forming at least about 97% of the total seed, including at least about 98%, 99% or more of the seed. The population of onion seed may be particularly defined as being essentially free from non-hybrid seed. The seed population may be separately grown to provide an essentially homogeneous population of onion plants according to the invention. Also encompassed are plants grown from seeds of onion variety DULCIANA and plant parts thereof such as a leaf, pollen, an ovule, a bulb and a cell. Another aspect refers to an onion plant, or a part thereof, having all or essentially all the physiological and morphological characteristics of an onion plant of onion variety DULCIANA. In another aspect of the invention, a tissue culture of regenerable cells of a plant of variety DULCIANA is provided. The tissue culture will preferably be capable of regenerating plants capable of expressing all of the physiological and morphological characteristics of a plant of the invention, and of regenerating plants having substantially the same genotype as other such plants. Examples of some such physiological and morphological characteristics include those traits set forth in Table 1 herein. The regenerable cells in such tissue cultures may be derived, for example, from embryos, meristems, cotyledons, pollen, leaves, anthers, roots, root tips, pistil, flower, seed and stalk. Thus, a tissue culture may comprise regenerable cells from embryos, meristems, cotyledons, pollen, leaves, anthers, roots, root tips, pistil, flower, seed and bulbs. Still further, the present invention provides onion plants regenerated from a tissue culture of the invention, the plants having all the physiological and morphological characteristics of a plant of the invention. The invention also concerns methods of vegetatively propagating a plant of the invention. In certain embodiments, the method comprises the steps of: (a) collecting tissue capable of being propagated from a plant of the invention; (b) cultivating said tissue to obtain proliferated shoots; and (c) rooting said proliferated shoots to obtain rooted plantlets. In some of these embodiments, the method further comprises growing plants from said rooted plantlets. In yet another aspect of the invention, processes are provided for producing onion seeds, plants and bulb, which processes generally comprise crossing a first parent onion plant with a second parent onion plant, wherein at least one of the first or second parent onion plants is a plant of the variety designated DULCIANA. These processes may be further exemplified as processes for preparing hybrid onion seed or plants, wherein a first onion plant is crossed with a second onion plant of a different, distinct variety to provide a hybrid that has, as one of its parents, the onion plant variety DULCIANA. In another embodiment of the invention, onion variety DULCIANA is crossed to produce onion seed derived of the variety designated DULCIANA. In any cross herein, either parent may be the male or female parent. In these processes, crossing will result in the production of seed. The seed production occurs regardless of whether the seed is collected or not. In one embodiment of the invention, the first step in “crossing” comprises planting seeds of a first and a second parent onion plant, often in proximity so that pollination will occur for example, mediated by insect vectors. Alternatively, pollen can be transferred manually. Where the plant is self-pollinated, pollination may occur without the need for direct human intervention other than plant cultivation. A second step may comprise cultivating or growing the seeds of the first and the second parent onion plants into plants that bear flowers. A third step may comprise preventing self-pollination of the plants, such as by emasculating the male portions of flowers, (e.g., treating or manipulating the flowers to produce an emasculated parent onion plant). Self-incompatibility systems may also be used in some hybrid crops for the same purpose. Self-incompatible plants still shed viable pollen and can pollinate plants of other varieties but are incapable of pollinating themselves or other plants of the same variety. A fourth step for a hybrid cross may comprise cross-pollination between the first and second parent onion plants. In certain embodiments, pollen may be transferred manually or by the use of insect vectors. Yet another step comprises harvesting the seeds from at least one of the parent onion plants. The harvested seed can be grown to produce an onion plant or hybrid onion plant. The present invention also provides the onion seeds and plants produced by a process that comprises crossing a first parent onion plant with a second parent onion plant, wherein at least one of the first or second parent onion plants is a plant provided herein, such as from variety DULCIANA. In another embodiment of the invention, onion seed and plants produced by the process are first filial generation (F1) hybrid onion seed and plants produced by crossing a plant in accordance with the invention with another, distinct plant. The present invention further contemplates plant parts of such an F1 hybrid onion plant, and methods of use thereof. Therefore, certain exemplary embodiments of the invention provide an F1 hybrid onion plant and seed thereof. In still yet another aspect, the present invention provides a method of producing a plant or a seed derived from variety DULCIANA, the method comprising the steps of: (a) preparing a progeny plant derived from said variety by crossing a plant of variety DULCIANA with a second plant; and (b) selfing the progeny plant or crossing it to the second plant or to a third plant to produce a seed of a progeny plant of a subsequent generation. The method may additionally comprise: (c) growing a progeny plant of a further subsequent generation from said seed of a progeny plant of a subsequent generation and selfing the progeny plant of a subsequent generation or crossing it to the second, the third, or a further plant; and repeating the steps for 3 or more times, e.g., an additional 3-10 generations to produce a further plant derived from the aforementioned starting variety. The further plant derived from variety DULCIANA may be an inbred variety, and the aforementioned repeated crossing steps may be defined as comprising sufficient inbreeding to produce the inbred variety. In the method, it may be desirable to select particular plants resulting from step (c) for continued crossing according to steps (b) and (c). By selecting plants having one or more desirable traits, a plant is obtained which possesses some of the desirable traits of the starting plant as well as potentially other selected traits. One aspect of the invention refers to a method of producing an onion plant comprising crossing an onion plant of variety DULCIANA with a second onion plant one or more times. This method comprises in one embodiment selecting progeny from said crossing. In another aspect of the invention, an onion plant of variety DULCIANA comprising an added heritable trait is provided, e.g., an Essentially Derived Variety of DULCIANA having one, two or three physiological and/or morphological characteristics which are different from those of DULCIANA and which otherwise has all the physiological and morphological characteristics of DULCIANA, wherein a representative sample of seed of variety DULCIANA has been deposited under NCIMB/ATTC Accession Number 42706. The heritable trait may comprise a genetic locus that is, for example, a dominant or recessive allele. In one embodiment of the invention, a plant of the invention is defined as comprising a single locus conversion. For example, one, two, three or more heritable traits may be introgressed at any particular locus using a different allele that confers the new trait or traits of interest. In specific embodiments of the invention, the single locus conversion confers one or more traits such as, for example, herbicide tolerance, insect resistance, disease resistance and modulation of plant metabolism and metabolite profiles. In further embodiments, the trait may be conferred by a naturally occurring gene introduced into the genome of the variety by backcrossing, a natural or induced mutation, or a transgene introduced through genetic transformation techniques into the plant or a progenitor of any previous generation thereof. When introduced through transformation, a genetic locus may comprise one or more genes integrated at a single chromosomal location. Thus, the invention comprises a method of producing a plant comprising an added desired trait, the method comprising introducing a transgene conferring the desired trait into a plant of onion variety DULCIANA. For example, in certain embodiments, the invention provides methods of introducing a desired trait into a plant of the invention comprising: (a) crossing a plant of variety DULCIANA with a second onion plant that comprises a desired trait to produce F1 progeny, (b) selecting an F1 progeny that comprises the desired trait(s), e.g., one, two, three or more desired trait(s), (c) crossing the selected F1 progeny with a plant of variety DULCIANA to produce backcross progeny, and (d) selecting backcross progeny comprising the desired trait(s) and which otherwise has all the physiological and morphological characteristics of variety DULCIANA. Optionally, steps (c) and (d) can be repeated one or more times, e.g., three or more times such as three, four, five, six or seven times, in succession to produce selected fourth, fifth, sixth, seventh or eighth or higher backcross progeny that comprises the desired trait. The invention also provides onion plants produced by these methods. Still yet another aspect of the invention refers to the genetic complement of an onion plant variety of the invention. The phrase “genetic complement” is used to refer to the aggregate of nucleotide sequences, the expression of which defines the phenotype of, in the present case, an onion plant of, or a cell or tissue of that plant. A genetic complement thus represents the genetic makeup of a cell, tissue or plant, and a hybrid genetic complement represents the genetic make-up of a hybrid cell, tissue or plant. The invention thus provides onion plant cells that have a genetic complement in accordance with the onion plant cells disclosed herein, and plants, seeds and plants containing such cells. Plant genetic complements may be assessed by genetic marker profiles, and by the expression of phenotypic traits that are characteristic of the expression of the genetic complement, e.g., gene expression profiles, gene product expression profiles and isozyme typing profiles. It is understood that a plant of the invention or a first generation progeny thereof could be identified by any of the many well-known techniques such as, for example, Simple Sequence Length Polymorphisms (SSLPs), Randomly Amplified Polymorphic DNAs (RAPDs), DNA Amplification Fingerprinting (DAF), Sequence Characterized Amplified Regions (SCARs), Arbitrary Primed Polymerase Chain Reaction (AP-PCR), Amplified Fragment Length Polymorphisms (AFLPs) (see, e.g., EP 534 858), and Single Nucleotide Polymorphisms (SNPs). In still yet another aspect, the present invention provides hybrid genetic complements, as represented by onion plant cells, tissues, plants, and seeds, formed by the combination of a haploid genetic complement of an onion plant of the invention with a haploid genetic complement of a second onion plant, preferably, another, distinct onion plant. In another aspect, the present invention provides an onion plant regenerated from a tissue culture that comprises a hybrid genetic complement of this invention. In still yet another aspect, the invention provides a method of determining the genotype of a plant of the invention comprising detecting in the genome of the plant at least a first polymorphism. The method may, in certain embodiments, comprise detecting a plurality of polymorphisms in the genome of the plant, for example by obtaining a sample of nucleic acid from a plant and detecting in said nucleic acids a plurality of polymorphisms. The method may further comprise storing the results of the step of detecting the plurality of polymorphisms on a computer readable medium. In one embodiment of the invention, the invention provides a method for producing a seed of a variety derived from DULCIANA comprising the steps of (a) crossing an onion plant of variety DULCIANA with a second onion plant; and (b) allowing seed of a variety DULCIANA-derived onion plant to form. This method can further comprise steps of (c) crossing a plant grown from said variety DULCIANA-derived onion seed with itself or a second onion plant to yield additional variety DULCIANA-derived onion seed; (d) growing said additional variety DULCIANA-derived onion seed of step (c) to yield additional variety DULCIANA-derived onion plants; and optionally (e) repeating the crossing and growing steps of (c) and (d) to generate further variety DULCIANA-derived onion plants. For example, the second onion plant is of an inbred onion variety. In certain embodiments, the present invention provides a method of producing onions comprising: (a) obtaining a plant of the invention, wherein the plant has been cultivated to maturity, and (b) collecting an onion bulb from said plant. The invention also provides for a food or feed product comprising or consisting of a plant part described herein preferably an onion bulb or part thereof and/or an extract from a plant part described herein. The food or feed product may be fresh or processed, e.g., canned, steamed, boiled, fried, blanched and/or frozen, etc. Any embodiment discussed herein with respect to one aspect of the invention applies to other aspects of the invention as well, unless specifically noted. Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and any specific examples provided, while indicating specific embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. DEFINITIONS In the description and tables herein, a number of terms are used. In order to provide a clear and consistent understanding of the specification and claims, the following definitions are provided: The term “about” is used to indicate that a value includes the standard deviation of error for the device or method being employed to determine the value. The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and to “and/or.” When used in conjunction with the word “comprising” or other open language in the claims, the words “a” and “an” denote “one or more” unless specifically noted. The terms “comprise,” “have” and “include” are open-ended linking verbs. Any forms or tenses of one or more of these verbs, such as “comprises,” “comprising,” “has,” “having,” “includes” and “including,” are also open-ended. For example, any method that “comprises,” “has” or “includes” one or more steps is not limited to possessing only those one or more steps and also covers other unlisted steps. Similarly, any plant that “comprises,” “has” or “includes” one or more traits is not limited to possessing only those one or more traits and covers other unlisted traits. The terms mentioned above also comprise the term “contain” which is limited to specific embodiments. Thus, one embodiment of the invention, when the terms “comprise,” “have” and “include” are used to describe a plant, part thereof or a process, refers to an embodiment wherein the limiting term “contain” is used. As used herein, “onion plant” or “onion” is a plant of genus Allium or a part thereof (e.g. a bulb). Onion includes all kinds of onions, such as short-day, intermediate-day and long-day onions according to bulb initiation in response to various lengths of daylight. Generally, a “short-day” length type onion plant (short-day, or SD, onion) responds to 11 to 12 hours of daylight for the initiation of bulb formation; an “intermediate-day” length type onion plant (intermediate-day, or ID, onion) needs 12 to 14 hours of daylight; and a “long-day” length type onion plant (long-day, or LD onion) requires about 14 or more contiguous hours of daylight for bulb formation to start. Onion includes, e.g., Allium aggregatum (e.g., chalottes and potato onion), Allium cepa and Allium fistulosum , and hybrids such as Allium xproliferum, Allium xwakegi , and the triploid onion Allium xcornutum. Allium cepa L. (common onion) is a cool season (tolerant of frost) biennial plant. By “biennial plant” it is meant that Allium cepa L. produces a bulb in the first season and seeds in the second. Onion plants may be grown at any temperature that allows for the growth and development of the plant. “Cultivated onion” refers to plants of Allium , i.e. varieties, breeding lines or cultivars of the species Allium cepa , cultivated by humans and having good agronomic characteristics; preferably such plants are not “wild plants”, i.e. plants which generally have much poorer yields and poorer agronomic characteristics than cultivated plants and e.g. grow naturally in wild populations. “Wild plants” include for example ecotypes, PI (Plant Introduction) lines, landraces or wild accessions or wild relatives of a species. “USDA descriptors” are the plant variety descriptors described for onion in the “Objective description of Variety Onion Allium cepa L.”, ST-470-16 (as published by U.S. Department of Agriculture, Agricultural Marketing Service, Science and Technology, Plant Variety Protection Office, Beltsville, Md. 20705 (available on the world wide web at www.ams.usda.gov/AMSv1.0/) and which can be downloaded from the world wide web at http://www.ams.usda.gov/AMSv1.0/getfile?dDocName=STELDEV3003776. “UPOV descriptors” are the plant variety descriptors described for onion in the “Guidelines for the Conduct of Tests for Distinctness, Uniformity and Stability, TG/46/7 (Geneva 2009), as published by UPOV (International Union for the Protection of New Varieties and Plants, available on the world wide web at upov.int) and which can be downloaded from the world wide web at http://www.upov.int/edocs/tgdocs/en/tg046.pdf and is herein incorporated by reference in its entirety. “RHS” refers to the Royal Horticultural Society of England which publishes an official botanical color chart quantitatively identifying colors according to a defined numbering system, The chart may be purchased from Royal Horticulture Society Enterprise Ltd RHS Garden; Wisley, Woking; Surrey GU236QB, UK, e.g., the RHS color chart: 2007 (The Royal Horticultural Society, charity No: 222879, PO Box 313 London SW1P2PE; sold by, e.g., TORSO-VERLAG, Obere Grüben 8•D-97877 Wertheim, Article-No.: Art62-00008 EAN-Nr.: 4250193402112). “Genotype” refers to the genetic composition of a cell or organism. “Phenotype” refers to the detectable characteristics of a cell or organism, which characteristics are the manifestation of gene expression. As used herein, the term “plant” includes the whole plant or any parts or derivatives thereof, preferably having the same genetic makeup as the plant from which it is obtained, such as plant organs (e.g. harvested or non-harvested onion bulbs (tubers), leaves etc.), plant cells, plant protoplasts, plant cell and/or tissue cultures from which whole plants can be regenerated, plant calli, plant cell clumps, plant transplants, seedlings, hypocotyl, cotyledon, plant cells that are intact in plants, plant clones or micropropagations, or parts of plants (e.g. harvested tissues or organs), such as plant cuttings, vegetative propagations, embryos, pollen, ovules, flowers, leaves, seeds, clonally propagated plants, roots, stems, root tips, grafts, parts of any of these and the like. Also any developmental stage is included, such as seedlings, cuttings prior or after rooting, mature plants or leaves. By “bulb” or “onion bulb” is meant the (commercially) (harvested,) edible portion of the onion plant. An onion bulb comprises an apex and concentric, enlarged fleshy leaf bases, also called fleshy scale leaves (see, e.g., FIG. 1 ). Onion bulbs may be developing onion bulbs or mature onion bulbs. “Harvested plant material” refers herein to plant parts (e.g. a bulb detached from parts of the plant (such as leaves) or the rest of the plant) which have been collected for further storage and/or further use. “Maturity” refers to the development stage of an onion bulb when said onion bulb has fully developed (reached its final size). In particular embodiments “maturity” is defined as the mature state of bulb development and optimal time for harvest. Typically, maturity of a bulb is reached when the vegetative phase of an onion plant is over and leaves and neck of the onion plant dry out. As used herein, a “mature onion bulb” refers to any onion bulb that is ready for harvest. Generally, when 25-50% of the onion leaf tops have fallen over, the onion is ready for harvest. “Harvested seeds” refers to seeds harvested from a line or variety, e.g. produced after self-fertilization or cross-fertilization and collected. A plant having “(essentially) all the physiological and morphological characteristics” means a plant having essentially all or all the physiological and morphological characteristics when grown under the same environmental conditions of the plant of DULCIANA from which it was derived, e.g. the progenitor plant, the parent, the recurrent parent, the plant used for tissue- or cell culture, etc. The skilled person will understand that a comparison between onion varieties should occur when said varieties are grown under the same environmental conditions. For example, the plant may have all characteristics mentioned in Table 1 when grown under the conditions of the field trial described in this application. In certain embodiments, the plant having “essentially all the physiological and morphological characteristics” are plants having all the physiological and morphological characteristics, except for certain characteristics, such as one, two or three, mentioned, e.g. the characteristic(s) derived from a converted or introduced gene or trait and/or except for the characteristics which differ in an EDV. So, the plant may have all characteristics mentioned in Table 1, except for one, two or three characteristics of Table 1, in which the plant may thus differ. A plant having one or more or all “essential physiological and/or morphological characteristics” or one or more “distinguishing characteristics” (such as one, two, three, four or five) refers to a plant having (or retaining) one or more, or all, or retaining all except one, two or three of the distinguishing characteristics mentioned in Table 1 when grown under the same environmental conditions that distinguish DULCIANA from most similar variety SERENGETI such distinguishing characteristics being selected from (but not limited to): Color of bulb skin; bulb height; column length of sheath (height from soil line to base of lowest succulent leaf; plant height above soil line to highest point of any foliage; and maturity (see e.g. Table 1). In a further embodiment, DULCIANA can be distinguished from SERENGETI, when grown under the same environmental conditions, by using the further distinguishing characteristics being selected from (but not limited to): length of leaf (before maturity yellowing begins); width of leaf; thickness of leaf (at mid-length of longest leaf); interior bulb color; and bulb weight (see e.g. Table 1). The physiological and/or morphological characteristics mentioned above are commonly evaluated at significance levels of 1%, 5%, 8% or 10% significance level, when measured under the same environmental conditions. For example, a progeny plant of DULCIANA may have one or more (or all, or all except one, two or three) of the essential physiological and/or morphological characteristics of DULCIANA listed in Table 1, or one or more or all (or all except one, two or three) of the distinguishing characteristics of DULCIANA listed in Table 1 and above, as determined at the 1% or 5% significance level when grown under the same environmental conditions. As used herein, the term “variety” or “cultivar” means a plant grouping within a single botanical taxon of the lowest known rank, which grouping, irrespective of whether the conditions for the grant of a breeder's right are fully met, can be defined by the expression of the characteristics resulting from a given genotype or combination of genotypes, distinguished from any other plant grouping by the expression of at least one of the said characteristics and considered as a unit with regard to its suitability for being propagated unchanged. The terms “gene converted” or “conversion plant” in this context refer to onion plants which are often developed by backcrossing wherein essentially all of the desired morphological and physiological characteristics of parent are recovered in addition to the one or more genes transferred into the parent via the backcrossing technique or via genetic engineering. Likewise a “Single Locus Converted (Conversion) Plant” refers to plants which are often developed by plant breeding techniques comprising or consisting of backcrossing, wherein essentially all of the desired morphological and physiological characteristics of an onion variety are recovered in addition to the characteristics of the single locus having been transferred into the variety via, e.g., the backcrossing technique and/or by genetic transformation. Likewise, a double loci converted plant/a triple loci converted plant refers to plants having essentially all of the desired morphological and physiological characteristics of given variety, expect that at two or three loci, respectively, it contains the genetic material (e.g., an allele) from a different variety. A variety is referred to as an “Essentially Derived Variety” (EDV) i.e., shall be deemed to be essentially derived from another variety, “the initial variety” when (i) it is predominantly derived from the initial variety, or from a variety that is itself predominantly derived from the initial variety, while retaining the expression of the essential characteristics that result from the genotype or combination of genotypes of the initial variety; (ii) it is clearly distinguishable from the initial variety; and (iii) except for the differences which result from the act of derivation, it conforms to the initial variety in the expression of the essential characteristics that result from the genotype or combination of genotypes of the initial variety. Thus, an EDV may be obtained for example by the selection of a natural or induced mutant, or of a somaclonal variant, the selection of a variant individual from plants of the initial variety, backcrossing, or transformation by genetic engineering. In one embodiment, an EDV is a gene converted plant. “Plant line” is for example a breeding line which can be used to develop one or more varieties. “Hybrid variety” or “F1 hybrid” refers to the seeds of the first generation progeny of the cross of two non-isogenic plants. For example, the female parent is pollinated with pollen of the male parent to produce hybrid (F1) seeds on the female parent. “Progeny” as used herein refers to plants derived from a plant designated DULCIANA. Progeny may be derived by regeneration of cell culture or tissue culture or parts of a plant designated DULCIANA or selfing of a plant designated DULCIANA or by producing seeds of a plant designated DULCIANA. In further embodiments, progeny may also encompass plants derived from crossing of at least one plant designated DULCIANA with another onion plant of the same or another variety or (breeding) line, or with a wild onion plant, backcrossing, inserting of a locus into a plant or selecting a plant comprising a mutation or selecting a variant. A progeny is, e.g., a first generation progeny, i.e. the progeny is directly derived from, obtained from, obtainable from or derivable from the parent plant by, e.g., traditional breeding methods (selfing and/or crossing) or regeneration. However, the term “progeny” generally encompasses further generations such as second, third, fourth, fifth, sixth, seventh or more generations, i.e., generations of plants which are derived from, obtained from, obtainable from or derivable from the former generation by, e.g., traditional breeding methods, regeneration or genetic transformation techniques. For example, a second generation progeny can be produced from a first generation progeny by any of the methods mentioned above. Especially progeny of DULCIANA which are EDVs or which retain all (or all except 1, 2 or 3) physiological and/or morphological characteristics of DULCIANA listed in Table 1, or which retain all (or all except 1, 2, or 3) of the distinguishing characteristics of DULCIANA described elsewhere herein and in Table 1, are encompassed herein. The term “traditional breeding techniques” encompasses herein crossing, selfing, selection, double haploid production, embryo rescue, protoplast fusion, marker assisted selection, mutation breeding etc. as known to the breeder (i.e. methods other than genetic modification/transformation/transgenic methods), by which, for example, a genetically heritable trait can be transferred from one onion line or variety to another. “Crossing” refers to the mating of two parent plants. “Cross-pollination” refers to the fertilization by the union of two gametes from different plants. “Backcrossing” is a traditional breeding technique used to introduce a trait into a plant line or variety. The plant containing the trait is called the donor plant and the plant into which the trait is transferred is called the recurrent parent. An initial cross is made between the donor parent and the recurrent parent to produce progeny plants. Progeny plants which have the trait are then crossed to the recurrent parent. After several generations of backcrossing and/or selfing the recurrent parent comprises the trait of the donor. The plant generated in this way may be referred to as a “single trait converted plant”. “Selfing” refers to self-pollination of a plant, i.e., the transfer of pollen from the anther to the stigma of the same plant. “Regeneration” refers to the development of a plant from cell culture or tissue culture or vegetative propagation. “Vegetative propagation”, “vegetative reproduction” or “clonal propagation” are used interchangeably herein and mean the method of taking part of a plant and allowing that plant part to form at least roots where plant part is, e.g., defined as or derived from (e.g. by cutting of) a bulb or part thereof, leaf, pollen, embryo, cotyledon, hypocotyl, cells, protoplasts, meristematic cell, root, root tip, pistil, anther, flower, shoot tip, shoot, stem, petiole, etc. When a whole plant is regenerated by vegetative propagation, it is also referred to as a vegetative propagation. “Locus” (plural loci) refers to the specific location of a gene or DNA sequence on a chromosome. A locus may confer a specific trait. “Linkage” refers to a phenomenon wherein alleles on the same chromosome tend to segregate together more often than expected by chance if their transmission was independent. “Marker” refers to a readily detectable phenotype, preferably inherited in codominant fashion (both alleles at a locus in a diploid heterozygote are readily detectable), with no environmental variance component, i.e., a heritability of one (1). “Allele” refers to one or more alternative forms of a gene locus. All of these loci relate to one trait. Sometimes, different alleles can result in different observable phenotypic traits, such as different pigmentation. However, many variations at the genetic level result in little or no observable variation. If a multicellular organism has two sets of chromosomes, i.e. diploid, these chromosomes are referred to as homologous chromosomes. Diploid organisms have one copy of each gene (and therefore one allele) on each chromosome. If both alleles are the same, they are homozygotes. If the alleles are different, they are heterozygotes. As used herein, the terms “resistance” and “tolerance” are used interchangeably to describe plants that show no symptoms to a specified biotic pest, pathogen, abiotic influence or environmental condition. These terms are also used to describe plants showing some symptoms but that are still able to produce marketable product with an acceptable yield. Some plants that are referred to as resistant or tolerant are only so in the sense that they may still produce a crop, even though the plants are stunted and the yield is reduced. “Tissue Culture” refers to a composition comprising isolated cells of the same or a different type or a collection of such cells organized into parts of a plant. “Transgene” or “chimeric gene” refers to a genetic locus comprising a DNA sequence which has been introduced into the genome of an onion plant by transformation. A plant comprising a transgene stably integrated into its genome is referred to as “transgenic plant”. “Haploid” refers to a cell or organism having one set of the two sets of chromosomes in a diploid. “Diploid” refers to a cell or organism having two sets of chromosomes. “Polyploid” refers to a cell or organism having three or more complete sets of chromosomes. “Triploid” refers to a cell or organism having three sets of chromosomes. “Tetraploid” refers to a cell or organism having four sets of chromosomes. “Average” refers herein to the arithmetic mean. The term “mean” refers to the arithmetic mean of several measurements. The skilled person understands that the appearance of a plant depends to some extent on the growing conditions of said plant. Thus, the skilled person will know typical growing conditions for oniondescribed herein. The mean, if not indicated otherwise within this application, refers to the arithmetic mean of measurements on at least 10 different, randomly selected plants of a variety or line. “Substantially equivalent” refers to a characteristic that, when compared, does not show a statistically significant difference (e.g., p=0.05) from the mean. DRAWINGS The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present teachings in any way. FIG. 1 shows the differences in bulb shape and bulb color of typical onion bulbs of DULCIANA and SERENGETI. DETAILED DESCRIPTION OF THE INVENTION The invention provides methods and compositions relating to plants, plant parts, seeds and progenies of onion variety DULCIANA. Variety DULCIANA exhibits a number of improved traits including: 1) a pinkish yellow color of bulb skin, e.g. RHS Orange-White Group 159A and Greyed-Yellow Group 160 C; 2) a (average) bulb height that is between about 6.0 and 8.4 cm, or preferably between about 6.6 and 7.8 cm, or between about 7.0 and 7.4 cm or even about 7.2 cm; 3) a (average) column length of sheath that is between about 40 and 52 mm, or preferably between 43 and 49 mm or even between about 45 and 47 mm, or even about 46 mm; 4) a (average) plant height above soil line to highest point of any foliage that is at least between about 58 cm and 68 cm, or preferably between about 60 cm and 64 cm or even between about 62 cm and 64 cm, or even about 63 cm; 5) early maturity (e.g. between 75-90 days). In a further embodiment, further characteristics are at least one selected from: 6) (average) length of leaf (before maturity yellowing begins) that is at least between about 33 cm and about 58 cm, or preferably between about 43 cm and about 49 cm, or even between about 45 cm and 48 cm or even about 46 cm; 7) (average) width of leaf that is at least between about 15 mm and 25 mm, or preferably between about 18 mm and 23 mm, or even between about 20 mm and 22 mm, or even about 21 mm; 8) (average) thickness of leaf (at mid-length of longest leaf) that is at least between about 1.25 mm and 2.44 mm, or preferably between about 1.4 mm and 1.8 mm, or even between about 1.6 mm and 1.8 mm, or even about 1.7 mm; 9) an cream colored bulb interior, e.g. RHS White group 155A; 10) a (average) bulb weight of at least 200 grams, or preferably at least about 210 grams, 215 grams, 220 grams, 225 grams, 230 grams, 235 grams, 240 grams, or even about 241 grams. Development of DULCIANA The hybrid DULCIANA was made from male and female proprietary inbred lines developed by Nunhems. The female parent of DULCIANA and its maintainer was developed out of an internal breeding line. This inbred was developed over a period of 14 years/7 generations of inbreeding using single bulb selfing. The male parent was developed from a [fertile×fertile] cross of two Nunhems inbred lines over a period of 8 generations of single bulb selfings. The female and male parents were crossed to produce hybrid (F1) seeds of DULCIANA. The seeds of DULCIANA can be grown to produce hybrid plants and parts thereof (e.g. onion bulbs). The hybrid DULCIANA can be propagated by seeds or vegetative. The hybrid variety is uniform and genetically stable. This has been established through evaluation of horticultural characteristics. Several hybrid seed production events resulted in no observable deviation in genetic stability. DULCIANA has been observed for more than three generations in different trials on different locations and during seed increase. Coupled with the confirmation of genetic stability of the female and male parents the Applicant concluded that DULCIANA is uniform and stable. Breeding of Onion Plants of the Invention One aspect of the current invention concerns methods for crossing an onion variety provided herein with itself or a second plant and the seeds and plants produced by such methods. These methods can be used for propagation of a variety provided herein, or can be used to produce hybrid onion seeds and the plants grown therefrom. Such hybrid seeds can be produced by crossing the parent varieties of the variety. The development of new varieties using one or more starting varieties is well known in the art. In accordance with the invention, novel varieties may be created by crossing a plant of the invention followed by multiple generations of breeding according to such well known methods. New varieties may be created by crossing with any second plant. In selecting such a second plant to cross for the purpose of developing novel varieties, it may be desired to choose those plants that either themselves exhibit one or more selected desirable characteristics or that exhibit the desired characteristic(s) when in hybrid combination. Once initial crosses have been made, inbreeding and selection take place to produce new varieties. For development of a uniform variety, often five or more generations of selfing and selection are involved. Uniform varieties of new varieties may also be developed by way of double-haploids. This technique allows the creation of true breeding varieties without the need for multiple generations of selfing and selection. In this manner, true breeding varieties can be produced in as little as one generation. Haploid embryos may be produced from microspores, pollen, anther cultures, or ovary cultures. The haploid embryos may then be doubled autonomously, or by chemical treatments (e.g. colchicine treatment). Alternatively, haploid embryos may be grown into haploid plants and treated to induce chromosome doubling. In either case, fertile homozygous plants are obtained. In accordance with the invention, any of such techniques may be used in connection with a plant of the invention and progeny thereof to achieve a homozygous variety. Backcrossing can also be used to improve an inbred plant. Backcrossing transfers one or more heritable traits from one inbred or non-inbred source to an inbred that lacks those traits. The exact backcrossing protocol will depend on the characteristic(s) or trait(s) being altered to determine an appropriate testing protocol. When the term variety DULCIANA is used in the context of the present invention, this also includes plants modified to include at least a first desired heritable trait such as one, two or three desired heritable trait(s). This can be accomplished, for example, by first crossing a superior inbred (recurrent parent) to a donor inbred (non-recurrent parent), which carries the appropriate genetic information (e.g., an allele) at the locus or loci relevant to the trait in question. The progeny of this cross are then mated back to the recurrent parent followed by selection in the resultant progeny (first backcross generation, or BC1) for the desired trait to be transferred from the non-recurrent parent. After five or more backcross generations with selection for the desired trait, the progeny are heterozygous at loci controlling the characteristic being transferred, but are like the superior parent for most or almost all other loci. The last backcross generation would be selfed to give pure breeding progeny for the trait being transferred. The parental onion plant which contributes the desired characteristic or characteristics is termed the non-recurrent parent because it can be used one time in the backcross protocol and therefore need not recur. The parental onion plant to which the locus or loci from the non-recurrent parent are transferred is known as the recurrent parent as it is used for several rounds in the backcrossing protocol. Many single locus traits have been identified that are not regularly selected for in the development of a new inbred but that can be improved by backcrossing techniques. Single locus traits may or may not be transgenic; examples of these traits include, but are not limited to, male sterility, herbicide resistance, resistance to bacterial, fungal, or viral disease, insect resistance, restoration of male fertility, modified fatty acid or carbohydrate metabolism, and enhanced nutritional quality. These comprise genes generally inherited through the nucleus. Direct selection or screening may be applied where the single locus (e.g. allele) acts in a dominant fashion. For example, when selecting for a dominant allele providing resistance to a bacterial disease, the progeny of the initial cross can be inoculated with bacteria prior to the backcrossing. The inoculation then eliminates those plants which do not have the resistance, and only those plants which have the resistance allele are used in the subsequent backcross. This process is then repeated for all additional backcross generations. Although backcrossing methods are simplified when the characteristic being transferred is a dominant allele, recessive, co-dominant and quantitative alleles may also be transferred. In this instance, it may be necessary to introduce a test of the progeny to determine if the desired locus has been successfully transferred. In the case where the non-recurrent variety was not homozygous, the F1 progeny would not be equivalent. F1 plants having the desired genotype at the locus of interest could be phenotypically selected if the corresponding trait was phenotypically detectable in a heterozygous or hemizygous state. In the case where a recessive allele is to be transferred and the corresponding trait is not phenotypically detectable in the heterozygous of hemizygous state, the resultant progeny can be selfed, or crossed back to the donor to create a segregating population for selection purposes. Non-phenotypic tests may also be employed. Selected progeny from the segregating population can then be crossed to the recurrent parent to make the first backcross generation (BC1). Molecular markers may also be used to aid in the identification of the plants containing both a desired trait and having recovered a high percentage of the recurrent parent's genetic complement. Selection of onion plants for breeding is not necessarily dependent on the phenotype of a plant and instead can be based on genetic investigations. For example, one can utilize a suitable genetic marker which is closely genetically linked to a trait of interest. One of these markers can be used to identify the presence or absence of a trait in the offspring of a particular cross, and can be used in selection of progeny for continued breeding. This technique is commonly referred to as marker assisted selection. Any other type of genetic marker or other assay that is able to identify the relative presence or absence of a trait of interest in a plant can also be useful for breeding purposes. Procedures for marker assisted selection applicable to the breeding of onion are well known in the art. Such methods will be of particular utility in the case of recessive traits and variable phenotypes, or where conventional assays may be more expensive, time consuming or otherwise disadvantageous. Types of genetic markers which could be used in accordance with the invention include, but are not necessarily limited to, Simple Sequence Length Polymorphisms (SSLPs), Simple Sequence Repeats (SSR), Randomly Amplified Polymorphic DNAs (RAPDs), DNA Amplification Fingerprinting (DAF), Sequence Characterized Amplified Regions (SCARs), Arbitrary Primed Polymerase Chain Reaction (AP-PCR), Amplified Fragment Length Polymorphisms (AFLPs), and Single Nucleotide Polymorphisms (SNPs). Onion varieties can also be developed from more than two parents. The technique, known as modified backcrossing, uses different recurrent parents during the backcrossing. Modified backcrossing may be used to replace the original recurrent parent with a variety having certain more desirable characteristics or multiple parents may be used to obtain different desirable characteristics from each. The varieties and varieties of the present invention are particularly well suited for the development of new varieties or varieties based on the elite nature of the genetic background of the variety. In selecting a second plant to cross with DULCIANA for the purpose of developing novel onion varieties, it will typically be preferred to choose those plants that either themselves exhibit one or more selected desirable characteristics or that exhibit the desired characteristic(s) when in hybrid combination. Examples of desirable characteristics may include, but are not limited to herbicide tolerance, pathogen resistance (e.g., insect resistance, nematode resistance, resistance to bacterial, fungal, and viral disease), male fertility, improved harvest characteristics, enhanced nutritional quality, increased antioxidant content, improved processing characteristics, high yield, improved characteristics related to the bulb flavor, texture, size, shape, durability, shelf life, and yield, increased soluble solids content, uniform ripening, delayed or early ripening, adaptability for soil conditions, and adaptability for climate conditions. Of course, certain traits, such as disease and pest resistance, and high yield are of interest in any type of onion variety or variety. Plants of the Invention Derived by Genetic Engineering Many useful traits that can be introduced by backcrossing, as well as directly into a plant, are those that are introduced by genetic transformation techniques. Genetic transformation may therefore be used to insert a selected transgene into the onion variety of the invention or may, alternatively, be used for the preparation of varieties containing transgenes that can be subsequently transferred to the variety of interest by crossing. Methods for the transformation of plants, including tomato, are well known to those of skill in the art. Techniques which may be employed for the genetic transformation of onion include, but are not limited to, electroporation, microprojectile bombardment, Agrobacterium -mediated transformation, pollen-mediated transformation, and direct DNA uptake by protoplasts. To effect transformation by electroporation, one may employ either friable tissues, such as a suspension culture of cells or embryogenic callus or alternatively one may transform immature embryos or other organized tissue directly. In this technique, one would partially degrade the cell walls of the chosen cells by exposing them to pectin-degrading enzymes (pectolyases) or mechanically wound tissues in a controlled manner. To effect pollen-mediated transformation, one may apply pollen pretreated with DNA to the female reproduction parts of onion plants for pollination. A pollen-mediated method for the transformation of onion is disclosed in U.S. Pat. No. 6,806,399. A particularly efficient method for delivering transforming DNA segments to plant cells is microprojectile bombardment. In this method, particles are coated with nucleic acids and delivered into cells by a propelling force. Exemplary particles include those comprised of tungsten, platinum, and preferably, gold. For the bombardment, cells in suspension are concentrated on filters or solid culture medium. Alternatively, immature embryos or other target cells may be arranged on solid culture medium. The cells to be bombarded are positioned at an appropriate distance below the macroprojectile stopping plate. An illustrative embodiment of a method for delivering DNA into plant cells by acceleration is the BIOLISTICS Particle Delivery System, which can be used to propel particles coated with DNA or cells through a screen, such as a stainless steel or Nytex screen, onto a surface covered with target onion-cells. The screen disperses the particles so that they are not delivered to the recipient cells in large aggregates. It is believed that a screen intervening between the projectile apparatus and the cells to be bombarded reduces the size of projectiles aggregate and may contribute to a higher frequency of transformation by reducing the damage inflicted on the recipient cells by projectiles that are too large. Microprojectile bombardment techniques are widely applicable, and may be used to transform virtually any plant species. Agrobacterium -mediated transfer is another widely applicable system for introducing gene loci into plant cells. An advantage of the technique is that DNA can be introduced into whole plant tissues, thereby bypassing the need for regeneration of an intact plant from a protoplast. Modern Agrobacterium transformation vectors are capable of replication in E. coli as well as Agrobacterium , allowing for convenient manipulations. Moreover, recent technological advances in vectors for Agrobacterium -mediated gene transfer have improved the arrangement of genes and restriction sites in the vectors to facilitate the construction of vectors capable of expressing various polypeptide coding genes. The vectors described have convenient multi-linker regions flanked by a promoter and a polyadenylation site for direct expression of inserted polypeptide coding genes. Additionally, Agrobacterium containing both armed and disarmed Ti genes can be used for transformation. In those plant species where Agrobacterium -mediated transformation is efficient, it is the method of choice because of the facile and defined nature of the gene locus transfer. The use of Agrobacterium -mediated plant integrating vectors to introduce DNA into plant cells is well known in the art (see, e.g., U.S. Pat. No. 5,563,055). Transformation of plant protoplasts also can be achieved using methods based on calcium phosphate precipitation, polyethylene glycol treatment, electroporation, and combinations of these treatments which are well known in the art. Transformation of plants and expression of foreign genetic elements is exemplified in Choi et al. (1994), and Ellul et al. (2003). A number of promoters have utility for plant gene expression for any gene of interest including but not limited to selectable markers, scoreable markers, genes for pest tolerance, disease resistance, nutritional enhancements and any other gene of agronomic interest. Examples of constitutive promoters useful for onion plant gene expression include, but are not limited to, the cauliflower mosaic virus (CaMV) P-35S promoter, which confers constitutive, high-level expression in most plant tissues, including monocots; a tandemly, partially duplicated version of the CaMV 35S promoter, the enhanced 35S promoter (P-e35S) the nopaline synthase promoter, the octopine synthase promoter; and the figwort mosaic virus (P-FMV) promoter (see, e.g., U.S. Pat. No. 5,378,619) and an enhanced version of the FMV promoter (P-eFMV) where the promoter sequence of P-FMV is duplicated in tandem, the cauliflower mosaic virus 19S promoter, a sugarcane bacilliform virus promoter, a commelina yellow mottle virus promoter, and other plant DNA virus promoters known to express in plant cells. A variety of plant gene promoters that are regulated in response to environmental, hormonal, chemical, and/or developmental signals can be used for expression of an operably linked gene in plant cells, including promoters regulated by (1) heat, (2) light (e.g., pea rbcS-3A promoter; maize rbcS promoter; or chlorophyll a/b-binding protein promoter), (3) hormones, such as abscisic acid, (4) wounding; or (5) chemicals such as methyl jasmonate, salicylic acid, or Safener. It may also be advantageous to employ organ-specific promoters. Exemplary nucleic acids which may be introduced to the onionvarieties of this invention include, for example, DNA sequences or genes from another species, or even genes or sequences which originate with or are present in the same species, but are incorporated into recipient cells by genetic engineering methods rather than classical reproduction or breeding techniques. However, the term “exogenous” is also intended to refer to genes that are not normally present in the cell being transformed, or perhaps simply not present in the form, structure, etc., as found in the transforming DNA segment or gene, or genes which are normally present and that one desires to express in a manner that differs from the natural expression pattern, e.g., to over-express. Thus, the term “exogenous” gene or DNA is intended to refer to any gene or DNA segment that is introduced into a recipient cell, regardless of whether a similar gene may already be present in such a cell. The type of DNA included in the exogenous DNA can include DNA which is already present in the plant cell, DNA from another plant, DNA from a different organism, or a DNA generated externally, such as a DNA sequence containing an antisense message of a gene, or a DNA sequence encoding a synthetic or modified version of a gene. Many hundreds if not thousands of different genes are known and could potentially be introduced into an onion plant according to the invention. Non-limiting examples of particular genes and corresponding phenotypes one may choose to introduce into an onion plant include one or more genes for insect tolerance, such as a Bacillus thuringiensis (B.t.) gene, pest tolerance such as genes for fungal disease control, herbicide tolerance such as genes conferring glyphosate tolerance, and genes for quality improvements such as yield, nutritional enhancements, environmental or stress tolerances, or any desirable changes in plant physiology, growth, development, morphology or plant product(s). For example, structural genes would include any gene that confers insect tolerance including but not limited to a Bacillus insect control protein gene as described in WO 99/31248, herein incorporated by reference in its entirety, U.S. Pat. No. 5,689,052, herein incorporated by reference in its entirety, U.S. Pat. No. 5,500,365 and U.S. Pat. No. 5,880,275, herein incorporated by reference it their entirety. In another embodiment, the structural gene can confer tolerance to the herbicide glyphosate as conferred by genes including, but not limited to Agrobacterium strain CP4 glyphosate resistant EPSPS gene (aroA:CP4) as described in U.S. Pat. No. 5,633,435, herein incorporated by reference in its entirety, or glyphosate oxidoreductase gene (GOX) as described in U.S. Pat. No. 5,463,175, herein incorporated by reference in its entirety. Alternatively, the DNA coding sequences can affect these phenotypes by encoding a non-translatable RNA molecule that causes the targeted inhibition of expression of an endogenous gene, for example via antisense- or cosuppression-mediated mechanisms. The RNA could also be a catalytic RNA molecule (e.g., a ribozyme) engineered to cleave a desired endogenous mRNA product. Thus, any gene which produces a protein or mRNA which expresses a phenotype or morphology change of interest is useful for the practice of the present invention. Deposit Information A total of 2500 seeds of the hybrid variety DULCIANA were deposited according to the Budapest Treaty by Nunhems B. V. on Dec. 15, 2016, at the NCIMB Ltd., Ferguson Building, Craibstone Estate, Bucksburn, Aberdeen AB21 9YA, United Kingdom (NCIMB). The deposit has been assigned Accession Number NCIMB 42706. A deposit of DULCIANA and of the male and female parent line is also maintained at Nunhems B. V. Access to the deposit will be available during the pendency of this application to persons determined by the Director of the U.S. Patent Office to be entitled thereto upon request. Subject to 37 C.F.R. §1.808(b), all restrictions imposed by the depositor on the availability to the public of the deposited material will be irrevocably removed upon the granting of the patent. The deposit will be maintained for a period of 30 years, or 5 years after the most recent request, or for the enforceable life of the patent whichever is longer, and will be replaced if it ever becomes nonviable during that period. Applicant does not waive any rights granted under this patent on this application or under the Plant Variety Protection Act (7 USC 2321 et seq.). Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity and understanding, it will be obvious that certain changes and modifications may be practiced within the scope of the invention, as limited only by the scope of the appended claims. All references cited herein are hereby expressly incorporated herein by reference. Characteristics of Dulciana SERENGETI is considered to be the most similar variety to DULCIANA. SERENGETI is a commercial variety from Nunhems. In Table 1 a comparison between DULCIANA and SERENGETI is shown based on a trial in the USA. Trial location: Bakersfield, (Shafter Rd), Calif., USA (coordinates: 35°13′54″ N, 118°54′12″ W). Planting date: Dec. 16, 2011; evaluation date Mar. 15, 2012. Two replications of 15 plants each, from which 20 plants or plant parts were randomly selected, were used to measure characteristics. In Table 1 the USDA descriptors of DULCIANA (this application) and reference SERENGETI (commercial variety) are listed. In accordance with one aspect of the present invention, there is provided a plant having the physiological and morphological characteristics of onion variety DULCIANA. A description of the physiological and morphological characteristics of onion variety DULCIANA is presented in Table 1. TABLE 1 Comparison between values* of DULCIANA and SERENGETI Application Comparison Variety Variety Descriptor DULCIANA SERENGETI 1. TYPE: 1 = Bulb 2 = Bunching 1 1 1 = short day; 2 = long day 1 1 Adaptation range 35N to 35S 35N to 35S Degree mean latitude Maturity (days) 1 2 1 = early (75-90); 2 = medium (100-120); 3 = late (>130) 2. PLANT: Height above soil line to highest point of any foliage 63 cm 73 cm Shorter than comparison variety 10 cm — 1 = erected (Spartam Gem); 1 2 2 = intermediate; 3 = floppy (Epoch) 3. LEAF: Length (before maturity yellowing begins) 46 cm 60 cm Width 21 mm 27 mm Thickness (at mid-length of longest leaf) 1.7 mm 2.2 mm Color: 2 2 1 = light green (Early Grano); 2 = medium green (Yellow Bermuda); 3 = blue green (Australian Brown U.C. No. 1) Color Chart Name RHS Yellow Green RHS Yellow Green Group Group Color Chart Code 147B 147B Bloom: 2 2 1 = none-glossy; 2 = light (Early Grano); 3 = medium (Crystal Wax); 4 = heavy (California Early Red) 4. SHEATH: Column length (height from soil line to base of lowest 46 mm 88 mm succulent leaf) 5. INFLORESCENCE: Pollen viability 1 = sterile; 2 = fertile 2 2 6. BULB: Size (harvested) 3 3 1 = small (Red Creol); 2 = medium (Australian Brown U.C. No. 1); 3 = large (Early Grano) Shape ¼ (between a ¼ (between a 1 = Globe (White Sweet Spanish) globe and a top globe and a top 2 = Deep Globe (Abundance) shape) shape) 3 = Flt. Globe (Australian Brn. U.C. No. 1) 4 = Top Shape (Texas Grano 502) 5 = Deep Flat (Granex) 6 = Thick Flat (Ebenezer) 7 = Flat (Crystal Wax) 8 = Torpedo-Long Oval (Italian Red) Height 7.2 cm 7.7 cm Diameter 8.3 cm 8.4 cm Shape Index 0.87 0.92 1 = invaginate; 2 = evaginate 2 2 Color (skin): 04 05 01 = Brown (Australian Brn. U.C. No. 1) (RHS (RHS 02 = Purplish Red (Italian Red) Orange-White Greyed-Yellow 03 = Buff Red (Red Creole) 159C + 162C + 04 = Pinkish Yellow (Ebenezer) Greyed-Yellow Greyed-Orange 05 = Brownish Yellow (Mt. Danvers) 160C) 163A) 06 = Deep Yellow (Brigham Yellow Globe) 07 = Medium Yellow (Early Yellow Globe) 08 = Pale Yellow (Yellow Bermuda) 09 = White (White Sweet Spanish) 10 = Other (Specify) Color (interior) 5 5 1 = Pink; 2 = Red; 3 = Purplish Red; 4 = White; (RHS (RHS 5 = Cream; 6 = Light Green-Yellow; 7 = Dark Green- White White Yellow 155A) 155B) Weight** 241 grams 287 grams Scales: 1 1 1 = Few (Crystal Wax) 2 = Medium (Australian Brown U.C. No. 1) 3 = Many (Sweet Spanish) Scales: 3 3 1 = Thick (Australian Brown U.C. No. 1) 2 = Medium (Red Creole) 3 = Thin (Crystal Wax) Scale retention: 3 3 1 = Very Good (Australian Brn. U.S. No. 1) 2 = Good (Ebenezer) 3 = Fair (Red Wethersfield) 4 = Poor (Crystal Wax) Pugence: 1 1 1 = Mild (Early Grano) 2 = Medium (Crystal Wax) 3 = Strong (White Creole) Storage: 3 3 1 = Good (Ebenezer) 2 = Fair (Yellow Globe Danvers) 3 = Poor (Crystal Wax) 7. DISEASE RESISTANCE 0 = not tested; 1 = susceptible 2 = resistant Black Mold 0 0 Neck Mold 0 0 Puple Blotch 0 0 Smut 0 0 Mildew 0 0 Pink root 2 2 Smudge 0 0 Yellow dwarf 0 0 8. INSECT RESISTANT 0 = not tested; 1 = susceptible 2 = resistant Thrip 0 0 Other (specify) Indicate a variety that most closely resembles that SERENGETI DULCIANA submitted: Leaf height (mm) Leaf color Leaf bloom/wax Flower stalk Maturity at same location (D days) Flower ball Bulb color Bulb size Bulb shape *These are typical values. Values may vary due to environment. Other values that are substantially equivalent are also within the scope of the invention. **No USDA descriptor As described above, variety DULCIANA exhibits desirable agronomic traits, including: 1) a pinkish yellow bulb skin color, e.g. RHS Orange-White Group 159A and Greyed-Yellow Group 160C, whereas SERENGETI has a brownish yellow bulb skin color, e.g. RHS Greyed-Yellow Group 162C and Greyed-Orange Group 163A; 2) a (average) bulb height that is at least about 4%, or preferably about 4.5%, 5%, 5.5%, 6%, or even about 6.5% smaller than the bulb height of SERENGETI; 3) a (average) column height of sheath (height form soil line to base of lowest succulent leaf) that is at least about 35%, or preferably about 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, or even about 47.7% smaller than the column height of sheath of SERENGETI; 4) a (average) plant height above soil line to highest point of any foliage that is at least about 7.5%, or preferably about 8%, 9%, 10%, 11%, 12%, 13%, or even about 13.7% smaller than the plant height above soil line to highest point of any foliage of SERENGETI; 5) early maturity (75-90 days), whereas SERENGETI has medium maturity (100-120 days). In a further embodiment, variety DULCIANA exhibits other desirable agronomic traits, including: 6) a (average) length of leaf (before maturity yellowing begins that is at least about 15%, or preferably about 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, or even about 23.3% smaller than the leaf length of SERENGETI; 7) a (average) leaf width that is at least about 15%, or preferably about 16%, 17%, 18%, 19%, 20%, 21%, 22%, or even about 22.2% smaller than the leaf width of SERENGETI; 8) a (average) thickness of leaf (at mid-length of longest leaf) that is at least about 15%, or preferably about 16%, 17%, 18%, 19%, 20%, 21%, 22%, or even about 22.7% smaller than the leaf thickness of SERENGETI; 9) a cream colored bulb interior, e.g. RHS White Group 155A, whereas SERENGETI has a lighter cream color, e.g. RHS White Group 155B; 10) a (average) bulb weight that is at least about 10%, or preferably about 11%, 12%, 13%, 14%, 15%, or even about 16% smaller than the bulb weight of SERENGETI. REFERENCES The following references, to the extent that they provide exemplary procedural or other details supplementary to those set forth herein, are specifically incorporated herein by reference: U.S. Pat. No. 5,463,175 U.S. Pat. No. 5,500,365 U.S. Pat. No. 5,563,055 U.S. Pat. No. 5,633,435 U.S. Pat. No. 5,689,052 U.S. Pat. No. 5,880,275 U.S. Pat. No. 5,378,619 U.S. Pat. No. 6,806,399 WO 99/31248 EP 0 534 858 Choi et al., Plant Cell Rep., 13: 344-348, 1994. Ellul et al., Theor. Appl. Genet., 107:462-469, 2003.
The invention relates to the field of Allium in particular to a new variety of Allium cepa L. designated DULCIANA plants, seeds and bulbs thereof as well as plant breeding methods involving DULCIANA.
82,056
BACKGROUND It has been known that two-handled shovels, particularly snow shovels, provide a second handle that allows the user to lift without bending at the waist and to therefore use leg muscles rather than back muscles. As a result, considerable strain and possible injuries are avoided. Despite the considerable health advantages of a two-handled shovel, and the stress and strain that may be avoided by its use, few two-handled shovels are actually used and sold on the commercial market. One reason may be that the public still remains generally ignorant of the advantages of a second handle, but other reasons include the unwillingness of the public to buy tools with non-removable second handles or to buy new tools with second handles to replace existing tools without second handles. Additionally, the inability of most second handles to adjust to fit both the user and the job makes them only marginally better than no second handle at all. Two-handled shovels that have been disclosed to date generally provide advantages to the user, but frequently present problems not present in an unmodified shovel. Often the construction of two-handled shovels tends to weaken the shovel itself, by requiring that holes be drilled, or other modifications made, in the handle shaft to attach the second handle. Other two-handled shovels tend to weigh substantially more than before modified, and most make no provision for the user to use the shovel in its unmodified manner, if desired. Often either no provision is made to accommodate left-handed users, or the second handle may be a compromise between left- and right-handed users, and not particularly well-suited for use by either. Some other two-handled shovel designs fail to provide a means for the user to adjust the location of attachment of the second shovel up or down the primary handle of the shovel, to accommodate the height of the user. For the foregoing reasons, there is a need for an attachment, adaptable for use with any existing shovel, snow shovel, rake, hoe, pitchfork or other tool already owned by a user, that may be used to provide a second handle. The attachment should be removable, and easily installed on a second tool. The attachment should provide a means to adjust between left-handed, right-handed and neutral positions. The attachment should be adjustable up and down the tool's handle shaft between locations appropriate to tall or short users. The attachment should be adjustable between tools having a narrow handle shaft diameter and tools having a wider handle shaft diameter. The attachment should allow adjustment of the angle between the second handle and the primary handle. The attachment should be extremely strong, and inexpensive to manufacture. SUMMARY The present invention is directed to an apparatus that satisfies the above needs. A novel second handle attachment is disclosed that is usable with any tool, such as a snow shovel, shovel, or pitch fork, having a handle shaft. The second handle attachment of the present invention provides: (a) Left and right clamshell brackets, each bracket having: (a) A notch structure. When the brackets are put face-to-face the notch structures form an opening that wraps around a tool's handle shaft, and may be clamped against that shaft. (b) A pivot hole. When the brackets are put face-to-face the pivot holes line up, and support a pivot bolt. (c) A locking pin hole. The brackets' locking pin holes also line up and support a locking pin. (b) A second handle having a body portion and a grip portion, the grip portion typically with a grip cover. The second handle also provides a pivot hole and a locking pin hole. The second handle may be pivoted freely on the pivot bolt between the clamshell brackets until the locking pin is installed. (c) A locking pin, which is carried in the clamshell brackets' pin holes and by the locking pin hole in the second handle. When the locking pin is installed, the second handle is prevented from pivoting with respect to the brackets. (d) Bolts to bias the clamshell brackets together, thus squeezing the shovel's (or other tool's) handle shaft, and fixing the second handle attachment onto the shovel. A preferred version of the second handle attachment of the present invention also provides: (a) Left and right clamshell brackets having either a V-shaped or a semicircular-shaped notch structure, so that when the brackets are face-to-face, the opening between the brackets will be approximately square or approximately round. (b) A cotter pin hole in the locking pin, and a cotter pin to pass through that hole. The locking pin prevents rotation of the second handle. The cotter pin prevents the locking pin from becoming dislodged. (c) A bushing to be used to increase the diameter of a tool's handle shaft having a smaller diameter. The bushing provides a hollow, cylindrical body having a lengthwise slit, and may be flexed to adapt to various smaller diameter tool handle shafts. (d) A spacer, having a hollow, cylindrical body, incrementally longer than the thickness of the second handle. The spacer is used on one of the bolts biasing the clamshells together, to prevent the clamshells from clamping down on the end of the second handle, in the area of the second handle pivot hole and locking pin hole. Thus the spacer allows the second handle to pivot between the clamshell brackets (when the locking pin is removed). It is therefore a primary advantage of the present invention to provide a novel second handle attachment that is adaptable to a variety of tools having handle shafts such as shovels, rakes, snow shovels, pitch forks, hoes and long handled tree trimmers or window washing tools. Another advantage of the present invention is to provide a second handle attachment that allows use of a shovel or other tool without bending over, and therefore reduces lower back strain and related problems. Another advantage of the present invention is to provide a second handle attachment that allows use with existing tools, already owned by the user. Another advantage of the present invention is to provide a second handle attachment that is attachable to long handled tree trimming and window washing equipment that allows the user to obtain the leverage needed to better control such equipment. Another advantage of the present invention is to provide a second handle attachment that adjusts up and down the handle shaft of the tool, to allow adjustment for the height of the user. Another advantage of the present invention is to provide a second handle attachment that adjusts in a rotary manner about the handle shaft of the tool, to allow adjustment for left-handed, right-handed or ambidextrous users. Another advantage of the present invention is to provide a second handle attachment having a second handle that pivots so that the angle between the second handle and the handle shaft of the tool may be fixed at a desired position. Another advantage of the present invention is to provide a second handle attachment having one or more bushings that can be used to adapt the handle shaft of the tool to a diameter appropriate for use by the second handle attachment. A still further advantage of the present invention is to provide a second handle attachment that is economical to manufacture and of extremely rugged construction. DRAWINGS These and other features, aspects, and advantages of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings where: FIG. 1 shows a side view of the second handle attachment of the invention attached to a portion of a handle shaft of a tool; FIGS. 2A, 2B and 2C show overhead views of the second handle attachment attached to a snow shovel, illustrating the ability of the second handle attachment to rotate between left- and right-handed positions; FIGS. 3A, 3B, and 3C show side views of the second handle attachment attached to a snow shovel, illustrating the ability of the second handle attachment to pivot to adjust the angle of the second handle with respect to the handle shaft of the tool; FIGS 4A and 4B show views of the second handle attachment attached to a snow shovel, illustrating the ability of the second handle attachment to be adjusted up and down the handle shaft of a tool, to compensate for users' different heights; FIGS. 5A and 5B show side views of the second handle attachment attached to a snow shovel, illustrating how longer or shorter second handle bodies may create different versions of the second handle attachment of the invention; FIGS. 6A and 6B show top views of the second handle attachment attached to a snow shovel, illustrating a further means by which the second handle attachment of the invention may be adjusted to compensate for left- or right-handed users, and also illustrating a snow shovel with a D-shaped handle; FIGS. 7A , 7B and 7C are sectional views of the version of the invention of FIG. 1, taken on the 7--7 line, having the second handle and bolts removed for clarity, illustrating the use of a bushing to adjust for tool handle shafts of differing diameters; FIGS. 8A and 8B are side views of left and right clamshell brackets of a second version of the invention, having semicircularly shaped notch structures; FIGS. 9A and 9B are top views of the clamshell brackets of FIG. 8, showing how the semicircularly shaped notch structures form a generally circular opening when the brackets are arrayed face-to-face; FIG. 10 show an exploded top view of the second handle attachment; FIG. 11 shows a side view of the cotter pin used to secure the locking pin; FIGS. 12A and 12B show side views of the left and right clamshell brackets of the version of the invention of FIG. 1, having V-shaped notch structures; FIG. 13 shows a side view of the second handle without a handle grip cover, FIG. 14 shows a side view of the second handle attachment; FIG. 15 shows a perspective view of the bushing of FIG. 7A; and FIG. 16 shows a perspective view of the spacer seen in FIGS. 7 and 10. DESCRIPTION As seen in particular in FIGS. 1 and 10, the second handle attachment of the present invention provides a handle structure that is attachable to the handle of a shovel, snow shovel, rake hoe, pitch fork or other similar tool. The second handle attachment provides left and right clamshell brackets 20 which grip a handle shaft 101 of a tool 100. A second handle 40 is held between the clamshell brackets and may be pivoted between three positions, each having a different angle with respect to the handle shaft 101, where the handle 40 may be locked into place by means of a locking pin 60. FIG. 1 shows a side view of the second handle attachment carried by a tool 100 having a handle shaft 101. FIG. 10 shows an exploded view of the second handle attachment, to better show the relationship of the various components. As seen in FIGS. 7 and 12, a first version of the invention provides clamshell brackets 20 having a generally square opening 21 that is formed by a V-shaped notch structure 34. A second version of the invention provides clamshell brackets 20 having a generally round opening 36 that is formed by a semicircular notch structure 35, and is seen in FIGS. 8 and 9. The clamshell brackets of both versions of the invention are made from 3/16" thick zinc plated steel having a width of 1.5 inches and a length, before bending the notch structure 34, 35, of approximately 5 inches. The square opening 21, formed by the V-shaped notch structure 34, is best seen in FIGS. 7A, 7B, and 7C, where the opening 21 is formed between left and right clamshell brackets when they are face-to-face, as they are in these figures. A right clamshell bracket 20, having a V-shaped notch structure 34, is seen in FIG. 12A. A V-shaped notch structure 34 provides an inner angle portion 28 and an outer angle portion 29. A pivot hole 22, sized to accept a 5/16 inch bolt, is an equal distance from three locking pin holes 23, 24, and 25, which are sized to accept a 1/4 inch locking pin. Pin hole 23 is positioned, as seen in FIG. 12A, so that when second handle 40 is attached to both pivot hole 22 and locking pin hole 23 the handle is perpendicular to the bracket 20, and parallel to a handle shaft 101 (not shown) gripped by the bracket. Similarly, locking pin hole 24 is positioned so that when second handle 40 is attached to both pivot hole 22 and pin hole 24 the handle is at 45 degrees to the bracket 20. And finally, locking pin hole 25 is positioned, as seen in FIG. 12A, so that when second handle 40 is attached to both pivot hole 22 and pin hole 25 the handle is in-line with the bracket 20, and perpendicular to a handle shaft (not shown) gripped by the bracket. Inner securing bolt hole 26 and outer securing bolt hole 27 are located on either side of V-shaped notch structure 34 and are sized to accept 5/16 inch bolts. A left clamshell bracket 20, having a V-shaped notch structure 34, is seen in FIG. 12B. This bracket is the mirror image of the right clamshell bracket 20 of FIG. 12A having a V-shaped notch structure. A right clamshell bracket 20, having a semicircularly shaped notch structure 35, is seen in FIG. 8A. This version of the invention differs only from the V-shaped notch version in that the notch is semicircular. A left clamshell bracket 20, having a semicircularly shaped notch structure 35, is seen in FIG. 8B. This bracket is the mirror image of the right clamshell bracket 20 of FIG. 8A having a semicircular shaped notch structure. As seen in FIG. 10, the left and right clamshell brackets 20 are put together by means of nut and bolt pairs 90, or alternatively by a similar fastening device. The bolts used are 5/16 inch diameter bolts 1 13/8 inches long, having 18 threads per inch. The nuts used have a nylon bush locking mechanism. The bolts include a pivot bolt 91, a spacer bolt 92, and a tightening bolt 93. The pivot bolt 91 goes through pivot hole 45 of the second handle 40 and pivot holes 22 of the left and right brackets 20. The spacer bolt goes through the cylindrical spacer 94 and the inner securing bolt hole 26 of each bracket 20. The tightening bolt 93 goes through outer securing bolt hole 27 of each bracket 20, and is the bolt primarily used to tighten the brackets 20 about the handle shaft 101 of a tool 100, The second handle 40 is seen in top view in FIG. 10, and in side view in FIGS. 13 and 14. The handle 40 is made from approximately 16 inches of steel having a 0.5 inch square cross section. A comparison of the views of the handle seen in FIGS. 10 and 13 reveal that the handle 40 is generally constructed in one plane. As seen in FIG. 10, the second handle 40 pivots between the clamshell brackets about pivot bolt/nut 91. The second handle 40 provides a handle grip portion 47 and a body portion 54. The body 54 provides a straight end portion 41, an angled bend 43, an angled middle portion 42, and a 90 plus degree bend 44. A locking pin hole 46 is drilled near the end of the straight portion 41, as seen in FIG. 13, and a pivot hole 45 is drilled between the locking pin hole 46 and the end 55 of the handle 40. The second handle 40 may be fixed in place, to prevent rotation. As seen in FIG. 10, a locking pin 60, having a head, a cylindrical body, and a cotter pin hole 61 in the body opposite the head, is sized to fit into any of the locking pin holes 23, 24, 25 in the brackets 20, and through the locking pin hole 46 in the second handle 40. A cotter pin 70, seen in FIGS. 11 and 14, is used to keep the locking pin 60 in place. A plastic or rubber grip cover 48, similar to those used on bicycle handlebars, is put on the grip portion 47 of the second handle 40. The grip cover 48 provides a body 50, having an open end 49 and a closed end 51. The dosed end 51 provides an air hole 53 so that air may be exhausted when the grip is installed. Typically, however, grip cover 48 will be cylindrical in design, and will not need the air hole when installed over the handle grip portion 47, which is one-half inch square in cross section. A tread pattern 52 is typically provided, to increase the user's frictional grip on the second handle 40. The grip cover 48 is typically put on the steel handle grip portion 47 by first applying an evaporative rubber or plastic lubricant. Next, an air ram tool is used to force the grip cover 48 over the handle grip portion 47. Alternatively, a rubber mallet may be used to install the grip covers. A spacer 94 is used to keep the spacer nut/bolt 92 from pinching the brackets 20 against the area about the pivot hole 45 of the straight portion 41 of the body 54 of the handle 40. As seen in FIG. 10, the length of the spacer is approximately equal to, or incrementally greater than, the width of the second handle 40. As seen in FIG. 16, the spacer is a short cylindrical tube. It is made of steel and is typically zinc plated to resist corrosion. To accommodate tools 100 having handle shafts 101 of differing diameters, bushings 80 are provided. A generally cylindrical bushing 83, having a lengthwise slit 81, is seen in FIG. 15, and in cross-section in FIG. 10. A half-cylindrical bushing 82 is seen in cross-section in FIG. 7C. Both bushings are typically made from pvc pipe having a schedule 40 thickness, although a variety of similar materials would serve adequately. The slit 81 in the bushing 83 allows the bushing to be adapted, by flexing it slightly, to handle shafts of differing cross-sections. The half-cylindrical bushing 82 increases the handle shaft 101 diameter somewhat less that the notched cylindrical bushing 83. To use the second handle attachment of the invention, the user must assemble the second handle attachment generally as seen in FIG. 10. Depending on whether the user is left- or right-handed, either of the configurations illustrated in FIGS. 6A or 6B may be preferable. These two figures differ in that the angled middle portion 42 of the second handle 40 is on the left in FIG. 6A, and on the right in FIG. 6B. Every individual user should decide which is preferable, and assemble the second handle 40 between the clamshell brackets 20 with the pivot bolt/nut 91 in the appropriate manner. The user must then evaluate the diameter of the handle shaft 101 of the tool 100 being used. If the handle shaft 101 is of larger diameter 102, such as seen in FIG. 7B, then no bushing is needed. If the handle shaft is of smaller diameter 103, such as seen in FIG. 7A, then a cylindrical bushing 83 should be placed over the handle shaft. If the handle diameter is of intermediate diameter 107, such as seen in FIG. 7C, then a half bushing 82 should be used. The bushing (if any) should be selected so that the handle shaft 101 may be held firmly between the clamshell brackets 20, when nut/bolt combinations 92, 93 are tightened. Spacer nut/bolt 92 tightens the brackets 20 against the spacer, while tightening nut/bolt 93 creates a highly frictional fit between the brackets and the handle shaft 101. If a D-shaped handle 106, such as the one seen in FIG. 6B is present, the user must actually remove the tightening nut/bolt 93 and separate the left and right clamshell brackets prior to mounting the brackets on the handle shaft 101. If no D-shaped handle is present, the bracket may be loosened slightly, and slipped over the end of the handle shaft 101. Referring to FIGS. 4A and 4B, the user must then slide the second handle attachment up and down the handle shaft 101, until it is a comfortable distance from the tool implement 104 (shovel, rake, hoe, etc.). Factors that may influence the decision on how far from the tool implement 104 the second handle attachment should be include the height of the user and the type of tool and use involved. Referring to FIGS. 2A, 2B and 2C, the user must determine the angle of rotation about the handle shaft 101 of the tool 100. The angle may be influenced by whether the user is left- or right-handed, and also by whether the user intends to switch hand positions during use. The top-view of the snow shovel of FIG. 2A shows the configuration appropriate to use by a user who intends to use his left hand on the second handle. The top-view of FIG. 2C would be appropriate for use of the right hand on the second handle. FIG. 2B would be appropriate if the user intends to switch hand positions during use. The user then tightens the bolts, thereby securing the second handle attachment to the tool's handle shaft. Referring to FIGS. 3A, 3B and 3C, the user may alter the angle of the second handle 40 with respect to the handle shaft 101. With the locking pin 60 removed, the user simply pivots the handle 40 until the locking pin hole 46 lines up with either locking pin hole 23, 74, or 25. The user then inserts the locking pin 60 into the appropriate locking pin hole until the cotter pin hole 61 appears on the other side. The user then inserts the cotter pin 70 into the cotter pin hole 61. Alternatively, the second handle attachment may be used without locking the handle in place, although this is not recommended. Once attached, the user holds the grip cover 48 with the hand that would otherwise be used to grip the handle shaft nearer the tool implement. In the case of a shovel or a snow shovel, the user lifts up on the second handle attachment. In the case of a rake or hoe, the user pushes down. In either case, the user does not bend over, as would be the case without the second handle attachment. The previously described versions of the present invention have many advantages, including the ability to attach the second handle attachment to the handle shaft of any tool. The second handle attachment will adjust for differing diameters of handle shafts. It will adjust up or down the handle shaft to accommodate the height of the user. It will rotate about the handle shaft to accommodate left- or right-handed users, or users who intend to alternate hands. The angle of the second handle to the handle shaft may also be adjusted. Although the present invention has been described in considerable detail and with reference to certain preferred versions, other versions are possible. For example a variety of opening shapes could be used (other than the generally square opening created by use of V-shaped notch structures and the generally circular opening created by the use of semicircular shaped notch structures) by means of differently shaped clamshell brackets. As seen in FIGS. 5A and 5B, a second handle 40 having a longer or shorter body 54 may be used. Also, locking pin 60 could itself be locked into place by a structure other than cotter pin 70. For example, the locking pin could be replaced by a nut and bolt. FIG. 5 also illustrates, in a general sense, that alterations of the relative dimensions of the second handle attachment may be made, if desired or needed. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained here.
A second handle attachment for a tool having a handle shaft, such as a shovel, is disclosed. The second handle attachment provides a grip portion that a user may grab so that the shovel may be used without the user bending over. In this manner, back injury and strain is reduced. The second handle attachment provides two clamshell brackets which are bolted into a rigid relationship with the tool's handle shaft. The attachment also provides a rotating second handle that may be locked into place at any of several angular relationships with the tool handle shaft. The second handle provides a grip portion that is typically covered by a plastic or rubber grip cover. The second handle attachment may be transferred among any type of shovel, rake, snow shovel, hoe or pitch fork. It may be adjusted up or down the handle shaft, to accommodate taller or shorter users. It may be rotated to accommodate right-handed, left-handed or ambidextrous users. A bushing is provided so that the second handle attachment may be used with a light weight rake having a smaller diameter handle shaft, as well as a shovel having a larger diameter handle shaft.
23,506
FIELD OF TECHNOLOGY The present disclosure relates to a method for controlling the pump power of an optical amplifier. BACKGROUND Wavelength Multiplex Division (WDM) technology) offers the option of connecting transmitters and receivers in different places directly via optical paths of a network, without an electro-optical conversion being required at nodes. In the future it will also be possible to set up and clear down optical paths as required with the aid of optical switching matrices. Compared to the current prior art, major cost savings can be achieved without having to compromise the flexibility of the connections. However the dropping and adding of transmitted signals in channels of a multiplex transmission system causes strong variations in power on individual link sections. To avoid bit errors at the end of the link the amplifier gain for the channels continuing to be transmitted or those being added may not change. FIG. 1 shows the average gain G of all channels over time for an individual amplifier stage and for two different cases, in which case it has been assumed that at time zero the input power reduces by 19 dB by dropping channels. If the pump power is kept constant (see the solid curve), the gain G of 20 dB before the dropping process increases to a constant value of 30 dB after the dropping process. A further curve drawn in this Figure shows, by way of illustration, the timing curve when using a simple integral controller which ensures that the average gain after a synchronization process with a duration of over 20 ms again amounts to 20 dB. The overshoots and undershoots can be greatly reduced by more complex regulation, but cannot be completely eliminated. In a cascade of amplifiers the end result can thus be an accumulation of power variations and thus bit errors or even destruction of the receive diodes. Overshoots and undershoots can be almost completely eliminated if the pump power required after a change in the input signal to maintain the gain under stable conditions is already known at the time of the change of load at the input. The actual difficulty lies in calculating this pump power in advance with the highest possible accuracy. A simplest solution to this provides for choosing a linear approach for the required pump power as a function of the signal input power at the optical amplifier. This aspect is described in U.S. Pat No. 6,414,788 B1 and U.S. Pat. No. 6,341,034 B1, the contents of which are incorporated by reference in their entirety. In this case two constant parameters are employed. With this method however the following significant influencing variables are not taken into account: The required pump power not only depends on the input power but also on the gain of the relevant amplifier stage. Since the stage of an amplifier can exhibit very different gain values, depending on use and channel occupation, marked variations emerge which adversely affect the determination of the correct pump power to be set. No account is taken of the fact that the pump power required depends on the wavelength of the surviving channels in a drop process. This also applies to the so-called “gain ripple”. “Fitting parameters” for determining the pump power values to be set are defined at the start of operation, so that aging effects lead to increasing variations as the operating life increases. Non-linear effects in an amplification fiber of a fiber amplifier, such as “Excited State Absorption” in an Erbium-doped fiber of an EDFA (Erbium Doped Fiber Amplifier), continue to be ignored and thus lead to additional deviations. To take account of the spectral dependency it is proposed in document 6341034 that a spectral filter be fitted before an input monitor at the optical amplifier. The wavelength dependency of the method can thus be improved, if not eliminated entirely. Because of the high costs of components however this method is unlikely to be used. In U.S. Pat. No. 6,366,393, which is also incorporated by reference in its entirety as in the document previously mentioned, a control unit for the gain of an optical amplifier is presented which opts for a linear approach for the required pump power as a function of the signal input power at the optical amplifier. The error implied in this approach is correct by means of a correction loop which is located after the amplifier and contains a microprocessor. This correction does not include wavelength dependency, making the method slow and imprecise. In US Patent Publication 2003/0053200, which is also incorporated by reference in its entirety, the pump power of the optical amplifier is set using a feed forward control loop. In this case a small part of the WDM signal is routed through a filter of which the filter transfer function is adapted to the characteristics of the amplifier. The signal input power is weighted selectively by the filter as a function of the wavelength. The influence of the wavelengths with above-average effects on the decay rate of the amplifier energy level excited is increased or decreased in this case. The signal arrives at a photo detector after the filter which is connected to a control unit of the pump power of the amplifier. In US Patent Publication 2001/0043389, which is incorporated by reference in its entirety, the amplifier gain is controlled by means of a forward and backward loop. The forward loop (feed forward loop) controls the amplifier by means of a fast photo diode, which measures the input power. The backward loop regulates the amplifier gain slowly depending on the output power of the amplifier. The two loops are connected to one another for checking the pump laser unit. The gain of the amplifier is essentially set by the backward loop, whereas the forward loop includes the compensation of offsets in the gain curve of the optical amplifier. In U.S. Pat. No. 6,407,854, which is incorporated by reference in its entirety, a feed-forward control of an optical amplifier in a WDM system is presented. The pump power of the amplifier is set via a control unit which measures the input power of the amplifier and controls the current of the pump laser diodes as a function of the measurement level. In this case the electrical signal of the pump laser diodes can be changed by multiplication by a factor or by addition of an offset, to guarantee a gain curve of the amplifier which remains constant over the entire wavelength range. With this method synchronization processes of less than 200 μs are achieved. In “Superior high-speed automatic gain controlled erbium-doped fiber amplifier”, Nakaji H., Nakai Y., Shigematsu M and Nishimura M., Optical Fiber Technology 9 (2003), pp. 25-35, a method for suppressing cyclic gain variations over time in a surviving channel of a WDM during the adding or dropping of further channels of the WDM signal is described. An EDFA is used for amplification of the WDM signal which operates with a pump source at 980 nm or with a pump source at 1480 nm. When a pump laser in the wavelength range of 1480 nm is used and with an optimum setting of the control parameters for a specific application case overshoots during dropping of a channel can be almost completely avoided. By contrast, when a pump laser in the range of 980 nm is used a small overshoot occurs after dropping of channels. If the pump power is now reduced or adapted to a new value, not as assumed above at the point of switching, but somewhat earlier, e.g. by a delay element connected upstream from the amplifier, the overshoot when using a pump source at 980 nm can be almost completely eliminated. This method is based on the fact that the reduction of the output power (effect) is detected later than the reduction of the input power (cause), so that the gain control is made to think for a period corresponding to the delay that there is a strong increase in gain to which it reacts by reducing the pump power. Experimental gain measurements can be verified from this literature reference. In any event a very short duration overshoot continues to occur. This method, which is referred to below as the “feedback method” is well suited to laboratory experiments but can barely be used for commercial systems, since the optimal time delay depends on the number of surviving channels, no specification is known for predefining this optimum delay and the control parameters are only optimized for a specific event. In practice any given events, i.e. the dropping of a different number of channels for example, are taken into account. The time delay should be constantly recalculated and set for this, which would however be impossible or unrealizable in real time. Thus the wavelength-dependent gain curve experiences unavoidable variations for one or more surviving channels which adversely affect the broadband gain, in addition to the known timing variations of the channel-related gain. For these reasons this method is not suitable for current optical switching networks. SUMMARY Under an exemplary embodiment, a method and system is disclosed which guarantees the optimum control of the pump power of an optical amplifier for amplification of an optical multiplex signal with a number of channels, so that when the input or output power at the optical amplifier is changed, the wavelength-dependent gain curve for signals of active channels to be amplified is maintained. Starting from a stable state, which was set by regulation for example, especially of the corresponding pump power of an optical amplifier, with which an optical wavelength division multiplex signal with a number of channels is amplified and in which a change of the input power or output power of the wavelength division multiplex signal is detected, in accordance with the embodiment, after the change to the input power, a new value of the measured pump power is calculated and set so that the gain curve of the amplifier only changes minimally. The new pump power to be set can be computed shortly after the dropping or adding of active channels and still set in good time, since the gain of an EDFA remains quasi-constant as a function of the wavelength in a short period of time. A significant advantage of the disclosed method is to be seen in the fact that many significant influencing variables such as the current gain value, the wavelength dependency of active channels, aging effects and non-linear effects of the amplification are taken into account when calculating the new pump power to be set, so that a highly accurate determination of the optimum pump power is quickly undertaken and disruptive transients, i.e. amplitude and duration of overshoots, are effectively suppressed. New pump powers can also be continuously calculated and set for example, as well as being calculated and set in advance. In such cases interpolation values from the previously calculated pump powers can continue to be determined. By measuring the output power shortly after a jump is detected, the wavelength dependency can be fully taken into account. Aging effects are compensated for since the advance calculation of the pump power is undertaken relative to the previously available stable state of the amplification. Likewise, the current amplifier gain is included in the calculation and non-linear effects in the amplified fiber, as for example with “Excited State Absorption”, are taken into account. “Gain Ripple” also does not lead to any change in the gain of the individual channels. What is of particular importance is that this method, as well as those already used in the prior art, does not need any additional measurement devices or components and is therefore greatly of interest from the cost standpoint. In the following description, an inventive method is illustrated preferably for an amplifier stage which contains an Erbium-doped fiber. The method can however also be used for a number of cascaded amplifier stages with possibly different amplification fibers and/or pump sources. An exemplary embodiment for using a number of pump sources in an amplifier stage is even explicitly described. A model is also disclosed, which enables a new pump power required to be determined or calculated from a previously available stable state of the optical amplifier. To this end, further restricted aspects are also considered it and their influences on the model analyzed. BRIEF DESCRIPTION OF THE DRAWINGS The various objects, advantages and novel features of the present disclosure will be more readily apprehended from the following Detailed Description when read in conjunction with the enclosed drawings, in which: FIG. 1 illustrates an average gain of channels for an individual amplifier stage according to the prior art; FIG. 2 illustrates the timing gain curve for dropping of active channels with feed forward controlling; FIG. 3 illustrates the gain spectrum of an EDFA for 80 active channels; FIG. 4 illustrates a gain curve over time of a surviving channel (extract from FIG. 2 ); FIG. 5 illustrates gain variations over time for the channels within 10 ms after the drop time; FIG. 6 illustrates gain variations over time for the channels within 25 μs after the drop time; FIG. 7 illustrates actual and model-related pump power to be set as a function of the input power; FIG. 8 illustrates variations between required and model-related pump power values to be set; FIG. 9 illustrates a dynamic control concept; FIG. 10 illustrates gain curves over time of the surviving channel with different drop times of the other channels (a) Drop time: 1 μs (b) Drop time: 10 μs (c) Drop time: 100 μs (d) Drop time: 1 ms (e) Drop time: 10 ns to 1 ms; and FIG. 11 illustrates an amplitude of the overshoot for different drop times of channels, FIG. 12 : the regulated power distribution of a three-stage fiber amplifier. DETAILED DESCRIPTION FIG. 2 shows a gain curve G over time during dropping of active channels with feed forward controlling in a single-stage Erbium-doped fiber amplifier, with the pump power required with reduced input power for maintaining the gain being set at the point at which the load changes. An undershoot is completely suppressed in this case. A description is given below of how, starting from a known operating state of the fiber amplifier, the pump power required to maintain the gain P pump after can be calculated. The method is explained with reference to a suitable modeling of the amplifier process in the Erbium-doped fiber. All the power specifications below relate to the start or the end of the doped fiber. Available measuring devices (including photo diodes) are however generally calibrated to record powers present at the input or output of the amplifier or the amplifier card. Passive components such as couplers and isolators are mostly located between the inputs and outputs of the amplifier card as well as the corresponding ends of the amplification fiber. In this case a correction of the power specifications by the attenuation losses of the upstream and downstream components is also required. Likewise losses between the measuring device for the pump light and the coupling-in point in the Erbium-doped fiber are taken into consideration. The powers actually coupled into or out of the doped fiber are the result of the correction. In addition a further correction step is required in order to determine the actual effective pump power, since, as a result of the loss mechanism in the fiber, not all photons coupled into the doped fiber participate in the amplification process. This is especially required for the use of pump sources with an emission wavelength in the range of 980 nm, since in this case ions which have already been excited, which are at a higher energy level, can absorb pump power, whereby pump photons are lost to the actual amplification process. This process is referred to as the “pump excited state absorption (ESA)”. To make a distinction, the term for the effective pump power Peff is introduced which designates the pump power effectively available to the amplification process. All power variables subsequently specified are to be used in the linear scale (mW). Starting from the pump power P pump coupled-in in the fiber the effective pump power Peff can be calculated with the aid of the equation P eff = P 0 · ln ⁢ { 1 + P pump P 0 } , with the symbol P 0 standing for a correction parameter. This should be known during the operation of the amplifier in a transmission system and is best defined on calibration of the amplifier card. The characteristic parameters P 0 are therefore determined together with a second characteristic parameter G norm before the calculation process within the framework of the fiber amplifier through measurement. With this measurement the pump power required for maintenance of a predetermined gain value is plotted against the input or output power of the fiber amplifier. In this case it is of advantage not to change the channel assignment and to realize different input powers by the same attenuation of all channels. The measurement process makes use of the fact that the pump power required to maintain a predetermined gain value of an Erbium-doped fiber without loss mechanisms is a linear function of the input power. For the larger pump power values, a deviation from a straight line occurs. This deviation is conditional on the pump ESA. The parameter P 0 is now determined by fitting. To this end, the effective pump powers produced from the measured pump powers are calculated for different values of P 0 and the curve is approximated by a straight line in accordance with the minimum error square criterion. The total of the error squares is shown as a function of P 0 . The value now selected for P 0 is that value which leads to a minimum total of the error squares. This value produces a curve, which describes the effective pump power P eff as linear function of the input power of the amplifier. The second characteristic parameter G norm for the fiber amplifier can now be derived from the slope of the straight lines determined in this way. The change in the effective pump power P eff is logically combined with corresponding changes to the input power via the proportionality constant. α = λ _ signal λ pump · G sig - 1 G norm . where the two wavelengths λ signal and λ pump designate the mean signal wavelength or the pump wavelength. The parameter G sig = P sig , out P sig , in generally represents the relationship between an input signal power and an output signal power. Since, apart from G norm , all other variables are known, the second characteristic parameter can now be uniquely determined. The value of G norm typically lies in the range between 0.95 and 1.00. After the determination of the two calibration parameters P 0 and G norm the pump power required to maintain the gain after a switching process P pump after is now calculated. Starting from the measured pump power P pump before before the switching process, the effective pump power P eff before can be calculated with the following formula P eff before = P 0 · ln ⁢ { 1 + P pump before P 0 } . ( 1 ) With the sum signal power P sig vor before the switching process the value of the effective pump power for the signal power P sig before after the switching process is produced as P eff after = P eff before + λ _ signal λ pump · 1 G norm · { P sig , out after - P sig , in after - P sig , out before + P sig , in before } ( 2 ) with the formula expressions occurring having the following meaning: P sig,out after the accumulated output power produced after the switching process with the gain remaining the same (i.e. stable state), P sig,in after the accumulated input power after the switching process, P sig,out before the accumulated output power before the switching process, P sig,in before the accumulated output power after the switching process, The two wavelengths λ signal and λ pump stand for the average signal wavelength after the switching process or for the pump wavelength respectively. From the effective pump power to be set after the switching process, the actual pump power to be set by the control at the fiber input can now be defined by inversion of equation (1), which leads to the result P pump after = P 0 · [ exp ⁢ { P eff after P 0 } - 1 ] . ( 3 ) As a general rule, the precise channel occupancy after the switching process is only known with a clear delay and is thus not available for regulation. In this case, the average wavelength of the signal with full occupancy of the amplification band can be employed for the average signal wavelength. Under specific circumstances, equation (2) can be simplified, so that simplifications of the amplifier structure become possible. Two possible simplifications are illustrated below: For calculating the pump power P pump after after the switching process, in accordance with eqn. (2) the accumulated powers on the input and output side must be known both before and also after the switching process. Because of the required regulation times of a few μs, both the measurement devices at the input of the amplifier stage and also those at the output have short measurement times. This demand for short measurement times can however be restricted to the point in time after the switching process, since it is assumed that the switching process starts from a stable state. Individual amplifier stages typically exhibit a gain of 20 dB or more, which means that the output powers are approximately two orders or magnitude greater than the input powers. Especially critical as regards the dynamic behavior are also switching processes in which the accumulated input power and thus also the accumulated output power fall sharply (e.g. by more than 10 dB). This means however that the second term in the curly brackets of eqn. (2) P sig,in nach , is far smaller than the other terms and can consequently be ignored. This means that the equation for P eff after ≈ P eff before + λ _ signal λ pump · 1 G norm · { P sig , out after - P sig , out before + P sig , in before } ( 4 ) can be simplified. In this equation P sig,out after is the only variable for which only short periods are available for its measurement. Thus the use of the fastest possible photo diodes is only appropriate for measurement of the accumulated output powers whereas slower measurement equipment can be used to measure the accumulated output power. This is of interest, since by dispensing with a bias voltage, the sensitivity of photo diodes can be increased because of the lower dark current. On the other hand, a simplification of eqn. (2) is produced for the case in which the average amplifier gain does not change, which poses a significant problem for the calculation of the output power produced after the switching process where the gain curve remains the same. In this case equation (2) can be transformed into P eff after = P eff before + λ _ signal λ pump · G sig - 1 G norm · { P sig , in after - P sig , in before } ⁢ ⁢ with ⁢ ⁢ G sig = P sig , out before P sig , in before . ( 5 ) Again only a fast measuring device is required, in this case for measurement of the accumulated output power. The equation can however be rewritten so that short measurement times are only needed for the measurement equipment at the output of the Erbium-doped fiber. It should be pointed out here however that the gain of an amplifier stage of an EDFAs is as a rule, especially if does not contain a smoothing filter, different for the individual channels. When a number of pump sources are used in the optical amplifier the basic method is identical to the method with only one pump source. Initially the pump powers available in the reference state are converted separately in accordance with equation (1) into effective pump powers, with under some circumstances different parameters P 0 having to be used for the individual pump sources. The effective pump powers P eff,i before are then subsequently weighted with the quotients from the average signal wavelength λ signal and the relevant pump wavelength λ i pump . The sum of these variables produces an auxiliary variable X eff before : X eff before = ∑ i = 1 N ⁢ λ pump i λ _ signal · P eff , i before , with N designating the number of pump sources The auxiliary variable X eff after to be set after the switching process correspondingly produces: X eff after = X eff vor + 1 G norm · { P sig , out after - P sig , in after - P sig , out before + P sig , in before } . It is of little consequence for the maintenance of the gain how greatly the individual pump sources contribute to this required value. However there can be preferences, which, for example, are the result of the requirement for the optimum possible noise figure and depend on the selected pump configuration. Once the contributions of the individual pump sources are defined, these are multiplied by the quotients from the average signal wavelength λ signal and the corresponding pump wavelength λ i pump . This means that the relevant effective pump powers are now available again, which are converted according to equation (3) into the actual pump powers P pump after (i). The method described above is based on the assumption, which is almost always fulfilled, that the pump powers coupled-in at the location of an amplifier fiber feature wavelengths from different absorption bands. FIG. 3 shows an example of the curve of gain G as a function of the wavelength for 80 channels of a WDM signal. As an example the case in which all channels except for the marked surviving channel UK are dropped is now considered. The actual goal of the regulation is not to keep the average gain, as results from an overall power measurement at the input and at the output of the stage, constant. Instead, it is necessary to make sure that the gain curve does not change over the wavelength, since only then does the power which falls on the relevant receiver remain constant over time. In the above example this requires a change of average gain. The dynamic properties of an Erbium-doped fiber are helpful in determining a new required gain. Even with a sudden change of the input power the average occupancy inversion and thereby the gain profile only changes slowly. FIG. 4 shows a section of the gain over time of the solid line curve already shown in FIG. 1 for a pump power which remains constant with a jump in the input power of 19 dB and for example for the surviving channel UK, which for large periods of time asymptotically approaches a limit value of 30 dB. Within the first 10 μs after the switching process, the gain of the observed channel only changes slightly however. This period of time can therefore be used to determine the desired output power after the switching process and the corresponding average gain with changed spectral power distribution. For the exemplary embodiment presented above, in which all of 80 channels except one channel are preferably dropped at 1531.9 nm, the dynamic behavior of the fiber amplifier EDFA is shown in the further FIGS. 5 and 6 . The changes in gain for individual channels over time DG(t) are shown for different wavelengths (curves shown in the range of 0 dB) as well as the change in the average gain (curve shown with a jump at appr. 2 5 dB) in relation to the state before the switching process at t=0 ms. The dashed horizontal line shown at appr. 2 5 dB specifies the gain change after the synchronized state is reached. FIG. 6 is slowed-down version of FIG. 5 in the range of a few milliseconds before and after the switching process of channels. The next Figure, FIG. 7 shows a required, i.e. nominal pump power P_PUMP shown by solid curves KA, KB, KC, KD as a function of the input power P_IN of the fiber amplifier, which is to be set for maintaining different average gain values 5, 10, 15, 20 dB according to a switching process according to FIG. 4 to 6 . For verification of the method described above, starting from the data point with the maximum input power in each case, the pump power is determined in accordance with the above method according to the equations (1) to (6) and the relevant result is shown by dots in FIG. 7 . In this case there is a very good match between the pump powers determined by simulation with the previously calculated values. By way of illustration FIG. 8 shows, in accordance with curves KA, KB, KC, KD and the points entered from FIG. 7 , the relative deviation DEV between the required nominal pump power and the inventive prior calculation of the pump power. In this case the maximum relative deviation amounts to appr. 5%. It was previously assumed that the input power when channels are dropped falls immediately from a start value to an end value. In the following section, a method is now described with effects occurring on the remaining overshoots of the gain for the case described, in which the input power during a fall time (see FIGS. 10 a to 10 e with FIG. 11 ) falls linearly from its start value to the end value. Under these assumptions FIG. 9 shows a dynamic control concept for executing the method. Initially a check is made as to whether the input power has been constant for a predetermined period of time (step 1 ). If it has been, the amplifier is driven with the conventional control concept with feedback (step 11 ) (see e.g. Mann, Schiffelgen, Froriep, “Einführung in the Regelungstechnik (introduction to control technology)”, Hanser-Verlag, Munich, 7th edition, 1997). If a stable state is reached here (step 12 ), this is defined as a new reference state (step 13 ). If on the other hand the input power is not constant, i.e. if a change of the input power is detected during the predetermined period (step 1 ), a switch is made to the inventive feed forward operation (step 21 ). The pump powers to be set are calculated (step 22 ) and set (step 23 ) in this case after each time interval based on the last reference state and the current values for the input power and the output power. Subsequently another check is again made as to whether the input power has already been constant for a constant period of time (step 1 ). As before, starting from 80 channels, all channels except for one are preferably dropped at 1531.9 nm. Changes in gain over time of the surviving channel with different drop times or periods of 1 μs, 10 μs, 100 μs and 1 ms are shown in FIGS. 10 a , 10 b , 10 c and 10 d by means of a solid line curve and also for fall times of between 10 ns and 1 ms in FIG. 10 e overlaid over each other, with the time and the value of the maximum change in gain G max being shown by a dot. For better understanding, the curve shown by a dotted line shows the timing of the falling input power in the linear scale. A slight overshoot is typically produced with a sudden change in the input power, and an exact advance calculation of the pump power needed in the stable state. Basically the opportunity would exist for these errors to accumulate with a repeated application of the predictive setting of the pump power using the current measured output power and for a divergence of the method to result. This is however not the case. In FIG. 10 e the changes in gain produced for the different fall times in the range of 10 ns to 1 ms of the “surviving” channel are shown overlaid, with the dots again marking the maximum change in gain G max in each case. Notably the synchronization process for large lengths of time is only slightly dependent on the fall time. To supplement FIG. 10 e , FIG. 11 shows the overshoot occurring DEV max as a function of the fall time T fall . For fall times of less than 1 μs a constant value is produced, whereas for larger fall times the strength of the overshoot reduces the more the fall time increases. Furthermore FIG. 12 shows the controlled power distribution OPT_POW of a three-stage fiber amplifier consisting of the amplifier stages S 1 , S 2 and S 3 , of which the gain can be varied with the aid of a variable attenuation element att connected between the first amplifier stages S 1 , S 2 . A further optical module DCF can be inserted between the two last stages S 2 , S 3 , which for example allows the adding and dropping of wavelength-related channels or compensation of the link attenuation. In this case the power distribution OPT_POW along the entire fiber amplifier for different operating states is shown. The power curve POW 1 shows the power distribution obtaining in the fiber amplifier before the switching process, which has reached a stable state and offers and for which an existing channel occupancy offers an optimum noise figure. To avoid overshoots and undershoots or to keep them as low as possible, the individual amplifier stages are kept at constant gain directly after the switching process with the aid of feed forward controlling, so that a second power curve shown POW 2 is produced directly after the switching process. Since however this is not optimal as regards the noise figure, a slow regulation after the input signal is stable ensures that the power curve slowly moves from the second power curve POW 2 to a further power curve POW 3 shown here as a broken line. This process takes place slowly so that this function can be undertaken using conventional regulation. Since the gain of the individual amplifier stages S 1 , S 2 , S 3 should not change in a first time interval, the accumulated signal powers to be set after the switching process at the input of each stage can be calculated independently of each other. The pump powers required can be determined directly on the basis of the formulae already presented. Under some circumstances the available computing power is not sufficient to calculate the new pump powers required in real time after the switching process. In this case there is the option of prophylactically creating a table directly after a stable state is reached which contains the pump power required for maintenance of the gain for a suitable number of signal input powers which serve as reference values for in interpolation in the switching processes. While the invention has been described with reference to one or more exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
The present disclosure relates to a method for regulating a pump power of an optical amplifier, where a multiplexed broadband optical signal having several channels is amplified at a certain gain value while a change in power is detected at the input or output of the amplifier. A new pump power is calculated and adjusted based on a previously provided stable gain state of the optical amplifier after detecting the change in power such that deviations of the gain value remain minimal as planned temporary interface transients during a specific interval. The new pump power is thus calculated very accurately and quickly according to a model that takes into account the actual gain value, the wavelength dependence of active channels, aging effects, and non-linear amplification effects.
50,849
BACKGROUND OF THE INVENTION The present invention relates to an apparatus and method of forming a liquid film of a development solution for processing a thin film coated on a substrate. In a photolithographic process for manufacturing a semiconductor device, a photoresist is coated on a wafer surface, and the resultant photoresist coating film is pattern-exposed and then developed by being exposed to a developing solution. In a conventionally-employed developing method (shown in FIGS. 1 and 2), a wafer W is vacuum-adsorbed by a spin chuck 111 and a supply nozzle 113 is positioned in such a way that spray holes 112 are placed in the proximity of an upper central portion of the wafer W. The supply nozzle 113, which has a length substantially equal to a diameter of wafer W, has numerous spray holes 112 arranged linearly along the longitudinal direction of the supply nozzle 113. A developing solution 10 is simultaneously sprayed from the numerous spray holes 112 to the wafer W, thereby mounting the developing solution 10 on the wafer W, as shown in FIG. 1. Thereafter, the wafer W is rotated by an angle of 180° while continuously supplying the developing solution 10 from the supply holes 112. In this way, a film of the developing solution 10 is formed over an entire surface of the wafer W. Note that the wafer must not be rotated in excess of 180° in order to prevent an initially supplied developing solution (proceeding developing solution) from being contaminated with a newly supplied developing solution (following developing solution). If the proceeding developing solution is contaminated with the following developing solution, a contaminated portion differs in resolution from a non-contaminated portion. As a result, the film is not developed uniformly. However, the conventionally-employed method has the following problems. Before the developing solution is sprayed from the supply nozzle 113 to the wafer W, a predetermined amount of the developing solution is sprayed and discarded into the drain cup. This is called "dummy dispense". However, when the "dummy dispense" is carried out, liquid drops are attached to a tip portion of the supply nozzle 113 (i.e., around the spray holes 112), and the particles floating in the air are sometimes attached to the liquid drops. When the liquid drops are dried, the particles may drop on the wafer W, contaminating the wafer W. The developing solution 10 is supplied by blowing a pressurized gas into a developing solution tank. The pressurized gas pushes out the developing solution 10 from the developing solution tank toward the supply nozzle 113. Therefore, gaseous ingredients of the pressurized gas are dissolved in the developing solution 10. The dissolved gaseous ingredients appear as micro bubbles on the wafer surface after the developing solution is sprayed. Due to the presence of micro bubbles, some regions of the film are not developed well (due to resolution impossible) or developed insufficiently (due to insufficient resolution), leading to developing defects. Since the wiring width of the circuit pattern has been reduced more and more in the recent days, the developing defect, even it is small, results in a fetal damage. Another method is proposed as shown in FIG. 3. In the method, the supply nozzle 113 is placed along an orientation flat (O. F.) of the wafer W. The developing solution 10 is allowed to spray toward a non-pattern formation region outside the pattern formation region. Subsequently, the supply nozzle 113 is scan-moved along the surface of the wafer W in a Y-axis direction while spraying the developing solution. However, the length of the orientation flat (O. F.) is shorter than the diameter of the wafer W, the initially mounted developing solution 10 is spread sideward. Consequently, no developing solution 10 is applied in some regions and the developing solution 10 is applied but insufficient in other regions. In this case, even if the developing solution 10 is supplied from the nozzle 113 in a larger amount, the same phenomena are resulted. As a result, the film is not developed uniformly. Furthermore, in the case where a large-size (e.g., 12 inches) wafer W is used, a V notch 88 (shown in FIG. 16) is employed as crystal-orientation identification means in place of the orientation flat (O. F.). Therefore, the developing solution is initially mounted on an inevitably narrower space, resulting in non-uniform development. BRIEF SUMMARY OF THE INVENTION An object of the present invention is to provide an apparatus and method for forming a liquid film capable of forming a liquid film uniformly on a surface of a substrate and preventing contamination of the substrate with particles. A liquid film formation apparatus according to the present invention comprises: a substrate holding portion for holding a substrate substantially horizontally so as to allow a pattern-to-be-formed surface to face upward; a liquid-receiving base surrounding the substrate held by the substrate holding portion and having a liquid-receiving face which is placed at substantially the same level as that of an upper surface of the substrate; a supply nozzle having a process-liquid spray section whose length is equal to or longer than the width of an effective region of the substrate; and a moving mechanism for moving the supply nozzle in the direction perpendicular to the longitudinal direction of the supply nozzle; in which the substrate holding portion seals a slit formed between the liquid-receiving base and the outer peripheral portion of the substrate so as not to leak out the process solution from the slit, and the process solution is supplied from the supply nozzle to the liquid-receiving base to mount the process solution on the liquid-receiving base, and the process solution is subsequently mounted over an entire surface of the substrate by spraying the process solution from the supply nozzle while moving the supply nozzle. A method of forming a liquid film according to the present invention comprises the steps of: (a) bringing a liquid-receiving base in contact with a periphery or in vicinity of a substrate held horizontally, the liquid-receiving base having a liquid-receiving face which is placed at substantially the same level of that of an upper surface of the substrate; (b) mounting a process solution on the liquid-receiving base by supplying the process solution from a supply nozzle having a spray portion whose length is equal to or longer than a width of an effective region of the substrate; and (c) supplying the process solution from the supply nozzle while moving the supply nozzle in a direction perpendicular to the longitudinal direction of the supply nozzle, thereby mounting the process solution over an entire upper surface of the substrate. According to the present invention, the process solution is initially mounted so as to cover the width of the effective region of the substrate (e.g. in a length equal to the diameter of the substrate). The mount of the process solution is extended along the integrated flat surface consisting of the wafer W and the liquid-receiving base therearound, at the same time, the process solution is supplied from the supply nozzle to form a liquid film of the process solution on the upper surface of the substrate. Hence, the process solution is mounted in an effective area of the substrate in the direction along which the process solution is mounted by being supplied from the supply nozzle, thereby suppressing the outward-spread of the process solution. As a result, the liquid film can be formed uniformly in thickness over the entire surface of the substrate. Then, even if the supply nozzle increases in moving speed, developing can be effected reliably in a high throughput. Furthermore, even if particles are attached to the supply nozzle, it is possible to prevent the particles from being transferred from the nozzle to the substrate (wafer) and attached on the substrate. To describe more specifically, when the particles are attached to a tip portion of the supply nozzle, there is a high possibility that the particles contaminate the process solution when the process solution (developing solution) is supplied from the supply nozzle and initially mounted on the substrate. Whereas, in the present invention, the process solution is initially mounted on the liquid-receiving base positioned outside the substrate. Therefore, the process solution is not virtually spread toward the substrate. Even if the process solution is spread, the amount of the spread process solution is negligibly small. Hence, it is possible to prevent the contamination of the substrate with particles. Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate presently preferred embodiments of the invention, and together with the general description given above and the detailed description of the preferred embodiments give below, serve to explain the principles of the invention. FIG. 1 is a schematic view for explaining a method of forming a liquid film on a substrate by use of a conventional apparatus; FIG. 2 is a schematic plan view for explaining a conventional method; FIG. 3 is a schematic plan view for explaining a comparative method; FIG. 4 is a schematic plan view showing a substrate process system; FIG. 5 is a front view of showing the substrate process system; FIG. 6 is a cross sectional view of an apparatus for forming a liquid film according to an embodiment of the present invention, accompanied with a block diagram of peripheral elements; FIG. 7 is a perspective view of a gist portion of the apparatus according to the embodiment of the present invention; FIG. 8 is a plan view of a gist portion of the apparatus according to the embodiment of the present invention; FIG. 9 is a schematic plan view of the apparatus according to the embodiment of the present invention; FIG. 10 a cross sectional view of a nozzle moving mechanism, a developing nozzle, and a stand-by section, partly in section; FIG. 11 is a long-side sectional view of the developing nozzle; FIG. 12 is a short-side cross sectional view of the developing nozzle; FIG. 13 is a flow chart showing a method of forming a liquid film according to an embodiment of the present invention; FIGS. 14A to 14C are schematic views for explaining a method of forming a liquid film; FIGS. 15 to 15C are plan views schematically showing a surface state of a wafer treated by a comparative method; FIG. 16 is a plan view for explaining a method of forming a liquid film according to another embodiment of the present invention; and FIG. 17 is a plan view for explaining a method of forming a liquid film according to still another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION Now, various preferable embodiments of the present invention will be described with reference to the accompanying drawings. As shown in FIG. 4, a wafer process system has a cassette section 10, a process section 12, and an interface section 14. A light-exposure apparatus (not shown) is connected to the wafer process system via the interface section 14. The cassette section 10 has a cassette table 20 and a sub-arm mechanism 22. Four projections 20a are formed on the cassette table 20. Cassettes CR are positioned rightly on the cassette table 20 by means of the projections 20a. A transfer passage 22a is provided along the cassette table 20. A first sub-arm mechanism 22 runs on the transfer passage 22a. The first sub-arm mechanism 22 has a back and forth mechanism for moving a wafer holder back and forth, an X-axis moving mechanism for moving the wafer holder in an X-axis, a Z-axis moving mechanism for moving the wafer holder in a Z-axis direction, and a θ rotation mechanism for swinging the wafer holder about the Z-axis. The first sub-arm mechanism 22 plays a role in taking out the wafer W from the cassette CR and transporting it to the process section 12. The process section 12 has a main arm mechanism 24. Five process units G1 to G5 are provided so as to surround the main arm mechanism 24. The main arm mechanism 24 has a wafer holder, a back and forth mechanism for moving the wafer holder back and forth, a Z-axis moving mechanism for moving the wafer holder in the Z-axis direction, and a θ rotation mechanism for swinging the wafer holder about the Z-axis. The main arm mechanism 24 plays a role in transporting the wafer W to each of units G1 to G5. The wafer W is transferred between the first sub arm mechanism and the main arm mechanism 24 via a loading/unloading unit of a third group G3. As shown in FIG. 5, first and second process units G1 and G2 are arranged in a front side of the wafer process system. Each of the first and second process units has a resist coating unit (COT) and a developing unit (DEV). The developing unit (DEV) is arranged above the resist coating unit (COT). Above the developing unit (COT), a fine filer unit (FFU) 18 is arranged. The FFU 18 houses a filter and a fan which are responsible for removing particles and organic substances, thereby sending a clean air downward. By the function of FFU 18, a down-flow of clean air can be generated within the developing unit (DEV) and the resist coating unit (COT). Note that FFU 18 is provided also in the upper portions of the cassette section 10 as well as in the interface section 14. The third group G3, which is arranged near the cassette section 10, has a baking unit, a cooling unit, an adhesion unit, and a loading/unloading unit, all stacked tandemly in multiple stages. The fourth group G4, which is arranged near the interface section 14, has a baking unit, a cooling unit, a washing unit, and a loading/unloading unit, all stacked tandemly in multiple stages. The fifth group G5 may be arbitrarily provided and additionally provided in case of process unit shortage. The fifth group G5 is arranged in a back side of the wafer process system and provided along the rail 25 and movably in the Y-axis direction. The interface section 14 includes a second sub arm mechanism 26, a stand-by section 28, and a buffer cassette BR. The interface section 14 has a transportation passage 26a therein. A second sub-arm mechanism 26 runs on the transportation passage 26a. The second sub-arm mechanism 26 includes a wafer holder, a back-and-forth moving mechanism for moving the wafer holder back and forth, an X-axis moving mechanism for moving the wafer holder in the X-axis direction, a Z-axis moving mechanism for moving the wafer holder in a Z-axis direction, and a θ-rotation mechanism for swinging the wafer holder about the Z-axis. The second sub arm mechanism 26 is responsible for transporting the wafer W to each of the stand-by section 28, the buffer cassette BR, and the light-exposure apparatus (not shown). Now, referring to FIGS. 6 to 8, we will explain the developing unit (DEV) serving as an apparatus for forming a liquid-film will be explained. The developing unit (DEV) has a spin chuck 2, a tray section 30, a supply nozzle 40, a cup 53 and developing solution supply mechanisms 42 to 47. The spin chuck 2 has a motor 3 for spin-rotating the wafer W about the Z-axis, an adsorption-holding mechanism (not shown) for vacuum-adsorbing the wafer W at a central rear surface of the wafer W, and a liftable cylinder 4 for moving the wafer W in the Z-axis direction. The rotation axis 3a of the motor 3 is introduced into the cup 53 through a hollow member 50. The motor 3 is supported by the rod 4a of the liftable cylinder 4 via a connecting support member 5. The spin chuck 2 is moved up by projecting the rod 4a from the cylinder 4. When the upper edge surface of the spin chuck 2 comes in contact with the rear surface of the wafer W, the wafer W is adsorbed and held by the spin chuck 2. The tray section 30, rectangular or square in shape, is placed horizontally by being supported at four corners by the hollow member 50 via four supporting mallets 51. The tray section 30 has a peripheral holding portion (substrate holding portion) 31, a liquid-receiving base 32, and an embankment 33. The peripheral holding portion 31 (ring form), holds the wafer W at a peripheral portion of the rear surface. The liquid-receiving base 32 (ring form) is continuously provided along outer peripheral edge of the peripheral holding portion 31 and at a higher position than the peripheral holding portion 31. To be more specific, there is a difference (step) in height between the liquid-receiving base 32 and the peripheral holding portion 31. The rise of the step is substantially the same as the thickness of the wafer W. When the wafer W is mounted on the tray section 30 and held by the peripheral holding portion 31, the upper surface of the wafer W is equal in level to the upper surface of the liquid-receiving base 32 to thereby form the same plane. Note that the step-rise between the members 31 and 32 may be larger or shorter than the thickness of the wafer W. The embankment 33 is continuously formed on the peripheral edge of the liquid-receiving base 32 so as to stand outwardly and upwardly. The embankment 33 prevents the developing solution 1 from flowing down from the tray section 30 and assists the liquid-receiving base 32 to store the developing solution 10. The height of the embankment 33 is, for example, 3 mm. The liquid-receiving base 32, square or rectangular in shape, whose side is larger than the diameter of the wafer W. In the region of the wafer W facing the orientation flat (O. F.), the inner edge of the liquid-receiving base 32 is substantially parallel to the outer edge thereof. A liquid-receiving face 32a is formed therein. As shown in FIG. 6, the width L of the liquid-receiving face 32a is about 3 mm. The cup 53 is formed so as to surround the side and lower parts of the tray section 30. The cup 53 is responsible for receiving a liquid (developing solution and rinse solution) scattering toward the outside of the apparatus. The received liquid is discharged from the bottom of the cup 53 and flows out through a discharge passage 54. As shown in FIG. 9, a developing solution supply nozzle 40 and a rinse nozzle 70 are arranged respectively at a home position so as to sandwich the cup 53. The supply nozzle 40 is arranged near one side of the cup 53 (square shape). The rinse nozzle 70 is arranged near the opposite side of the cup 53. The nozzles 40 and 70 are linear nozzles extending in the X-axis direction. Numerous holes are arranged at the liquid spray portion. A grab arm 60 is positioned near the cup 53. The grab arm 60 is constituted of a ball screw 61, a stepping motor 62, a ball nut 63, a horizontal arm 64, a chuck portion 65, a liftable mechanism for the chuck portion 65 (not shown), a pair of nails 65a, and a driving mechanism for opening/closing the pair of nails 65a. The ball screw 61 is provided at least between the home position for the supply nozzle 40 and the home position for the rinse nozzle 70 and extends along the Y-axis direction. The grab arm mechanism 60 is provided outside and above the cup 53. The grab arm mechanism 60 selectively holds either the nozzle 40 or the nozzle 70 and transport it from the home position to an operating position. As shown in FIG. 10, a stand-by section 80 is provided at the home position for the supply nozzle 40. A liquid spray portion 40d of the nozzle 40 is inserted into an inner atmosphere 81 of the stand-by section 80. The inner atmosphere 81 is set at the most suitable humidity/temperature. Therefore, the inside of a liquid passage 40e is prevented from being dried. The nozzle 40 is connected to a member 67 by way of a member 66. A plurality of recesses 67a are formed at the side portions of the member 67. When the chuck portion 65 is operated, the nails 65a are engaged with the corresponding recesses 67a. In this mechanism, the chuck portion 65 is connected to the supply nozzle 40. Such grab arm mechanism 60 is disclosed in U.S. Pat. No. 5,672,205. Next, referring to FIG. 6, we will explain the supply system for supplying the developing solution to the nozzle 40. A developing solution supply line 46 is formed from the tank 42 to the nozzle 40. The developing solution 10 is stored in the tank 42. A pressurized N 2 gas is introduced into the tank 42 from a N 2 gas supply source 47. The supply line 46 is sequentially equipped with a filter 43, a flow rate counter 44, and an open/shut valve 45. Initiation and termination of the developing solution 10 to the nozzle 40 is controlled by the open/shut valve 45. As shown in FIG. 9, a rinse nozzle 70 is placed on a tray section (not shown) outside the cup 53. The rinse nozzle 70 is communicated with the pure water supply source (not shown) via a supply line (not shown). After completion of the developing process, the rinse nozzle 70 is transported by the grab arm mechanism 60 and washes the wafer W and the liquid-receiving base 32 while pouring pure water thereto. As shown in FIGS. 6 and 7, four rinse nozzles 7 are arranged below the spin chuck 2. Each of the rinse nozzles 7 is communicated by way of a supply line 7a with a pure wafer supply source (not shown) disposed outside the cup 53. The supply line 7a is introduced into the cup 53 through the hollow member 50. The liquid spray portion of the rinse nozzle 7 is inclined upwardly so as to pour pure water onto the peripheral portion of the rear surfaces of the tray section 30 and the wafer W when the tray section 30 is descended. Next, the developing solution supply nozzle 40 will be explained with reference to FIGS. 11 and 12. The developing solution supply nozzle 40 is a uni-directionally extending linear nozzle. The nozzle 40 is constituted of a main body case 40a, a top cover 40b, a liquid store portion 40c, a liquid spray portion 40d, spray holes 40e, and seal rings 40f. The top cover 40b is covered over the main body case 40a. The developing solution 10 is introduced into the liquid store portion 40c by way of a pipe 46 formed through the top cover 40b. The lower portion of the liquid store portion 40c is communicated with numerous spray holes 40e. The length of the liquid spray portion 40d is virtually equal to the diameter of the wafer W. For instance, if the wafer W has a diameter of 200 mm, the length of the liquid spray portion 40d is 204 mm. Numerous spray holes 40e are linearly arranged in the liquid discharge portion 40d. Now, referring to FIGS. 13, 14A to 14C, we will explain a method of forming a liquid film of a developing solution on the wafer W by use of the aforementioned apparatus. The wafer W is transferred to the second sub-arm mechanism 26 from the light exposing apparatus (not shown) and transferred to the main arm mechanism 24 via a loading/unloading unit belonging to the fourth group G4. The main arm mechanism 24 transfers the wafer W to the developing unit DEV of the first group G1. A shutter (not shown) is opened (Step S1) and the wafer W is loaded into the developing unit DEV (Step S2). Then the spin chuck 2 is ascended to above the cup 53 (Step S3). The wafer W is transferred from the holder of the main arm mechanism 24 to the spin chuck 2 (Step S4). After the holder of the main arm mechanism 24 is withdrawn, the shutter is closed (Step S5). Then, the spin chuck 2 is descended (Step S6). In this manner, the wafer W is transferred from the spin chuck 2 to the tray section 30 (Step S7). The grab arm mechanism 60 grabs a supply nozzle 4 and transfers it to the position outside the orientation flat (0. F.) and above the liquid-receiving base 32 (Step S8). In the step S8, the supply nozzle 40 is positioned so that the distance between the spray holes 40e and the liquid-receiving base 32 is set at about 1 mm. As shown in FIG. 14A, the spray of the developing solution 10 from the supply nozzle 40 is initiated. The developing solution 10 is mounted on the liquid-receiving base 32 along a side of the tray section 30 in a depth of about 1.2 mm (Step S9). While the supply nozzle 40 is maintained at the same level and the developing solution 10 is sprayed at a rate of 25 cc/second, the supply nozzle 40 is moved at a speed of about 10 cm/second toward the opposite side of the tray section 30 (Step S10). As shown in FIG. 14B, the supply nozzle 40 is scan-moved along the upper surface of the wafer W to thereby mount the developing solution 10 over the entire surface of the wafer W. The supply nozzle 40 is stopped at the liquid-receiving base 32 between the aforementioned opposite side of the tray section 30 and the wafer W (Step S11). Simultaneously, supply of the developing solution 10 is terminated (Step S12). The developing solution initially mounted on the liquid-receiving base 32 is partially spread over the upper surface of the wafer W to form a liquid film (about 1.2 mm thick) of the developing solution 10 over the upper surface of the wafer W, through the steps of S9 to S12. It is preferable that the thickness of the liquid film of the developing solution 10 should be about 1.2 mm or more. A small slit is formed between the inner peripheral edge of the liquid-receiving base 32 and the outer peripheral edge of the wafer W. However, the small slit is bottomed by the peripheral holding portion 31. Hence, the developing solution is introduced into the slit but the amount thereof is negligibly small. The supply nozzle 40 is withdrawn from the tray section 30 (Step 13). Instead, the rinse nozzle 70 is transported to the tray section 30 and placed at a right position (Step S14). After the development process is performed in a predetermined time, the tray section 30 is descended as shown in FIG. 14C. The developing solution 10 is discharged from the wafer W and liquid-receiving base 32 (Step S15). While the wafer W is rotated by the spin chuck 2 and the rinse nozzle 70 is moved from one side of the tray section 30 to the opposite side thereof, pure water is sprayed to wash away the developing solution 10 from the liquid-receiving base 32 and the surface of the wafer W. Furthermore, the rinse nozzle 70 placed on the upper side of the wafer W is moved to a center of the wafer, thereby supplying pure wafer to the wafer W. In this way, the developing solution 10 still left on the wafer is shaken off (Step S16). On the other hand, pure water is sprayed to the rear-surface peripheral edge portion of the wafer W to wash away the developing solution 10 supplied to the rear-surface peripheral edge portion. Simultaneously, the tray section 30 is rinsed. The spray of the pure water from the washing nozzles 70 and 7 is terminated and the rotation speed of the spin chuck 2 is increased, thereby shaking off the developing solution to dry the wafer W (Step S17). The spin chuck 2 is ascended (Step S18) and the shutter is opened (Step S19). Then, the holder of the main arm mechanism 24 is inserted into the developing unit (DEV). The spin chuck 2 is descended (Step S20). The wafer W is transferred from the spin chuck 2 to the main arm mechanism 24 (Step S21). The wafer W is unloaded from the developing unit DEV (Step S22) and then the shutter is closed (Step S23). According to the aforementioned embodiment, even if the particles are attached to the supply nozzle 40, it is possible to prevent the particles from moving from the nozzle 40 to the surface of the wafer W and attached thereto. When the particles are attached to the tip portion of the supply nozzle 40, the developing solution 10 may be contaminated with the particles when the developing solution is mounted on the wafer by being supplied from the supply nozzle 40. However, in this embodiment, since the developing solution is initially mounted onto the liquid-receiving base 32 outside the wafer W, even if the developing solution is spread toward the wafer W, it spreads in the extent of about 3/13. Therefore, the wafer W is prevented from being contaminated with the particles. In this embodiment, the developing solution is initially mounted so as to cover a width of the effective area of the wafer W. To be more specific, the length of the mounted developing solution is equal to the diameter of the wafer W. While the initially mounted developing solution is extended along a so-called single plane which consists of the wafer W and the peripheral liquid-receiving base 32, the developing solution 10 is supplied from the supply nozzle 40 to form a liquid film of the developing solution 10 on the surface of the wafer W. Therefore, even if a scan speed (moving speed) of the supply nozzle 40 is increased, a liquid film can be formed uniformly over the entire surface of the wafer W. Consequently, the developing process is performed with a high reliability while ensuring a high throughput. Then, we will take the aforementioned method explained with reference to FIG. 3 as a comparative example. In this comparative example, the wafer W is mounted on a table smaller than the wafer. The developing solution 10 is initially supplied from a nozzle 113 along an orientation flat (O. F.). The nozzle 113 is scan-moved along the wafer W to thereby mount the developing solution 10 over the entire surface of the wafer W. In the comparative example, the nozzle 113, whose length is equal to the diameter of the wafer W, is scan-moved while spraying the developing solution 10 at a flow rate of 25 cc/second. FIGS. 15A, 15B, and 15C show the surface states of the wafers W respectively in the cases where the nozzle 113 moves from one end of the wafer W to the other end for 1 second, 3 seconds and 5 seconds. The hatched area in the figures corresponds to the region with no the developing solution 10 coated thereon. The wafer used herein has 8 inch in diameter. As is apparent from the results, when the nozzle 113 is moved uni-directionally without using the liquid-receiving base, a non-coating area is produced even if the supply nozzle 113 is moved slowly over the wafer for 5 seconds. Whereas, in the present invention, the developing solution is initially mounted on the wafer for 0.3 seconds, and thereafter, the supply nozzle is moved in as short a time as 0.5 seconds. However, the liquid film is formed uniformly on the wafer surface without the non-coating area of the developing solution 10. As shown in FIG. 16, the developing solution is initially mounted on a region including a part of the wafer W. In the case shown in the figure, a V notch 88 is formed on the wafer W. As shown in FIG. 17, the wafer W may be adsorbed and held by the spin chuck 2 in place of the peripheral holding portion 31. The wafer may be held by a pair of liquid-receiving bases 32a and 32b (provided both sides of the wafer) in contact with the outer peripheral edge of the wafer W in such a way that the developing solution 10 may not flow down from between the pair of liquid-receiving bases 32a, 32b and the wafer W. The present invention is not limited to a semiconductor wafer W and may be applied to a glass substrate for a liquid crystal display apparatus (LCD substrate). In consideration of the enlargement of the LCD substrate, if the LCD substrate is held by the periphery holding portions, it is possible to prevent distortion of the LCD substrate. As a result, a liquid film can be formed highly uniformly. The process liquid is not limited to the developing solution and a resist solution may be used. Additional advantages and modifications will readily occurs to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
A liquid film formation apparatus comprises a substrate holding portion for holding a substrate substantially horizontally so as to allow a pattern-to-be-formed surface to face upward, a liquid-receiving base surrounding the substrate held by the substrate holding portion and having a liquid-receiving face which is placed at substantially the same level as that of an upper surface of the substrate, a supply nozzle having a process-liquid spray section whose length is equal to or longer than the width of an effective region of the substrate, and a moving mechanism for moving the supply nozzle in the direction perpendicular to the longitudinal direction of the supply nozzle, in which the substrate holding portion seals a slit formed between the liquid-receiving base and the outer peripheral portion of the substrate so as not to leak out the process solution from the slit, and the process solution is supplied from the supply nozzle to the liquid-receiving base to mount the process solution on the liquid-receiving base, and the process solution is subsequently mounted over an entire surface of the substrate by spraying the process solution from the supply nozzle while moving the supply nozzle.
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FIELD OF THE INVENTION This invention relates to an electrocautery surgical tool having relatively pivoted tissue engaging jaws, such as scissors jaws, dissector jaws and the like. BACKGROUND OF THE INVENTION Surgical tools with relatively pivoted tissue engaging jaws, such as scissors-like jaws, and relatively pivoted finger grip handles have been known. For example, Shutt U.S. Design Pat. No. 274,096 shows a device of this general type having an elongate tubular portion interconnecting a proximal hand engageable handle and distal patient tissue engaging jaws. Bales, et al U.S. Pat. No. 5,295,956, particularly in FIGS. 10A-10C shows a surgical scissors device in which a scissors jaws are connected to the proximal pair of finger engageable handles by an elongate tubular extension. As has been common in the past to construct such devices of surgical stainless or the like. Prior devices of that type tend to be complex and hence expensive to manufacture. Such devices, because costly, need to be reusable, and thus must be sterilizable between uses to reduce the risk of cross contamination of successively treated patients. Accordingly, the objects and purposes of this invention include provision of a surgical tool with relatively pivoted tissue engaging jaws. In one embodiment, the inventive surgical tool is to be constructed with at least a proximal handle structure of moldable plastics material and to be disposable. In one embodiment, the tool is to be capable of electrocautery of tissue, preferably through at least one of the jaws. In at least one embodiment, the tool is to be provided with an electrical connection between an exposed electrocautery terminal connectable to a conventional electrocautery electrical source and conductive, elongate jaw actuating structure extending between the proximal handle structure and a distal jaw. In at least one embodiment, the inventive device includes a simple structure for converting pivoting motion of a hand actuable trigger into reciprocating motion for transfer lengthwise of the tool to pivot a distal jaw. In at least one embodiment of the invention, the distal jaw is rotatable about the length axis of the surgical tool for changing the roll orientation of the jaw with respect to tissue to be worked without need to impart roll motion to the proximal handle. In at least one embodiment, tubular elongate extension unit, interposed between the proximal handle structure and distal jaw, is provided, adjacent the handle, with a hand rotatable wheel carried on the axis of the extension unit and in turn carrying a flushing port suppliable with irrigation liquid or the like transferrable distally therefrom along the tubular extension unit to the distal jaw at a surgical site for applying irrigation liquid to a surgical site. In a preferred embodiment, the tool is configured for laparoscopic surgery wherein a distal jaw unit and tubular extension unit are configured for insertion into the surgical site through a laparoscopic cannula, wherein the jaw unit and tubular extension unit are of minimum diameter so as to minimize the diameter of the laparoscopic cannula required, and wherein the jaw unit in its closed condition is readily insertable through such a laparoscopic cannula and, upon emergence from the distal end of such laparoscopic cannula, into a surgical site, can be actuated to pivotally open a pair of jaws in the jaw unit to a width beyond the outside diameter of the laparoscopic cannula, to engage and work patient tissue at the surgical site. Further objects and purposes of the present invention will be apparent to persons acquainted with apparatus of this general type upon reading the following specification and inspecting the accompanying drawings. SUMMARY OF THE INVENTION A handpowered, low cost, disposable laparoscopic surgical tool has a proximal hand engageable unit, an elongate extension unit and a distal jaw unit. Pulling a trigger of the hand engageable unit forwards an extension rod in the extension unit to pivot the jaws together. In one embodiment of the invention, the handle unit is primarily of molded plastic material for low cost and disposability. In an embodiment, electrocautery contact with the extension unit is through a bendable spring element. In an embodiment specially shaped links and connected jaw portions improve strength and control in opening and closing the jaws. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a partly schematic elevational view of a tool embodying the invention. FIG. 2 is an exploded pictorial view of the proximal and mid-portions of the FIG. 1 tool. FIG. 3 is an enlarged fragmentary elevational view of the handle unit body of FIG. 1. FIG. 4 is an enlarged pictorial view of the handle unit cover of FIG. 1. FIG. 5 is an enlarged elevational view of the trigger of FIG. 1. FIG. 6 is an enlarged pictorial view showing a fragment of the body of the handle unit. FIG. 7 is a fragmentary elevational view of the FIG. 6 body with additional structure installed. FIG. 8 is an enlarged cross-sectional view substantially taken on the line 8--8 of FIG. 7. FIG. 9 is a sectional view substantially taken on the line 9--9 of FIG. 8. FIG. 9A is a pictorial view of the slotted pin of FIGS. 8 and 9. FIG. 10 is an elevational view of the spring contact of FIG. 8. FIG. 11 is a pictorial view of such spring contact. FIG. 12 is an enlarged fragmentary elevational view of the extension tube of FIG. 8. FIG. 13 is a sectional view substantially taken on the line 13--13 of FIG. 12. FIG. 14 is a rear view of the rotator knob 130 of FIG. 8. FIG. 15 is an enlarged fragmentary view of the actuating rod of FIG. 8. FIG. 16 is a proximal end view of such rod. FIG. 17 is a sectional view substantially taken on the line 17--17 of FIG. 15. FIG. 18 is a sectional view substantially taken on the line 18--18 of FIG. 15. FIG. 19 is a fragment of the distal end of the FIG. 15 rod taken from above in FIG. 15. FIG. 20 is an exploded pictorial view of the jaw unit of FIG. 1. FIG. 21 is an enlarged pictorial view of a jaw of FIG. 20. FIG. 22 is an enlarged pictorial view of the FIG. 20 jaw unit. FIG. 23 is a view like FIG. 22 with the jaws partially open. FIG. 24 is a view like FIG. 22 with the jaws fully open. FIG. 25 is an elevational view of a FIG. 20 jaw with its corresponding actuating link. FIG. 26 is an elevational view taken in central cross-section of the FIG. 20 jaw unit showing the parts in alternative positions. FIG. 27 is a reduced size fragmentary top view taken substantially from the top of FIG. 22 and showing the relationship of jaws, link and extension tube and their assembled side-by-side relation. DETAILED DESCRIPTION A laparoscopic surgical tool 10 (FIG. 1) embodying the invention comprises a proximal handle unit 11 hand engageable by a surgeon for laparoscopic surgery, a distal jaw unit 12 insertable into a surgical site SS for working of tissue of a patient undergoing laparoscopic surgery, and an intervening elongate extension unit for supporting and actuating the jaw unit upon manipulation of the handle unit. The jaw unit 12 and extension unit 13 are diametrally compactly sized to allow insertion into a conventional laparoscopic cannula, a fragment of which is indicated at 14 in FIG. 1 by way of example. The cannula 14 guides entry of the jaw unit 12 into the surgical site SS, for surgical working of tissue therein. The extension unit 13 thus serves both to support and actuate the jaw unit 12. The handle unit 11 (FIG. 2) comprises a body 20, a trigger 21 and a cover 22. The body 20 and cover 22 are opposed, shallow, generally cup-shaped elements which when fixed together, as generally indicated in FIG. 1, form a chamber 23 (FIG. 2) for enclosing additional parts of the tool, including the top of the trigger 21. Integrally fixed to and angling rearward and downward from the body 20 is an extension bar 24 (FIG. 2) terminating in a thumb ring 25 engageable by the thumb of the user. Such body, extension bar, thumb ring, trigger, and cover are preferably of suitable rigid molded plastic material. The body 20 and cover 22 have opposed parallel side walls 28 and 29 respectively, from the perimeters of which perimeter rims 30 and 31 respectively extend toward each other as generally indicated FIGS. 3 and 4. The perimeter rims 30 and 31 on the body 20 and cover 22 abut, with the cover assembled on the body as shown in FIGS. 1 and 8, to enclose the chamber 23. The body 20 and cover 22 may be located in accurate registry and held together by any convenient means. In the embodiment shown in FIGS. 3 and 4, for example, opposed, hollow, generally cylindrical bosses 32 extend laterally toward each other and may be fixed coaxially together, as by sizing coaxially aligned bosses 32 to telescope one into to the other, or as by sizing coaxially opposed hollow bosses 32 to receive a common coaxial connector pin, as at 33 in FIG. 4. It will be understood that the bosses 32 appearing in the present drawings are not to scale. The cover 22 is intended to be permanently affixed to the body 20 in a last stage of assembly of the tool 10, as by the use of adhesive bonding, solvent bonding, localized heat (e.g. laser) bonding, or the like, around the perimeter of the rims 30 and 31, or by friction fit of laterally opposed bosses 32 with respect to each other, or the like. The trigger 21 (FIGS. 2 and 5) comprises a depending multiple finger loop 40 surmounted by an upstanding arm 41. The arm 41 has a trigger pivot hole 42 intermediate its ends and a drive hole 43 adjacent the top of the arm 41 and spaced above the trigger pivot hole 42. Both holes extend through the arm in a direction perpendicular to the plane of the arm, and hence to the plane of the page in FIG. 5. The drive hole 43 is elongated vertically so as to be oval in shape. A central slot 44 (FIG. 2) in the top of the arm 41 extends forwardly/rearwardly therethrough and opens upward therefrom. The bottom of the slot is below the bottom of the hole 43. The bottom portion of the rims 30 and 31 of the body 20 and cover 22 are notched in opposition to each other to thereby form a downward opening window 45, upward through which the arm 41 of the trigger 21 is received into the chamber 23 enclosed by the body 20 and cover 22, as seen in FIG. 7. There the trigger 21 is pivotally supported, for movement in the plane of the paper (and hence parallel to the planes of the body 20 and cover 22) by pivotal insertion of the lower central boss 32 of the body 20 through the trigger pivot hole 42, such that rearward displacement of the depending finger loop 40 of the trigger 21 pivots forward the upper end of the arm 41, including the drive hole 43 therein, for purposes of appearing hereinafter. The elongate extension unit 13 comprises an elongate axially shiftable actuation rod 50 snugly but axially slidably housed in an elongate extension tube 51 (FIG. 10). It will be understood that the tool 10 is relatively small. For example in one unit constructed according to the invention, the outside diameter of the extension tube 51 is somewhat less than 0.190 inch. The elongate extension unit 13 rotatably mounts on front and rear bearings in the handle unit 11. The perimeter rim 30 at the forward (rightward in FIG. 2) end of the body 20 protrudes laterally toward the cover 22 to form a lateral tab 52 (FIG. 6). The tab 52 fits snugly into a corresponding notch 53 (FIG. 4) in the forwardmost reach of the perimeter rim 31 of the cover 22. A bearing hole 54 (FIG. 6) extends forward through the tab 52 and acts as a front bearing for snugly and rotatably supporting a portion of the extension tube 51, as generally shown in FIGS. 7 and 8. In the preferred embodiment shown, the plane of abutment of the perimeter rims 30 and 31 of the body 20 and cover 22 contains the center of the hole 54 and the central axis of the elongate extension unit 13. The rear bearing for the extension tube is spaced rearward (leftward in FIG. 3) from, and is coaxially along with, the front bearing hole 54 in the tab 52 (FIG. 6). In the preferred embodiment shown, such rear bearing is formed by laterally opposing rear bearing parts 60 and 61 fixed to and extending laterally inboard from the inner surfaces of the side walls 28 and 29, respectively, of the body 20 and cover 22 respectively. In the preferred embodiment shown, such bearing parts 60 and 61 are integrally molded into the body 20 and cover 22 respectively. The rear bearing 60, 61 is here disposed approximately above the forward end of the downwardly opening trigger window 45. The rear bearing part 60 on the body side wall 28 (FIGS. 3 and 6) is, as seen from the front as in FIG. 6, generally U-shaped, having top and bottom legs 62 and 63 protruding toward the cover 22 and flanking a hemi-circular (here semi-circular) bearing groove 64. In the embodiment shown, the shaped rear bearing part 60 is relatively thick in the front/rear direction (from left to right in FIG. 6) and is divided into front and rear bearing webs 65 and 66 by top, middle and bottom relief slots 70 extending laterally from the side wall 28 of the housing 20 toward the opposing cover 22. The top, middle and bottom relief slots 70 prevent distortion of the axially relatively thick rear bearing part 60 during molding, where the body 20 is of molded plastics material. The rear portion of the extension tube 51 (FIGS. 2 and 7) has an annular groove 73, preferably of rectangular cross section, which snugly but rotatably fits, both radially and axially, in the semi-circular bearing groove 64 in the rear bearing part 60. The generally U-shaped rear bearing part 60 thus is the axial thrust bearing for the extension tube 51. The rear bearing part 60 also constrains the rear portion of the extension tube against movement upward or downward and toward the housing side wall 28. The rear bearing part 61 of the cover 22, in the assembled apparatus, engages the annular groove 73 in the extension tube 51 and prevents it from moving sideways (radially) out of the annular groove 73. Thus, the rear bearing 60, 61 acts as a radial thrust bearing to maintain coaxial location of the extension tube 51 while permitting its rotation about its own length axis. In the embodiment shown, the rear bearing part 61, as seen in FIG. 4, comprises a substantially T-shaped, pad-like protrusion (hereafter T-shaped pad) fixedly extending inward laterally from the side wall 29 of the cover 22. The T-shaped pad has a forward extending leg 74 and a vertically extending crosshead 75 at the rear end of the leg. The crosshead 75 rearwardly opposes the rear bearing web 66 of the 20 and the leg 74 extends forward to substantially the front end of the front bearing web 65, such that the leg 74 and the central portion of the crosshead 75 radially engage in the annular groove of the extension tube 51 in a radial thrust bearing manner, as well as assisting the rear bearing web 66 of the housing 20 in axially locating the extension tube 51, while supporting same for rotation. The rear bearing part 61 of the cover 22 further includes a finger 76 (FIG. 4) integrally fixed thereon and aimed laterally away from the cover side wall 29 toward the top portion of the rear bearing web 66 of the body, to assist same in preventing upward displacement of the rear portion of the extension tube 51, particularly as the upper part of the trigger arm 41 pivots upward into the central portion of its swing hereafter discussed. In this way, the proximal end portion of the extension tube 51 is held fixedly but rotatably about its own axis within the chamber 23. Spaced just forward of the rear bearing 60, 61 and protruding laterally in from the side walls 28 and 29 of the housing 20 and cover 22, are vertically extended, plate-like, laterally opposed, generally U-shaped saddles 90 and 91 (FIGS. 3, 4 and 6). The saddles 90 and 91, like the rear bearing parts 60 and 61 are very closely laterally opposed to each other but need not meet when the cover 22 is assembled on the housing 20. The laterally depressed central portions of the saddles 90 and 91 are sized to allow close passage therethrough of the rotatable extension tube 51 just forward of the annular locating groove 73 therein. The saddle 90 on the side wall 28 of the body 20 carries and locates a spring-like, electrically conductive metal contact 93 hereafter discussed in respect to FIGS. 6, 10 and 11. The U-shaped saddles 90 and 91 have a depressed central portion flanked by top and bottom horns 92 which protrude away from the respective side walls 28 and 29 of the body 20 and cover 22 respectively. The actuating rod 50, which is axially slidable within the extension tube 51 has a rear end portion extending rearwardly from the extension tube 51 and into the upward opening central slot 44 (FIG. 8) in the arm 41 of the trigger 21 and across the drive hole 43 therein. A slotted drive pin 82 extends axially through the drive hole 43 and is rotatable therein. An annular groove 81 coaxial in the actuating rod 50 coacts with the slotted drive pin 82 (FIGS. 2, 7 and 8) for connecting the top portion of the arm 41 of the trigger 21 to the rear end portion of the actuating rod 50 for forwarding of the actuating rod 50 along the extension tube 51 in response to a rearward pull on the depending finger loop 40 of the trigger 21 by the user of the tool 10. To this end, the drive pin 82 comprises a member, preferably of molded rigid plastics material, having a generally U-shaped diametrally extending notch 83 opening through one end thereof and sized to snugly but slidably receive diametrally therethrough the annularly grooved portion 81 of the actuating rod 50 (FIG. 8). The notch 83 is flanked at its diametrally opposite ends by diametrally opening generally U-shaped recesses 84 (FIGS. 8 and 9A) for receiving portions of the actuating rod 50 at the opposite ends of the annular recess 81. The axial length of the annular recess 81 is equal to or slightly larger than the diametral extent of the notch 83 and the diameter of the pin 82 is equal to or only slightly less than the minimum diameter of the hole 43, such that clockwise (FIG. 7) pivoting of the trigger 21 positively and axially shifts forward the actuating rod 50. As the trigger 21 (FIG. 7) is pivoted about its boss 32, its drive hole 43 moves through an arc whose major component of direction is parallel to the direction in which the actuating rod is constrained to move, i.e., along the length axis of the extension tube 51. However, the trigger and drive hole 43 are also a minor component of direction perpendicular to the length axis of the extension tube and hence to the direction of movement available to the actuating rod 50. Accordingly, the elongation of the drive hole 43 in the latter direction allows the drive pin 82 lost motion along the length of the oblong drive hole 43 in the upper end of the arm 41, so that the drive pin 82 does not tend to bend the actuating rod 50 as the drive pin pushes forward or pulls rearward the actuating rod during pivoting at the trigger 40. As seen in FIG. 8, the drive pin 82 is snugly trapped between the side walls 28 and 29 of the body 20 and cover 22 in the assembled condition of the tool 10. The drive pin 82 thereby cannot escape from the upstanding arm 41 of the trigger 21 and the rear end portion of the actuating rod 50, and must thus accomplish forward and rearward movement of the actuating rod 50 in response to manual rearward and forward pivoting of the finger loop 40 of the trigger 21. In this way the user of the tool can forwardly and rearwardly move the actuating rod 50 with respect to the extension tube 51 in which it is axially slidably guided. The front/rear movement of the actuating rod 50 with respect to the extension tube 51 accomplishes opening and closing movement of the jaw unit 12 (FIG. 1) at the front (distal) end of the tool 10 as hereafter discussed. To allow the jaw unit 12 to perform electrocauterization, an electrically conductive terminal pin 94 (FIG. 1) is provided on the handle unit 11 for connection to a conventional electric cauterizing current source schematically indicated at 95. More particularly, the current source 95 is connected, as indicated schematically by the dotted lines 96 and 97, respectively to the pin 94 and to the patient at the surgical site SS. As hereafter discussed, the terminal pin 94 is electrically connected to the extension tube 51 and the actuating rod 50 therein. The extension tube 51 and actuating rod 50 are of electrically conductive metal (in the preferred embodiment shown of surgical grade stainless steel.) The extension tube 51 and actuating rod 50 both are physically and electrically connected to the jaw unit 12 as hereafter more fully discussed. The terminal pin 94 is of electrically conductive material, preferably surgical grade stainless steel. The exposed upper end of the terminal pin 94 is diametrally slotted at 100 (FIG. 2) to make it radially springy in a direction transverse to the slot 100, to enable it better to be gripped by a conventional electrical connector, not shown, connected through the line 96 to the current source 95. The inner end portion of the terminal pin 94 is provided with an annular groove 101 used to fix the pin 94 in the handle unit 11. More particularly, the upper portion of the rims 30 and 31 of the body 20 and cover 22 include, preferably by integral molding therein, respective upward and rearward angled bosses 102 and 103 (FIG. 2). With the cover 22 installed along the body 20 as shown in FIG. 1, the bosses 102 and 103 abut each other to form a rearward angled composite boss 102, 103. An outwardly and rearwardly angled hole penetrates through the composite boss 102, 103 and comprises opposed grooves 104 and 105 (FIGS. 3 and 4), which define a composite hole 104, 105 communicating with the chamber 23. The outer end of the composite hole 104, 105 communicates with a radially enlarged, outwardly facing coaxial composite recess 106, 107 defined by opposed recess portions 106 and 107 respectively (FIGS. 3 and 4). In the assembled apparatus, the annular groove 101 of the pin 94 is trapped axially in the composite hole 104, 105, leaving a short inner end portion 110 of the terminal pin positively trapped inside the chamber 23 and a long outer end portion 111 of the terminal pin extending outboard of the composite recess 106, 107 and carrying outer end slot 100. In the preferred embodiment shown, the opposing recess portions 106 and 107 and the groove 104 are of circular cross section corresponding closely to that of the corresponding portions 101 and 111 of the contact pin 94. The groove 105 may be of circular cross section if desired but it can also be, as illustrated in FIG. 4, of the different cross section, here square, as desired. In any event, it is the boss portions 112 (FIGS. 3 and 4) surrounding the composite hole 104, 105, which extends radially into the annular groove 101 of the terminal pin 94 to axially trap same between the body 20 and cover 22. The contact spring 93 (FIGS. 10 and 11) here comprises a spring tempered stainless steel sheet of uniform thickness, preferably of elongate generally rectangular shape, and having a substantially flat, elongate central portion 120 provided with an elongate rectangular central hole 121. The lower end portion 122 of the contact 93 is bent in a U-shape. The upper end portion 123 of the contact 193 is bent substantially in an L-shape. The elongate central hole 121 extends substantially the full distance between the U-shaped and L-shaped end portions 122 and 123. A tab 124 bends up from the upper left (FIGS. 7 and 11) corner of the L-shaped end portion 123. In its installed position of FIGS. 6 and 7, the spring contact 93 abuts, with its U-shaped and L-shaped end portions 122 and 123, the interior face of the side wall 28 of the body 20 immediately below and above the saddle 90. The horns 92 of the saddle 90 protrude through the elongate hole 121 of the spring contact 93, leaving the central portion of the saddle 90 laterally outward of the flat central portion 120 of the spring contact 93. The flat central portion 120 of the spring contact 93 is spaced far enough from the body side wall 28 that the installed extension tube 51 bears forcibly against and bends slightly laterally outwardly, toward the body side wall 28, the central portion 120 of the spring contact 93, to assure firm and reliable electric current passing contact between the spring contact central portion 120 and rotatable extension tube 51. Indeed, the spring contact 93 is fixed in place on the horns 92 of the saddle 91 by the extension tube 51 pressing same laterally outward toward the side wall 28 of the body 20. Thus installed the spring contact 93 locates its tab 124 to face upward and rearward and extend laterally inboard away from the body side wall 28. The free edge of the tab 124 resiliently presses against the interior end of the electrical terminal pin 94, so as to make firm, reliable electrically conductive contact therewith. In this matter, electric current is passed through the pin 94 and contact 93 to the periphery of the extension tube 51 and to the actuating rod 50 therein. The outer periphery of the extension tube 51 is snugly and fixedly covered by an electrically insulated sheath 147 (FIGS. 8 and 20) which extends from within the front end of the knob 130 almost to the front end of the extension tube 51. In the preferred embodiment shown, the sheath is of conventional heat shrink tubing, for example of polytetrafluoroethylene (PTFE or Teflon brand) heat shrink tubing. The extension tube 50, immediately ahead of the body 20 and cover 22, carries a rotator knob 130 in fixed relation thereon, so that the user, by rotating the rotator knob 130, can thereby rotate the extension tube 51 and with it, the actuating rod 50 therein. In the embodiment shown in FIG. 14, the rotator knob 130 is a rigid molded plastics element having a flat rear face whose perimeter is substantially a five pointed star, providing circumferentially spaced flute-like finger grips 129. The rotator knob 130 preferably tapers from rear to front, as shown in FIG. 1, and a rear face is provided with material saving recesses 128 (FIG. 14). The knob 130 may be fixed to the extension tube 51 by any convenient means, but in the preferred embodiment shown such is done as follows. An axially extending keyway 131 (FIG. 8) in the rear portion of the extension tube 51 receives an axially extending key 132 fixed, preferably integrally radially, to the knob 130 and inwardly extending into the central bore 133 of the knob 130. The key 132 thus compels rotation of the extension tube 51 with the knob 130. The knob 130 is axially fixed on the extension tube 51 by any convenient means, here comprising knurling or grooving 134 on the periphery of the extension tube 51, which frictionally and or mechanically grips firmly the interior surface of the central bore 133 of the knob 130 in at least the rear portion thereof. In the preferred embodiment shown, provision is made for transfer of liquid to or from the surgical site SS longitudinally along the annular interface between the extension tube 51 and actuating rod 50. Thus, for example, irrigation liquid may be passed to the surgical site SS or, alternatively, liquid may be suctioned from the surgical site SS. In more detail, the front portion of the central bore 133 of the knob 130 is radially enlarged, as indicated at 135 in FIG. 8, at a location immediately ahead of the grooving 134. Spaced slightly forward of the grooving 134, the exterior peripheral surface of the extension tube 51 is provided with an axially spaced pair of annular grooves to respectively receive and resilient seals, preferably O-rings, 136 and 137. Such O-rings 136 and 137 bear snugly and sealingly but rotativably on the inner surface of the enlarged front bore portion 135 of the knob 130. A radial hole 140 penetrates the perforated extension tube 51 in axially spaced relation between the O-rings 136 and 137. Radially outboard of the hole 140, the knob 130 includes a radially outwardly extending tubular stack 141 having a coaxial liquid passage 142 connectable through a liquid conduit 143 to an irrigation liquid source LS or, if desired a gravity or suction liquid drain LD as schematically indicated in FIG. 8. The radially outer end of the stack 141 is provided with a conventional end fitting, preferably molded therein, here for example a Luer male fitting 144 suitable to fixedly and sealingly engage a conventional female Luer fitting on liquid line 143. A plug 145 may be inserted in the outer end of the stack 145 to close same when no liquid line 143 is connected thereto. To facilitate liquid flow between the liquid hole 140 and the jaw unit 12, along the annular area between the extension tube 51 and the actuating rod 50 the corresponding length of the actuating rod 50 is provided with at least one longitudinally extending flat 146 which increases radial spacing from the interior surface of the extension tube 51 and thereby provides a longitudinal channel for liquid flow between the liquid stack 141 and the surgical site SS. In the preferred embodiment shown, the actuating rod 50 carries several (here four) evenly circumferentially spaced ones of the elongate flats 146. It is contemplated that other forms of liquid channel may be provided between the extension tube 51 and actuating rod 50, such as keyways, etc. but the flats 146 are preferred for ease in manufacture. Attention is directed to the jaw unit 12 at the distal end of the tool 10. The distal (rightward in FIGS. 1 and 15) end of the actuating rod 50 includes an axially deep, diametrally and forwardly opening slot 150 (FIG. 19). A diametral hole 151 (FIGS. 15, 18 and 19) extends through the actuating rod 50 immediately adjacent the distal (rightward in FIG. 15) end thereof and perpendicularly crosses the width of the slot 150. The slot 150 thus forms the distal end of the actuating rod 50 as a forward opening yoke whose arms 152 diametrally oppose each other across the forward opening slot 150. In FIG. 20, the actuating rod 20 is shown in a position during assembly of the tool 10, namely with its distal end portion extended forwardly from the extension tube 51 preparatory to its connection to the links 200 hereafter described. The distal end of the extension tube 51 comprises a forwardly opening substantially rectangular, diametral slot 160 (FIGS. 12 and 23) of width slightly less than the inside diameter of the extension tube 51. The blind end 161 of the slot 160 is slotted to form a narrower, shorter subslot 162 (FIG. 12) of rectangular cross section and which at its forward end thus opens into the slot 160. The slot 160 and subslot 162 have the same central plane. The slot 160 and subslot 162 divide the forward end of the extension tube 51 into diametrally opposed arms 163. A diametral through hole 164 (FIGS. 12 and 20) extends through the arms 163 in a direction perpendicular to the central plane of the slot 160 and subslot 162. The jaw unit 12 comprises a pair of preferably identical jaws 170 (FIG. 20). In the particular embodiment shown, the jaws 170 are dissector jaws having distal end portions 171 which can be brought together for gripping tissue of a patient and moved apart to release same. It is also contemplated that jaws of other types and/or purposes, for example, scissors jaws (not shown) may be substituted. The jaws 170 are preferably identical to each other, and are used with one rotated at an 180° angle about its longitudinal axis with respect to the other. The proximal end portions 172 of the jaws 170 are each of generally circular perimeter shape, as seen in FIG. 25. The mid-portion 173 of each jaw extends forward, generally tangentially, from the proximal portion 172 to the distal end portion 171. The mid-portion 173, as seen in FIG. 20, is semi-circular in cross-section. The mid-portion 173 generally tapers toward the distal end portion 171, having either a semi-cylindrical rear part 174 and tapered front part 175 as in FIG. 20 or merely tapering as in FIGS. 21-24. The mid-portions 173 of the jaws 170 have opposed flat faces 176. The distal end portions 171 of the jaws 170 are of semi-circular cross-section and forwardly extend the reduced diameter end of the mid-portion 173 and have rounded noses 177. The distal end portions 171 also continue forward the flat face 176 of the mid-portion 173, but add a forwardly extending series of transverse serrations, or teeth, 181. The teeth 181 of the jaws 170 can closely oppose each other for gripping patient tissue as generally indicated in FIG. 22. The semi-circular rounded distal end portions 171 may be substantially cylindrical as in FIG. 20 or may taper forwardly, as in FIG. 22. The proximal end portions 172 of each extend in an imaginary plane perpendicular to the plane of the flat face 176 of the corresponding jaw. The proximal portion 172 is of flat faced, hockey puck-like shape and is offset to one side of the longitudinal central axis J (FIG. 20) of the jaw 170, and more particularly of the mid-portion 173 and distal end portion 171 of the jaw. Each jaw proximal portion has a central pivot hole 182 which extends coaxially therethrough and has a central axis H which is substantially perpendicular to the longitudinal axis J of the jaw. The opposed faces 183 of the puck-like proximal end portions 172 are relieved at 184. The relief 184 lies immediately behind the tangentially forwardly extending jaw mid-portion 173, as seen in FIG. 25. In the orientation of the jaw in FIG. 25, the relief 184 opens upward away from the pivot hole 182 and opens rearward. The bottom of the relief 184 comprises front and rear ramps 185 and 186 that rise gradually (the rear ramp 186 the more gradual of the two) to a peak close above the hole 182 to form a kind of gable roof over the hole 182. The front end of the front ramp 185 goes forward and upward to form a rear facing front wall 187 of the recess 184. The proximal and mid-portions 172 and 173 share a continuous flattened tangential edge which in the jaw orientation of FIG. 25 is substantially horizontal and at the top of the jaw. The jaws top (in FIG. 25) edge 190, shared by the proximal and mid-portions 172 and 173, is flattened and horizontal, substantially in parallel to the longitudinal extent of the jaw 170. A pivot stub shaft 191 protrudes laterally fixedly into the recess 184. A jaw pivot pin 192 (FIG. 20) extends through and beyond the diametral through hole 164 in the arms 163. One end 193 of the pin 192 is enlarged. The other end 194 of the pin 192 is conveniently peened over to form a further enlarged head indicated at 194 in FIG. 22. The enlarged ends 193 and 194 axially trap the pivot pin 192 in transverse spanning relation across the diametral slot 160 of the extension tube 51. The jaw pivot pin 192 extends through the pivot holes 182 in the puck-shaped proximal end portions 172 of the opposed jaws 170, which jaw end portions thus lie in parallel between the arms 163 at the distal end of the extension tube 51 and are pivotally supported on the extension tube 51 by the pivot pin 192. The jaws 170 are thus pivotable from their fully closed FIG. 22 position, through their FIG. 23 position, to their FIG. 24 90° open position. More particularly, the puck-like proximal end portions 172 of the jaws 170 are spaced side-by-side from each other in the diametral slot 160, leaving a space therebetween for links 200 discussed hereinafter. Each jaw 170 is connected to the distal end of the actuating rod 50 (FIG. 20) by a generally P-shaped actuating link 200. Each link 200 is of flat rigid stock having a relatively large planar head 201 with a generally domed proximal end 202 and substantially parallel, forwardly extending edges 203 and 204. Each link 200 further includes a neck 205 extending forward from the head 201. The neck 205 is substantially narrower than the head 201 as measured in a direction perpendicular to the edges 203 and 204. The leg 205 continues forward the edge 203. A hole 206 is provided in the domed proximal portion 202 of the head 201. The head 201 and arm 205 form a generally L-shaped structure, leaving a relatively large notch facing forward, and in FIG. 25 downward. Such notch is defined by an interior edge 10 extending forward along the leg 205 opposite from the edge 203, and further leaving a forward facing edge 11 which is the forward edge of the head 201. The forward end portion of the leg 205 bulges slightly into the notch at 212 to leave room for a hole 213 in the distal end portion of the leg 205 for pivotally receiving therein the pivot stub shaft 191 of the corresponding jaw 170, as seen in FIG. 25. In this way, the arm 205 of each link 201 connects pivotally to the proximal end portion 172 of the corresponding jaw in an eccentric manner, so that forward movement of the links 200 tends to close the distal portions of the jaws together, toward their FIG. 22 position, and rearward pulling of the links pivots the jaws in the opposite direction, namely toward their open FIG. 24 position. The link 200 (FIG. 25) with its head 201 and neck 205 has a perimeter profile which may be thought to caricature, or cartoon, the head and neck of a turkey, complete with caricature beak at the join of edges 211 and 204 and caricature eye at 206. The rear ends of the links 200 are pivotally connected by a pivot pin 214 (FIG. 20) extending through their rear pivot holes 206 and through the diametral holes 151 in the arms 152 of the actuating rod 50. In the assembled tool 10, the proximal ends 202 and pivot holes 206 of the planar head 201 of the links 200 are thus relatively pivotally retained in the forward opening slot 150 of the actuating rod 50 for pivotal motion with respect thereto and for forward and rearward movement upon corresponding forward and rearward movement of the actuating rod 50. Successive front, mid and rear positions of the actuating rod 50 and far actuating link 200 are shown in FIG. 26 in solid line, chain line and dotted line respectively and are referenced by characters 50F, 50M and 50R, respectively and 200F, 200M and 200R, respectively. As further seen in FIG. 26, these positions of the actuating rod 50 and link 200 correspond to the respective closed, mid and open positions of the corresponding jaw 170 indicated at 170F, 170M and 170R in solid, chain and dotted lines, respectively in FIG. 26. Just as the assembled jaws 171 are rolled 180° about their length axis with respect to each other, so to are the links 200, as generally indicated in exploded relation in FIG. 20. Thus, in use, the two necks 205 are spaced close above and below the pivot pin 192 of the jaws 171. The plate-line links 200, need to be unbendable in use, but of sufficiently small thickness to fit side-by-side in the actuating rod forward slot 150 in a freely pivotable manner, as generally shown in FIGS. 22-24. The location of the jaws 170 and links 200 with respect to the slot 160 of the extension tube 51 is seen from the top in FIG. 27, without minor visual distortions that may appear in the pictorial FIGS. 22-24. OPERATION The apparatus may be assembled as follows. With the links 200 assembled to the respective jaws 170, the links 200 may be inserted rearward into the forward opening slot 150 (in its exposed assembly position of FIG. 20) and pivoted there by insertion of the pin 214. The actuating rod 50, and with it the links 200 and jaws 170, may then be pulled rearward, so the links 200 and the rear portions of the jaws 170 enter the slot 160 in the front end of the extension tube 51, sufficient to allow insertion of the jaw pivot pin 192 to pivotally mount the jaws on the forward end of the extension tube 51. Thereafter, the free protruding end 194 of the pin 192 can be peened to maintain the pin 192 axially trapped on the arms 163 of the extension tube 51. The sheath 147 may be applied to the extension tube 51 either before or after installation of the jaws 170 and links 200 with respect thereto but is installed on the extension tube 51 preferably before installation of the knob 130 thereon. With the electrically insulating sheath 147 and O-rings 136 and 137 (FIG. 8) fixed on the extension tube 51, the knob can be forced axially onto the rear end portion of the extension tube to its operative FIG. 8 position. The extension tube 51, containing the actuating rod 50, can then be inserted rearwardly through the bearing hole 54 and past the spring contact plate 93 and rear bearing part 60. With the actuating rod 50 thus pulled far enough rearward in the extension tube 51, and the upper end of the trigger 21 inserted upward through the window 45, the rear end portion of the actuating rod 50 enters the slot 44 in the top portion of the trigger and is pivotally secured in place therein by lateral insertion of the slotted drive pin 82 to operatively connect the actuating rod 50 to the trigger 21. The electrode pin 94 can then be placed laterally into the boss 102 (FIG. 7) with its inner end 110 in electrical abutting contact with the edge of the tab 124 of the contact spring 93. The cover 22 can then be fixed rim-to-rim on the body 20. The tool 10 is operated as follows. The tool 10 is useable in laparoscopic surgery by insertion of the closed jaw unit 12 and elongate extension 13 (FIG. 1) through the usual laparoscopic cannula 14, which has previously been inserted in a conventional manner into the surgical site SS. The tool is normally handled and actuated by one hand of the user, the thumb of such hand inserted in the thumb ring 25 and one or more fingers inserted in the depending loop of the trigger 21. Pulling the bottom of the trigger 21 rearward toward the thumb loop 25 forwards the top of the trigger 21, by pivotal movement of the trigger 21 around the corresponding boss 32 (FIG. 7). The shallow arcuate movement of the top of the trigger 21, generally indicated by the adjacent arrow in FIG. 7, acts through the drive pin 82 to forward the actuating rod 50. The minor vertical component of trigger pivoting motion is absorbed by the vertical lost motion of the drive pin 82 in the oblong hole 43 in the top of the trigger and does not tend to vertically bend the rear end of the actuating rod 50, but instead applies purely axial urging thereto. Such forward movement of the actuating rod 50 moves the opposed jaws 170 to their closed position 170F (FIGS. 24 and 26). This closed position is a normal position of the jaws for insertion of the tool into the laparoscopic cannula since it minimizes the width (or diameter) of the distal portion of the tool and enables it easily to pass through the laparoscopic cannula. Once the jaw unit 12 has been inserted through the laparoscopic cannula 14 into the surgical site SS, as shown in FIG. 1, the jaws 170 (FIGS. 22-24) can be moved from closed to open position by moving the lower part of the trigger 21 forwardly to rock the upper end of the trigger 21 rearwardly and thereby pull the actuating rod 50 rearwardly, as generally indicated in the sequence from 50F to 50R in FIG. 26. In opening the jaws 170, the legs 205 of the links 200 move rearwardly in a shallow generally horizontal arc (note the sequential positions of the pin 191 in FIG. 26). Accordingly, each rearward moving arm 205 moves radially outward slightly to clear the top of the hill formed by the saw ramps 185 and 186 (FIG. 25). As seen in FIG. 26, each arm 205 at most rises only to the outer edge of the extension tube front slot 160, so that the electrical insulating sheath 147 does not interfere with actuating motion of the links 200. The configuration of the jaw recess 187 (FIG. 25) and corresponding link 200 represents a best compromise between desirably minimizing the outside diameter of the extension tube 51 and forwardmost extension of its surrounding electrically insulating sheath 147, with sufficient link stiffening and hence resistance to bending as to enable the link 200 to forcibly push, as well as pull, on the jaw stub shaft 191 during forcible pulling and pushing of the trigger 21. To this end, the shape and depth of the jaw recess 184 is selected to allow maximum width of the link neck 205, particularly to maximize the amount of link neck material surrounding the pivot pin 191 and to maximize the width of the link neck 205 where it merges into the link head 201. The substantial width of the link head 201 at its forward end portion, from which the neck 205 forwardly extends, permits maximizing of spacing between the parallel, forward extending edges 203 and 204 of the head 201 to allow them to lie closely to the surrounding sheath. This configuration also allows the forward portion of the link head 201 adjacent the neck 205 to lie close behind the puck-shaped jaw portion 172 in the forward position of the link 200. Maximizing the width of the link head 201 roughly halfway between the pivot holes 206 and 205 thereof, by maximizing the widthwise spacing of the link head edges 203 and 204, advantageously allows each link head 201 in this area between edges 203 and 204 to reinforce the other link 200 against any tendency to twist between its front and rear ends, particularly when the links 200 are pushing the jaws 170 closed, to grip forcibly-a portion of patient tissue. Also, the configuration of the link 200 and the attached rear portion of the jaw 170 advantageously allows the user to open the dissector jaws very widely and yet be capable of easily and carefully controlling the relative position of the jaws. The plate-like links 200 (FIGS. 22-24 and 26) must be very thin to pivotally fit side-by-side with each other between the puck-like proximal end portions 172 of the jaws 170 in the extension tube forward slot 160, in view of the small outside diameter extension tube 51 required to slidably insert in a conventional laparoscopic surgical cannula 14 (FIG. 1). For example, in one unit constructed according to the invention, the height (vertically in FIGS. 20 and 27) of the puck-like jaw proximal end portion 172 was about 0.186 inch, the outside diameter of the extension tube 51 was about 0.188 inch, and the width of its front slot 160 was about 0.095 inch (less than 1/10 inch). In the same unit, the thickness of each puck-like jaw proximal end portion 172 was about 0.45 inch and the thickness of the recess 184 therein was sufficient to accommodate a link 200 of about 0.018 inch thick. This left about 0.001 inch clearance at the sliding interfaces between the extension tube 51 (at the forward slot 160 thereof), the jaw proximal end portions 172 and the links 200. Though of relatively stiff material (preferably surgical grade stainless steel), nevertheless a link 200, and particularly a link neck 205, only 0.018 inch thick (approximately the combined thickness of pages 1-5 of the present specification) would be expected to bend responsive to a relatively small lengthwise compressive force thereto, with the link unsupported. In the same unit built according to the invention, the minimum width of the link neck 205 was about 0.047 inch (approximately 3/64 inch, about the maximum allowed by the space between the pivot pin 192 and the sheath 147). On the other hand, the width between the flat edges 203 and 204 of the link head 201, which head is spaced from and does not need to clear the pin 192, was about 0.175 inch (a bit over 11/64 inch), to maximize the stiffness of the head 201 in response to axial compressive forces on the link 200. With these very thin links 200 (i.e., 0.018 inch in such one unit constructed according to the invention), sufficient link stiffness and resistance to bending (as to enable the link 200 to forcibly push on the jaw stub shaft 191 sufficient to press the jaws 170 to forcibly grip a portion of patient tissue) is here achieved by close lateral support of the link by laterally adjacent structure. More particularly, the narrow neck 205 of each link is closely laterally slidably backed on one side by the side of the recess 184 in the corresponding jaw 170, which jaw 170 is in turn laterally backed by the extension tube 51 at the edge of the slot 160. The link narrow neck 205 is laterally supported on the other side by the proximal portion 172 of the other jaw 170, diametrally remote from the recess 184 therein, which other jaw rear end portion is in turn laterally backed by the material of extension tube 51 at the other side of the slot 160 therein. As seen in FIG. 26, most of the narrow link neck 205 is continuously closely sandwiched in slidable but laterally supported relation between the laterally imposed jaw rear end portions. Further, the length portion of the neck 205 laterally supported between proximal end portions of adjacent jaws 170 is maximized with the jaws closed or almost closed, as in tissue grasping relation, and is only lessened with the jaws pulled apart. Thus as maximum gripping force is applied to the jaws by forward pushing on the actuating rod 50, the jaw necks 205 are in their range of maximum lateral support between the cheeks of the adjacent jaw rear end portions. Also, the narrowed rear end portions 202 of the links 200 are closely laterally supported by the lateral edges of the reduced width subslot 162 of the extension tube 51. The widest portion of the link 200, between the parallel top and bottom edges 203 and 204 in FIG. 25, while not laterally supported by the jaws 170 or extension tube 51, nevertheless resists bending upon axial compression of the link due to its short axial length, its maximized lateral (vertically in FIG. 25) width and the close side-by-side mutual support against bending one toward the other achievement of the cheek-to-cheek sliding abutment of these two portions of links 200. The result is that the links 200 are capable of transmitting substantially higher axially compressive forces than would have otherwise been expected. The very small clearances laterally between the extension tube slot edges, jaw proximal end portions and link necks maximizes the lateral support and hence resistance to bending imparted to the link necks by the sandwiching jaw rear end portions and extension tube slot edges. Slight interference to sliding between the parts is tolerable since it adds to the resistance to bending of the link necks. In a figurative sense, the link necks almost become an interior part of a solid block although one in which they are allowed to translate and pivot in their own plane. In some instances, it may be desirable during surgery to pass an electric cauterizing current through the jaws 170 to patient tissue, for cauterizing same. This may be true in the case of dissector type jaws as well as with jaws of other types, such as conventional jaws (not shown) capable of scissors-like cutting. To that end, the electric cauterizing current source 95 can in a conventional manner be connected by electric conductors 96 and 97 (FIG. 1) to the terminal pin 94 at the proximal portion of the tool 10, as well as to the patient near the surgical site SS. Cauterizing current is conducted by the spring-like contact 93 from the inner end 110 of the electric terminal pin 94 to the extension tube 51. Such electrical contact is particularly reliable due to bearing of the spring contact edge 124 forcibly and resiliently against the inner end portion 110 of the pin 94 and due to the resilient self-urging of the mid-portion of the springy contact member 93 radially against the periphery of the extension tube 51, such contact being continuous despite possible rotation of the extension tube 51 by user rotation of the knob 130. Thus, electric current is supplied to the extension tube 51 as well as to the actuating rod 51 electrically contacting the interior thereof, through the pivot pins 192 and 214 (FIG. 20) of shafts 191 and links 200 to the jaws 170, all of which are of electrically conductive material, preferably surgical grade stainless steel. As mentioned, liquid flow is permitted between the surgical site SS and the stack 141 on the rotate knob 130. Thus, for example, during a surgical procedure, irrigation liquid from a liquid source LS (FIG. 8) can be admitted to the stack 141 on the rotate knob 130 to thus feed through the hole 140 and along the flats 146 on the actuating rod 50 (and thus within the extension tube 51) to enter the surgical site SS adjacent the jaws 170. It will be noted that the tool 10 can be manufactured inexpensively, the parts being of molded plastics material in the handle unit 11, and so can be sold and used as a disposable, for disposal after a surgical procedure on a single patient, thereby avoiding the expense of and risks associated with resterilization. The human hand is formed such that it can apply more force to the finger loop of the trigger 21 in pulling it rearwardly toward the thumb ring (by clenching the hand into a fist) than by pushing the finger loop of the trigger forwardly. In consequence, the closing force applied to the jaws and hence their gripping force on patient tissue is maximized at least in part due to the arrangement of the links 200 to close the jaws 170 in response to such a fist clenching, rearward pull on the lower portion of the trigger 21. Although a particular preferred embodiment of the invention has been disclosed in detail for illustrative purposes, it will be recognized that variations or modifications of the disclosed apparatus, including the rearrangement of parts, lie within the scope of the present invention.
A handpowered, low cost, disposable laparoscopic surgical tool has a proximal hand engageable unit, an elongate extension unit and a distal jaw unit. Pulling a trigger of the hand engageable unit forwards an extension rod in the extension unit to pivot the jaws together. In one embodiment of the invention, the handle unit is primarily of molded plastic material for low cost and disposability. In an embodiment, electrocautery contact with the extension unit is through a bendable spring element. In an embodiment specially shaped links and connected jaw portions improve strength and control in opening and closing the jaws.
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BACKGROUND OF THE INVENTION [0001] The present invention relates to a monodirectional impeller for centrifugal electric pumps having a permanent-magnet synchronous motor. [0002] It is known that permanent-magnet synchronous electric motors have a general structure which comprises a stator, provided with an electromagnet constituted by a lamination pack and by corresponding windings, and a rotor, which is arranged between two pole shoes formed by the stator and is crossed axially by a shaft which is rotatably connected to a supporting structure. [0003] These motors are bidirectional, i.e., at startup the rotor can be induced equally to turn clockwise or counterclockwise. [0004] This characteristic depends on a plurality of factors, including the arrangement of the polarities of the rotor with respect to the magnetic field generated between the pole shoes of the stator pack when the induction windings are supplied with AC current. [0005] For this reason, permanent-magnet synchronous motors are currently widely used where the direction of rotation is not important; accordingly, for example they are coupled, in centrifugal pumps, to radial-vane impellers which ensure the same performance in both directions of rotation. [0006] In order to increase the efficiency of synchronous-motor electric pumps without resorting to the use of particular electronic starting devices, it is convenient to use vanes which are orientated with a certain curvature profile, which clearly presumes a single direction of rotation of the motor. [0007] Accordingly, electronic starter devices have been devised which guide the motor so that it starts in a single direction of rotation; as an alternative thereto, mechanical devices have been devised which block the rotor when it tends to start in the wrong direction of rotation (reference should be made for example to patent application PD98A000003 of Jan. 8, 1998 in the name of this same Applicant). [0008] In this manner, monodirectional behavior is ensured in any operating condition assumed by the electric pump. [0009] However, the system may generate noise during starting and is a limitation as regards reliability (for high-power pumps), since there is a mechanical device which is subjected to repeated stresses, especially during starting. [0010] A particularly important alternative for a monodirectional synchronous electric pump without mechanical devices for stopping the rotor and without electronic devices (which are reliable but expensive) is constituted by what is disclosed in patent application PD98A000058 of Mar. 19, 1998 in the name of this same Applicant. [0011] This patent application discloses a device which is able to start, with limited power levels, loads which have high moments of inertia, such as impellers with orientated vanes of a centrifugal pump. [0012] In particular, this is a driving device with a larger angle of free rotation between the rotor and the impeller, so as to obtain, with respect to conventional mechanical couplings, several advantages: [0013] reduction of the starting torque for starting the motor; [0014] a consequent reduction of the level of vibrations generated during synchronous operation; [0015] the motor is rendered monodirectional by means of the correct design of the vanes of the impeller, so that the power absorbed by the load in one direction of rotation is greater than the available power of the motor and is smaller in the opposite direction of rotation. [0016] Therefore, by designing the motor and the vanes of the impeller so that the power absorbed by the load in one direction of rotation is greater than the available power of the motor and smaller in the opposite direction of rotation, in the first case the impeller goes out of step with respect to the motor, is halted and automatically reverses its motion, whereas in the second case it is driven normally. [0017] It is thus possible to render the pump monodirectional by utilizing the difference in power between what the motor is able to deliver and the power absorbed by the load in the two directions of rotation (the rotor stops because the power required by the impeller in the wrong direction of rotation is greater than the power that the motor can deliver). [0018] Although this system provides a fundamental advantage with respect to the prior art, it still has limitations, because monodirectionality is ensured only within a flow-rate/head range; accordingly, it is used in applications where the hydraulic working point does not vary beyond certain limits or, in other words, where the characteristic curve of the duct does not undergo significant variations (this is the case, for example, of washing pumps for dishwashers). [0019] In the accompanying drawings FIG. 1 plots, for both directions of rotation of the motor, the power absorbed by the motor as a function of the required flow-rate. [0020] The line A plots the correct direction of rotation, the line B plots the wrong direction of rotation, and the straight line C represents the maximum power that can be delivered by the motor. [0021] The chart shows three flow-rates Q 1 , Q 2 and Q 3 , which correspond to three working points, and it is clear that only Q 1 and Q 2 are the flow-rates for which a single direction of rotation is ensured, since the maximum power that the motor is able to deliver (straight line C) is greater than the power required by the impeller when it turns in the correct direction of rotation (line A) and is smaller than the power required by the impeller when it turns in the opposite direction (line B). [0022] For the flow-rate Q 3 , instead, there is a condition in which both power levels, in both directions of rotation, are lower than the maximum deliverable power and therefore monodirectional behavior is not possible. SUMMARY OF THE INVENTION [0023] The aim of the present invention is therefore to eliminate the above-noted drawbacks of the above-cited device related to patent application [0024] Within this aim, a consequent primary object is to provide a pump which is monodirectional over the entire available flow-rate range. [0025] Another object is to provide all of the above in a constructively simple manner. [0026] Another object is to have no effect on noise levels. [0027] Another object is to provide an impeller, if necessary, with deformable vanes enclosed between a double fluid conveyance wall (closed impeller). [0028] This aim and these and other objects which will become better apparent hereinafter are achieved by an impeller for centrifugal electric pumps having a permanent-magnet synchronous motor, characterized in that its vanes are deformable at least along part of their extension and can change their curvature, when loaded, in one direction of rotation, so that the power required for rotation in that direction is greater than the maximum power that can be delivered by the motor. [0029] Conveniently, in one embodiment, this aim and these objects are achieved by an impeller for centrifugal electric pumps having a permanent-magnet synchronous motor, characterized in that it comprises: [0030] a first disk-like element provided with curved nondeformable vanes which are monolithic therewith, [0031] an annular element, whose dimensions are contained within the inlet dimensions of said nondeformable vanes and which is provided with means for coupling to said first disk-like element, said annular element being provided with flexibly deformable vanes which cantilever outward, are interposed between the nondeformable ones, and are adapted to modify, when loaded, their curvature in one of the directions of rotation so that the power required for rotation in that direction is greater than the maximum power that can be delivered by the motor, [0032] a second disk-like element, which encloses, together with said first disk-like element, the set of vanes and is rigidly coupled to said nondeformable vanes, leaving the deformable ones free. BRIEF DESCRIPTION OF THE DRAWINGS [0033] Further characteristics and advantages of the invention will become better apparent from the detailed description of embodiments thereof, illustrated only by way of non-limitative example in the accompanying drawings, wherein: [0034] [0034]FIG. 1 is a chart which plots, for conventional centrifugal pumps, the flow-rate as a function of the power required in the two directions of rotation; [0035] [0035]FIG. 2 is a sectional view of an impeller according to the invention in a first embodiment, arranged inside a volute of a centrifugal pump; [0036] [0036]FIG. 3 is an exploded view of the components of FIG. 2; [0037] [0037]FIG. 4 is a plan view of an impeller according to the invention in a second embodiment; [0038] [0038]FIG. 5 is a side view of the impeller of FIG. 4; [0039] [0039]FIG. 6 is a sectional view of an impeller according to the invention in a third embodiment, arranged inside a volute of a centrifugal pump; [0040] [0040]FIG. 7 is a chart which plots, for centrifugal pumps with impellers according to the invention, the flow-rate as a function of the power required in the two directions of rotation; [0041] [0041]FIG. 8 is a side view of another impeller according to the invention; [0042] [0042]FIG. 9 is a front view of the impeller of FIG. 8; [0043] [0043]FIG. 10 is an exploded perspective view of the impeller of FIG. 8. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0044] With reference to FIGS. 2 and 3, in a first embodiment the impeller according to the invention comprises a disk 10 with a central hollow cup-shaped body 11 which is a component of a driving device 12 described in greater detail hereinafter. [0045] A plurality of vanes 13 protrudes from a ring 16 which is located on the outside of the cup-shaped body 11 in a corresponding seat 10 a of the disk 10 . [0046] The vanes 13 are monolithic with respect to the ring 16 , which affects only their part that lies closest to the center. [0047] The peripheral part can therefore perform flexing movements arising from the elastic characteristics of the material of which they are made. [0048] The vanes 13 can also be rigidly coupled to the ring 16 (axial and torsional retention) in various manners: by interlocking and/or interference, ultrasonic welding, adhesive bonding. [0049] The peripheral regions 14 of the vanes 13 are therefore flexibly deformable, as mentioned, and said deformation is greater for the wrong direction of rotation and is optionally limited by the stroke limiting teeth 15 which protrude from the disk 10 alternately with the vanes 13 . [0050] In order to center the vanes 13 with respect to the teeth 15 , the ring 16 has axial teeth 17 to be inserted in appropriately provided holes 18 of the disk 10 . [0051] As regards the driving device 12 , it comprises said hollow body 11 and a cover 19 which can also be rigidly coupled to the ring 16 with the vanes 13 . [0052] The hollow body 11 is provided with an axial hole 20 for the shaft 21 of the rotor, not shown in the figures, of the motor. [0053] An O-ring gasket 23 acts on the shaft 21 and is accommodated in a corresponding seat of the hollow body 11 . [0054] The hermetic seal of the device 12 is ensured not only by the gasket 23 but also by the closure of the lid 19 , which is provided by ultrasonic welding, adhesive bonding or other known methods on the hollow body 11 . [0055] It is possible to provide alternative embodiments which are not hermetic or in which the lid 19 is monolithic with the ring 16 . [0056] In said ring, a tooth 24 protrudes from the inner wall and is therefore rigidly coupled to the impeller assembly; said tooth 24 interacts with a tooth 25 which protrudes from a ring 26 which can rotate about a shank 27 which is mounted with interference on the shaft 21 and is rigidly coupled thereto. [0057] A tooth 28 protrudes radially from the shank 27 and interacts, in its rotation, with the tooth 25 of the ring 26 , whose axial extension is such as to affect the path of the rotation of both teeth 24 and 25 . [0058] Said teeth are arranged axially so that they do not interfere with each other. [0059] Accordingly, the rotation of the shaft 21 starts the rotation of the tooth 28 , makes said tooth interact with the tooth 25 , turning it until it interferes with the tooth 24 , and finally makes the rotor turn the impeller. [0060] Grease, with a shock-absorbing function, can be conveniently placed inside the hollow body 11 . [0061] [0061]FIGS. 2 and 3 also illustrate the volute 29 in which the impeller is arranged. [0062] With reference now to FIGS. 4 and 5, an impeller according to the invention, in a second embodiment which is simplified with respect to the preceding one, comprises a disk 110 , from which a coaxial shank 111 with a hole 112 for the shaft of the rotor (not shown for the sake of simplicity) protrudes centrally on one side, and from which a plurality of vanes 113 with a curved profile protrudes on the other side. [0063] The impeller as a whole is formed monolithically. [0064] According to the invention, the vanes 113 are flexibly deformable along at least part of their extension, so as to modify their curvature, when loaded, in one of the two directions of rotation so that the power required for rotation in that direction is greater than the maximum power that can be delivered by the motor. [0065] The deformability of the vanes arises from the flexibility of their peripheral regions 114 , which are provided separately from the disk 110 by the molding step by way of an appropriate shaping of the mold. [0066] By providing the impeller as a single part made of plastics, with the peripheral regions 114 divided from the rest, said regions flex, when loaded, in the wrong direction of rotation and modify their curvature so that in practice they block the rotation. [0067] Conveniently, teeth 115 protrude from the disk 110 in the peripheral region, are alternated with the vanes 113 , and advantageously act as stop elements which avoid excessive curvatures of said vanes 113 in the wrong direction of rotation, thus avoiding excessive stresses thereto. [0068] The flexibility of the material would of course allow flexing in the correct direction of rotation as well, but the curvature of the vanes 113 , which matches the fluid threads that form during the rotation of the impeller, causes deformation in the correct direction of rotation to be very limited in practice. [0069] With reference to FIG. 6, in a third embodiment the impeller according to the invention comprises a disk 210 with a cup-shaped central hollow body 211 which is a component of a driving device 212 similar to the one of the first embodiment. [0070] A plurality of vanes 213 protrudes from a ring 216 which is arranged on the outside of the cup-shaped body 211 in a corresponding seat 210 a of the disk 210 . [0071] The vanes 213 are monolithic with respect to the ring 216 , which affects only the part of said vanes that lies closest to the center. [0072] The peripheral part can therefore perform flexing movements arising from the characteristics of the material of which the vanes are made. [0073] The vanes 213 can also be rigidly coupled to the ring 216 (axial and torsional retention) in various manners: by interlocking and/or interference, ultrasonic welding, adhesive bonding. [0074] The peripheral regions 214 of the vanes 213 are therefore, as mentioned, flexibly deformable, and said deformation is greater for the wrong direction of rotation and is limited by teeth 215 which protrude from the disk 210 alternately with the vanes 213 . [0075] In order to center the vanes 213 with respect to the teeth 214 , the ring 216 has axial teeth 217 to be inserted in appropriately provided holes 218 of the disk 210 . [0076] Also in this case, the cover 219 is separate from the ring 216 , but it is also possible to provide alternative embodiments in which the cover 219 is monolithic with the ring 216 . [0077] In this embodiment, the lid 219 of the hollow body 211 has, at its end, a seat 230 for a first shim ring 231 made of ceramic material, sintered material or similar hard material. [0078] A second shim ring 232 made of ceramic material, sintered material or similar hard material is accommodated in a seat 233 provided at the end of a cylindrical support 234 which is supported by a bush 235 which is rigidly coupled, by means of radial spokes 236 , to a ring 237 which is inserted with interference in a corresponding seat 238 of the volute 229 . [0079] As an alternative, the support 234 can be monolithic with the bush 235 . [0080] The ring 232 acts as an axial thrust bearing in order to adjust, in cooperation with the ring 231 , the position that the impeller assumes in the volute 229 and maximize hydraulic efficiency. [0081] With reference now to FIG. 7, said figure is a chart which plots the flow-rate as a function of power and wherein: [0082] the line D is the curve related to an impeller with the flexible vanes according to the invention, with the wrong direction of rotation; [0083] the line C represents the maximum power that the motor can deliver; [0084] the line A plots the curve related to an impeller with flexible vanes, in the correct direction of rotation. [0085] The line D clearly shows that for any flow-rate in the wrong direction of rotation, the flexible vane requires more power than the motor can generate (straight line C). [0086] Accordingly, the motor cannot start in the wrong direction. [0087] FIGS. 8 to 10 illustrate another possible configuration of the impeller. [0088] In this case, the impeller according to the invention, which is entirely made of plastics, is generally designated by the reference numeral 310 and comprises a first disk-like element 311 (which is monolithic with respect to a bush 311 a ) which monolithically supports, in this case, three curved nondeformable vanes 312 which are angularly equidistant and, at the center, a rounded shank (which is separated from their inlet region). [0089] The impeller 310 further comprises an annular element 314 , whose dimensions are contained within the inlet dimensions of said nondeformable vanes 312 ; said annular element has means 315 (described in greater detail hereinafter) for coupling to said first disk-like element 311 . [0090] The annular element 314 supports, so that they cantilever outward in this case, three curved flexibly deformable vanes 316 which are angularly equidistant and are to be arranged alternately with the nondeformable vanes 312 . [0091] The annular element 14 is in fact accommodated in a complementarily shaped seat 317 of the first disk-like element 311 . [0092] The flexibly deformable vanes 316 end externally with respect to the dimensions of the nondeformable vanes 312 , with respect to which they have slightly smaller axial dimensions. [0093] The flexibly deformable vanes 316 are adapted to modify, when loaded, their curvature in one direction of rotation so that the power required for rotation in that direction is higher than the maximum power that the motor (not shown for the sake of simplicity) can deliver. [0094] The impeller 310 further comprises a second disk-like element 318 , which encloses, together with said first disk-like element 311 , the set of vanes 312 and 316 and is rigidly coupled, by ultrasonic welding, adhesive bonding or other known methods, to the nondeformable vanes 312 , leaving free the flexibly deformable vanes 316 , which have slightly smaller axial dimensions. [0095] The second disk-like element 318 has a central hole and its edge 319 protrudes axially so as to form the inlet region for the fluid to be pumped. [0096] As regards the coupling means 315 , they comprise a shaped portion 320 which is for example polygonal (dodecagonal in the figures), is provided on the internal surface of the annular element 314 , and mates with a complementarily shaped surface 321 of the seat 317 . [0097] The coupling means 315 comprise a specific number of tabs 322 which are substantially radial, are angularly equidistant, protrude from the annular element 314 , are inserted between the vanes 316 and end with respective axially elongated hooks 323 , which engage by snap action, after elastic deformation, the first disk-like element 311 by insertion in suitable through holes 324 thereof. [0098] The seat 317 of course has a shape which also accommodates the tabs 322 . [0099] The hooks 323 inserted in the through holes 324 prevent any axial movement of the assembly constituted by the disk 314 and the vanes 316 . [0100] The coupling means 315 determine the exact mutual positioning of the vanes 312 and 316 . [0101] The peripheral part of the vanes 316 can thus perform flexing movements which arise from the elastic characteristics of the plastic material of which they are made. [0102] The deformation is greater for the wrong direction of rotation, and the vanes 316 modify their curvature so that in practice they block the rotation. [0103] The flexibility of the material would of course also allow flexing in the correct direction of rotation, but the curvature of the vanes 316 , which matches the fluid threads that form during the rotation of the impeller 310 , causes the deformation in the correct direction of rotation to be very small in practice. [0104] In practice it has been observed that the intended aim and objects of the present invention have been achieved. [0105] With the flexible-vane impeller, monodirectionality is in fact ensured for all flow-rates/heads. [0106] This is achieved in a constructively simple manner and has no effect on noise levels. [0107] The invention thus conceived is susceptible of numerous modifications and variations, all of which are within the scope of the inventive concept. [0108] Thus, for example, the change in the curvature of the vanes can be provided by means of a hinge, even of the film type, which connects each peripheral part to the central one. [0109] In the embodiment of FIGS. 8, 9 and 10 , even if the flexible vanes yield due to wear, the nondeformable vanes continue to give their constant contribution to the pumping action. [0110] All the details may further be replaced with other technically equivalent elements. [0111] In practice, the materials employed, so long as they are compatible with the contingent use, as well as the dimensions, may be any according to requirements. [0112] The disclosures in Italian patent applications Nos. PD2000A000176 and PD2001A000110, from which this application claims priority, are incorporated herein as reference.
A monodirectional impeller for centrifugal electric pumps having a permanent-magnet synchronous motor, having vanes which are deformable at least along part of their extension so as to change their curvature, when loaded, in one direction of rotation, so that the power required for rotation in that direction is greater than the maximum power that can be delivered by the motor.
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BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to a novel cyclic peptide and its preparation. [0003] 2. Description of Related Art [0004] Peptide 6A is a degradation of fibrinogen β chain analogue which has been known to increase coronary artery and femoral artery blood flow. In 1978(1), peptide 6A was first isolated and purified from the β chain of human fibrinogen by Belew et al.(2). The composition of peptide 6A was confirmed as Ala-Arg-Pro-Ala-Lys (SEQ ID NO: 25). This peptide increases coronary artery and femoral artery blood flow in dogs. In 1997, the inventors prepared peptide 6A and its analogues by solution method and observed that these peptides have good potency for relaxing vascula, lowering blood pressure and anti-thrombosis. The synthetic techniques and functions of these compounds have been described in CN Patent No. 1146458. However, in 1990, the inventors observed that peptide 6A had no additional benefit on the parameters of thrombolysis when injected intravenously (i.v.) together with tissue plasminogene activator in dogs with coronary artery thrombosis. The results indicated that peptide 6A might be degraded rapidly by angiotensin-converting enzyme (ACE) in lung during intravenous administration since peptide 6A is the substrate of this enzyme. In addition, peptide 6A and its analogues, which were synthesized by the inventors in 1997, had excellent anti-thrombosis ability, but their half-life in vivo was quite short, consequently unable to exhibit long-term potency. [0005] In order to solve the problems described above, the inventors considered that a cyclic peptide usually has the characteristic of restricted conformations afford good stability toward peptidase. Therefore, the inventors tried to synthesize peptide 6A and its analogues as cyclic forms to avoid degradation caused by ACE; moreover, so that the cyclic compounds will not lose thrombolytic effects. At this moment, a new cyclic compound and also a new technique to convert linear peptide 6A and its analogues to cyclic forms are needed. SUMMARY OF THE INVENTION [0006] It is one object of the present invention to provide novel cyclic peptides that have long-term thrombolytic potency. [0007] It is another object of the present invention to provide a method for preparing novel cyclic peptides describes above. [0008] According to the present invention, it is provided a novel cyclic peptide of the following formula (I) (SEQ ID NO: 1): cyclo(Xaa-Arg-Pro-Ala-Lys)  (I) [0009] wherein Xaa is Ala, Gly, Glu, Gln, Asp, Asn, Arg or Lys. [0010] The formula (I) (SEQ ID NO: 1) cyclic peptide can be synthesized by the following method 1 or method 2. [0011] Method 1: [0012] First, at least one peptide with an N-terminal protecting group is provided, wherein said peptide is selected from the group consisting of: [0013] B-Xaa-Arg(T)-Pro-Ala-Lys(Z′)-OH (SEQ ID NO: 2), [0014] B-Arg(T)-Pro-Ala-Lys(Z′)-Xaa-OH (SEQ ID NO: 3), [0015] B-Pro-Ala-Lys(Z′)-Xaa-Arg(T)-OH (SEQ ID NO: 4), [0016] B-Ala-Lys(Z′)-Xaa-Arg(T)-Pro-OH (SEQ ID NO: 5), and [0017] B-Lys(Z′)-Xaa-Arg(T)-Pro-Ala-OH (SEQ ID NO: 6); wherein Xaa is Ala, Gly, Glu, Gln, Asp, Asn, Arg or Lys; B is N-terminal protecting group of the peptide chain; Z′ is the side chain protecting group of Lys residue; and T is the side chain protecting group of Arg residue. [0018] p-Nitrophenol, an adequate organic solvent and a coupling agent were then added to activate the C-terminal group of said peptide and to form a first intermediate. [0019] After that, the N-terminal protecting group was removed from the first intermediate to form a second intermediate. [0020] The second intermediate is dissolved in an appropriate organic solvent and undergoes a cycloaddition reaction to form a third intermediate. [0021] Finally, the side chain protecting groups of Lys and Arg residues were removed from the third intermediate to form the final product. [0022] Method 2: [0023] First, a peptide with an N-terminal protecting group is provided, wherein said peptide is selected from the group consisting of: [0024] B-Xaa-Arg(T)-Pro-Ala-Lys(Z′)-OH (SEQ ID NO: 2), [0025] B-Arg(T)-Pro-Ala-Lys(Z′)-Xaa-OH (SEQ ID NO: 3), [0026] B-Pro-Ala-Lys(Z′)-Xaa-Arg(T)-OH (SEQ ID NO: 4), [0027] B-Ala-Lys(Z′)-Xaa-Arg(T)-Pro-OH (SEQ ID NO: 5), and [0028] B-Lys(Z′)-Xaa-Arg(T)-Pro-Ala-OH (SEQ ID NO: 6); [0029] wherein Xaa is Ala, Gly, Glu, Gln, Asp, Asn, Arg or Lys; B is the N-terminal protecting group of peptide chain; Z′ is the side chain protecting group of Lys residue; and T is the side chain protecting group of Arg residue. [0030] The N-terminal protecting group of said peptide was then removed to form a first intermediate. [0031] The first intermediate was dissolved in an appropriate organic solvent, and a coupling agent was subsequently added to perform direct coupling reaction, which provides a second intermediate. [0032] Finally, the protecting groups on the side chain of the Lys and Arg residues of the second intermediate were removed to form the cyclic peptide as formula (I). [0033] The formula (I) cyclic peptide has a thrombolytic potency, and the peptides therefore can be used as a drug for relaxing blood vessel, lowering blood pressure and anti-thrombosis, and can be further applied to treat thrombosis, hypertension, and myocardial infarction. BRIEF DESCRIPTION OF THE DRAWINGS [0034] [0034]FIG. 1 shows P6A (SEQ ID NO: 25) and P6A analogue synthesis path, wherein AA represents the corresponding protected L-Ala, Gly, L-Lys, and L-Gln. [0035] [0035]FIG. 2 shows the Compound (5-8) (SEQ ID NO: 11-14) synthesis path, wherein AA represents the corresponding protected L-Ala, Gly, Lys, and Gln. DETAILED DESCRIPTION OF THE INVETION [0036] The present invention provides a method to converse the linear peptide 6A and its analogues into cyclic structures whose backbone conformation mobility is restricted. Thus, the degradation rate of cyclic peptide of the present invention decreases dramatically and therefore its half-life in vivo will be prolonged. [0037] In the present invention, peptides 6A and the analogues, respectively, are prepared by solid phase or solution phase synthesis. The corresponding cyclic pentapeptide is also prepared by the same methods. The thrombolytic effect was evaluated on a rat model of thrombolysis. [0038] The present invention provides a cyclic peptide of the following formula (I) (SEQ ID NO: 1): cyclo(Xaa-Arg-Pro-Ala-Lys)  (I) [0039] wherein the Xaa is Ala, Gly, Glu, Gln, Asp, Asn, Arg, or Lys. [0040] The formula (I) cyclic peptide can be prepared by solid phase or liquid phase synthesis method. [0041] The following linear pentapeptide groups are prepared through conventional solid phase or solution synthesis method, using an amino acid comprising an L-protecting group as the starting material: [0042] B-Xaa-Arg(T)-Pro-Ala-Lys(Z′)-OH (SEQ ID NO: 2), [0043] B-Arg(T)-Pro-Ala-Lys(Z′)-Xaa-OH (SEQ ID NO: 3), [0044] B-Pro-Ala-Lys(Z′)-Xaa-Arg(T)-OH (SEQ ID NO: 4), [0045] B-Ala-Lys(Z′)-Xaa-Arg(T)-Pro-OH (SEQ ID NO: 5), [0046] B-Lys(Z′)-Xaa-Arg(T)-Pro-Ala-OH (SEQ ID NO: 6); [0047] wherein the Xaa is Ala, Gly, Glu, Gln, Asp, Asn, Arg, or Lys; B is the N-terminal protecting group of peptide chain; Z′ is the side chain protecting group of Lys residue; and T is the side chain protecting group of Arg residue. The protecting group B described above is a conventional N-terminal protecting group, and preferably selected from a group comprising Boc, Fmoc, Z, Adoc, Bpoc, Trt, and Nps; at least one protecting group Z on the side chain of Lys residue is selected form the group comprising 4-ClZ, 2-ClZ, 2,4-Cl 2 Z, 3,4-Cl 2 Z, 3-ClZ, 2,6Cl 2 Z, Boc, Tos and Cu; and, at least one protecting group T on the side chain of Arg residue is selected from the group comprising Tos, No 2 , Z, Z 2 , Mbs, Mts (2,4,6-trimethylbenzosulfidyl), Boc, and Adoc. [0048] The linear pentapeptides described above are used as starting materials to perform cyclization. The present invention for the fist time discloses two cyclization methods applicable to the linear pentapeptides described above. The first is called “p-nitrophenol ester method”, which uses p-nitrophenol as an activator to activate the inert —COOH group on the C-terminus of peptide chain. A labile —COONp group are thus obtained and then the intramolecular cyclization occurs naturally. The later one is called “direct coupling method”, using coupling agents to perform cyclization under appropriate conditions. The details of the two methods are described as follows. [0049] 1. p-Nitrophenol Ester Method [0050] Linear pentapeptides comprising an N-terminal protecting group as described above are provided. p-Nitrophenol, proper organic solvents and a coupling agent are added to activate the C-terminal group of the peptides and a first intermediate forms; wherein the organic solvents are not limited, preferably at least one is selected from the group comprising THF, Dioxane, DMF, DMSO, ethyl acetate, dichloromethane, and trichloromethane; the coupling agents are conventional ones used in amino acid synthesis, preferably at least one is selected from the group comprising DCC, HOBt, HONb, HOSu, and p-nitrophenol. An example of the first intermediate is Boc-Xaa-Arg(T)-Pro-Ala-Lys(Z′)-ONp, and the rest can be conceived by those skilled in the art. [0051] The N-terminal protecting group of first intermediate was then removed by reacting a deprotecting agent and the first intermediate to form a second intermediate; wherein the choices of deprotecting agents depend on the N-terminal protecting groups, based on the prior arts, preferably at least one is selected from the group comprising HCl/ethyl acetate, HCl/dichlorocyclohexane, trifluoroacetatic acid, H 2 /Pd, C, and pyridine. An example of the first intermediate is HCl-Xaa-Arg(T)-Pro-Ala-Lys(Z′)-ONp, and the rest can be conceived by those skilled in the art. [0052] The second intermediate is then dissolved in proper organic solvents and undergoes cyclization to form a third intermediate; wherein the organic solvents are as described above, and the cyclization is performed by adding at least one agent selected from the group comprising Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , KHCO 3 , TEA, NH 3 , NMM, and N(C 2 H 5 ) 3 so that C-terminus and N-terminus on the peptide chain react with each other, thus the O, Np, or ONp group leaving naturally, and form a cyclic compound. An example of third intermediate is cyclo(Xaa-Arg(T)-Pro-Ala-Lys(Z′)). It should be noticed that from the beginning step to the present step, all the side chains on the Arg and Lys residue of intermediate have protecting groups. [0053] Therefore, the side chain protecting groups on Lys and Arg residue should be removed to form the final compound. The deprotecting reaction is performed by reacting the third intermediate with the second deprotecting agents, wherein the second deprotecting agents are selected according to the desired deprotecting group, preferably at least one is selected from hydrofluoric acid, triflouroacetatic acid, trifluoromethyl sulfonic acid, H 2 /Pd, and C. A final compound example is cyclo(Xaa-Arg-Pro-Ala-Lys) (SEQ ID NO: 1), and the rest can be conceived by those skilled in the art. [0054] 2. Direct Coupling Method: [0055] A linear peptide having an N-terminal protecting group as described above is provided. The N-terminal protecting group was removed by reacting with a first deprotecting agent to form a first intermediate, wherein the first deprotecting agent is selected according to the N-terminal protecting group, and preferably selected from the group comprising HCl/ethyl acetate, HCl/dichlorocyclohexane, trifluoroacetatic acid, H 2 /Pd, C, and pyridine. An example of the first intermediate is HCl-Xaa-Arg(T)-Pro-Ala-Lys(Z′)-OH, and the rest can be conceived by those skilled in the art. [0056] The first intermediate is then dissolved in proper organic solvents, and coupling agents are added to perform a coupling reaction which results in providing a second intermediate; wherein the organic solvents are not specified, preferably at least one is selected from the group comprising anhydrous THF, dioxane, DMF, DMSO, ethyl acetate, and dichloromethane; the coupling agents are those used in conventional amino acids synthesis, preferably at least one selected from the group comprising DCC, HOBt, HONb, HOSu, and p-nitrophenol. The pH value of reaction preferably ranges from 6.0 to 8.0. The reaction temperature preferably ranges from 50° C. to 90° C.; and the pH value is adjusted by alkali, preferably at least one of which is selected from the group comprising Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , TEA, NH 3 , and NMM. The cyclization is completed at this step, and a second intermediate example is cyclo(Xaa-Arg(T)-Pro-Ala-Lys(Z′)), and the rest can be conceived by those skilled in the art. [0057] As described above, there are still protecting groups attached to side chains on Arg and Lys residue of the cyclic compounds. Thus, the protecting groups on Arg and Lys residue of the final compound should be removed and the method is as described above. A final compound example is cyclo(Xaa-Arg-Pro-Ala-Lys) (SEQ ID NO: 1), and the rest can be conceived by those skilled in the art. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT [0058] Chemical Synthesis [0059] Reactant Preparation [0060] L-protected amino acids, DCC and HOBt were purchased from Sigma Chemical Co.; anhydrous THF was distilled from Na under normal temperatures; Dry DMF and dioxane were distilled from calcium chloride and treated with 4A molecular sieve; linear peptides were prepared by a solution method utilizing Boc chemistry. DCC was used as a coupling agent both in linear and cyclic peptide synthesis; the reaction was monitored by ninhydrin reactions, and the Boc protecting group was removed by 4-6 mol/L HCl/EtOAc. Chromatography was performed on Qingdao Silica gel H. Melting points were determined with a microscopic hostage apparatus, and were uncorrected. [0061] ESI-Mass spectra were obtained on ES-S989X-HO; optical rotation was determined on Polartronic-D polarimeter of Schmidt+Haensch Company. [0062] 1. The Preparation of the Following Compounds (1) to (4): (SEQ ID NO: 7) Boc-Ala-Arg(Tos)-Pro-Ala-Lys(Z′)OBZl (1) (SEQ ID NO: 8) Boc-Gly-Arg(Tos)-Pro-Ala-Lys(Z′)OBZl (2) (SEQ ID NO: 9) Boc-Lys(Z′)-Arg(Tos)-Pro-Ala-Lys(Z′)OBZl (3) (SEQ ID NO: 10) Boc-Gln-Arg(Tos)-Pro-Ala-Lys(Z′)OBZl (4) [0063] General procedure of compounds (1) to (4) (SEQ ID NO: 7-10) synthesis: Beginning with Boc protected lysine, using DCC/HOBt as a coupling agent, and utilizing a solution method to elongate the peptide chain. The synthetic route was outlined in scheme 1, see FIG. 1. Detailed descriptions are as follows. [0064] First, the benzyl(Bz1) protecting group is attached to the Boc-protected lysine's C-terminus. The reaction is: [0065] The N-terminal Boc protecting group is then removed, and Boc-Ala and DCC are subsequently added to perform polymerization. The reaction is: [0066] Repeat steps (iii) and (iv), and Boc-Pro is added to complete step (v) to form tripeptides. Compounds (1) (SEQ ID NO: 7) to (4) (SEQ ID NO: 10) are prepared by similar schemes. [0067] The physical data of compounds (1) (SEQ ID NO: 7) to (4) (SEQ ID NO: 10) are listed as follows: [0068] Compound (1) (SEQ ID NO: 7), yield, 88%, mp 84-85° C. [0069] [α] D 20 -33 (C2, CHCl 3 ), FAB-MS (m/e) 1020[M+1] + ; [0070] Compound (2) (SEQ ID NO: 8), yield, 82%, mp 76-77° C. [0071] [α] D 20 -43 (C2, CHCl 3 ), FAB-MS (m/e) 1211[M+1] + , 1028[M+Na] + ; [0072] Compound (3) (SEQ ID NO: 9), yield, 78%, mp 72-74° C. [0073] [α] D 20 -46 (C2, CHCl 3 ), FAB-MS (m/e) 1211[M+1] + ; [0074] Compound (4) (SEQ ID NO: 10), yield, 87%, mp 83-85° C. [0075] [α] D 20 -9 (C0.3, CHCl 3 ), FAB-MS (m/e) 1077[M+1] + . [0076] 2. The Preparation of Compounds (5) to (8): (SEQ ID NO: 11) Boc-Pro-Arg(Tos)-Ala-Lys(Z′)-AlaOBzl (5) (SEQ ID NO: 12) Boc-Pro-Arg(Tos)-Gly-Lys(Z′)-AlaOBzl (6) (SEQ ID NO: 13) Boc-Pro-Arg(Tos)-Lys(Z′)-Lys(Z′)-AlaOBzl (7) (SEQ ID NO: 14) Boc-Pro-Arg(Tos)-Gln-Lys(Z′)-AlaOBzl (8) [0077] General procedure of compounds (5) (SEQ ID NO: 11) to (8) (SEQ ID NO: 14) synthesis: Beginning with Boc protected alanine, using DCC/HOBt as a coupling agent, and utilizing a solution method to elongate the peptide chain. The synthetic route was outlined in scheme 2, see FIG. 2. [0078] The physical data of the compounds (5) (SEQ ID NO: 11) to (8) (SEQ ID NO: 14) are listed as follows: [0079] Compound (5) (SEQ ID NO: 11), yield, 68%, mp 146-148° C. [0080] [α] D 20 -22 (C0.5, CHCl 3 ), TOF-MS (m/e) 1020[M+1] + , 1041[M+Na] + , 1058[M+K] + ; [0081] Compound (6) (SEQ ID NO: 12), yield, 72%, mp 78-80° C. [0082] [α] D 20 -22 (Cl, CHCl 3 ), TOF-MS (m/e) 1006[M+1] + , 1028[M+Na] + , 1044[M+K] + ; [0083] Compound (7) (SEQ ID NO: 13), yield, 62%, mp 80-82° C. [0084] [α] D 20 -27 (C0.5, CHCl 3 ), TOF-MS (m/e) 1211[M+1] + , 233[M+Na] + , 1249[M+K] + ; [0085] Compound (8) (SEQ ID NO: 14), yield, 78%, mp 90-92° C. [0086] [α] D 20 -24 (CO0.2, CHCl 3 ), TOF-MS (m/e) 1077[M+1] + ; [0087] 3. The Preparation of Compounds (9) (SEQ ID NO: 15) to (16) (SEQ ID NO: 22): (SEQ ID NO: 15) Boc-Ala-Arg(Tos)-Pro-Ala-Lys(Z′)OH  (9) (SEQ ID NO: 16) Boc-Pro-Arg(Tos)-Ala-Lys(Z′)-AlaOH (10) (SEQ ID NO: 17) Boc-Gly-Arg(Tos)-Pro-Ala-Lys(Z′)OH (11) (SEQ ID NO: 18) Boc-Pro-Arg(Tos)-Gly-Lys(Z′)-AlaOH (12) (SEQ ID NO: 19) Boc-Lys(Z′)-Arg(Tos)-Pro-Ala-Lys(Z′)OH (13) (SEQ ID NO: 20) Boc-Pro-Arg(Tos)-Lys(Z′)-AlaOH (14) (SEQ ID NO: 21) Boc-Gln-Arg(Tos)-Pro-Ala-Lys(Z′)OH (15) (SEQ ID NO: 22) Boc-Pro-Arg(Tos)-Gln-Lys(Z′)-AlaOH (16) [0088] A methanol solution of 0.2 mmol compounds (5,6,7,8) (SEQ ID NO: 11, 12, 13, 14)was cooled in an ice-water bath, 2.0 ml of 2 mol/L NaOH was added dropwise with stirring. The reaction mixture was stirred for 30 min. When thin layer chromatography (TLC) indicated that the reaction was complete, the solution was neutralized with 2 mol/L HCl. After removal of methanol the mixture was filtered, and the filtrate was washed with water for several times, then the filtrate was put in a drier for overnight. [0089] 4. Cyclo[Ala-Arg(Tos)-Pro-Ala-Lys(Z′)] (17) (SEQ ID NO: 23) Preparation [0090] Method 1: p-nitrophenol Ester Method. [0091] 0.2 mmol Boc-Ala-Arg(Tos)-Pro-Ala-Lys(Z′)OH (SEQ ID NO: 15) and 0.3 mmol p-nitrophenol were dissolved in anhydrous THF(5 ml), cooled in an ice water bath, 0.3 mmol DCC was added and stirred for 3 h, then the reaction was increased to room temperature. 18 h later the mixture was filtered and the solvent was evaporated to dryness in vacuo. The residue was triturated with ethyl ether and a yellow Boc-Ala-Arg(Tos)-Pro-Ala-Lys(Z′)ONp powder was obtained. After removing Boc with 4N HCl/EtOAc, the obtained Hcl-Ala-Arg(Tos)-Pro-Ala-Lys(Z′)ONp was dissolved in 12 ml dioxane, 2 ml 0.1 mol/L Na 2 CO 3 and 2 ml 0.1 mol/L NaHCO 3 were added and stirred for 2 h. After the solvent was removed, the residue was purified by chromatography to afford the desired product 8 mg (5%), mp 118-120° C., [α] D 20 -21 (C0.2, CHCl 3 ), TOF-MS(m/e) 812[M+1] + . [0092] Method 2: Direct Coupling Method [0093] Boc was removed from 0.2 mmol Boc-Ala-Arg(Tos)-Pro-Ala-Lys(Z′)OH (SEQ ID NO: 15) with 4N Hcl/EtOAc and the obtained Hcl-Ala-Arg(Tos)-Pro-Ala-Lys(Z′)OH was dissolved in 200 ml dry DMF(10 −3 M), NMM was added to bring the solution to PH 7, 1 mmol DCC was added and the mixture was stirred at 70° C. for 3 days. The solvent was evaporated in vacuo, the residue was purified by chromatography to afford the desired product 29 mg (18%), the other physical data were the same as method 1. [0094] Method 3: Proline and Alanine as Coupling Sites. [0095] Boc was removed from 0.2 mmol. Boc-Pro-Arg(Tos)-Ala-Lys(Z′)-AlaOH(10) (SEQ ID NO: 16), and OH-Pro-Arg(Tos)-Ala-Lys(Z′)-AlaOH was then dissolved in 200 ml DMF(10 −3 M), the procedure was followed as in method 2 to obtain the product. Product data were the same as method 1 and 2 except the yield was 9%. [0096] 5. Cyclo[Gly-Arg(Tos)-Pro-Ala-Lys(Z′)] (18) (SEQ ID NO: 24) Preparation [0097] Method 1: Direct Coupling Method. [0098] Boc was removed from 0.2 mmol Boc-Gly-Arg(Tos)-Pro-Ala-Lys(Z′)OH (SEQ ID NO: 17) with 4N Hcl/EtOAc. The obtained HCl-Gly-Arg(Tos)-Pro-Ala-Lys(Z′)OH was dissolved in 200 ml dry DMF(10 −3 M) and the following procedure was the same as method 2 Cyclo[Ala-Arg(Tos)-Pro-Ala-Lys(Z′)] (17) (SEQ ID NO: 23) preparation. The desired product yield was 31%, mp 102-104 C, [α] D 20 -30(Cl, CHCl 3 ), ESI-MS(m/e), 798[M+1] + , 820[M+Na] + . [0099] Method 2: Proline and Glycine as Coupling Sites. [0100] Boc was removed from 0.2 mmol Boc-Gly-Arg(Tos)-Pro-Ala-Lys(Z′)OH(12) (SEQ ID NO: 18) and the following synthetic procedure was the same as method 1. The yield was 29% and other physical data were the same as obtained in method 1. [0101] 6. Compound (P6A, GP6A, KP6A, QP6A, Cyclo P6A, Cyclo GP6A, and KP6A) Preparation: H-Ala-Arg-Pro-Ala-LysOH (19) (SEQ ID NO: 25) (P6A) H-Gly-Arg-Pro-Ala-LysOH (20) (SEQ ID NO: 26) (GP6A) H-Lys-Arg-Pro-Ala-LysOH (21) (SEQ ID NO: 27) (KP6A) H-Gln-Arg-Pro-Ala-LysOH (22) (SEQ ID NO: 28) (QP6A) Cyclo(Ala-Arg-Pro-Ala-Lys) (23) (SEQ ID NO: 29) (Cyclo P6A) Cyclo(Gly-Arg-Pro-Ala-Lys) (24) (SEQ ID NO: 30) (Cyclo GP6A) Cyclo(Lys-Arg-Pro-Ala-Lys) (25) (SEQ ID NO: 31) (Cyclo KP6A) [0102] Compound 1,2,3,4,17,18 or 21 (SEQ ID NO: 7, 8, 9, 10, 23, 24, 27) was respectively subjected in the reaction vessel and mixed with 1 ml thioether, 1 ml thioanisole and 1 ml of anisole. The mixture was cooled with liquid N 2 and liquid anhydrous HF (2 ml) was added and stirred at 0° C. for 60 min. The mixture was then dried in vacuo and the crude product was precipitated by addition of ethyl ether. The precipitate was desalted on Sephadex G 10 using water as eluent and collected by ninhydrin reaction. The collection was lyophilized and white power was obtained. The related data were as follows: [0103] Compound (19) (SEQ ID NO: 25), yield, 80%, mp 168-170° C. [0104] [α] D 20 -44 (C2, H 2 O), FAB-MS (m/e) 542[M+1] + ; [0105] Compound (20) (SEQ ID NO: 26), yield, 78%, mp 168-171° C. [0106] [α] D 20 -81 (C 1 , H 2 O), FAB-MS (m/e) 528[M+1] + ; [0107] Compound (21) (SEQ ID NO: 27), yield, 82%, mp 138-140° C. [0108] [α] D 20 -65 (C 1 , H 2 O), FAB-MS (m/e) 597[M+1] + ; [0109] Compound (22) (SEQ ID NO: 28), yield, 80%, mp 180-182° C. [0110] [α] D 20 -65 (C 1 , H 2 O), FAB-MS (m/e) 599[M+1] + ; [0111] Compound (23) (SEQ ID NO: 29), yield, 53%, mp 196-200° C. [0112] [α] D 20 -64 (C0.5, H 2 O), ESI-MS (m/e) 524[M+1] + ; [0113] Compound (24) (SEQ ID NO: 30), yield, 64%, mp 138-140° C. [0114] [α] D 20 -67 (C0.5, H 2 O), TOF-MS (m/e) 510[M+1] + ; [0115] Compound (25) (SEQ ID NO: 31), yield, 60%, mp 170-174° C. [0116] [α] D 20 -61 (C0.5, H 2 O), TOF-MS (m/e) 581[M+1] + . [0117] B. Thrombolytic Effect [0118] The thrombolytic effect was evaluated by thrombolysis rat model. Among the 8 compounds, as following description, GP6A (SEQ ID NO: 26) and cyclic GP6A (SEQ ID NO: 30) have much more thrombolytic potency than the others. [0119] 1. Thrombus Preparation [0120] 0.1 ml Wistar rat blood was poured into a glass tube (length, 15 mm; external diameter, 5.0 mm; internal diameter, 2.5 mm) which was fixed vertically and the bottom was sealed with a rubber stopper. A stainless steel bolt was inserted quickly, the bolt diameter was 0.2 mm and the length was 12 mm. 15 min later, the bolt containing thrombus was taken out from the glass tube and weighed exactly. [0121] 2. Thrombolytic Effect of Various Peptides. [0122] Male Wistar rat weighing 220 g-280 g were anesthetized with pentobarbital sodium (80 mg/kg, i.p). The right arteria carotis communis and the left vena jugulars externa were separated. The bolt containing thrombus was put in the polyethylene tube and one end was inserted into the left vena jugulars externa. 50 IU/kg of heparin sodium was injected as anticoagulant, and the other tube end was inserted into the right arteria carotis communis. At this time the blood flowed from the right arteria carotis to the left vena jugulars externa via the polyethylene tube. Then normal saline solution, UK, GP6A (SEQ ID NO: 26), P6A (SEQ ID NO: 25) and KP6A (SEQ ID NO: 27) were injected in 6 min. The bolt was taken out and weighed after 1 h. The data are listed in Table 1 and Table 2, statistical data analysis was carried out by using student's t test, p<0.05 was considered significant. TABLE 1 Thrombus Reduction with NS, UK, GP6A, and CycloGP6A Group Dosage m/mg NS  3 ml/kg  0.76 ± 7.40 UK 20,000 IU/kg 12.81 ± 5.15 a GP6A  5 μmol/kg  9.31 ± 3.94 a GP6A 10 μmol/kg 13.17 ± 4.13 a GP6A 20 μmol/kg 16.81 ± 544 a,b CycloGP6A  5 μmol/kg  8.35 ± 2.76 a CycloGP6A 10 μmol/kg 17.31 ± 4.29 a CycloGP6A 20 μmol/kg 18.38 ± 2.08 a,b,c [0123] [0123] TABLE 2 Thrombus Reduction with NS, UK, P6A, CycloP6A, KP6A, and CycloKP6A Group Dosage m/mg NS 3 ml/kg  0.76 ± 7.40 UK 20,000 IU/kg 12.81 ± 5.15 a P6A 5 μ mol/kg  6.07 ± 2.14 a CycloP6A 5 μ mol/kg 10.62 ± 3.15 a KP6A 5 μ mol/kg  0.28 ± 2.13 CycloKP6A 5 μ mol/kg  6.13 ± 2.31 a [0124] From the results shown in Table 1 and 2, the thrombolytic effect among the 6 compounds, except KP6A (SEQ ID NO: 27), are close to that of the positive control group, UK, i.e., they perform excellent thrombolytic effects. As to the compounds with the same formula, the thrombolytic effect of cyclic forms is better than that of the linear form, especially GP6A. If high concentration cycloGP6A (SEQ ID NO: 30) is used (>10 μmol), the thrombolytic effect is even better than UK (2000 IU/Kg). It shows that the cyclo pentapeptides of the present invention do exhibit excellent thrombolytic effect, which is better than thrombolytic effect of UK. [0125] At the same time, the inventor also found out that transforming the structure of peptide 6A and its analogues from linear form to cyclic forms does increase their half-life, which in turn prolongs the pharmaceutical effect in vivo; the finding is in accordance with the thrombolytic experiments described above. Therefore, the cyclic peptides of the present invention significantly mitigate the disadvantage, e.g. rapid degradation of peptide 6A, in the prior art, and serves as a medicine with long-term thrombolytic potency. Besides, the cyclic peptides of the present invention can be further applied to treat many embolism diseases, such as coronary thrombosis, cerebral artery embolism, and phlebitis. The peptide 6A of the prior art already exhibits the thrombolytic effect and serves to reduce blood pressure, extend blood vessel diameter, while the high stability of the cyclic peptide of the present invention exhibits even better ability to treat vascular sclerosis, heart disease, myocardial infarction, stroke and high blood pressure. [0126] Although the present invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the scope of the invention as hereinafter claimed. 0 SEQUENCE LISTING <160> NUMBER OF SEQ ID NOS: 31 <210> SEQ ID NO 1 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Formula (I) <220> FEATURE: <221> NAME/KEY: Cyclopeptide <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: X=A,G,E,Q,D,N,R,K <220> FEATURE: <221> NAME/KEY: misc_feature <222> LOCATION: (1)..(1) <223> OTHER INFORMATION: Xaa can be any naturally occurring amino acid <400> SEQUENCE: 1 Xaa Arg Pro Ala Lys 1 5 <210> SEQ ID NO 2 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: used for cyclopeptide synthesis <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: X=A,G,E,Q,D,N,R,KN-blocked and side chain protected <220> FEATURE: <221> NAME/KEY: misc_feature <222> LOCATION: (1)..(1) <223> OTHER INFORMATION: Xaa can be any naturally occurring amino acid <400> SEQUENCE: 2 Xaa Arg Pro Ala Lys 1 5 <210> SEQ ID NO 3 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: used for cyclopeptide synthesis <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: X=A,G,E,Q,D,N,R,KN-blocked and side chain protected <220> FEATURE: <221> NAME/KEY: misc_feature <222> LOCATION: (5)..(5) <223> OTHER INFORMATION: Xaa can be any naturally occurring amino acid <400> SEQUENCE: 3 Arg Pro Ala Lys Xaa 1 5 <210> SEQ ID NO 4 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: used for cyclopeptide synthesis <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: X=A,G,E,Q,D,N,R,KN-blocked and side chain protected <220> FEATURE: <221> NAME/KEY: misc_feature <222> LOCATION: (4)..(4) <223> OTHER INFORMATION: Xaa can be any naturally occurring amino acid <400> SEQUENCE: 4 Pro Ala Lys Xaa Arg 1 5 <210> SEQ ID NO 5 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: used for cyclopeptide synthesis <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: X=A,G,E,Q,D,N,R,KN-blocked and side chain protected <220> FEATURE: <221> NAME/KEY: misc_feature <222> LOCATION: (3)..(3) <223> OTHER INFORMATION: Xaa can be any naturally occurring amino acid <400> SEQUENCE: 5 Ala Lys Xaa Arg Pro 1 5 <210> SEQ ID NO 6 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: used for cyclopeptide synthesis <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: X=A,G,E,Q,D,N,R,KN-blocked and side chain protected <220> FEATURE: <221> NAME/KEY: misc_feature <222> LOCATION: (2)..(2) <223> OTHER INFORMATION: Xaa can be any naturally occurring amino acid <400> SEQUENCE: 6 Lys Xaa Arg Pro Ala 1 5 <210> SEQ ID NO 7 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 1 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N-, C-both blockedside chain protected <400> SEQUENCE: 7 Ala Arg Pro Ala Lys 1 5 <210> SEQ ID NO 8 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 2 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N-, C-both blockedside chain protected <400> SEQUENCE: 8 Gly Arg Pro Ala Lys 1 5 <210> SEQ ID NO 9 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 3 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N-, C-both blockedside chain protected <400> SEQUENCE: 9 Lys Arg Pro Ala Lys 1 5 <210> SEQ ID NO 10 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 4 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N-, C-both blockedside chain protected <400> SEQUENCE: 10 Gln Arg Pro Ala Lys 1 5 <210> SEQ ID NO 11 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 5 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N-, C-both blockedside chain protected <400> SEQUENCE: 11 Pro Arg Ala Lys Ala 1 5 <210> SEQ ID NO 12 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 6 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N-, C-both blockedside chain protected <400> SEQUENCE: 12 Pro Arg Gly Lys Ala 1 5 <210> SEQ ID NO 13 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 7 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N-, C-both blockedside chain protected <400> SEQUENCE: 13 Pro Arg Lys Lys Ala 1 5 <210> SEQ ID NO 14 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 8 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N-, C-both blockedside chain protected <400> SEQUENCE: 14 Pro Arg Gln Lys Ala 1 5 <210> SEQ ID NO 15 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 9 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N- blocked and side chain protected <400> SEQUENCE: 15 Ala Arg Pro Ala Lys 1 5 <210> SEQ ID NO 16 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 10 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N- blocked and side chain protected <400> SEQUENCE: 16 Pro Arg Ala Lys Ala 1 5 <210> SEQ ID NO 17 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 11 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N- blocked and side chain protected <400> SEQUENCE: 17 Gly Arg Pro Ala Lys 1 5 <210> SEQ ID NO 18 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 12 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N- blocked and side chain protected <400> SEQUENCE: 18 Pro Arg Gly Lys Ala 1 5 <210> SEQ ID NO 19 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 13 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: N- blocked and side chain protected <400> SEQUENCE: 19 Lys Arg Pro Ala Lys 1 5 <210> SEQ ID NO 20 <211> LENGTH: 4 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 14 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(4) <223> OTHER INFORMATION: N- blocked and side chain protected <400> SEQUENCE: 20 Pro Arg Lys Ala 1 <210> SEQ ID NO 21 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 15 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(4) <223> OTHER INFORMATION: N- blocked and side chain protected <400> SEQUENCE: 21 Gln Arg Pro Ala Lys 1 5 <210> SEQ ID NO 22 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 16 <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(4) <223> OTHER INFORMATION: N- blocked and side chain protected <400> SEQUENCE: 22 Pro Arg Gln Lys Ala 1 5 <210> SEQ ID NO 23 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 17 <220> FEATURE: <221> NAME/KEY: CYCLOPEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: side chain protected <400> SEQUENCE: 23 Ala Arg Pro Ala Lys 1 5 <210> SEQ ID NO 24 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Compound 18 <220> FEATURE: <221> NAME/KEY: CYCLOPEPTIDE <222> LOCATION: (1)..(5) <223> OTHER INFORMATION: side chain protected <400> SEQUENCE: 24 Gly Arg Pro Ala Lys 1 5 <210> SEQ ID NO 25 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Fibrinogen beta <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <300> PUBLICATION INFORMATION: <301> AUTHORS: Belew M, Gerdin B, Lindeberg G, Porath J, Saldeen T, Wallin R. <302> TITLE: Structure-activity relationships of vasoactive peptides derived from fibrin or fibrinogen degraded by plasmin <303> JOURNAL: Biochim Biophys Acta. <304> VOLUME: 621 <305> ISSUE: 2 <306> PAGES: 169-178 <307> DATE: 1980-02-27 <308> DATABASE ACCESSION NUMBER: Pubmed <309> DATABASE ENTRY DATE: 2003-03-26 <313> RELEVANT RESIDUES: (1)..(5) <400> SEQUENCE: 25 Ala Arg Pro Ala Lys 1 5 <210> SEQ ID NO 26 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: GP6A <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <400> SEQUENCE: 26 Gly Arg Pro Ala Lys 1 5 <210> SEQ ID NO 27 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: KP6A <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <400> SEQUENCE: 27 Lys Arg Pro Ala Lys 1 5 <210> SEQ ID NO 28 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: QP6A <220> FEATURE: <221> NAME/KEY: PEPTIDE <222> LOCATION: (1)..(5) <400> SEQUENCE: 28 Gln Arg Pro Ala Lys 1 5 <210> SEQ ID NO 29 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Cyclo P6A <220> FEATURE: <221> NAME/KEY: CYCLOPEPTIDE <222> LOCATION: (1)..(5) <400> SEQUENCE: 29 Ala Arg Pro Ala Lys 1 5 <210> SEQ ID NO 30 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Cyclo GP6A <220> FEATURE: <221> NAME/KEY: CYCLOPEPTIDE <222> LOCATION: (1)..(5) <400> SEQUENCE: 30 Gly Arg Pro Ala Lys 1 5 <210> SEQ ID NO 31 <211> LENGTH: 5 <212> TYPE: PRT <213> ORGANISM: Artificial <220> FEATURE: <223> OTHER INFORMATION: Cyclo KP6A <220> FEATURE: <221> NAME/KEY: CYCLOPEPTIDE <222> LOCATION: (1)..(5) <400> SEQUENCE: 31 Lys Arg Pro Ala Lys 1 5
This invention relates to cyclic peptides, with the following formula (I) (SEQ ID NO: 1), cyclo(Xaa-Arg-Pro-Ala-Lys)  (I) where Xaa is Ala, Gly, Glu, Gln, Asp, Asn, Arg or Lys. The cyclic peptides have thrombolytic effects. This invention also relates to cyclic peptide preparations.
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[0001] This patent application is a continuation of U.S. patent application Ser. No. 14/162,979 filed on Jan. 24, 2014. U.S. patent application Ser. No. 14/162,979 is a continuation of U.S. patent application Ser. No. 13/538,637 filed on Jun. 29, 2012. U.S. patent application Ser. No. 13/538,637 is a continuation of U.S. patent application Ser. No. 11/237,564 filed on Sep. 28, 2005. U.S. patent application Ser. Nos. 14/162,979, 13/538,637 and 11/237,564 are hereby incorporated by reference. TECHNICAL FIELD [0002] The present invention relates in general to securing transmitted electronic documents and, more particularly, to enforcing a rights management policy on transmitted electronic documents. BACKGROUND INFORMATION [0003] Security of transmitted electronic documents has been the subject of great attention in the data processing industry. The misuse or misappropriation of confidential information is a serious threat to electronic commerce. Even the perceived risk of insufficient integrity will render a data processing method unworthy for commercial use. System administrators and service providers have been responsible for creating policies and implementing procedures for ensuring the security of files transferred over a network. The majority of security measures has been focused on controlling access to infrastructure, such as a network domain or a storage media. For example, securing documents sent by e-mail was primarily accomplished by restricting access to a given e-mail account. Another common method is to compress or encrypt documents sent via e-mail. However, due to the unsecured nature of e-mail, many forms of business and transactions are still not conducted using e-mail messages and documents. Also, these kinds of policies do not have any effect on a user or a file after the document has been received via e-mail and made available for further processing. [0004] Therefore, newer security architectures have emphasized providing security in the user environment at the application level, when the document is manipulated by the receiving party. Typically, point of use security methods require global coverage of an IT system with the corresponding installation of central tools and distributed agents. This kind of additional digital rights management infrastructure added to an IT system requires a large initial investment and significant administration effort over time. A centralized system can also be very inflexible and may not meet the specific needs of individual stakeholders. For example, if the system architecture requires that every document be registered with the authenticating server, then the system must rely upon the authenticating server for rights management policies. Such an architecture is inherently limited to securing participants within the domain, which inherently limits the scope of the security provided. Thus, there is a need for a simplified, decentralized method for securing e-mail messages and documents at their point of use, that can be universally used by any recipient of an e-mail message. [0005] A common problem of practicality when transmitting encrypted content is that the sender and recipient are required to exchange keys in advance of the actual transmission. If a sender wants to send an encrypted document securely to a recipient, prior art methods have required that the sender possess the public key of the recipient before the encrypted content is transmitted. [0006] Another aspect of digital rights management that has yet to be addressed is the time-dependent nature of many usage rights policies. When the digital rights to a document that already has been transmitted need to be changed, prior art systems have not offered simple, transparent solutions. For example, a frequent requirement in business communications is the widespread distribution of documents in advance of a specific date when such documents may be accessed by a large number of recipients. There has been no solution available that provides a robust, integrated, and automated solution to this common scenario. [0007] Therefore, there is a need for a simple, flexible digital rights management system for transmitting documents and messages via e-mail, such that users may freely exchange encrypted data. The system should be decentralized and enable flexible management of digital rights over time, without requiring a global IT installation and additional administration. SUMMARY OF THE INVENTION [0008] The present invention addresses the foregoing needs by providing a solution with point of use digital rights management for transmission of files via e-mail. The present invention utilizes a cryptocontainer, having a unique structure and properties, for packaging digital content upon transmission via e-mail. The digital content may comprise electronic documents and data files, or any other type of digital media content. The sender of the secured documents configures the cryptocontainer using an authoring tool for generating and distributing cryptocontainers, whereby the authoring tool applies a public key belonging to a key server. The authoring tool provides for assigning specific access rights to individual documents that may very over time. The access rights may be customized for individual recipients of the cryptocontainer. Only after validated authorization and decryption may the e-mail recipient of the cryptocontainer be granted their access rights to specific content in the cryptocontainer. [0009] The present invention additionally solves the problem of a sender wanting to send an encrypted document securely to a recipient, whose public key the sendor does not possess. The present invention employs a key server to deciper a session key for the encrypted content. Instead of encrypting the session key for the recipient, the session key is encrypted for the key server. The key server authenticates the recipient independently (from an authenticating entity) and releases the session key to the recipient only after the recipient's authentication certificate is obtained. [0010] The access rights are enforced according to the time-dependent scheme defined in the authoring tool of the cryptocontainer for that specific user. During the entire process of transmitting and receiving e-mail messages and documents, the exchange of cryptographic keys remains totally transparent to the users of the system. There is no requirement that senders and recipients manually exchange keys. The present invention provides additional security in that the transmitted content of a cryptocontainer is only decrypted in a second decryption step, only after an initial decryption has provided authentication of the recipient's identity. Otherwise, the transmitted content is not decrypted. Senders of e-mail may be so assured that the digital content transmitted may only be received by an authorized user and may only be further processed subject to the conditions of use as designated by the sender. [0011] Additionally, the present invention provides for digitally signing electronic documents with authentication of the signature. The electronic signature in the present invention relies upon and is compliant with 15 U.S.C. §7001, ELECTRONIC RECORDS AND SIGNATURES IN COMMERCE, General Rule of Validity, of which subsection (a) recites: 15 U.S.C. §7001. General rule of validity In general Notwithstanding any statute, regulation, or other rule of law (other than this subchapter and subchapter II of this chapter), with respect to any transaction in or affecting interstate or foreign commerce— a signature, contract, or other record relating to such transaction may not be denied legal effect, validity, or enforceability solely because it is in electronic form; and a contract relating to such transaction may not be denied legal effect, validity, or enforceability solely because an electronic signature or electronic record was used in its formation. The intent of each signature may be further specified by the signing individual with a text entry accompanying the signature. [0017] In one example of the present invention, a marketing department may use the usage rights timeline to make an upcoming brochure unavailable until a given date. On the given date only the recipients in the user groups “Internal Sales” and “Management” can have rights to view and print the brochure. A week after “External Sales” is given rights to view and distribute the brochure in “view only” form. Two-weeks later on the pre-determined release date the brochure can be freely distributed and printed by its recipients. [0018] In another example of the present invention, a financial service sends an e-mail listing the latest quarterly earning reports of “ACME Company” to its distribution list 24-hours before its public release. The service company utilizes the usage rights timeline to ensure that the information is disclosed to all of its recipients at the same time. Employees of the financial service are given permission to only view, but not distribute, the information some hours before its public disclosure. At the given pubic release time, the employees will be able to freely distribute the “ACME Company” earnings report to members of the public. [0019] Thus an object of the present invention is to enable the widespread and transparent use of e-mail documents and messages for highly secure applications. [0020] Another object of the present invention is to provide for decryption of content in a second step following an initial authentication of recipient on receipt of an e-mail message, and to deny decryption of content in case the recipient cannot be authenticated. [0021] Another object of the present invention is to provide a secure mechanism for digital rights management of documents transmitted over a network using a transactional authentication methodology for enforcement of usage rights policies, such that access to a server is only required for initiating access granted to secured documents. [0022] An object of the present invention is to provide a mechanism whereby senders of secured e-mail messages may rely upon an e-mail address for identifying an authenticated recipient, without the requirement of contacting the recipient or exchanging keys with the recipient in advance of sending an e-mail message. [0023] An additional object of the present invention is to provide a means for displaying the security rating of an e-mail client over a given time period. [0024] Another object of the present invention is to provide a means for assigning usage permissions to individuals and user groups of selected individuals. [0025] A further object of the present invention is to provide time-dependent digital rights for digital content transmitted via e-mail, such that the user-specific rights may change or evolve as a function of elapsed time. [0026] A further object of the present invention is to provide time-dependent digital rights for digital content transmitted via e-mail, such that the user-specific rights may be modified in response to actions by the user of the digital content or by third-parties. [0027] Another object of the present invention is to provide a mechanism for digitally authenticating an electronic signature transmitted via e-mail. The electronic signature may be augmented with a text line where the signer may specify the intent of the signature. [0028] An additional object of the present invention is to provide for the migration and back-up of encrypted data and encryption tools to another physical hardware platform. [0029] Another object of the present invention is to prohibit the circumvention of restricted processing rights for digital content by using a hardware overlay technique for rendering the digital content visible on a display device. [0030] A further object of the present invention is to provide an audit trail of all documents sent and received using a secured e-mail transmission system. [0031] The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. BRIEF DESCRIPTION OF THE DRAWINGS [0032] For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which: [0033] FIG. 1 is a flow chart of an encryption process in an embodiment of the present invention; [0034] FIG. 2 is a flow chart of a decryption process in an embodiment of the present invention; [0035] FIG. 3 is a display of a security rating of an e-mail client in an embodiment of the present invention; [0036] FIG. 4 illustrates a graphical user interface element for defining usage rights in an embodiment of the present invention; [0037] FIGS. 5 and 5A illustrate graphical user interfaces for electronic signatures in an embodiment of the present invention; [0038] FIGS. 6-12 illustrate a graphical user interface in an embodiment of the present invention; [0039] FIG. 13 illustrates network components in one embodiment of the present invention; and [0040] FIGS. 14A-F illustrate a graphical user interface in an embodiment of the present invention. DETAILED DESCRIPTION [0041] In the following description, numerous specific details are set forth such as specific word or byte lengths, etc. to provide a thorough understanding of the present invention. However, it will be obvious to those skilled in the art that the present invention may be practiced without such specific details. In other instances, well-known circuits have been shown in block diagram form in order not to obscure the present invention in unnecessary detail. For the most part, details concerning timing considerations and the like have been omitted inasmuch as such details are not necessary to obtain a complete understanding of the present invention and are within the skills of persons of ordinary skill in the relevant art. [0042] Refer now to the drawings wherein depicted elements are not necessarily shown to scale and wherein like or similar elements are designated by the same reference numeral through the several views. [0043] The present invention provides a solution with point of use digital rights management for transmission of files via e-mail. The present invention utilizes a cryptocontainer, having a unique structure and properties, for packaging digital content upon transmission via e-mail. The digital content may comprise electronic documents and data files, or any other type of digital media. Any reference herein to electronic documents, documents, files, messages, data, media, and other content may be used interchangeably and refers universally to digital content which may be transmitted over a network or stored in a memory or storage device. The sender of the secured documents configures the cryptocontainer using an authoring tool for generating and distributing cryptocontainers, whereby the authoring tool applies a public key belonging to an key server. The authoring tool provides for assigning specific access rights, which may vary over time, to individual documents. The access rights may be customized for individual recipients of the cryptocontainer. Only after validated authorization and decryption may the e-mail recipient be granted access rights to specific content in the cryptocontainer. [0044] In FIG. 13 , network components in one embodiment of the present invention are illustrated. A sending platform 320 runs the authoring tool and is operated by the author. The author creates a cryptocontainer, symbolized by 325 , and sends it via e-mail to the recipient operating the receiving platform 321 , which runs the viewing tool. A server 330 may provide services to the sending platform 320 or to the receiving platform 321 . The server 330 may represent a public web server that both platforms 320 , 321 may connect to via the Internet. In one embodiment, the server 330 is a public web server for accessing the authoring tool or the viewing tool as web services. The server 330 may rely upon an key server 340 to perform the operations of the present invention. In one embodiment, the server 330 and key server 340 represent network services that are executed on a single physical platform, such that servers 330 and key server 340 are combined into a single entity. The key server 340 may rely upon an authenticating server 350 for authenticating e-mail addresses of authors and recipients of cryptocontainers 325 . The authentication server 350 may be operated by a third-party as a public commercial service for authenticating users via e-mail addresses for clients. [0045] Referring to FIG. 1 , a process 115 , 120 for sending encrypted content according to an embodiment of the present invention is illustrated in flow chart form, from begin 101 to end 150 . An initial configuration process 115 must be performed before the authoring and sending process 120 may be executed, if not previously carried out, according to a determination 110 . In one example of practicing the present invention, the entire procedure of 115 may be omitted after one instance of installation 115 has been performed. In another example, the determination if the authoring tool is installed 110 may result in either steps 111 and 122 , singly or in combination, being executed for the purpose of updating a prior installation or recertifying a prior authentication. [0046] The installation of the authoring tool 111 comprises all actions required for obtaining an installable, licensed version of the authoring tool, for performing an installation, and for configuring an authoring tool for use on a given sending platform 320 . The installation step 111 may also include steps for verifying the network connection of the sending platform 320 , comprising configuration of hardware and software components, such that an e-mail service is made bi-directionally operational on the sending platform. Additionally, step 111 may also encompass communicating with an key server 340 for obtaining or validating the key server's public key, which is used by the authoring tool on the sending platform 320 . In one example, installation 111 of the authoring tool is performed by installing the authoring tool as an application to be executed on the sending platform 320 . In another example, installation 111 of the authoring tool is performed by activating a license to use the authoring tool as web service to be executed on an Internet server 330 . [0047] The author is an individual who operates the authoring tool on the sending platform 320 for creating, modifying, and distributing cryptocontainers 325 , containing electronic documents and digital data. The author is also the individual who assigns the usage rights 128 for each document in the cryptocontainer 325 . The author is therefore the author and also the sender of the cryptocontainer 325 , however, no assumption is made herein as to the authoring of the actual digital content transmitted in the cryptocontainer 325 in various embodiments of the present invention. [0048] The step of authenticating an author 122 may be performed by the key server 340 on the basis of the author's e-mail address from an authenticating server 350 . The key server 340 creates a user license for the author, signs the author's license and public key with the key server's private key, and stores this as a hash value for authenticating messages from the author (step 122 ). In one embodiment of the present invention, the authoring tool may be installed for use by the author on a sending platform 320 , such as a computer system, such that the authentication of the author 122 involves sending a hardware fingerprint, which identifies the sending platform, to the key server 340 for authentication by an authenticating server 350 . The hardware fingerprint may comprise the following information unique to the computer on which the authoring tool is installed: BIOS version number, video card BIOS creation date, primary HDD serial number, MAC address of a network adapter. In another example, the hardware fingerprint may comprise a unique identifier of the CPU, main system board, or other component of the sending platform computer 320 . [0049] In another embodiment of the present invention, the authoring tool may be installed on server 330 and used as a web service in an Internet browser, such that the authentication of the author 122 relies upon a unique biometric identification of the author that is sent to the key server 340 for authentication by an authentication server 350 . In one example a biometric USB device installed on a public computer system may be used by the author for generating the unique biometric identification. The biometric identification is used by the key server 340 to obtain the author's license from the authenticating server 350 in the same manner as the hardware fingerprint. In another example of practicing the present invention, the authoring tool is integrated as an additional feature in a standard e-mail client program. [0050] After the installation steps 115 have been completed at least once without error, the process in 120 may be repeated as required to send a plurality of secured e-mail messages containing cryptocontainers 325 . According to another embodiment of the present invention, installation of the authoring tool 111 may also comprise the transferring (or migration) of an existing installation of a working version of the authoring tool from a previous sending platform to the current sending platform 320 . The transferring (or migration) may include all existing data and archived documents along with the necessary re-validation and re-authentication (as in 122) on the current sending platform 320 . [0051] The sending process is illustrated by the process steps 120 in FIG. 1 . Upon authentication 122 by an authenticating server 350 , the author is granted full access to the authoring tool on the sending platform 320 by the key server 340 . One first step may be entry of the recipient list 124 . Individual recipients may be assigned membership to one or more user groups 610 , 613 (see FIG. 6 ), which may be used for managing usage rights for each document in the cryptocontainer 325 . After entry of the recipient list, the author may add the digital content to the cryptocontainer 325 by selecting the required files 125 . In 127 the author may also optionally choose to electronically sign certain documents (see FIGS. 5 and 12 ). The authoring tool generates a symmetric session key 126 for each cryptocontainer 325 . In the recipient list section of the cryptocontainer 325 , a session key and a list of recipients' e-mail addresses is recorded. This entire section of the cryptocontainer 325 is encrypted not for the recipients but for the key server 340 . The key server's public key is used to encrypt the recipient list section using asymmetric encryption. In alternative embodiments of the sending process 120 , the order of the steps 124 - 127 may be rearranged to accommodate a flexible workflow. The order of the steps 124 - 127 is generally not constrained by the authoring tool. [0052] For each document and recipient, a usage rights timeline may be defined by the author in step 128 . The usage rights timeline gives an author the ability to set usage permissions on digital content (digital rights management controls, see FIG. 4 ) which evolve in accordance with time or specific actions. In its simplest form, the usage rights timeline can be used to deny access to files on a specific time and date. In its full use, the usage rights timeline can be used to quickly set complex usage permission structures that change with time. Using the usage rights timeline, authors can create keyframes 1110 (see FIG. 11 ), which are sets of predefined rights states that exist for a specified period of time. Different usage permissions can be applied to each keyframe 1110 , enabling usage states to evolve in a pre-determined fashion. The usage rights timeline is enforced by the viewing tool, installed in process 220 (see FIG. 2 ). [0053] After the author determines the recipients, content, and usage rights for the cryptocontainer 325 , encryption 130 is performed by the authoring tool. During encryption 130 of the cryptocontainer 325 , the recipient list section and the content payload are encrypted separately with different session keys. The session keys are encrypted with the public key of a the key server 340 . In one embodiment of the current invention, the key server 340 is maintained by a service provider who also provides the license for the authoring tool on the sending platform 320 , and public access rights to the key server 340 are restricted to license holders of the authoring tool. In another embodiment, the viewing tool is distributed freely to the public, including access rights to the key server 340 for viewing documents sent in cryptocontainers 325 according to their assigned usage rights. [0054] In one embodiment of the present invention, each individual operation performed on a cryptocontainer 325 , such as obtaining a session license from an authorizing server or adding a document for viewing or printing encrypted in the cryptocontainer 325 , is recorded in a log which may serve as an audit trail 131 for reconstructing events that occurred involving the cryptocontainer 325 . The audit trail 131 may also include each time that usage rights keyframes 1110 were defined and the files and recipients to which those keyframes 1110 were assigned. [0055] The final step in the sending process 120 is transmitting the cryptocontainer 325 via e-mail 132 . The cryptocontainer 325 may be sent 132 with an standard e-mail client program from the sender to each recipient on the recipient list. In one embodiment of the present invention, the authentication process requires the author to use the computer that has been certified from the key server 340 for the author's sending e-mail address. In another example, a biometric identification has been performed to authenticate the sender, which in turn, permits the sender to work on any suitable public sending platform 320 . In one case, the sender may use a unique biometric identification with a web service version of the authoring tool on the sending platform 320 . The transmission of the cryptocontainer from the sending platform 320 may be performed with any wired or wireless network connection that supports e-mail transmission. In one example, the sending platform is a handheld wireless device that provides a suitable e-mail client service. In another example, the cryptocontainer may be sent to an intermediary, from where the cryptocontainer is further distributed to the recipients on the recipient list. [0056] Referring to FIG. 2 , a process 220 for receiving encrypted content according to an embodiment of the present invention is illustrated in flow chart form, from begin 201 to end 250 . An initial configuration process 215 must be performed before the receiving process 220 may be executed, if not previously carried out, according to a determination 210 . In one example of practicing the present invention, the entire procedure of 215 may be omitted after one instance of installation 215 has been performed. In another example, the determination if the viewing tool is installed 210 may result in either steps 211 and 222 , singly or in combination, being executed for the purpose of updating a prior installation or recertifying a prior authentication. [0057] The installation of the viewing tool 211 comprises all actions required for obtaining an installable, licensed version of the viewing tool, for performing the installation, and for configuring the viewing tool for use on a given receiving platform 321 . The installation step 211 may also include steps for verifying the network connection of the receiving platform 321 , comprising configuration of hardware and software components, such that an e-mail service is made bi-directionally operational on the receiving platform. In one example, installation 211 of the viewing tool is performed by installing the viewing tool as an application to be executed on the receiving platform 321 . In another example, installation 211 of the viewing tool is performed by activating a license to use the viewing tool as service executed on web server 330 in a web browser, whereby the web browser is used to access a web e-mail client. Next, authentication of the recipient 222 is performed by the key server 340 using an authentication server 350 . [0058] In one embodiment of the present invention, the viewing tool is installed for use by the recipient on a receiving platform 321 , such as a computer system, such that the authentication of the recipient 222 involves sending a hardware fingerprint, which identifies the sending platform 321 , to the key server 340 for authentication by an authenticating server 350 . Step 222 may encompass communicating with an key server 340 for validating the recipient's identity and transmitting a passport certificate, obtained from an authenticating server 350 , identifying the recipient's computer (with a hardware fingerprint) and registering the recipient's computer passport and e-mail address. [0059] In another embodiment of the present invention, the viewing tool may be installed on the web server 330 and used as a web service in an Internet browser, such that the authentication of the recipient 222 relies upon a unique biometric identification that is sent to the key server 340 for authentication by an authenticating server 350 . In one example, the recipient may use a web mail service to access a primary e-mail account held by the recipient, whereby a biometric USB device is installed on a public computer system used by the recipient for generating the biometric identification. The unique biometric identification is used by the authenticating server 350 to generate the recipient's license in the same manner as the hardware fingerprint. In another example of practicing the present invention, the viewing tool is integrated as an additional feature in a standard e-mail client program. [0060] In one example of the present invention, after the installation 215 has been completed once without error, the process in 220 may be repeated as required to receive a plurality of secured e-mail messages on the receiving platform 321 . According to another embodiment of the present invention, installation of the viewing tool 211 may also comprise the transferring (or migration) of an existing installation of a working version of the viewing tool from a previous receiving platform to a current receiving platform 321 . The transferring (or migration) may include all existing data and archived documents and be accompanied with a required re-validation and re-authentication (as in 222 ) on the current receiving platform 321 . [0061] In FIG. 2 , the core receiving process is illustrated by the process steps 220 . The entire receiving process in FIG. 2 is triggered by receipt of the cryptocontainer 325 via e-mail 205 by the recipient. Note that the recipient is not required to be in possession of any public keys. If the recipient is not authenticated and no viewing tool is installed, the installation process 215 will automatically be triggered upon accessing the cryptocontainer 325 . This process requires only a standard e-mail client. If the recipient is authenticated and a viewing tool is installed, process 220 may be initiated. [0062] The authentication step 222 may be precluded to some extent when a recipient already possesses a valid public key. This preauthentication begins when the viewing tool sends a certificate that authenticates the recipient to the key server 340 from the sending platform 321 . In one case, an acceptable certificate is signed by an authentication server 350 and contains the recipient's e-mail address. This is taken as valid proof by the key server 340 , that at some point in the past, the process has taken place by which the recipient had obtained that certificate and there is confidence that it could only have been obtained from a known authentication server 350 . If the key server 340 receives a certificate for a recipient containing a public key and an e-mail address that is signed by a known authenticating server 340 , then the recipient's identity is considered authentic. The recipient is preauthenticated by issuing the certificate. When the recipient actually contacts the key server 340 for a session key, reauthenticate is not required. [0063] As a first step in process 220 , a decryption of the recipient list 224 is performed. Step 224 begins with the author's public key, signed by the server's private key, being sent to the key server 340 by the viewing tool from the receiving platform 321 . Then the encrypted recipient list and session keys are sent to the key server 340 by the viewing tool from the receiving platform 321 . The recipient list is decrypted 224 by the key server 340 . Next, the key server 340 compares 226 the recipient's identity with the recipient list of the cryptocontainer 325 . If there is no match, then the recipient is denied access 230 to the cryptocontainer 325 by the key server 340 and no further action may be taken by the recipient on the cryptocontainer 325 . The denial of access 230 is enforced by the viewing tool on the receiving platform 321 . In this case 230 , no session key is issued to the recipient by the key server 340 for the cryptocontainer 325 . If the recipient does match the recipient list, then the key server 340 will issue 228 a session license for the recipient to open the contents of the cryptocontainer 325 on the receiving platform 321 . In step 228 , the key server 340 re-encrypts the session keys with the recipient's public key and sends the re-encrypted session keys back to the recipient's viewing tool on the receiving platform 321 . The recipient's viewing tool receives the re-encrypted session keys and the decrypts them only when they are required to access a particular file in the cryptocontainer 325 . The recipient may now decrypt and access 232 the content in the cryptocontainer 325 on the receiving platform 321 . However, a recipient's access to individual documents may further be restricted by a usage rights timeline that is used to enforce 234 the policies in individual keyframes applicable to the recipient. If the content is closed by the recipient, the steps in process 220 may be repeated for each access to the cryptocontainer 325 on the receiving platform 321 . [0064] The usage rights timeline is enforced 234 by the viewing tool, installed in process 211 . When the recipient opens a cryptocontainer 325 , the viewing tool checks the time from a local time source or from a secured Internet time server. The viewing tool then enforces the rights schema 234 as designated by the content author using the usage rights timeline for the current time. As long as the viewing tool is active, it periodically checks the time and enforces the usage rights 234 for the given time. In one example, a secured time server is the primary time source and a secondary, local time source is used only when the primary time source is unavailable, thereby ensuring enforcements of rights schema 234 , regardless if a network connection is maintained or not by the receiving platform 321 . [0065] One particularly unique aspect of the enforcement 234 of usage rights in process 220 is the use of a hardware-overlay technique for displaying secured documents. The viewing tool may use hardware overlay to render files directly from video hardware rather than by using software rendering. The advantage of this approach is that it helps to defeat many popular screen-capture products in a relatively simple fashion. In one embodiment of the present invention, during enforcement of usage rights 234 , each individual operation performed on a cryptocontainer 325 , such as obtaining a session license from an authorizing server or opening a document for viewing or printing encrypted in the cryptocontainer 325 , is recorded in a log which may serve as an audit trail 235 for reconstructing events that occurred involving the cryptocontainer 325 . The audit trail 235 may also include each time the content was accessed and each time access to the cryptocontainer 325 was denied 230 or each time usage rights were restricted 234 . [0066] Of particular significance is the transactional nature of the involvement of the authentication server 350 and the key server 340 in processes 120 and 220 . The transactional authentication methodology, as described in the embodiments of the present invention illustrated in FIGS. 1 and 2 , limits the involvement of the authentication server 350 and the key server 340 to a minimum, which, in turn, serves to make the entire system very flexible and efficient. In the sending process 120 , there is no requirement for the key server 340 to participate once an author has been authenticated by an authentication server 350 in 122 . The receiving process 220 requires active participation from the key server 340 only for discrete steps 224 , 226 , and 228 upon receipt of the cryptocontainer 325 , once a recipient has been authenticated by an authentication server 350 in 222 . Of particular importance in certain embodiments of the present invention is that the enforcement of usage rights timeline policies is performed by the viewing tool on the receiving platform 321 , and does not require any involvement by the key server 340 . This unique feature of the present invention enables widespread distribution and use of secured digital rights management for e-mail documents by providing a practical and efficient architecture. [0067] Referring now to FIG. 3 , a display 300 of the security rating of an e-mail client is shown. The display 300 shows the values of the total number of e-mail messages sent as well as the number of those that were secured items. The values may be reset after a time period has elapsed. The display 300 also shows a ratio of the secured items sent. In one example, the percentage of secured items sent is used to calculate a security rating. [0068] In FIG. 4 , a graphical user interface element 400 is illustrated for defining usage rights in an embodiment of the present invention. The interface panel permits the definition of usage rights for specific files. Usage rights are presented in one example of a graphical user interface in a spreadsheet format 410 with files 411 on the left side and the usage rights 412 related to a specific data element 413 selected on the top. Tabs are used to toggle between the different data elements 413 : Files, Folders, User Groups, Signature Lines and Containers. The exemplary user interface 400 is shown with the tab data element 413 (Files 411 ) selected. To allow a particular usage right 412 , a check is entered in the associated box. The interface 400 provides the ability to assign a wide variety of usage rights 412 to files, folders, user groups, signature lines and the cryptocontainer 325 itself. In one example, the usage rights for files comprise: viewing, printing, export, delete, item visible, show thumbnail, rename, move. In one example, the usage rights for folders comprise: folder visible, delete, export, rename, file visible, move, open. In one example, the usage rights for folders comprise: folder visible, delete, export, rename, file visible, move, open. [0069] In FIG. 5 , a graphical user interface 500 is illustrated for electronic signatures in an embodiment of the present invention. The electronic signature for a given document 511 may include an additional qualifier for the signature as a text field 510 . In one example the purpose of the signature may be entered in this text field. In another example, the signer may choose from a predefined list of signature qualifiers. The electronic signature in the present invention relies upon and is compliant with 15 U.S.C. §7001. In FIG. 5A , a confirmation panel 550 is illustrated of a valid electronic signature. The purpose and terms of the signature 552 are shown along with the e-mail address of the signee 551 , and the document 511 for which the signature is valid. [0070] FIG. 6 illustrates a graphical user interface 600 of an authoring tool in a default state in an embodiment of the present invention. The authoring tool is used to construct and distribute a cryptocontainer 325 . At the top, the authenticated e-mail address 614 of the author is shown. This is the sending e-mail address of the cryptocontainer 325 . The panel 600 is the basic screen where all common tasks are performed in the authoring tool. To the left panels User Groups 610 , 613 , Files 611 , and Signatures 612 can be added. The Files panel 611 displays the files to be protected and in panel 611 each file is identified by a filename and a filepath or network location path to that filename, such that the aggregate filepath identifying the file is unique and valid. The Signatures panel 612 displays any electronic signatures that have been performed on specific files in 611 by the author. The main workspace is defined by tabs which indicate the currently selected User Group 610 , 613 . In the default state, only Authors and Recipients are defined as User Groups 610 , 613 . Within a single user group, for example as shown in 600 , Recipients, the list of authorized recipients within the selected User Group may be listed in the Group Members 615 panel. The permissions panel 616 corresponds to the usage rights user interface 400 in FIG. 4 . Below, the Rights Timeline panel 617 indicates the time span to which the selected permissions apply. Each element in panel 617 is a keyframe in the usage rights timeline. [0071] FIG. 7 illustrates a graphical user interface 700 of an authoring tool during entry of files 710 to a cryptocontainer 325 in an embodiment of the present invention. Files 710 may be added to Files panel 611 using the Import File or Import Folder button, or by dragging and dropping over panel 611 . When the author saves the cryptocontainer, the files will be securely encrypted inside a cryptocontainer 325 . The permissions panel 616 displays each individual file 710 as a separate line item 711 . The permissions panel 616 corresponds to the usage rights user interface 400 in FIG. 4 . [0072] FIG. 8 illustrates a graphical user interface 800 of an authoring tool during entry of recipients 810 to a cryptocontainer 325 in an embodiment of the present invention. The list of recipient e-mail addresses 810 may be entered in the group members panel 615 . This ensures that the files 710 , 711 will be seen only by recipients 810 that are approved by the author. [0073] FIG. 9 illustrates a graphical user interface 900 of an authoring tool during entry of user groups 613 to a cryptocontainer 325 in an embodiment of the present invention. Recipients 810 can be categorized into groups 613 , which are created in the, User Groups panel 610 . Sorting recipients 810 into user groups 613 enables advanced control of usage rights 412 for each group 613 . [0074] FIG. 10 illustrates a graphical user interface 1000 of an authoring tool during assignment of user rights 412 for user groups 613 in a cryptocontainer 325 in an embodiment of the present invention. After sorting recipients 810 into user groups 613 , each user group 613 can be assigned different user rights 412 to individual files 710 , 711 . This permits cryptocontainer 325 files to be sent to multiple recipients 810 who have different usage rights 412 . [0075] FIG. 11 illustrates a graphical user interface 1100 of an authoring tool during assignment of user rights 412 over time in a cryptocontainer 325 in an embodiment of the present invention. For files 710 that are time sensitive, individual keyframes 1110 in the Rights Timeline panel 617 define the exact days, hours, and seconds that files 710 may be accessed. The Rights Timeline panel 617 indicates the time span to which the selected usage rights 412 apply. Each element in panel 617 is a keyframe 1100 in the usage rights timeline. [0076] FIG. 12 illustrates a graphical user interface 1200 of an authoring tool performing an electronic signature 511 in a cryptocontainer 325 in an embodiment of the present invention. The signature panel 500 enables the author to electronically sign 511 individual files 710 in the cryptocontainer 325 . The electronic signature in the present invention relies upon and is compliant with 15 U.S.C. §7001. [0077] In another embodiment of the present invention, the functionality of the authoring tool may be adapted for a quick method for creating a cryptocontainer from within a host application. As illustrated in FIGS. 14A and 14B , an adapted version of the authoring tool is accessible via a user interface toolbar 1402 . This toolbar automates the inclusion all of cryptocontainer data elements that are required for configuring the cryptocontainer to be accessible by authorized recipients. The cryptocontainer data elements from the toolbar comprise: email addresses of the intended recipients 1405 , data files 1407 , usage permissions 1411 and timeline settings 1412 . [0078] In FIG. 14A , one embodiment of the toolbar interface 1402 is shown as an add-in feature 1400 to a commercially available host e-mail client program (Outlook® by Microsoft Corp., Redmond, Wash.). The recipient list 1405 and data files 1407 are entered directly in the host application and are copied automatically by the toolbar interface 1402 . A rights template 1411 may be selected along with the timeline settings 1412 for the selected rights. The process of creating and sending the cryptocontainer is executed by a single user command button 1410 . [0079] In FIG. 14B , an embodiment of the toolbar interface 1402 is shown as an add-in feature 1401 to a commercially available host document processing program (Word by Microsoft Corp., Redmond, Wash.). In this example, the toolbar interface 1402 assumes that the document 1415 being processed by the host application comprises the digital content to be sent. A rights template 1411 may be selected along with the timeline settings 1412 for the selected rights. The process of creating and sending the cryptocontainer is triggered by the user command button 1410 . The recipient list may be entered into a dialog panel. [0080] In FIG. 14C , a simplified timeline entry dialog 1403 is illustrated. The timeline 1412 is specified for a given rights profile 1411 and is stored with the rights profile 1411 . The simplified timeline 1403 comprises three keyframes. The first keyframe 1417 is “Do Not Open Until” and represents the activation time for the data files in the cryptocontainer. The second keyframe is the viewing keyframe (not shown) between the first 1417 and third 1418 keyframes and represents the usage period by the recipient. The third keyframe 1418 is “Expire After” and represent the expiration date of the usage rights in the profile 1411 . [0081] The toolbar interface 1402 allows authors retrieve usage permissions from a pre-defined template. The process for generating a pre-defined template using the authoring tool (see FIGS. 14D-14F ) is separate from the standard cryptocontainer creation process, as previously described above. An author may select a pre-defined rights profile template directly from a drop-down menu 1411 in the toolbar interface 1402 . In one example, the toolbar interface 1402 comprises default rights templates for “View Only” and “Encrypt Only” access to the cryptocontainer. [0082] The toolbar interface 1402 may exist as a plug-in to a host software application 1401 or to an e-mail client 1400 that provides for the addition of third party plug-ins. The toolbar interface 1402 may be used with a web mail e-mail client or with a locally installed e-mail client program. In one embodiment of the toolbar interface 1402 , a single mouse click (on button 1410 ) may suffice for creating a cryptocontainer, for assigning access rights to documents sent with a cryptocontainer, and for sending a cryptocontainer within an e-mail application program. In another example, from host application programs such as document, spreadsheet or graphic applications, the author may be required to enter the e-mail addresses of the recipients before the cryptocontainer is created. In that case, the toolbar interface 1402 may assume that the author is attempting to send the current document 1415 being processed in the host application in a cryptocontainer. When the appropriate button 1410 on the toolbar interface is clicked, the required cryptocontainer elements are retrieved by the host application program that the toolbar interface 1402 resides in. In one example, a “Send secure” button 1410 represents the toolbar interface 1402 in a host application, as illustrated in FIGS. 14A and 14B . The source of the required cryptocontainer elements may comprise the following items: [0083] 1. E-mail Client Host Applications 1400 a. Recipients list is gathered from the e-mail addresses 1405 entered in the “to:”, “cc:”, and “bcc:” fields; b. Files are gathered from the “File Attachments” field 1407 and/or the email message body and are included in the cryptocontainer as separate files which can be assigned usage rights; c. Usage permissions are gathered from the template chosen in the toolbar interface 1402 drop-down menu 1411 ; and d. Timeline rights are gathered from time and date data entered into a dialog window 1403 by the author. The data elements provided are “Do not open until” and “Expires on”. When complete these elements create 3 keyframes that will be applied to the cryptocontainer elements 1405 , 1407 . [0088] 2. Other Host Applications 1401 a. Recipients list is gathered from the e-mail addresses entered by the author from a prompted dialog window interface. b. Files comprise the current document(s) 1415 that the author is processing in the host application. The author may be prompted to save the current document(s) 1415 before inclusion in the cryptocontainer. c. Usage permissions are gathered from the template chosen in the toolbar drop-down menu 1411 by the author. d. Timeline rights are gathered from time and date data 1412 entered into a dialog window by the author. [0093] In one embodiment of the toolbar interface 1402 , all recipients are included into the same User Group. Also, included files 1407 , 1415 may be assigned usage rights according to the chosen template setting 1411 (i.e. View Only, Encrypt Only). Timeline rights 1412 may be assigned to any rights template 1411 . In another example embodiment of the toolbar interface 1402 , the creation of rights timeline templates 1411 , wherein the times and dates of settings are relative to the date and time they are applied, may be specified and stored in advance. For example, an author may create a plurality of keyframes, each with a set of associated rights. When saved in advance as a template 1411 , only the relative difference to an arbitrary start time for each starting and ending times of each keyframe is stored, thereby allowing authors to create complex usage scenarios that may be rapidly retrieved and reused on demand at any time in the future. [0094] As basic examples of rights templates 1411 , “View Only” and “Encrypt Only” may be pre-defined as default selections for rights templates 1411 in the toolbar interface 1402 . The “View Only” template (see FIGS. 14D-14F ) may have the following rights enabled: View, Item Visible and Show Thumbnails. The “Encrypt Only” template may have the following rights enabled: View, Item Visible, Show Thumbnails and Extract. In one example, the “Encrypt Only” template merely assures the safe transmission of the files between the sender (i.e. the author of the cryptocontainer) and the recipient, without applying further usage rights that are enforced by the viewing tool. [0095] Users may additionally create new rights templates by operating the authoring tool and choosing a selected rights schema within the Usage Permissions window. In FIG. 14D , a template entry is illustrated for the “Do Not Open Until” keyframe 1417 , 1420 (see FIG. 14C ) in the “View Only” rights profile template 1411 . As reflected in the first cryptocontainer keyframe 1417 , 1420 , Item Visible and Show Thumbnails are the only enabled rights 1421 . In FIG. 14E , a template entry is illustrated for the viewing keyframe 1425 in the “View Only” rights profile template 1411 . As reflected in the second cryptocontainer keyframe 1425 , Item Visible, Show Thumbnails and Viewing are the only enabled rights 1426 . In FIG. 14E , a template entry is illustrated for the “Expire After” keyframe 1418 , 1430 (see FIG. 14C ) in the “View Only” rights profile template 1411 . As reflected in the third cryptocontainer keyframe 1418 , 1430 , Item Visible and Show Thumbnails are the only enabled rights 1431 . [0096] The author may then select the “Save as Template” command in the authoring tool, whereby the chosen rights schema will then be saved as a template that automatically populates the toolbar interface drop-down menu 1411 . The rights template exists as a unique entity independent of the other cryptocontainer elements to which it will be applied. In one example embodiment of a rights template, an author may choose to create a template entitled “View & Print,” which would allow recipients rights only for viewing and printing files in the cryptocontainer (but not forwarding, editing, copying, etc.). Other templates may be created with any combination of user rights and timeline settings as required. [0097] Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
A method and system for transmission of digital content via e-mail with point of use digital rights management is disclosed. The secured access rights to the digital content may be customized for individual recipients by the sender, and may evolve over time. The access rights are enforced according to a time-dependent scheme. A key server is used to arbitrate session keys for the encrypted content, eliminating the requirement to exchange public keys prior to transmission of the digital content. During the entire process of transmitting and receiving e-mail messages and documents, the exchange of cryptographic keys remains totally transparent to the users of the system. Additionally, electronic documents may be digitally signed with authentication of the signature.
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[0001] This application is a Continuation of co-pending application Ser. No. 11/907,486, filed on Oct. 12, 2007, and Japanese Patent Application No. 280013/2006 filed on Oct. 13, 2006, the entire contents of which are hereby incorporated by reference and for which priority is claimed under 35 U.S.C. § 120. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates to a digital camera that controls the emission amount of a flash using face information included in a subject, and a method therefor. [0004] 2. Description of the Related Art [0005] Generally, digital cameras initiate image taking before the shutter release button is depressed, and exposure control and focus control are performed using the image obtained during that period. The image obtained during that period is also used for a flash control to obtain an adequate emission amount of a flash. In the past, the method in which the adequate amount of flash is obtained based on the overall brightness of the obtained image has been commonly used. Recently, however, a flash control method in which face detection is performed on the obtained image, and emission amount of the flash is controlled according to existence or nonexistence of a face, or the proportion of the detected face in the image. [0006] For example, U.S. Patent Application Publication No. 20030071908 describes a method in which emission amount of a flash is reduced if a face is detected and the ratio of the face in the image is greater than or equal to a predetermined value. Further, U.S. Patent Application Publication No. 20060044422 describes a method in which emission amount of a flash is obtained using only the image data of a region corresponding to a face in the image, or using image data in which a region corresponding to a face in the image is weighted greater than for the other regions. [0007] Further, when a person is imaged with a flash at night or in a dark place, the eyes of the person may sometimes be imaged in red or gold (hereinafter, collectively referred to as “red eye” including gold and other colors). It is known that the red eye phenomenon occurs when the pupils of the eyes are opened widely. Consequently, some digital cameras have a function to emit a flash to close the pupils to a certain degree prior (hereinafter referred to as “redeye reduction emission”) to performing flash photography, and thereafter performing ordinary flash photography as described, for example, Japanese Unexamined Patent Publication No. 2001-215404. [0008] The methods described in U.S. Patent Application Publication Nos. 20030071908 and 20060044422 may obtain an image of appropriate brightness without halation in the face portion or without the face portion becoming too dark, if the content of image data obtained for face detection is identical to the content of image data obtained for light control. But, the position of a face included in the image data obtained for light control may sometimes differ from the position of the face detected from the image data obtained for face detection, since the face detection is performed prior to exposure control and focus control. In this case, the emission amount obtained based on the data of a region extracted as the region corresponding to the face may not become an optimum amount. Further, a more inadequate emission amount may be set in comparison with a case where the emission amount is obtained without considering the face, depending on an object newly located in the region where the face was detected as a result of the change in the face position. [0009] The aforementioned problem is particularly serious for flash photography involving the redeye reduction emission. The redeye reduction emission is primarily performed for closing the pupils to a certain degree, and the imaging is suspended for a certain time which is required by the pupils to contract in response to the redeye reduction emission, so that it is more likely that the aforementioned problem occurs in comparison with imaging without the redeye reduction emission. [0010] It is an object of the present invention to provide a digital camera capable of invariably performing a flash emission with an appropriate amount by solving the problem arising from the movement of the subject or digital camera during the time frame between the face detection and light control in imaging involving the redeye reduction emission described above. SUMMARY OF THE INVENTION [0011] The present invention proposes the following digital cameras and control methods as the means for solving the problem described above. [0012] A first digital camera of the present invention includes: an imaging unit such as a CCD (Charge Coupled Device) for generating image data representing a subject; a flash unit for emitting a flash; a face detection unit for performing face detection on the image data generated by the imaging unit; and an emission control unit for causing the flash unit to perform a redeye reduction emission and a main emission. The face detection unit performs face detection on redeye reduction emission image data representing the subject at the time of the redeye reduction emission performed by the flash unit, and supplies the result of the detection to the emission control unit. The emission control unit determines the emission amount for the main emission using a detection result of the detection performed on the redeye reduction emission image data. [0013] A first method of the present invention is a method for controlling the first digital camera described above. The method includes the steps of: while causing the flash unit to perform a redeye reduction emission, generating redeye reduction emission image data representing the subject when the redeye reduction emission is performed; performing detection of face information on the redeye reduction emission image data; determining the emission amount for main emission of the flash using a detection result of the detection; and causing the flash unit to perform the main emission with the determined emission amount. [0014] The referent of “main emission” as used herein means an essential emission in flash photography, i.e., the emission of a required and sufficient amount of light onto a subject for obtaining an image of the subject. The referent of “redeye reduction emission” as used herein means an emission performed prior to a main emission with an intention to close the pupils of the eyes of a subject to a certain degree so that the eyes of the subject will not be imaged in red due to reflected light from the pupils in the main emission. The referent of “using a detection result of the detection” as used herein means to use a result showing that a face is not detected, a result showing that a face is detected, or information of the detected face (position, size, and the like). [0015] In the first digital camera and method, the face detection result used for the determination of the emission amount for the main emission is the detection result of face detection performed on the image data obtained when the redeye reduction emission is performed. Thus, the time interval between the acquisition of image data for face detection and the acquisition of image data for light control becomes relatively short, and the probability that the subject or digital camera is moved during that time interval becomes smaller than in the conventional digital cameras. Further, when face detection is performed on image data obtained at night or in a dark place without light, the face may not sometimes be detected successfully. But in the first digital camera and method described above, face detection is performed on image data obtained when a redeye reduction emission is performed, so that the face may be detected with relatively high accuracy. [0016] A second digital camera of the present invention includes: an imaging unit for generating image data representing a subject; a flash unit for emitting a flash; a face detection unit for performing face detection on the image data generated by the imaging unit; and an emission control unit for causing the flash unit to perform a redeye reduction emission and a main emission. Here, the face detection unit performs face detection on image data generated by the imaging unit during the period after the time point when the redeye reduction emission is performed and before the time point when the main emission is performed, and supplies detection results of the detection to the emission control unit. The emission control unit determines the emission amount for the main emission using the detection results supplied from the face detection unit and causes the flash unit to perform the main emission with the determined emission amount. [0017] A second method of the present invention is a method for controlling the second digital camera described above. The method includes the steps of: causing the flash unit to perform a redeye reduction emission; generating image data representing the subject during the period after the time point when the redeye reduction emission is performed and before the time point when a main emission is performed; performing detection of face information on the generated image data; determining the emission amount for the main emission of the flash using a result of the detection; and causing the flash unit to perform the main emission with the determined emission amount. [0018] In the second digital camera and method of the present invention, the face detection result used for the determination of the emission amount for the main emission is one of the detection results of face detection performed on one of image data sets obtained during the period after the time point when the redeye reduction emission is performed and before the time point when the main emission is performed. Thus, the time interval between the acquisition of image data for face detection and the acquisition of image data for light control becomes relatively short, and the probability that the subject or digital camera is moved during that time interval becomes smaller than in the conventional digital cameras. In particular, if the latest result of the detection results obtained during that time frame is used for the determination of the emission amount for the main emission, the face position in the image data for face detection and the face position in the image data for light control substantially correspond to each other, so that the problem arising from the change in the face position does not occur. [0019] The present invention further provides a third digital camera having both of the functions of the first and second digital cameras described above and one of the functions is used selectively. BRIEF DESCRIPTION OF THE DRAWINGS [0020] FIG. 1A is an overview of the digital camera according to an embodiment of the present invention (normal view). [0021] FIG. 1B is an overview of the digital camera according to an embodiment of the present invention (view with a built-in flash being popped up). [0022] FIG. 1C is an overview of the digital camera according to an embodiment of the present invention (view with an external flash being attached). [0023] FIG. 2 illustrates an internal structure of the digital camera. [0024] FIG. 3 illustrates the relationship, in an ordinary digital camera, between the operation of the shutter release button and the performance of the digital camera. [0025] FIG. 4 illustrates the relationship, in a first embodiment, between the operation of the shutter release button and the performance of the digital camera. [0026] FIG. 5 is a flowchart illustrating a process of flash photography of the digital camera according to the first embodiment. [0027] FIG. 6A illustrates an example light control process using face information. [0028] FIG. 6B illustrates an example light control process without using face information. [0029] FIG. 7 illustrates the relationship, in a second embodiment, between the operation of the shutter release button and the performance of the digital camera. [0030] FIG. 8 is a flowchart illustrating a process of flash photography of the digital camera according to the second embodiment. [0031] FIG. 9 illustrates the relationship, in a third embodiment, between the operation of the shutter release button and the performance of the digital camera. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0032] Hereinafter, as exemplary embodiments of the present invention, single-lens reflex digital cameras having flash photography functions and methods for controlling the emission amount of the flash of the digital cameras will be described. Structure of the Digital Camera [0033] FIGS. 1A to 1C illustrate overviews of a digital camera 1 according to an embodiment of the present invention. As illustrated in FIG. 1A , the digital camera 1 includes, on the upper side thereof, a shutter release button 2 , a mode dial 3 for selecting an imaging mode, a built-in flash 4 , and a hot shoe 5 , which is a receptacle for attaching an accessory. [0034] The shutter release button 2 has a two-step mechanism to allow two different operational instructions to be given. For example, in photography using an auto exposure (AE) function and auto focus (AF) function, the digital camera 1 performs preparatory operations for the photography, such as exposure control, focus control, and the like, when the shutter release button 2 is lightly depressed (halfway depression). Under this state, when the shutter release button 2 is depressed strongly (full depression), the digital camera 1 initiates the exposure and records image data corresponding to a single screen obtained by the exposure in a memory card. [0035] The built-in flash 4 swings up (pops up) when a flash pop up button 6 , provided on the side, is depressed, as illustrated in FIG. 1B . Further, the flash pops up automatically in a certain imaging mode. The popped up built-in flash 4 emits light two or three times in association with a second step depression of the shutter release button 2 . When the redeye reduction emission function is disabled, two emissions are performed, one of which is a preliminary emission (pre-emission) for measuring the amount of light reflected back from a subject, and other of which is a main emission for supplying a sufficient amount of light to the subject for photography (for obtaining an appropriate amount of exposure). If the redeye reduction emission function is enabled, a redeye reduction emission is further performed prior to the preliminary emission. [0036] The operation of the built-in flash 4 depends not only on the operation of the shutter release button 2 , but also on the imaging mode selected by the mode dial 3 and flash emission mode set on the setting screen. Imaging modes include “AUTO” in which all of the settings for photography are set automatically by the camera, “MANUAL” in which all of the settings for photography are set manually by the user. Further, “Program Auto”, “Shutter-Priority Auto”, “Aperture-Priority Auto”, “Shake Reduction”, “Natural Photo”, “Portrait”, “Landscape”, “Night Scene”, and the like are provided as the imaging mode. As for the flash emission mode, “AUTO Flash”, “Forced Flash” , “Slow Synchronization”, “Redeye Reduction”, “Redeye Reduction +Slow Synchronization”, and the like are provided. [0037] The digital camera 1 set to “AUTO” mode as the imaging mode, and to “AUTO Flash” as the flash emission mode causes the built-in flash to pop up automatically and to emit a flash in association with the shutter release button 2 , if it determines that flash photography is required. On the other hand, the “Natural Photo” is a mode in which non-flash emission photography is performed. Therefore, in the digital camera 1 set to this mode, the operation of the shutter release button 2 does not cause the built-in flash 4 to function. The digital camera 1 set to “Redeye Reduction” or to “Redeye Reduction+Slow Synchronization” for the flash emission mode performs a redeye reduction emission for preventing a redeye phenomenon by contracting the pupils of a subject. The digital camera 1 set to “Portrait” for the imaging mode also performs the redeye reduction emission automatically if a predetermined condition is satisfied. Also, in each of the other modes, the operation of the built-in flash 4 is predetermined so as to meet the purpose of the mode. [0038] In the digital camera 1 , an external flash 7 may be attached to the hot shoe 5 and used, as illustrate in FIG. 1C . The external flash 7 is mechanically and electrically connected to the digital camera 1 when attached to the hot shoe 5 , and emits a flash according to the mode selected by the mode dial 3 in association with a second step depression of the shutter release button 2 , as in the built-in flash 4 . Hereinafter, description will be made focusing on the example embodiment illustrated in FIGS. 1A and 1B , but the present invention is applicable to any digital camera regardless of whether the flash is a built-in or external type. [0039] Next, the internal structure of the digital camera 1 will be described briefly with reference to FIG. 2 . As illustrated in FIG. 2 , the digital camera 1 has an imaging system which includes a lens 12 , a lens drive unit 16 , an aperture 13 , an aperture drive unit 17 , a CCD 14 , and a timing generator (TG) 18 . The lens 12 includes a plurality of functional lenses, including a focus lens for focusing the camera onto a subject, a zoom lens for realizing a zoom function, and the like. The lens drive unit 16 includes a small motor, such as a stepping motor, and controls the position of each of the functional lenses so that the distance of the lens from the CCD 14 meets the purpose of the lens. The aperture 13 includes a plurality of aperture blades. The aperture drive unit 17 includes a small motor, such as a stepping motor, and controls the positions of the aperture blades so that the opening size of the aperture meets the purpose of the aperture. The CCD 14 is a CCD with five million to twelve million pixels, having primary color filters, and outputs stored charges in response to an instruction signal from the timing generator 18 . The timing generator 18 sends a signal to the CCD 14 to cause the CCD 14 to store charges therein only during a desired time period, thereby the shutter speed is controlled. [0040] The digital camera 1 further includes: an A/D converter unit 15 for converting output signals of the CCD 14 to digital signals; an image input control unit 23 for transferring image data outputted from the A/D converter unit 15 to other processing units through a system bus 34 ; and a SDRAM 22 for tentatively storing image data transferred from the image input control unit 23 . The image data stored in the SDRAM 22 are RAW format data. [0041] The digital camera 1 further includes: a flash 11 ; an emission control unit 19 for controlling the timing and emission amount of the flash 11 ; a focus control unit 20 for focusing a lens by instructing the lens drive unit 16 to move the lens; an exposure control unit 21 for sending an instruction signal to the aperture drive unit 17 and timing generator 18 ; and a face detection unit 24 for performing face detection on the image data stored in the SDRAM 22 . The emission control unit 19 , focus control unit 20 , and exposure control unit 21 may sometimes perform processing with reference to the face detection result performed by the face detection unit 24 , as well as the image data stored in the SDRAM 22 . As for the method for controlling exposure and focus with reference to the face detection result, a method as described, for example, in U.S. Patent Application Publication No. 20030071908 may be used. Whether or not the emission control unit 19 , focus control unit 20 , and exposure control unit 21 refer to the face detection result outputted from the face detection unit 24 depends on the selected imaging mode and other setting values. [0042] The digital camera 1 further includes an image processing unit 25 for performing image processing on the image data stored in the SDRAM 22 . The image processing unit 25 performs various finishing processes for making the image attractive, including color tone and brightness corrections, as well as correction of redeye if included, and stores back the processed image data in the SDRAM 22 again. [0043] The digital camera 1 further includes a display control unit 26 for controlling output of the image data stored in the SDRAM 22 to a liquid crystal display (LCD) 27 . The display control unit 26 performs pixel skipping on the image data stored in the SDRAM 22 in order to make the image data to an appropriate size for display before outputting to the liquid crystal display 27 . [0044] The digital camera 1 further includes a record/readout control unit 28 for controlling recording of the image data stored in the SDRAM 22 to a memory card 29 , and loading of image data recorded in the memory card 29 to the SDRAM 22 . The record/readout control unit 28 records the RAW data directly to the memory card 29 , or after converting to JPEG data through an image compression coding technique depending on user setting. More specifically, the record/readout control unit 28 records an Exif (Exchangeable Image File Format) file including image data and auxiliary information of the image data in the memory card 29 . When loading JPEG image data to the SDRAM 22 , the image data read out from the file are decoded and loaded into the SDRAM 22 . [0045] The digital camera 1 further includes an overall control unit 30 which includes a CPU (Central Processing Unit) 31 , a RAM (Random Access Memory) 32 having therein an operational/control program, and EEPROM (Electrically Erasable and Programmable Read Only Memory) 33 having therein various setting values. The overall control unit 30 detects the imaging mode selected through the mode dial and other user setting operations, and causes the setting contents to be stored in the EEPROM 33 . Then, according to the setting values stored in the EEPROM 33 , the overall control unit 30 sends signals instructing the processes to be performed and execution timings of the processes to the emission control unit 19 , focus control unit 20 , exposure control unit 21 , image input control unit 23 , face detection unit 24 , image processing unit 25 , display control unit 26 , and record/readout control unit 28 through the system bus 34 when the setting operation or imaging operation is performed. Control of Flash Emission Amount [0046] Hereinafter, control of flash emission amount by the emission control unit 19 will be described further. FIRST EMBODIMENT [0047] FIGS. 3 and 4 are drawings in which flows of processes of digital cameras that perform auto exposure control, auto focus control, and auto emission control using face detection results are arranged temporally from left to right, illustrating the relationships between the operations of the shutter release button and performance of the digital cameras. FIG. 3 illustrates the relationship between the operation and performance of an ordinary digital camera, and FIG. 4 illustrates the relationship between the operation and performance of a digital camera 1 according to the present embodiment. [0048] As illustrated in FIG. 3 , when a first step depression of the shutter release button is performed while the digital camera is in a wait state for a button operation, the digital camera performs AE/AF, and returns to a wait state for a button operation again after completing the AE/AF. In this state, if a second step depression of the shutter release button is performed, the digital camera performs a redeye reduction emission. Thereafter, light control is performed during the wait time for the pupils of a subject to contract to a certain degree in response to the redeye reduction emission, in which an amount of flash emission is determined by measuring an amount of light required by the subject. Then, the digital camera causes the flash to emit light with the determined amount (main emission), and causes the electronic shutter to open for a predetermined time for exposure. Then, the digital camera causes the image data generated by the exposure to be recorded on a memory card mounted in the digital camera, and returns to a wait state for a button operation. Note that the aforementioned performance of the digital camera is performance when a first step depressing operation of the shutter release button is performed and then after a while a second step depressing operation is performed. If the shutter release button is depressed directly to the second step, the digital camera performs a redeye reduction emission immediately after the AE/AF. [0049] As illustrated in FIG. 3 , in an ordinary digital camera, face detection is performed repeatedly before the shutter release button is depressed, and the detection result is used for AE/AF, and further for light control. In contrast, the digital camera 1 according to the present embodiment performs face detection on the image data obtained when a redeye reduction emission is performed, and performs light control using the detection result, as illustrated in FIG. 4 . [0050] FIG. 5 is a flowchart illustrating a process of flash photography of the digital camera according to the present embodiment. Hereinafter, process steps shown in the flowchart will be described in relation to the structure of the digital camera 1 shown in FIG. 2 . [0051] When a depressing operation of the shutter release button 2 is detected (S 101 ), the overall control unit 30 sends a notification signal to the focus control unit 20 and exposure control unit 21 , notifying of the shutter depression. In response to the notification signal, exposure control unit 21 performs auto exposure control (S 102 ), and the focus control unit 20 performs auto focus control (S 103 ). If the depressing operation detected in step S 101 is a first step depressing operation, the next step is not performed until a second depressing operation is detected. If the depressing operation detected instep S 101 is a second step depressing operation, the next step (S 104 ) is performed immediately after the completion of the auto focus control in step S 103 . [0052] The overall control unit 30 refers to the value representing ON or OFF of the redeye reduction emission function of the values set in the EEPROM (S 105 ), and if the value is “OFF”, the overall control unit 30 sends a signal to the emission control unit 19 instructing to perform light control without face consideration. If the referred value is “ON”, the overall control unit 30 sends a signal to the emission control unit 19 instructing to perform a redeye reduction emission. In response to the instruction signal, the emission control unit 19 causes the flash 11 to emit light with a predetermined amount (redeye reduction emission) (S 106 ). [0053] Further, the overall control unit 30 sends a signal to the face detection unit 24 instructing to perform face detection and to supply the detection result to the emission control unit 19 . In response to the instruction signal, the face detection unit 24 reads out an image from SDRAM 22 , obtained by the imaging unit and stored in the SDRAM 22 through the image input control unit 23 , and performs face detection (S 107 ). The detection result is supplied to the emission control section 19 as described above. [0054] The emission control section 19 refers to the supplied detection result (S 108 ), and if face information is included in the detection result, it performs light control with face consideration (S 109 ). After the light control with face consideration is performed, the process waits for a predetermined time to elapse from the redeye reduction emission in step S 106 (S 110 ), and then notifies the overall control unit 30 of the completion of the light control. If face information is not included in the detection result referred to in step S 108 , the emission control unit 19 performs light control without face consideration (S 112 ), and notifies the overall control unit 30 of the completion of the light control. [0055] In response to the notification, the overall control unit 30 controls each unit so that flash emission (main emission) is performed in synchronization with imaging (S 111 ). The emission control unit 19 causes the flash 11 to flash with an amount determined in step S 109 or step S 112 at a timing instructed by the overall control unit 30 . At the same timing, the exposure control unit conveys the aperture value and shutter speed determined in step S 102 to the aperture drive unit 17 and timing generator 18 to perform exposure. The image input control unit 23 transfers the image data supplied from the A/D converter unit 15 resulting from the exposure to the record/readout control unit 28 . The record/readout control unit 28 records the image data on the memory card 29 . This completes the flash photography. [0056] In the example process described above, light control without face consideration is performed when the redeye reduction emission function is “OFF”. But, an arrangement may be adopted in which face detection is also performed before step S 105 , and light control with face consideration is performed using the detection result obtained before step S 105 when the redeye reduction emission function is “OFF”. [0057] FIG. 6A illustrates an example process of light control with face consideration performed in step S 109 . When performing light control with face consideration, the emission control unit 19 first obtains face information included in the detection result (S 201 ), as illustrated in FIG. 6A . Then, as in the conventional light control method, it obtains an image obtained without flash emission, i.e., the latest image data stored in the SDRAM 22 (S 202 ). Further, it causes the flash 11 to perform preliminary emission, and obtains image data recorded through the preliminary emission and stored in the SDRAM 22 (S 203 ). Then, the flash control section 19 performs an arithmetic operation using the face information, non-emission image, and preliminary emission image to obtain the emission amount for main emission (S 204 ). For example, each of the preliminary emission image and non-emission image is divided into a plurality of regions, then the reflected light amount from each of the regions is estimated by obtaining the difference in the data with respect to each region, and the emission amount is determined based only on the reflected light amount from a region corresponding at least to a portion of the face, or an appropriate emission amount is determined by performing a weighted arithmetic operation weighted such that the reflected light amount from the region corresponding at least to a portion of the face has stronger influence than that of the region other than the region corresponding at least to a portion of the face. [0058] In the mean time, FIG. 6B is a flowchart illustrating an example process of light control without face consideration performed in step S 112 . When performing light control without face consideration, a non-emission image is obtained (S 301 ), then a preliminary emission image is obtained (S 302 ), and the emission amount for the main emission is obtained using the two images (S 303 ), as illustrated in FIG. 6B . For example, a reflected light amount from each region of the subject is estimated by obtaining the difference between the non-emission image and preliminary emission image, and the emission amount for the main emission is obtained based on the average value of the reflected amounts from the entire subject. [0059] Note that the light control processes performed in step S 109 and step S 112 are not limited to those described above. For example, the light control process may be a process that does not perform preliminary emission, and obtains an appropriate emission amount by estimating the reflected light amount from each region from the image of redeye reduction emission and non-emission image. [0060] As described above, the digital camera according to the present embodiment performs face detection on the image data obtained at the time of redeye reduction emission, and performs light control during the wait time from the time when the redeye reduction emission is performed to the time when the pupils react to the redeye reduction emission. This may reduce the time interval from the time when image data for face detection are obtained to the time when image data for light control are obtained, so that the light control may be performed using the face detection result while it is effective. Further, the image data obtained when the redeye reduction emission is performed have sufficient brightness for performing face detection, so that face detection may be performed more accurately in comparison with the face detection performed on image data obtained by non-emission imaging. This allows the emission amount obtained by the light control calculation to invariably become an appropriate value suitable for the situation of the subject. SECOND EMBODIMENT [0061] The digital camera according to a second embodiment of the present invention is a digital camera that performs face detection after a redeye reduction emission is performed, as in the digital camera according to the first embodiment, but differs in that it performs the face detection on image data obtained after the redeye reduction emission. The overview and internal structure of the digital camera according to the present embodiment are identical to those of the digital camera according to the first embodiment. Therefore, they will not be elaborated upon further here. [0062] FIG. 7 illustrates the relationship between the operation of the shutter release button and the performance of the digital camera according to the present embodiment. As illustrated in FIG. 7 , the digital camera according to the present embodiment continuously obtains image data even in non-emission state after a redeye reduction emission is completed, and repeatedly performs face detection. Then, it performs light control using the latest result of the face detection results obtained during a time before the main emission is performed. [0063] Further, the digital camera according to the present embodiment performs light control with face consideration using a result of face detection performed on image data obtained before the timing of redeye reduction emission when the redeye reduction function is “OFF”. The detection result may be the result obtained for AE/AF before the shutter release button is depressed, or the result obtained during the time frame after AE/AF and before the second step depressing operation. [0064] FIG. 8 is a flowchart illustrating a process of flash photography of the digital camera according to the present embodiment. Hereinafter, process steps shown in the flowchart will be described in relation to the structure of the digital camera shown in FIG. 2 . [0065] Of the setting values in the EEPROM, if the value indicating whether or not face detection is required is “positive” (required), the overall control unit 30 sends a signal to the face detection unit instructing to perform face detection and to supply the detection result to the emission control unit 19 , focus control unit 20 , and exposure control unit 21 . In response to the signal, the face detection unit 24 initiates face detection (S 401 ). The face detection is performed repeatedly until a depressing operation of the shutter release button 2 is detected. When the depressing operation of the shutter release button 2 is detected, the overall control unit 30 sends a notification signal to the emission control unit 19 , focus control unit 20 , and exposure control unit 21 notifying of the detection. In response to the notification signal, the exposure control unit 21 performs AE (S 403 ), the focus control unit 20 performs AF (S 404 ). [0066] The emission control unit 19 determines whether the notified depressing operation is a first step depressing operation or a second step depressing operation (S 405 ). If it is a first step depressing operation, the emission control unit 19 waits for a next notification signal from the overall control unit 30 (S 407 ), while continuously receiving the detection results from the face detection unit 24 (S 406 ). When a second step depressing operation is detected, the overall control unit 30 refers to the value indicating ON or OFF of the redeye reduction emission function of the setting values in the EEPROM (S 408 ). If the value is “ON”, the overall control unit 30 sends a signal to the emission control unit 19 instructing to perform a redeye reduction emission. In response to the instruction signal, the emission control unit 19 sets the emission amount to a value pre-stored for redeye reduction emission and causes the flash 11 to flash. This causes a redeye reduction emission to be performed (S 409 ). [0067] After the redeye reduction emission is performed, the emission control unit 19 continuously receives the detection results from the face detection unit 24 (S 410 ), and waits for a predetermined time to elapse (S 411 ). After the predetermined time has elapsed, the emission control unit 19 refers to the latest result of the face detection results received so far from the face detection unit 24 (S 412 ). The detection result referred to here is, in general, the latest result of the detection results obtained in step S 410 . [0068] In the mean time, if the value referred to in step S 408 is the value indicating that the redeye reduction emission function is “OFF”, the emission control unit 19 refers to the latest result of the detection results received so far from the face detection unit 24 (S 412 ). The detection result referred to here is the latest result of the detection results obtained in step S 406 , if the shutter release button 2 is depressed in two steps. If the time from the detection of the first step depressing operation to the detection of the second step depressing operation is extremely short and face detection is not completed during that time period, however, the detection result referred to here is the latest result of the detection results obtained in step S 401 . Further, if the shutter release button is depressed directly to the second step, the detection result referred to here is the latest result of the detection results obtained in step S 401 . [0069] If face information is included in the detection result referred to in step S 412 , the emission control unit 19 performs light control with face consideration (S 413 ). If the detection result does not include face information, the emission control unit 19 performs light control without face consideration (S 415 ). After the light control is completed, the emission control unit 19 notifies the overall control unit 30 of the completion. [0070] In response to the notification, the overall control unit 30 controls each unit so that flash emission (main emission) is performed in synchronization with imaging (S 414 ). The emission control unit 19 causes the flash 11 to flash with an amount determined in step S 413 or step S 415 at a timing instructed by the overall control unit 30 . At the same timing, the exposure control unit conveys the aperture value and shutter speed determined in step S 403 to the aperture drive unit 17 and timing generator 18 to perform exposure. The image input control unit 23 transfers the image data supplied from the A/D converter unit 15 resulting from the exposure to the record/readout control unit 28 . The record/readout control unit 28 records the image data on the memory card 29 . This completes the flash photography. For processes performed in steps S 413 and S 415 , example processes described in the first embodiment may be applied. [0071] As described above, the digital camera according to the present embodiment generates image data representing a subject and performs light control using detection result of the face detection performed on the generated image data during the wait time from the time when the redeye reduction emission is performed to the time when the pupils react to the redeye reduction emission. This results in the time period from the time when image data for face detection are obtained to the time when image data for light control are obtained becomes shorter than that of the first embodiment, so that the light control may be performed using the face detection result while it is effective. Further, even when the redeye reduction emission function is “OFF”, light control with face consideration is performed, which allows flash photography to be performed invariably with an appropriate emission amount. [0072] In the example process illustrated in FIG. 8 , if the latest face detection result does not include face information, light control without face consideration is performed. But, an arrangement may be adopted in which the detection result of the face detection performed immediately after step S 409 , i.e., the face detection performed on the image obtained at the time of the redeye reduction emission is stored without overwritten, and when the latest face detection result does not include face information, the stored detection result is referenced. This allows light control with face consideration to be performed if the detection result of the face detection performed on the image obtained at the time of the redeye reduction emission includes face information even if the latest face detection result does not include face information. [0073] The image obtained at the time of the redeye reduction emission allows a face to be detected easily, since the image is obtained with light being irradiated on the subject and the face portion is imaged brightly. Some of the images obtained without flash emission after the redeye reduction emission, however, are dark in the face portion and difficult to detect the face therefrom. Consequently, there may be a case in which a face is actually present, and the face is detected from the image obtained at the time of the redeye reduction emission, while the face is not detected from an image obtained without flash emission after the redeye reduction emission. As described above, if the detection result of the face detection performed on the image obtained at the time of the redeye reduction emission is stored for reference as required, even if a face is not detected successfully due to excessive darkness by the face detection performed on an image obtained without flash emission, light control with face consideration may be performed if the face is actually present. That is, it may prevent light control without face consideration from being performed when a face is actually present, and obtained face information may be utilized fully for the determination of flash emission amount. THIRD EMBODIMENT [0074] The digital camera according to a third embodiment of the present invention is a digital camera that has both of the functions of the digital cameras according to the first and second embodiments, and either one of the functions is used selectively. The overview and internal structure of the digital camera according to the present embodiment are identical to those of the digital cameras according to the first and second embodiments. Therefore, they will not be elaborated upon further here. [0075] As illustrated in FIG. 9 , the digital camera according to the present embodiment repeats acquisition of image data and face detection on the obtained image data in each of the following four periods: a first period lasting until a depressing operation of the shutter release button is performed; a second period from the time when a first step depressing operation is performed to the time when a second step depressing operation is performed; a third period during which a redeye reduction emission is performed; and a fourth period of non-emission state after the redeye reduction emission is completed. If the shutter release button is depressed directly to the second step (full depression), the second period does not exit, and the acquisition of image data and face detection on the obtained image data are repeated in each of the three periods of the first, third, and fourth periods. [0076] The latest detection result of each period or all of the detection results are supplied to the emission control unit 19 . The emission control unit 19 performs light control by selectively using all or some of the supplied detection results. [0077] In an example case, the emission control unit 19 initially refers to the face detection results in the third and fourth periods, and if a detection result including face information is obtained in either one of the periods, it performs light control with face consideration, i.e., the process illustrated in FIG. 6A using the face information. If detection results including face information are obtained in both of the periods, it uses the face information obtained in the fourth period. On the other hand, if neither of the detection results obtained in the third and fourth periods includes face information, it performs light control without face consideration, i.e., the process illustrated in FIG. 6B . Alternatively, the emission control unit 19 refers to the face detection result obtained in the first or second period, and if a detection result including face information is obtained in either the first or second period, it performs light control with face consideration using the face information. If neither of the detection results obtained in the first and second periods includes face information, it performs light control without face consideration. [0078] According to the process described above, highly accurate light control with face consideration may be performed using the latest face information obtained by the face detection performed immediately preceding the light control, as in the second embodiment. Further, even if a face is not detected successfully due to insufficient brightness by the immediately preceding face detection, the light control with face consideration may be performed using the detection result at the time of the redeye reduction emission, as in the first embodiment. Further, even when face information is not obtained during the period after the redeye reduction emission, light control identical to that of the conventional digital cameras may be performed using face information obtained prior to the redeye reduction emission. [0079] In an alternative embodiment, the emission control unit 19 initially refers to face detection results in the first period. If the face detection results in the first period do not include face information, it means that a person' s face is not present in the imaging field when the shutter release button is operated by the user. In this case, it is reasonable to think that the user is trying to image a subject other than a face. If a face should be detected by the face detection processes performed in the second to fourth periods, it is highly likely that the face is not the imaging target intended by the user. Accordingly, if the face detection results in the first period do not include face information, light control without face consideration, i.e., the process illustrated in FIG. 6B is performed. [0080] On the other hand, if face information is included in a face detection result when the shutter release button is operated, it is reasonable to think that the user is trying to image a person's face. Accordingly, when face information is included in the detection results of face detection in the first period, the detection results of face detection in the third and fourth are referenced. Then, if a detection result including face information is obtained in the third or fourth period, light control is performed using the face information. If a detection result including face information is not obtained in the third and fourth period, light control is performed using face information obtained in the first period. Alternatively, the light control may be performed using face information obtained in the second period. In this example, a determination is made in advance as to whether or not the imaging target is a person's face, so that emission amount control in line with the intention of the user may be performed. [0081] In the third embodiment, a plurality of detection results is supplied from the face detection unit to the emission control unit in each of a plurality of periods (time points) of different states. Then, the emission control unit selectively refers to the plurality of detection results and selects an arithmetic operation from a plurality of arithmetic operations based on the referenced detection result. Here, the method for defining a plurality of periods (time points) is not limited to that described above in which four periods from first to fourth periods are defined. Other methods are also conceivable. Further, the selection criterion for referencing the detection result, types of arithmetic operations, and criterion for selecting an arithmetic operation are not limited to the examples described above. [0082] So far, three exemplary embodiments have been described, but the present invention is not limited to these embodiments, and any method in which face detection is performed using image data obtained after a redeye reduction emission, and the flash emission amount is controlled using the result of the face detection belongs to the scope of the present invention.
A digital camera includes an imaging unit for generating image data, an emission unit for emitting a flash, a face detection unit for detecting face information in the image data, and an emission amount control unit for controlling the emission amount of a flash. A plurality of time points is set in a period from the time when generation of image data is started to the time when a flash is emitted, each as a time point where a detection result of the face detection unit is supplied to the emission control unit. The emission amount for the flash is obtained by selectively referring to the plurality of detection results and performing one of a plurality of arithmetic operations selected based on the referenced detection result.
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This Appln claims the benefit of U.S. Provisional 60/058,902 filed Sep. 12, 1997. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to methods for producing fertile transgenic Impatiens plants, to fertile transgenic Impatiens plants, and to transgenic seeds and progeny thereof. In particular, this invention is directed to transgenic Impatiens that express at least one macromolecule that confers resistance to Impatiens pathogens, confer improved tolerance to environmental stresses, or otherwise enhance the commercial value of the plant. 2. Background The Impatiens genus is a member of the family Balsaminaceae and comprises some five hundred to six hundred species, many of which are commercially cultivated as ornamental plants. Impatiens include plants originating from Africa, New Guinea, Celebes and Java. Grey-Wilson, IMPATIENS OF AFRICA (A. A. Balkema 1980); H. F. Winters, Am. Hotic., 52, 923 (1973). The Impatiens from Africa, India and the South Pacific include respectively, I. wallerana, I. balsamina, I. hawkeri. Among these I. wallerana, also known as I. sultani or I. holstii, is probably the most commonly grown. I. wallerana comprises the largest market share of all bedding plants sold in the United States and therefore is an important horticultural crop. The New Guinea Impatiens (NGI) encompasses a group of interbreeding species that include I. schlecteri Warb., I. herzogii K. Schum, I. linearifolia Warb., I. mooreana Schltr., I. hawkeri Bull, and other species of the same geographic origin which are interfertile. Java and Celebes Impatiens are known as I. platypetala Lindl. and I. platylpetala aurantiaca Steen, respectively. K. Han et al., Scientia Horticulturae, 32, 307 (1987). Insect pests and diseases caused by pathogens can kill Impatiens even under greenhouse conditions. Illustrative insect pests include whiteflies, mealybugs, thrips, aphids, and spider mites. Impatiens are also susceptible to diseases caused by fungi. Fungal infestation include infections by Rhizoctonia and Pythium, which can cause stunting or death of Impatiens. Impatiens is also susceptible to Botrytis blight, and infection by Alternaria and Fusarium. Furthermore, Impatiens is also subject to bacterial infection such as Pseudomonas infection. As for viral pathogens, Impatiens is primarily susceptible to infection by the tospovirus, Impatiens necrotic spot virus (INSV), but also is a known host for the related tospovirus, tomato spotted wilt virus (TSWV). Impatiens are also known to be hosts to tobacco mosaic virus (TMV), cucumber mosaic virus (CMV), and tobacco streak virus (TSV). Although chemical treatment can control certain of these insect pests and disease pathogens, such treatment can also have an adverse effect upon Impatiens. An alternative to chemical treatment is to genetically engineer transgenic Impatiens that express polypeptides capable of protecting the plant against the insects and pathogens. The production of transgenic plants can further be used to enhance the commercial value of Impatiens by conferring resistance to environmental stresses, such as, drought, salinity, heat, cold, frost, and sun. The production of transgenic plants can further be used to enhance the commercial value of Impatiens by controlling characteristics such as flower color, leaf color, flower size and pattern, early flowering, day neutrality, free branching, dwarfness, fragrance, among others. Other desired qualities include bioluminescence, seedling and plant vigor, and flower doubleness. Accordingly, there is a need for a method to introduce foreign genes into Impatiens to confer resistance to INSV, impart fragrance or drought tolerance, as well as other desired properties. However, there has been no report to date of the successful production of transgenic Impatiens. On the contrary, although researchers report the isolation of genes conferring resistance to tospoviruses in general, and INSV, in particular, these references do not disclose transformation of Impatiens. For instance WO 96/29420 to De Haan, describes transgenic plants resistance to Tospovirus, but discloses only transgenic tobacco. Similarly, EP 0566525 to Van Grinsven et al., discloses DNA constructs to transform plants to achieve resistance to INSV, but discloses only Nicotiana tabacum and Petunia hybrida transformation. Similarly, WO 95/24486 to Attenborough, et al., discloses antimicrobial proteins isolated from seed of Impatiens and transgenic plants produced from DNA constructs which encode such proteins. This reference, however, fails to report successful transformation of Impatiens disclosing instead only tobacco transformation. Furthermore, other researchers have described Impatiens as a desirable plant for transformation with, for example, pigment-inducing DNA constructs, EP 0524910 to Van Holst et al., or phytochrome polypeptide-encoding constructs, EP 0354687 to Hershey et al. These references do not disclose, however, actual transformation of Impatiens. Finally, Takeshi et al., Shokubutsu Soshiki Baiyo 12: 73 (1995); Chem. Abs. 122(25) 310945u, report transient gene expression in I. balsamina and I. wallerana mature pollen transformed with plasmid pBI221 via a N-2 laser method. This reference, however, fails to report stable integration of the DNA plasmid construct, or production of a transformed Impatiens plants. Thus, a need exists for a method to stably introduce foreign genes into Impatiens to enhance viral resistance, drought resistance, and impart fragrance as well as other traits that enhance the commercial value of this important ornamental crop. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method to produce transgenic Impatiens. It is a further object of this invention to provide transgenic Impatiens that express at least one macromolecule that confers protection against disease causing pathogens. These and other objects are achieved in accordance with one embodiment of the present invention by the provision of a method for producing transgenic Impatiens plants, comprising the steps of: (a) introducing an expression vector into a tissue explant medium to produce transformed explant, wherein said expression vector comprises a selectable marker gene and a second foreign gene, or (a') introducing two expression vectors into said tissue explant to produce transformed explant, wherein one of said expression vectors comprises a selectable marker gene, and wherein the second of said expression vectors comprises a second foreign gene; (b) culturing said transformed explant on a selection medium; (c) culturing said transformed explant on regeneration medium; and (d) recovering fertile transgenic plants from the transgenic explants capable of transmitting the foreign gene to progeny. Also provided is a method of Impatiens transformation wherein the tissue explant is pre-cultured prior to introducing the expression vector in the explant wherein the explant is pre-cultured in MS medium comprising from approximately 0.5 mg/L to 2 mg/L TDZ followed by MS medium containing auxin and cytokinin, preferably approximately 0.05 to 0.2 mg/L NAA and approximately 1 to 6 mg/L Zeatin. Also provided is a fertile transgenic Impatiens plant having stably integrated in the plant genome a foreign gene, wherein the transgenic plant is capable of transmitting the foreign gene to progeny. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic representation of plasmids pGV101 and pBI121 used in Agrobacterium transformation of Impatiens. DETAILED DESCRIPTION 1. Definitions In the description that follows, a number of terms are used extensively. The following definitions are provided to facilitate understanding of the invention. A structural gene is a DNA sequence that is transcribed into messenger RNA (mRNA) which is then translated into a sequence of amino acids characteristic of a specific polypeptide. A promoter is a DNA sequence that directs the transcription of a structural gene. Typically, a promoter is located in the 5' region of a gene, proximal to the transcriptional start site of a structural gene. If a promoter is an inducible promoter, then the rate of transcription increases in response to an inducing agent. In contrast, the rate of transcription is not regulated by an inducing agent if the promoter is a constitutive promoter. An isolated DNA molecule is a fragment of DNA that is not integrated in the genomic DNA of an organism. For example, a cloned Bacillus thuringiensis toxin gene is an illustration of an isolated DNA molecule. Another example of an isolated DNA molecule is a chemically-synthesized DNA molecule that is not integrated in the genomic DNA of an organism. An enhancer is a DNA regulatory element that can increase the efficiency of transcription, regardless of the distance or orientation of the enhancer relative to the start site of transcription. Complementary DNA (cDNA) is a single-stranded DNA molecule that is formed from an mRNA template by the enzyme reverse transcriptase. Typically, a primer complementary to portions of mRNA is employed for the initiation of reverse transcription. Those skilled in the art also use the term "cDNA" to refer to a double-stranded DNA molecule consisting of such a single-stranded DNA molecule and its complementary DNA strand. The term expression refers to the biosynthesis of a gene product. For example, in the case of a structural gene, expression involves transcription of the structural gene into mRNA and the translation of mRNA into one or more polypeptides. A cloning vector is a DNA molecule, such as a plasmid, cosmid, or bacteriophage, that has the capability of replicating autonomously in a host cell. Cloning vectors typically contain one or a small number of restriction endonuclease recognition sites at which foreign DNA sequences can be inserted in a determinable fashion without loss of an essential biological function of the vector, as well as a marker gene that is suitable for use in the identification and selection of cells transformed with the cloning vector. Marker genes typically include genes that provide tetracycline resistance or ampicillin resistance. An expression vector is a DNA molecule comprising a gene that is expressed in a host cell. Typically, gene expression is placed under the control of certain regulatory elements, including constitutive or inducible promoters, tissue-specific regulatory elements, and enhancers. Such a gene is said to be "operably linked to" the regulatory elements. A foreign gene or a transgene refers in the present description to a DNA sequence that is operably linked to at least one heterologous regulatory element. For example, a cDNA molecule encoding an insect toxin is considered to be a foreign gene. A recombinant host may be any prokaryotic or eukaryotic cell that contains either a cloning vector or expression vector. This term also includes those prokaryotic or eukaryotic cells that have been genetically engineered to contain the cloned gene(s) in the chromosome or genome of the host cell. A transgenic plant is a plant having one or more plant cells that contain an expression vector. In eukaryotes, RNA polymerase II catalyzes the transcription of a structural gene to produce mRNA. A DNA molecule can be designed to contain an RNA polymerase II template in which the RNA transcript has a sequence that is complementary to that of a specific mRNA. The RNA transcript is termed an antisense RNA and a DNA sequence that encodes the antisense RNA is termed an antisense gene. Antisense RNA molecules are capable of binding to mRNA molecules, resulting in an inhibition of mRNA translation. A ribozyme is an RNA molecule that contains a catalytic center. The term includes RNA enzymes, self-splicing RNAs, and self-cleaving RNAs. A DNA sequence that encodes a ribozyme is termed a ribozyme gene. An external guide sequence is an RNA molecule that directs the endogenous ribozyme, RNase P, to a particular species of intracellular mRNA, resulting in the cleavage of the mRNA by RNase P. A DNA sequence that encodes an external guide sequence is termed an external guide sequence gene. Impatiens as used herein includes species of the genus Impatiens as known to a skilled artisan, including selections of Africa, India, New Guinea, Java, and Celebes origin. Furthermore, the present invention can be used with both seed and vegetatively propagated Impatiens plant material. A fertile transgenic plant is a plant containing a foreign gene stably transformed into its genome including the nuclear, mitochondrial, and/or chloroplast genomes which is capable of transmitting the foreign gene to progeny via sexual reproduction. 2. Methods for Producing Transgenic Impatiens The procedures described herein provide a means to produce fertile transgenic Impatiens that contain an expression vector, and that express at least one foreign gene which can be transmitted to progeny. The foreign gene can be introgressed into other Impatiens plants by traditional breeding methods, well known to the skilled artisan. For example, the fertile transgenic Impatiens plant is crossed to non-transgenic Impatiens selections in order to combine the foreign gene with other traits of agronomic interest. Alternatively, a transgenic Impatiens plant containing a first foreign gene is crossed to a second fertile transgenic Impatiens plant containing a second foreign gene to produce progeny in which the first and second foreign genes are combined in the same plant selection. Methods for the vegetative or sexual propagation of Impatiens are well known. See, for example, Ball, V. (ed), Ball RedBook, Ball Publ, Batavia IL, pg. 567-583 (1998). Likewise, methods for breeding with Impatiens are well known including production of F1 hybrids. The selection of an appropriate expression vector will depend upon the method of introducing the expression vector into host cells. Typically, an expression vector contains: (1) prokaryotic DNA elements coding for a bacterial replication origin and an antibiotic resistance marker to provide for the growth and selection of the expression vector in the bacterial host; (2) eukaryotic DNA elements that control initiation of transcription, such as a promoter; (3) DNA elements that control the processing of transcripts, such as a transcription termination/polyadenylation sequence; and (4) a foreign gene operably linked to the DNA elements that control transcription initiation. Optionally, an expression vector can also contain a selectable marker gene, as described below. Expression vectors can be introduced into protoplasts, or into intact tissues or isolated cells. General methods of culturing plant cells and tissues are provided, for example, by Miki et al., "Procedures for Introducing Foreign DNA into Plants," in METHODS IN PLANT MOLECULAR BIOLOGY AND BIOTECHNOLOGY, Glick et al. (eds.), pages 67-88 (CRC Press, 1993), and by Dixon et al., PLANT CELL CULTURE: A PRACTICAL APPROACH, 2 nd Edition (IRL Press 1994). Methods of introducing expression vectors into plant tissue include direct gene transfer method such as microprojectile-mediated delivery, DNA injection, electroporation, and the like. See, for example, Gruber et al., infra; Miki et al., supra; Klein et al., Biotechnology 10:268 (1992). For example, expression vectors can be introduced into plant tissues using microprojectile-mediated delivery with a biolistic device. A generally applicable method of plant transformation is microprojectile-mediated transformation wherein DNA is carried on the surface of microprojectiles measuring 1 to 4 μm. The expression vector is introduced into plant tissues with a biolistic device that accelerates the microprojectiles to speeds of 300 to 600 m/s which is sufficient to penetrate plant cell walls and membranes. Sanford et al., Part. Sci. Technol. 5:27 (1987), Sanford, Trends Biotech. 6:299 (1988), Sanford, Physiol. Plant 79:206 (1990), and Klein et al., Biotechnology 10:268 (1992). Expression vectors are also introduced into plant tissues via direct infection or co-cultivation of plant tissue with Agrobacterium tumefaciens. Horsch et al., Science 227:1229 (1985). Descriptions of Agrobacterium vector systems and methods for Agrobacterium-mediated gene transfer are provided by Gruber et al., "Vectors for Plant Transformation," in METHODS IN PLANT MOLECULAR BIOLOGY AND BIOTECHNOLOGY, Glick et al. (eds.), pages 89-119 (CRC Press, 1993), Miki et al., supra, and Moloney et al., Plant Cell Reports 8: 238 (1989). Additionally, expression vectors may be introduced into the plant chloroplast genome by methods well known to the skilled artisan. See, U.S. Pat. Nos. 5,451,513 and 5,693,507. Foreign genes introduced into the chloroplast genome are maternally inherited. Transcription of the foreign gene may be controlled by a plant promoter or by a viral promoter, such as a Cauliflower Mosaic Virus (CaMV) 35S promoter and its derivative, the enhanced 35S version ("E35S"), a Figwort Mosaic Virus promoter, and the like. Gruber et al., supra. Odell et al., Nature 313:810 (1985); Kay et al., Science 236:1299 (1987). The polyubiquitin gene promoters from Arabidopsis thaliana, UBQ3 and UBQ10, Norris et al., Plant Mol. Biol. 21:895 (1993), are also useful for directing gene expression in transgenic Impatiens. Additional useful promoters from Arabidopsis include the TEFA 1 gene promoter from the Arabidopsis translation elongation factor 1 gene and two additional polyubiquitin gene promoters from Arabidopsis, UBQ11 and UBQ14. Norris et al., Plant Mol. Biol. 21:895 (1993); Callis et al., Genetics 139:921 (1995). Of these promoters, the preferred promoters are the 35S promoter, the E35S promoter, the UBQ3 promoter, and the UBQ10 promoter. Other promoters that are useful for phloem-specific expression of transgenes in Impatiens include the rolC gene promoter from Agrobacterium rhizogenes and the Commelina Yellow Mottle Virus (CoYMV) promoter which have been shown to direct high levels of transgene expression in the phloem of transgenic plants. Medberry and Olszewski, Plant J. 3:619 (1993); Nilsson et al., Plant Mol. Biol. 31:887 (1996). In order to select transformed cells, the expression vector contains a selectable marker gene, such as a herbicide resistance gene or an antibiotic resistance gene. For example, the neomycin phosphotransferase gene (nptII gene) confers resistance to kanamycin and G418, the aminoglycoside phosphotransferase IV gene (hygromycin phosphotransferase gene of E. coli) confers resistance to hygromycin, the phosphinothricin acetyltransferase gene confers resistance to phosphinothricine, the dihydrofolate reductase gene confers resistance to methotrexate, the 5-enolpyruvylshikimate-3-phosphate synthase gene confers resistance to glyphosate, the acetohydroxyacid synthase gene confers resistance to sulfonyl ureas and imidazolinones, chloramphenicol resistance is provided by the chloramphenicol acetyltransferase gene, and the 3"-adenylyltransferase gene confers resistance to spectinomycin and streptomycin. Fraley et al., Proc. Natl. Acad. Sci. U.S.A. 80:4803 (1983). Gritz and Davies, Gene 25:179 (1983), Wilmink and Dons, Plant Molec. Biol. Report. 11:165 (1993). Additional selectable marker genes of bacterial origin that confer resistance to antibiotics include gentamycin acetyltransferase, streptomycin phosphotransferase, aminoglycoside-3'-adenyl transferase, the bleomycin resistance determinant. Hayford et al., Plant Physiol. 86:1216 (1988), Jones et al., Mol. Gen. Genet. 210:86 (1987), Svab et al., Plant Mol. Biol. 14:197 (1990), Hille et al., Plant Mol. Biol. 7:171 (1986). Other selectable marker genes confer resistance to herbicides such as glyphosate, glufosinate or broxynil. Comai et al., Nature 317:741 (1985), Gordon-Kamm et al., Plant Cell 2:603 (1990), and Stalker et al., Science 242:419 (1988). Still other selectable markers confer a trait that can be identified through observation or testing, for example, β-glucuronidase or uidA gene (GUS) which encodes an enzyme for which various chromogenic substrates are known. Jefferson, et al., EMBO 6:3901 (1987). The use of such selectable marker genes is well-known to those of skill in the art. See, for example, Christou, "Application to Plants," in PARTICLE BOMBARDMENT TECHNOLOGY FOR GENE TRANSFER, Yang et al. (eds)., pages 71-99 (Oxford University Press 1994). The nptII gene is a preferred selectable markers. Post-transcriptional events such as processing of the 3'-end of a transcript and polyA addition are important steps of gene expression. Accordingly, expression vectors typically include DNA elements that control the processing of transcripts, such as a transcription termination/polyadenylation sequence. The 3'-flanking region from the nopaline synthase gene (nos) of Agrobacterium tumefaciens has proven to be a very efficient and versatile cis-acting sequence for transgene expression. The expression vector can contain cDNA sequences encoding a foreign protein, as well as the selectable marker gene each under the control of a different promoter. Alternatively, the selectable marker gene can be delivered to host cells in a separate selection expression vector by co-transformation with both vectors. The present invention also contemplates the production of transgenic Impatiens comprising an expression vector that produces antisense RNA. The binding of antisense RNA molecules to target mRNA molecules results in hybridization arrest of translation. Paterson, et al., Proc. Natl. Acad. Sci. USA, 74: 4370 (1987). A suitable antisense RNA molecule, for example, would have a sequence that is complementary to that of a viral mRNA species encoding a protein necessary for proliferation of the virus. Alternatively, an expression vector can be constructed that produces a ribozyme. Ribozymes can be designed to express endonuclease activity that is directed to a certain target sequence in a mRNA molecule. For example, Steinecke et al., EMBO J. 11:1525 (1992), achieved up to 100% inhibition of neomycin phosphotransferase gene expression by ribozymes in tobacco protoplasts. Similarly, Perriman et al., Antisense Research and Development 3:253 (1993), inhibited chloramphenicol acetyltransferase activity in tobacco protoplasts using a vector that expressed a modified hammerhead ribozyme. In the context of the present invention, appropriate target RNA molecules for ribozymes include mRNA species that encode viral proteins. In another approach to providing protection against virus infection, expression vectors can be constructed in which a promoter directs the production of RNA transcripts capable of stimulating RNase P-mediated cleavage of target mRNA molecules. According to this approach, an external guide sequence can be constructed for directing the endogenous ribozyme, RNase P, to a particular species of intracellular mRNA, which is subsequently cleaved by the cellular ribozyme. Altman et al., U.S. Pat. No. 5,168,053. Yuan et al., Science 263: 1269 (1994). Preferably, the external guide sequence comprises a ten to fifteen nucleotide sequence complementary to an mRNA species that encodes a protein essential for viral reproduction, and a 3'-NCCA nucleotide sequence, wherein N is preferably a purine. The external guide sequence transcripts bind to the targeted mRNA species by the formation of base pairs between the mRNA and the complementary external guide sequences, thus promoting cleavage of mRNA by RNase P at the nucleotide located at the 5'-side of the base-paired region. The preferable procedure for producing transgenic Impatiens includes harvesting and pre-culturing Impatiens tissue explants, preferably shoot tips, hypocotyl tips or node regions, most preferably shoot tips. However, Impatients tissue explants may be directly transformed and transformed explants, selected and regenerated into fertile transgenic plants. Any Impatiens plant can be transformed by the claimed method. Preferred Impatiens varieties include the seed Impatiens, such as, Super Elfin Scarlet, Super Elfin Twilight, and the New Guinea Impatiens, such as, Celebration Red, Celebration Deep Pink, Celebration Candy Pink and Celebration Cherry Star. Most preferably, the variety used is seed Impatiens Super Elfin Twilight or New Guinea Impatiens Celebration Deep Pink (U.S. Plant Patent No. 8409). Pre-culturing medium comprises medium described by Murashige and Skoog, Physiol. Plant 15: 473 (1962) (MS Medium) supplemented with ingredients selected from the following approximate combinations: TABLE 1 Zeatin (4-hydroxy-3-methyl-trans-2-butenylaminopurine) 1 mg/L 2 ip (N-2-isopentyl adenine) 15 mg/L BAP (6-benzylaminopurine) 15 mg/L 2 ip 20 mg/L, BAP 20 mg/L 2 ip 20 mg/L, Kinetin (6-furfurylaminopurine) 20 mg/L 2 ip 20 mg/L, BAP 10 mg/L, IAA (3-indole-acetic-acid) 0.01 mg/L 2 ip 20 mg/L, Kinetin 10 mg/L, IAA 0.01 mg/L 2 ip 20 mg/L, Zeatin 1 mg/L, IAA 0.01 mg/L NAA (1-naphthylacetic acid) 0.9 mg/L, BAP 2.25 mg/L 2, 4-D (2,4-dichlorophenoxyacetic acid) 0.8 mg/L, 2 ip 0.4 mg/L NAA 0.2 mg/L, Zeatin 6 mg/L NAA 0.05 mg/L, Zeatin 6 mg/L TDZ (1-phenyl-3-9],2,3-thiadiazol-5-yl) urea) 1 mg/L Preferably, explants are pre-cultured in a liquid MS medium containing TDZ (1 mg/L) for 5 days. Subsequently, the explants are preferably subcultured on a solid MS medium supplemented with NAA 0.05 mg/L and Zeatin 6 mg/L for 48 hours. Next, an expression vector is introduced into the pre-cultured explant via gene transfer methods known to those of skill in the art such as microparticle bambardment or Agrobacterium-mediated transformation. With regard to Agrobacterium-mediated transformation, the explant is suspended in an Agrobacterium suspension and is then wounded to facilitate inoculation. A preferred Agrobacterium gene-transfer system is the binary vector system, such as pBI121 containing the Agrobacterium T-DNA region, nptII gene, and a second foreign gene, Jefferson, et al., supra, and a helper plasmid, pGV101 containing the Ti plasmid Vir region. Next, the transformed explant is blot dry treated and transferred to fresh medium, preferably MS medium supplemented with approximately 0.05 mg/L NAA and 6 mg/L Zeatin without antibiotics for approximately two days. At which time, the explant may be transferred to selection medium, preferably comprising, MS medium supplemented with approximately 0.05 mg/L NAA and 6 mg/L Zeatin medium, further supplemented with the following antibiotic concentrations: approximately 500 mg/L carbenicillin, 100 mg/L. kanamycin, and 100 mg/L cefotaxmine. The explant is then subcultured approximately every week on regeneration medium, preferably, MS medium containing further ingredients selected from Table 1, more preferably being MS medium supplemented with approximately 0.05 mg/L NAA and 6 mg/L Zeatin, optionally containing selection ingredients, such as the antibiotics mentioned above, until axillary shoots develop. The above methods for transforming Impatiens may be supplemented or varied according to known methods for Impatiens shoot regeneration as exemplified by Stephens, et al., HortScience 20:362 (1985); Han, et al., Sci. Hortic. 32:307 (1987); Han, K. In vitro shoot regeneration from cotyledons of immature ovules of Impatiens platypetala Lindl., which are herein incorporated by reference. The regenerated plants are fertile and capable of transmitting a foreign gene to progeny. 3. Production of Transgenic Impatiens Expressing a Foreign Gene That Enhances Commercial Value (a) Inhibition of Plant Pests and Diseases The present invention provides a means to control insect pests and diseases of Impatiens plants. Impatiens are subject to attack by insect pests and pathogen-induced diseases under greenhouse conditions. Insect pests include whitefly, mealybugs, aphids, or thrips. Impatiens are also susceptible to diseases caused by fungi and bacteria. As for fungi, Impatiens are hosts to Rhizoctonia (Rhizoctonia solani), Pythium, Botrytis (Botrytis cinerea), Fusarium, and Alternaria. Bacteria infect Impatiens primarily through wounds such as the surface of a cutting made for vegetative propagation, or natural openings, such as hydathodes, lenticels, nectaries, and stomates. The most notable viral pathogen of Impatiens the tospovirus, Impatiens necrotic spot virus (INSV), but also is a known host for the related tospovirsu, tomato spotted wilt virus (TSWV), which causes symptoms similar to INSV. Impatiens are also known to be hosts to tobacco mosaic virus (TMV), cucumber mosaic virus (CMV), and tobacco streak virus (TSV). As a protection against insect pests, transgenic Impatiens can be produced that express insecticidal toxin genes. For example, the gram-positive bacterium Bacillus thuringiensis produces polypeptides that are toxic to a variety of insect pests, but have no activity against vertebrates and beneficial insects. Thompson, "Biological Control of Plant Pests and Pathogens: Alternative Approaches," in BIOTECHNOLOGY IN PLANT DISEASE CONTROL, Chet (ed.), pages 275-290 (Wiley-Liss, Inc. 1993). Suitable Bacillus thuringiensis toxins include cryIA δ-endotoxins which are highly toxic to lepidopteran insects and cryIIIA δ-endotoxins which are highly toxic to coleopteran insects. Geiser et al., Gene 48: 109 (1986), disclose the cloning and nucleotide sequence of a cryIA(b) δ-endotoxin gene. The transformation of plants with vectors comprising a cryIA(b) δ-endotoxin gene has been described by Williams et al., Bio/Technology 10: 540 (1992), Koziel et al., Bio/Technology 11: 194 (1993), and Fujimoto et al., Bio/Technology 11: 1151 (1993). Lereclus et al., Bio/Technology 10: 418 (1992), disclose the construction of a plasmid comprising structural genes encoding for cryIIIA and cryIAc. In addition, Adang et al., Plant Molec. Biol. 21: 1131 (1993), disclose the nucleotide sequence of a synthetic cryIIIA gene which was designed for optimal expression in plant cells. Moreover, DNA molecules encoding δ-endotoxin genes can be purchased from American Type Culture Collection (Rockville, Md.), under ATCC accession Nos. 40098, 67136, 31995 and 31998. Insecticidal toxins which are suitable for production of transgenic Impatiens include (1) a vitamin-binding protein such as avidin; (2) an enzyme inhibitor, for example, a protease inhibitor or an amylase inhibitor. See, for example, Abe et al., J. Biol. Chem. 262:16793 (1987) (nucleotide sequence of rice cysteine proteinase inhibitor), Huub et al., Plant Molec. Biol. 21:985 (1993) (nucleotide sequence of cDNA encoding tobacco proteinase inhibitor I), and Sumitani et al., Biosci. Biotech. Biochem. 57:1243 (1993) (nucleotide sequence of Streptomyces nitrosporeus α-amylase inhibitor); (3) an insect-specific hormone or pheromone such as an ecdysteroid and juvenile hormone, a variant thereof, a mimetic based thereon, or an antagonist or agonist thereof. See, for example, the disclosure by Hammock et al., Nature 344:458 (1990), of baculovirus expression of cloned juvenile hormone esterase, an inactivator of juvenile hormone; (4) an insect-specific peptide or neuropeptide which, upon expression, disrupts the physiology of the affected pest. For example, see the disclosures of Regan, J. Biol. Chem. 269:9 (1994) (expression cloning yields DNA coding for insect diuretic hormone receptor), and Pratt et al., Biochem. Biophys. Res. Comm. 163:1243 (1989) (an allostatin is identified in Diploptera puntata). See also Tomalski et al., U.S. Pat. No. 5,266,317, who disclose genes encoding insect-specific, paralytic neurotoxins; (5) an insect-specific venom produced in nature by a snake, a wasp, etc. For example, see Pang et al., Gene 116:165 (1992), for disclosure of heterologous expression in plants of a gene coding for a scorpion insectotoxic peptide; (6) an enzyme responsible for an hyperaccumulation of a monoterpene, a sesquiterpene, a steroid, hydroxamic acid, a phenylpropanoid derivative or another non-protein molecule with insecticidal activity; (7) an enzyme involved in the modification, including the post-translational modification, of a biologically active molecule; for example, a glycolytic enzyme, a proteolytic enzyme, a lipolytic enzyme, a nuclease, a cyclase, a transaminase, an esterase, a hydrolase, a phosphatase, a kinase, a phosphorylase, a polymerase, an elastase, a chitinase and a glucanase, whether natural or synthetic. See Scott et al., PCT application WO 93/02197, who disclose the nucleotide sequence of a callase gene. DNA molecules which contain chitinase-encoding sequences can be obtained, for example, from the ATCC under accession Nos. 39637 and 67152. See also Kramer et al., Insect Biochem. Molec. Biol. 23:691 (1993), who teach the nucleotide sequence of a cDNA encoding tobacco hookworm chitinase, and Kawalleck et al., Plant Molec. Biol. 21:673 (1993), who provide the nucleotide sequence of the parsley ubi4-2 polyubiquitin gene; (8) a molecule that stimulates signal transduction. For example, see the disclosure by Botella et al., Plant Molec. Biol. 24:757 (1994), of nucleotide sequences for mung bean calmodulin cDNA clones, and Griess et al., Plant Physiol. 104:1467 (1994), who provide the nucleotide sequence of a maize calmodulin cDNA clone; or (9) an insect-specific antibody or an immunotoxin derived therefrom. Thus, an antibody targeted to a critical metabolic function in the insect gut would inactivate an affected enzyme, killing the insect. Cf. Taylor et al., Abstract #497, SEVENTH INT'L SYMPOSIUM ON MOLECULAR PLANT-MICROBE INTERACTIONS (1994) (enzymatic inactivation in transgenic tobacco via production of single-chain antibody fragments). As discussed above, chitinase genes are useful for inhibiting insect pests. Chitinase also can be used for combating fungal pathogens. Methods for producing transgenic plants that express chitinase are described, for example, by Suslow et al., U.S. Pat. No. 5,554,521 (1996), and by Jaynes et al., U.S. Pat. No. 5,597,946 (1997). Additional antifungal genes include genes encoding β-1,3-glucanase, which degrades a major polysaccharide of fungal cell walls, and ribosome-inactivating protein, which inactivates fungal ribosomes. Full-length cDNAs of glucanase and ribosome-inactivating protein are disclosed in Leah et al., J. Biol. Chem. 266:1564 (1991). In addition, Logemann et al., Bio/Technology 10:305 (1992), demonstrate that the expression of a foreign ribosome-inactivating protein increases resistance to fungal disease in transgenic plants. Those of skill in the art are aware of additional polypeptides useful to protect plants against bacterial and fungal pathogens. See, for example, During, Molec. Breeding 2:297 (1996). Such polypeptides include the bactericidal native and recombinant cecropins, insect attacin, frog magainin, cereal thionins, T4 and hen egg white lysozymes, horseshoe crab tachyplesin I, Erwinia oligogalacturonide lyase. Moreover, a variety of plant disease resistance genes are available for use. Bent, The Plant Cell 8:1757 (1996). Preferred antibacterial and antifungal genes include DNA molecules that encode natural and synthetic lytic peptides and plant defensins. Lytic peptides are broad-spectrum antibiotic peptides that are active against Gram-negative and Gram-positive bacteria, fungi and protozoa. These peptides can be classified into many categories based upon their structure (e.g., linear vs. cyclic), their size (20-45 amino acids) and their source (e.g., insect, amphibian, plant). However, despite their apparent diversity, numerous defense-related peptides have the common features of being highly basic and being capable of forming amphipathic structures. These unifying features suggest that most peptides appear to act by a direct lysis of the pathogenic cell membrane. Their basic structure facilitates their interaction with the cell membrane, and their amphipathic nature allow them to be incorporated into the membrane ultimately disrupting its structure. Frog skin secretions of the African clawed frog, Xenopus laevis, have been discovered to be a particularly rich source of antibiotic peptides. Known peptides include magainins, PGL a , xenopsin, and caerulein. Gibson et al., J. Biol. Chem. 261:5341 (1986); Jacob and Zasloff, Ciba Found. Symp. 186:197 (1994); James et al., Anal. Biochem. 217:84 (1994); Maloy and Kari, Biopolymers 37:105 (1995); Wechselberger and Kreil, J. Molec. Endocrinol. 14:357 (1995). Magainins 1 and 2 have 23 amino acid residues in length, contain no cysteine, and form an amphipathic α-helix. PGL a is a small peptide processed from a larger precursor and is both cationic and amphipathic in nature. It has the somewhat unusual feature of containing a COOH-terminal amide group rather than the expected carboxyl group. Moreover, it has been reported that magainin 2 (but not magainin 1) and PGL a can interact synergistically with one another to exert enhanced levels of anti-microbial activity. Westerhoff et al., Eur. J. Biochem. 228:257 (1995). Insects have also been demonstrated to possess a variety of defense-related peptides. Cecropins from moths and flies are slightly larger than the frog-derived peptides (31-39 residues), are basic due to the presence of multiple arginine and lysine residues, and therefore interact strongly with the negatively charged lipid bilayers. Boman, Cell 65:205 (1991). Studies of these peptides have shown that they form an N-terminal α-helical region connected by a hinge region to a C-terminal α-helical domain. In addition to the naturally-occurring peptides, a wide array of synthetic analogs representing deletion, substitution and variable chain length derivatives have been generated for structure/activity relationship studies. A number of these synthetic variants exhibit increased antimicrobial activity against bacteria and fungi. Moreover, in some cases, not only has the anti-microbial potency of the synthetic lytic peptides increased dramatically, but their spectrum of anti-microbial activity has also broadened. The isolation and characterization of plant defensins from a number of plant species has revealed that these small peptides possess potent anti-microbial activity. Broekaert et al., Plant Physiol. 108:1353 (1995); Epple et al., FEBS Lett. 400:168 (1997). One of these defensins, Rs-AFP2 from radish seeds, has been extensively characterized. Terras et al., Plant Cell 7:573 (1995). A cDNA molecule that encodes this peptide has been cloned and overexpressed in tobacco. Transgenic tobacco which accumulate high levels of this peptide show enhanced resistance to infection by the fungal pathogen, Alternaria longipes. Preferred insect resistance genes include DNA molecules that encode tryptophan decarboxylase (TDC) and lectins. TDC catalyzes the decarboxylation and conversion of L-tryptophan into tryptamine. Tryptamine and secologanin, another secondary compound, are then condensed to form strictosidine, the precursor for all terpenoid indole alkaloids in Catharanthus roseus (periwinkle). The cloning and characterization of a TDC cDNA molecule from Catharanthus seedlings has been described by De Luca et al., Proc. Nat'l Acad. Sci. USA 86:2582 (1989). Thomas et al., Plant Physiol. 109: 717 (1995) demonstrated that tobacco plants which accumulated tryptamine adversely affected the development and reproduction of Bemisia tabaci (sweet potato whitefly). Whitefly emergence tests revealed that pupae emergence (to adulthood) on tryptamine-accumulating plants was typically reduced three to seven-fold relative to control plants. They speculated that tryptamine may exert its anti-whitefly effect(s) during either larval and pupal development and/or adult selection of a leaf for feeding and oviposition. Studies with the TDC gene are presented below. An alternative anti-whitefly strategy focuses on the use of lectins to disrupt the normal life cycle of insect pests. A considerably large number of artificial feeding studies have shown that a wide range of insects are susceptible to these compounds. One particular lectin, isolated from Galanthus nivalis (snowdrop plant), has been demonstrated to exhibit anti-insect activity against phloem-feeders like aphids and leafhoppers. The production of transgenic Impatiens that express GNA lectin is described below. In one approach for providing protection against viral infections, transgenic imatiens express a viral protein. The accumulation of viral coat or replicase proteins in transformed plant cells provides resistance to viral infection and/or disease development by the virus from which the coat protein gene was derived, as well as by related viruses. See Beachy et al., Ann. Rev. Phytopathol. 28: 451 (1990); Beachy, "Virus Resistance Through Expression of Coat Protein Genes," in BIOTECHNOLOGY IN PLANT DISEASE CONTROL, 3rd Edition, Chet (Ed.), pages 89-104 (Wiley-Liss, Inc. 1993). For example, coat protein-mediated resistance has been conferred upon transformed plants against alfalfa mosaic virus, cucumber mosaic virus, tobacco streak virus, potato virus X, potato virus Y, tobacco etch virus, tobacco rattle virus, and tobacco mosaic virus. Id. Alternatively, protection against viral disease can be achieved using a vector that expresses mammalian 2'-5' oligoadenylate synthetase. Truve et al., Bio/Technology 11: 1048 (1993), disclose the cloning and nucleotide sequence of a rat cDNA encoding 2'-5' oligoadenylate synthetase, a component of the mammalian interferon-induced antivirus response. Truve et al., also disclose that transgenic plants expressing 2'-5' oligoadenylate synthetase are protected against viral infection under field conditions. In a third approach to providing protection against viral infection, a transgenic imatiens expresses a viral genome antisense RNA. For example, antisense RNA has been used to confer resistance to cucumber mosaic virus, as disclosed by Rezaian et al., Plant Molec. Biol. 11: 463 (1988). Moreover, Day et al., Proc. Nat'l. Acad. Sci. 88: 6721 (1991), have demonstrated the use of antisense RNA to confer resistance to tomato golden mosaic virus. In a fourth approach to providing protection against viral infection, a transgenic imatiens expresses pokeweed antiviral protein (PAP), a ribosome-inhibiting protein found in the cell walls of Phytolacca americana. Lodge et al., Proc. Nat'l Acad. Sci USA 90: 7089 (1993), for example, show that PAP-expressing transgenic plants are resistant to a broad spectrum of plant viruses. Lodge et al. also disclose a method for isolating PAP cDNA. Alternatively, protection against INSV and TSWV has been described in EP 0566525 to Van Grinsven et al. and WO 96/29420 to De Haan, respectively. EP 0566525 describes the cloning of DNA constructs encoding TSWV putative viral movement protein, and reports conferring TSWV resistance to tobacco transformed with this construct. WO 96/29420 describes the cloning of DNA constructs encoding INSV RNAs, S, M, and L, and reports methods for using such constructs to confer INSV resistance to Nicotania tabacum and Petunia hybrida. (b) Expression of Foreign Genes That Confer Tolerance to Environmental Stresses Impatiens growers seek to produce plants with increased tolerance to environmental stresses such as drought, salinity and cold. A variety of genes have been shown to confer increased tolerance of drought, salinity and cold. Such genes include E. coli MnSOD gene (U.S. Pat. No. 5,538,878 to Thomas et al.), asparagine synthetase gene and asparagine synthetase promoter (U.S. Pat. No. 5,595,896 to Coruzzi et al.), Delta 1 -Pyrroline-5-Carboxylate Synthetase gene (U.S. Pat. No. 5,639,950 to Verma et al.; Kishor et al., Plant Physiol 108:1387 (1995)), bacterial fructan genes (Piloin-Smits et al., Plant Physiol. 107:125 (1995)), CAP85 and CAP160 genes (WO 94/17186 to Guy et al., and turgor-responsive gene trg-31 (Guerrero et al., Plant Mol. Biol. 21:929 (1993)). With the present invention, these genes can be employed to enhance tolerance to environmental stresses in Impatiens. (c) Expression of Foreign Genes That Affect Impatiens Plant Habit, Fragrance and Color Impatiens growers seek to also produce plants that have variegated foliage, enhanced germination, increased plant vigor, increased flower size and petal number, dwarfness or increased branching. Impatiens growers also seek to produce plants which are more compact (with short internodes and free branching), earlier to flower, and with bright and distinctly colored bracts. Although Impatiens have not been produced having fragrance, this would be a desirable new consumer trait. A variety of genes have been shown to create a more compact habit and earlier flowering in transgenic plants. These include the rol genes (A, B, and C) from Agrobacterium rhizogenes (U.S. Pat. No. 5,648,598), phytochrome genes such as phyA (McCormac et al., Planta 185: 162-170 (1991)), developmental genes such as lfy (Wegel and Nilsson, Nature 377: 495-496 (1995)), and the MADS-box containing family of genes such as apetala (Mandel and Yanofski, Nature 377: 522-524 (1995)), and OsMADS1 (Chung et. al., Plant Mol. Biol. 26: 657-665, (1994)). With the present invention, these genes can be employed to improve the habit and reduce the flowering time of imatiens, most preferably the genes OsMADS1 or phyA. A variety of genes have been shown to create modified color expression in transgenic plants. These include the crtO gene which can lead to the synthesis of the bright red pigment called astaxanthin, the lycopene cyclase gene which can lead to the synthesis of the orange pigment β-carotene, the β-carotene hydroxylase gene which can lead to the synthesis of the golden pigment zeaxanthin, as well as the genes in the flavonoid biosynthesis pathway which leads to the various anthocyananin pigments which can be red, blue, pale yellow, as well as a wide range of intermediates and pastels. With the present invention these genes can be employed to expand the color range in Impatiens. The preferred genes are crtO and lycopene cyclase. Several genes have been cloned which affect plant fragrance. These genes include, but are not limited to, the linalool synthase gene which causes the synthesis of aromatic linalool and the limonene synthase gene which causes synthesis of the fragrant limonene (Alonsa et al., J. Biol. Chem. 267: 7582-7587 (1992). Furthermore, tissue specific promoters have been reported for targeting genes for epidermal specific expression. For instance, U.S. Pat. No. 5,646,333 to Dobres et al. reports an epidermal specific Blec plant promoter useful for transforming plants with foreign fragrance enhancing genes. Therefore, with the present invention, genes which affect plant fragrance can be employed with epidermal specific promoters to create novel fragrances in Impatiens. Ethylene is a key regulator in plant growth and development. Ethylene affects seed germination, stem and root elongation, flower initiation, and senescence of leaves and flowers. Many important floricultural products are very sensitive to ethylene, and under current practice, plants are treated with silver thiosulfate to eliminate ethylene sensitivity. This practice, however, is being phased out because the use of silver thiosulfate has negative environmental consequences. Another means to confer ethylene insensitivity is to produce plants expressing a gene that affects the synthesis or perception of ethylene. Researchers have identified proteins associated with mutations in ethylene receptors or factors involved in ethylene signal transduction. For example, the Arabidopsis etr-1 and the tomato NR genes encode mutated receptors that confer dominant ethylene insensitivity. See, for example, Chang et al., Science 262: 539 (1993) and Wilkinson et al., Science 270: 1807 (1995). Moreover, the report of Wilkinson et al., Nature Biotechnology 15: 444 (1997), shows that the etr1-1 causes significant delays in flower senescence and flower abscission when expressed in transgenic petunia plants. Accordingly, the present invention contemplates the production of transgenic imatiens expressing a gene that confers ethylene insensitivity. Suitable genes are exemplified by genes that encode mutated ethylene receptors, such as the Arabidopsis etr1-1 and the tomato NR genes. Such plants are less likely to suffer injury during shipment or in retail outlet environments and will therefore be of higher quality and more attractive. Another gene that can be used to enhance imatiens plants is the Vitreoscilla hemoglobin gene ("vhb gene"), which is expressed by bacteria under oxygen-limited conditions. Khosla and Bailey, Nature 331:633 (1988). Holmberg et al., Nature Biotechnology 15:244 (1997), have shown that transgenic tobacco plants that express the vhb gene exhibit enhanced growth and a reduction in germination time, presumably due to an increased availability of oxygen and/or energy in the plant cells. Accordingly, the present invention also contemplates the production of transgenic imatiens plants that express the vhb gene. Cytokinins are believed to play a role in leaf senescence because a decline in leaf cytokine levels occurs in senescing leaves, while the external application of cytokinin can delay senescence. Additional evidence for the role of cytokinins was provided by the demonstration that the expression of a gene encoding isopentenyl transferase, the enzyme that catalyzes the rate-limiting step in cytokinin biosynthesis, in transgenic tobacco inhibited leaf senescence. Gan and Amasino, Science 270:1966 (1995). In this study, the expression of the isopentenyl transferase (IPT) gene was specifically targeted to senescing leaves and was negatively autoregulated to prevent overproduction of cytokinins. This was achieved by constructing an expression cassette comprising the IPT gene operatively linked to a promoter of an Arabidopsis senescence-associated gene, designated SAG12. Thus, transgenic imatiens can be produced that are characterized by a decreased rate of leaf senescence. Such imatiens plants express the IPT gene, which is under the control of a promoter of a senescence-associated gene, such as the promoter of the SAG12 gene. Studies have shown that floral organ development is controlled by a group of regulatory factors that contain a conserved MADS box domain, which is believed to be a DNA-binding domain. Schwarz-Sommer et al., EMBO J. 11:251 (1992). Genes that contain the MADS domain include the Antirrhinum majus PLENA gene, the A. majus SQUAMOSA gene, the A. majus DEFICIENS A gene, the A. majus GLOBOSA gene, the Arabidopsis thaliana APTELA1 and APETALA3 genes, the Arabidopsis AGAMOUS gene, and rice OsMADS24 and OsMADS45 genes. Bradley et al., Cell 72:85 (1993); Huijser et al., EMBO J. 11:1239 (1992); Brochman et al., Cell 68:683 (1992); Mandel et al., Nature 360:273 (1992); Sommer et al., EMBO J. 9:605 (1990); Trobner et al., EMBO J. 11:4693 (1992); Yanofsky et al., Nature 346:35 (1990); Greco et al., Mol. Gen. Genet. 253:615 (1997). Chung et al., Plant Molec. Biol. 26:657 (1994), cloned a gene from rice, designated as the OsMADS1 gene, that encodes a MADS-domain containing protein. Chung et al. showed that transgenic tobacco that express the OsMADS1 gene were characterized by early flowering and reduced apical dominance. Accordingly, early flowering transgenic Impatiens can be produced that express a foreign protein having the MADS box sequence. Suitable early flowering genes include the PLENA gene, the SQUAMOSA gene, the DEFICIENS A gene, the GLOBOSA gene, the APTELA1 gene, the APETALA3 gene, the AGAMOUS gene, the OsMADS24 gene, the OsMADS45 gene, and the OsMADS1 gene. The present invention, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention. All publications, patents, and parent applications are herein incorporated by reference to the same extent as if each individual publication, patent, or parent application were specifically and individualy indicated to be incorporated by reference in its entirety. EXAMPLES Example 1 Shoot Regeneration of Impatiens Impatiens Varieties Regenerated: Seed Impatiens: Super Elfin Scarlet, Super Elfin Twilight New Guinea Impatiens: Celebration Red, Celebration Deep Pink, Celebration Candy Pink, and Celebration Cherry Star Explant Used: Shoot tips, hypocotyl tips and node regions. Media: Medium according to Murashige and Skoog, Physiol. Plant 15: 473 (1962) (MS Medium) plus the following hormonal combinations: TABLE 2 Zeatin 1 mg/L 2 ip 15 mg/L BAP 15 mg/L 2 ip 20 mg/L, BAP 20 mg/L 2 ip 20 mg/L, Kinetin 20 mg/L 2 ip 20 mg/L, BAP 10 mg/L, IAA 0.01 mg/L 2 ip 20 mg/L, Kinetin 10 mg/L, IAA 0.01 mg/L 2 ip 20 mg/L, Zeatin 1 mg/L, IAA 0.01 mg/L NAA 0.9 mg/L, BAP 2.25 mg/L 2, 4-D 0.8 mg/L, 2 ip 0.4 mg/L NAA 0.2 mg/L, Zeatin 6 mg/L NAA 0.05 mg/L, Zeatin 6 mg/L TDZ 1 mg/L Results: Axillary shoots can be induced from all of the above media. Thus, shoot regeneration from meristematic regions was not limited by any hormonal combinations. However, the preferred medium for the transformation research was MS salts plus NAA 0.05 mg/L and Zeatin 6 mg/L. Example 2 Agrobacterium tumefaciens Preparation Strain: GV 101. Plasmid: pBI121, containing 35S promoter and GUS gene, and helper plasmid pGV101, containing the Ti plasmid Vir region. Medium: YEB medium TABLE 3______________________________________Bacto beef extract 5 g/L Bacto beef extract 1 g/L Peptone 5 g/L Sucrose 5 g/L MgSO4 2 × 10.sup.-3 M pH 7.2______________________________________ Example 3 Selection of Transformed Impatiens Super Elfin Twilight 1. Shoot tips from in vitro grown Impatiens Super Elfin Twilight were harvested (about 1-1.5 cm length) and pre-cultured on a liquid MS medium containing TDZ 1 mg/L for 5 days. Then the shoot tips were subcultured on a solid MS medium supplemented with NAA 0.05 mg/L and Zeatin 6 mg/L for 48 hours. 2. A start culture of pBI121 and helper plasmid pGV101 was grown in A. tumefaciens strain GV101 for two days at 30° C. The plasmids pBI121 and pGV101 are described in FIG. 1. 3. A620 on cells was read and titer determined (1.0 A620=5×10 8 cells/ml). 4. Cells were pelleted (4000 rpm, 10 minutes, 4° C.). 5. Cells were re-suspend in YEB to about 5×10 8 cells/ml. 6. The bacterial suspension was placed in a sterile petri dish. 7. Shoot tips were dipped in the bacterial suspension for several minutes, at which point the shoot tips were wounded with a needle. 8. The shoot tips were then blot dry treated on filter paper on a sterile plate. 9. The shoot tips were then transferred to fresh MS 0.05 mg/L NAA and 6 mg/L Zeatin medium without antibiotics for two days. 10. The shoot tips were next transferred to MS 0.05 mg/L NAA and 6 mg/L Zeatin medium with 500 mg/L carbenicillin, 100 mg/L. kanamycin, and 100 mg/L cefotaxmine. 11. The explants were then subcultured every week on the above selection medium until axillary shoots developed. Leaves from two different presumptive transformants designated 76-9 and 76-11 were analyzed for the presence of the reporter gene (GUS). GUS assays were performed according to known methods (See Jefferson et al., EMBO J. 6(13):3901-3907 (1987)). (i) 50 mg X-gluc was dissolved in 1 ml DMSO and added to 100 ml of: 10 mM EDTA disodium salt 100 mM NaPO 4 , pH 7.2 0.5 mM K 4 Fe(CH) 6 0.1% Triton X-100 pH to 7.3 with NaOH Ref: McCabe, et al., Biotechnology 6:923 (1988). (ii) 100 mg X-gluc was dissolved in 100 ml of 50 mM phosphate buffer. Leaves from both 76-9 and 76-11 express GUS activity while non-transformed control leaf tissue was negative. Accordingly, transgenic Impatiens plants were obtained. 12. Transformants 76-9 and 76-11 developed into plants with roots, stems and leaves on the selection medium. Transformants 76-9 and 76-11 were transferred to soilless medium and placed on a mist bench in the greenhouse for approximately 3 weeks. The plants were then transferred to soilless medium in 4 inch pots and placed in the greenhouse to flower. Upon flowering, the 76-9 and 76-11 plants were crossed as the female parents to I. wallerana selections 7565R0-1-H-1 and 7565R-2-4-3-1. Seeds were collected from each of these four crosses, germinated in soilless medium and plants were recovered. Example 4 According to the above examples New Guinea Impatiens Celebration Deep Pink was transformed and two transgenic plants were selected and assayed for GUS activity. These plants were designated, respectively, Line 1A and Line 1B. Both plants showed GUS activity when compared to non-transformed control.
Impatiens is a major ornamental bedding and potted plant, and is an important component of the U.S. floral industry. Susceptibility to insect pests and diseases caused by pathogens remains a problem for Impatiens production, even under greenhouse conditions. While chemical treatment can control certain insect pests and disease pathogens, such treatment can also have an adverse effect upon Impatiens. The methods described herein provide a means to genetically engineer transgenic Impatiens that express macromolecules capable of protecting the plant against the insects and pathogens. The production of transgenic plants can also be used to enhance the commercial value of Impatiens by controlling or enhancing native Impatiens characteristics.
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[0001] This application is a Continuation of copending application Ser. No. 13/500,596, filed on Apr. 5, 2012, which was filed as PCT International Application No. PCT/JP2010/069646 on Oct. 28, 2010, which claims the benefit under 5 U.S.C. §119(a) to Patent Application No. 200910226431.9, filed in China on Nov. 20, 2009, all of which are hereby expressly incorporated by reference into the present application. TECHNICAL FIELD [0002] The present invention relates to a cellular mobile communication system, and more particularly, to a method for allocating downlink transmission power in a cellular communication system employing downlink beam-forming technique. Accordingly, a method of notifying resource allocation for Demodulation Reference Signal (DMRS) is provided. BACKGROUND ART [0003] In the conventional designs for LTE systems, downlink reception at a User Equipment (UE) is facilitated by channel estimation and symbol detection based on Cell specific Reference Signal (CRS). Since the CRS is a common reference signal, operations such as downlink data transmission power allocating and precoding at a base station (eNB) side need to be signaled to the UE such that the channel estimation and symbol demodulation can be performed at the UE side. However, this causes some inconvenience for multi-user MIMO scheduling and power allocation. [0004] In discussion of technical researches and standards for IMT-Advanced (e.g., LTE-Advanced) technology, a beam-forming technique is introduced, in which a UE uses a dedicated DMRS for channel estimation and symbol detection and the same precoding operation is performed on both user data and the DMRS to improve the downlink transmission performance. [0005] The use of DMRS, which is subjected to the same operations as the data, makes the power allocation, precoding and scheduling for the UE more flexible at the base station. A certain offset is maintained between the power of the downlink data and the power of DMRS, such that the base station does not need to signal power allocation information. As for LTE/LTE-Advanced system, a certain offset is maintained between the power spectral density of data and the power spectral density of DMRS. In a DMRS design, however, there are a plurality of multiplexing approaches such as Frequency Division Multiplexing (FDM) and Code Division Multiplexing (CDM), such that it is difficult to maintain a fixed offset between the power of DMRS and the power of downlink data. Thus, the base station is still required to signal to the UE a power ratio between the DMRS and the downlink data, which causes a lot of inconveniences for multi-user power allocation in a Multi-User Multiple Input Multiple Output (MU-MIMO) mode. [0006] Additionally, in order to realize Single User Multiple Input Multiple Output (SU-MIMO) and MU-MIMO, the use of a dedicated DMRS makes the system overhead for DMRS vary with the change in the number of layers multiplexed on channel resources. Thus, for different numbers of the multiplexed layers, it is required for the UE to obtain corresponding DMRS resource information and to employ a corresponding channel estimation approach. In the MU-MIMO operation mode, different DMRS resources used by the individual UEs will result in a large amount of combinations and an increased system signaling overhead on the downlink. [0007] In light of the above, a solution for notification of DMRS resource allocation based on a fixed DMRS power offset is provided, capable of reducing signaling overhead for power allocation in the system, improving the efficiency of power amplifier and increasing the flexibility of system scheduling. A method of notifying antenna port resource allocation for DMRS is also provided. SUMMARY OF INVENTION [0008] In order to realize a flexible power allocation, a certain offset is maintained between the power of DMRS and the power of data. The DMRSs for all the layers involved in spatial multiplexing have the same power offset. A channel rank corresponds to a certain number of DMRS signals. For different numbers of DMRSs, there may be different approaches for DMRS multiplexing, such as CDM, FDM and a combination thereof. Therefore, a particular channel rank corresponds to a particular DMRS distribution pattern and a corresponding power offset parameter. [0009] A UE obtains the channel rank, the DMRS distribution pattern or the configuration information for a DMRS antenna port of the current system by means of signaling, so as to perform channel estimation and demodulation. Further, the UE in the MU-MIMO mode can detect DMRS allocation information for other UEs to perform suppression or cancellation of multi-user interferences. [0010] According to an embodiment of the present invention, a method of notifying resource allocation for Demodulation Reference Signal (DMRS) is provided, which comprises: notifying, by a base station, to a user equipment a power offset value between an average EPRE value for data symbols and an average EPRE value for the DMRS at each layer in a semi-static or static manner; notifying, by the base station, to the user equipment a current channel rank or a current DMRS distribution pattern for the user equipment dynamically; and determining, by the user equipment, an allocated DMRS antenna port based on a correspondence between the received channel rank and an allocation of DMRS antenna port, thereby obtaining resource allocation information for the DMRS. [0011] Preferably, the base station notifies, to individual user equipments in a Multi-User Multiple Input Multiple Output (MU-MIMO) mode, power offset values which are different from one another; the base station notifies, to individual user equipments in a Single User Multiple Input Multiple Output (SU-MIMO) mode, power offset values which are identical for the respective layers; or the base station notifies, to individual user equipments in a hybrid SU-MIMO/MU-MIMO mode, power offset values which are different from one another for the individual user equipments but identical for the respective layers of the same user equipment. [0012] Preferably, the base station dynamically notifies to the user equipment the DMRS distribution pattern, a start numbering of allocated DMRS antenna port and the current channel rank, or the number of layers, for the user equipment. In this case, the user equipment determines the allocated DMRS antenna port based on the DMRS distribution pattern, the start numbering of allocated DMRS antenna port and the current channel rank, or the number of layers, for the user equipment as notified, thereby obtaining the resource allocation information for the DMRS. [0013] More preferably, the base station sequentially allocates the numbering of the DMRS antenna port. [0014] Preferably, the base station dynamically notifies to the user equipment the DMRS distribution pattern and bit information associated with the allocation of the DMRS antenna port. In this case, the user equipment determines the allocated DMRS antenna port based on the DMRS distribution pattern and the bit information associated with the allocation of the DMRS antenna port as notified; and determines the current channel rank, or the number of layers, for the user equipment based on the total number of the allocated antenna port(s), thereby obtaining the resource allocation information for the DMRS. [0015] Preferably, the base station dynamically notifies to the user equipment the DMRS distribution pattern and the current channel rank, or the number of layers, for the user equipment. In this case, the user equipment determines the allocated DMRS antenna port based on the DMRS distribution pattern and the current channel rank, or the number of layers, for the user equipment as notified, as well as a start numbering of the DMRS antenna port determined from identification information associated with the user equipment itself, thereby obtaining the resource allocation information for the DMRS. [0016] More preferably, the base station sequentially allocates the numbering of the DMRS antenna port. [0017] More preferably, the start numbering of the DMRS antenna port is obtained by applying a mapping function shared between the base station and the user equipment to the identification information associated with the user equipment itself. [0018] Preferably, the base station dynamically notifies to the user equipment an index number in a shared DMRS allocation configuration table. In this case, the user equipment inquires the shared DMRS allocation configuration table based on the index number to determine the allocated DMRS antenna port and the total number of layer(s) transmitted by the base station, thereby obtaining the resource allocation information for the DMRS. [0019] Preferably, for all frequency bands for all the user equipments, a maximum value for the total number of layer(s) transmitted from the base station to all the user equipments is R max and the total rank or the total number of layer(s), R, as notified by the base station to the individual user equipments takes a value of R max ; and accordingly, if the base station notifies to the user equipment a DMRS distribution pattern, the DMRS distribution pattern corresponds to R max . [0020] Preferably, any one channel rank corresponds to only one DMRS distribution pattern; and any one DMRS distribution pattern corresponds to at least one channel rank. [0021] Preferably, the user equipment detects, in its own frequency band, a reception power or correlation for its unused DMRS antenna port to determine whether the DMRS antenna port is allocated to another user equipment; and performs, when a DMRS antenna port is determined as being allocated to another equipment, channel estimation on the DMRS antenna port to suppress or cancel interference from the another user equipment corresponding to the DMRS antenna port. BRIEF DESCRIPTION OF DRAWINGS [0022] The above and further objects, features and advantages will be more apparent from the following description of the preferred embodiments of the present invention with reference to the figures, in which: [0023] FIG. 1 is a schematic diagram illustrating a slot structure of the conventional LTE system (cf. 3GPP 36.211); [0024] FIG. 2 is a schematic diagram illustrating an exemplary DMRS distribution pattern when the channel rank (the total number of layers) R≦2; [0025] FIG. 3 is a schematic diagram illustrating an exemplary DMRS distribution pattern when the channel rank (the total number of layers) 2<R≦4; [0026] FIG. 4 is a schematic diagram illustrating an exemplary DMRS distribution pattern when the channel rank (the total number of layers) 4<R<8; [0027] FIG. 5 is a schematic diagram illustrating another exemplary DMRS distribution pattern when the channel rank (the total number of layers) 4<R≦8; [0028] FIG. 6 is a schematic diagram illustrating a further exemplary DMRS distribution pattern when the channel rank (the total number of layers) 4<R≦8; [0029] FIG. 7 is a schematic diagram illustrating relative magnitudes of average EPREs, Δ R , P DMRS i , and P DMRS — i ; [0030] FIG. 8 is another schematic diagram illustrating relative magnitudes among average EPREs, Δ R , P DMRS i , and P DMRS — i ; [0031] FIG. 9 is another schematic diagram illustrating relative magnitudes among average EPREs, Δ R , P DMRS i , and P DMRS — i ; [0032] FIG. 10 is another schematic diagram illustrating relative magnitudes among average EPREs, Δ R , P DMRS i , and P DMRS — i ; [0033] FIG. 11 is a schematic diagram illustrating a relationship among a channel rank R, a DMRS distribution pattern and Δ R ; [0034] FIG. 12 is a schematic diagram illustrating relative magnitudes between P DMRS — i and P i when R=2 and poweroffset=0 dB; [0035] FIG. 13 is a schematic diagram illustrating relative magnitudes between P DMRS — i and P i when R=3 and poweroffset=0 dB; [0036] FIG. 14 is a schematic diagram illustrating an allocation of DMRS antenna port; [0037] FIG. 15 is another schematic diagram illustrating an allocation of DMRS antenna port; [0038] FIG. 16 is another schematic diagram illustrating an allocation of DMRS antenna port; [0039] FIG. 17 is another schematic diagram illustrating an allocation of DMRS antenna port; and [0040] FIG. 18 is a schematic diagram illustrating a DMRS distribution pattern and an allocation of DMRS antenna port when channel resources for individual users in the MU-MIMO state do not completely overlap with each other. DESCRIPTION OF EMBODIMENTS [0041] Some particular embodiments of the present invention will be described in the following such that the implementation steps of the present invention can be clearly detailed. While these embodiments are directed to a mobile communication system utilizing a dedicated DMRS on downlink (particularly an LTE-Advanced cellular mobile communication system), it is to be noted that the present invention is not limited to these applications and can be applied to other related communication systems. [0042] In the following, the preferred embodiments of the present invention will be detailed with reference to the figures. In the present description, details and functions unnecessary for the present invention will be omitted, so as not to obscure the understanding the present invention. [0043] In an LTE system, a Cell-specific Reference Signal (CRS) is required for a user equipment (UE) to perform channel estimation and demodulation. The slot structure of the CRS is shown in FIG. 1 (see 3GPP 36.211 for further details). In contrast to LTE, a UE in an LTE-Advanced system performs channel estimation and symbol detection mainly by means of a precoding Demodulation Reference Signal (DMRS). On the downlink, the UE may be in one of the three following modes: SU-MIMO mode, in which all the layers belong to the same UE; MU-MIMO mode, in which each layer belongs to different UE; and Hybrid SU-MIMO/MU-MIMO mode, in which the same time-frequency channel resource(s) is/are multiplexed among a plurality of UEs and there is at least one UE in the SU-MIMO mode. [0047] If the total number of layers (channel rank) for all the UEs transmitted by the system over a given resource is R, the number of layers which is transmitted by the system for the UE over the same channel resource is r, the number of antennas at the base station side is M (M=8, for example) and the number of reception antennas at the UE side is also M, then r≦R, R≦M. If and only if the UE is in the SU-MIMO mode, in which case the number of UEs simultaneously served by the system is 1, then r=R. [0048] In order to reduce the overhead of the reference signal, different values of R may correspond to different multiplexing approaches of DMRS. Table 1 shows the different multiplexing approaches used for the DMRS for different values of R. [0000] TABLE 1 Number of Antennas No. Channel Rank CDM CDM + FDM M = 8 1 R = 2 ✓ 2 2 < R ≦ 4 ✓ 3 4 < R ≦ 8 ✓ ✓ 4 R = 1 M = 4 5 R = 2 ✓ 6 2 < R ≦ 4 ✓ 7 R = 1 M = 2 8 R = 2 ✓ 9 R = 1 [0049] In correspondence to Table 1, FIG. 2 gives an exemplary DMRS distribution pattern for the system with R≦2. In this pattern (Nos. 1, 4, 5 and 7-9 in Table 1), DMRSs corresponding to different layers are distinguished in a CDM manner. In such a case, the code length is 2, and an orthogonal sequence having a length of 2 as used by each DMRS is extended and mapped onto two (2) Resource Elements (REs). [0050] FIG. 3 gives an exemplary DMRS distribution pattern for the system with 2<R≦4. In this pattern (Nos. 2 and 6 in Table 1), DMRSs corresponding to different layers are distinguished in a CDM and a FDM manner. In such a case, the code length is 2, and an orthogonal sequence having a length of 2 as used by each DMRS is extended and mapped onto two (2) REs. [0051] FIGS. 4-6 give three exemplary DMRS distribution patterns for the system with 4<R≦8 (No. 3 in Table 1). [0052] In the pattern of Scheme 1 as shown in FIG. 4 , DMRSs corresponding to different layers are distinguished in a CDM and a FDM manner. In such a case, the code length is 4, and an orthogonal sequence having a length of 4 as used by each DMRS is extended and mapped onto four (4) REs. [0053] In the pattern of Scheme 2 as shown in FIG. 5 , DMRSs corresponding to different layers are distinguished in a CDM manner. In such a case, the code length is 8, and an orthogonal sequence having a length of 8 as used by each DMRS is extended and mapped onto eight (8) REs. [0054] In the pattern of Scheme 3 as shown in FIG. 6 , DMRSs corresponding to different layers are distinguished in a CDM and a FDM manner. In such a case, the code length is 4, and an orthogonal sequence having a length of 4 as used by each DMRS is extended and mapped onto four (4) REs. This pattern differs from Scheme 1 as shown in FIG. 4 in that it requires that the number of resource blocks allocated by the base station for the UE must be even. [0055] Power Allocation and Power Offset [0056] Ideally, the base station can dynamically allocate different transmission powers to data at each layer for a UE in the SU-MIMO mode, or to each UE in the MU-MIMO mode. Such dynamic power adjustment can be effectively adapted to channel variations, so as to improve spectral efficiency. To achieve this dynamic power allocation while reducing signaling overhead, a fixed ratio has to be maintained between the transmission power of DMRS and the transmission power of corresponding data. With an agreed fixed ratio, it is possible to perform symbol detection based on the result of DMRS channel estimation. Also, synchronous adjustment of transmission powers for DMRS and data symbols can be achieved dynamically. Further, as there is a plurality of multiplexing approaches for DMRS (such as FDM, CDM, etc.), the Energy Per Resource Element (EPRE) of DMRS varies from one multiplexing approach to another. In summary, after determining the transmission power for data at each layer, the base station determines the EPRE for DMRS at each layer based on the multiplexing approach of DMRS and the ratio between the transmission power of DMRS at each layer and the transmission power of data symbols at the corresponding layer. [0057] With a given channel rank R, the DMRS distribution pattern and the DMRS multiplexing approach can be determined accordingly. Different channel ranks R imply different DMRS distribution patterns and different overheads, with respect to the bandwidth usage of the UE, for all layers. Since, with a given channel rank R, the DMRS occupies a constant amount of time-frequency channel resources, the ratio between the transmission power of each DMRS and the transmission power of data symbols at the corresponding layer corresponds to the ratio between the average EPRE for the DMRS at the layer and the average EPRE for the data symbols at the layer. The average EPRE for the DMRS at a layer refers to the ratio between the total amount of EPREs of all the DMRSs at the layer and the total number of REs occupied by all the DMRSs within the bandwidth allocated to the UE. Likewise, the average EPRE for the data at a layer refers to the ratio between the total amount of EPREs of all the data symbols at the layer and the total number of REs occupied by the layer within the bandwidth allocated to the UE. The average EPRE for the DMRS at layer i is defined as P DMRS — i : [0000] P _ DMRS   _   i = 1 N  ∑ P _ DMRS   _   i [0000] where N denotes the number of REs occupied by all the DMRSs. [Exemplary Explanation for P DMRS — i ] [0058] As shown in FIG. 7 , an OFDM symbol in a resource block contains 12 REs; the total number of REs used by DMRS is N=3; the multiplexing approach is CDM; and the EPRE for the DMRS at layer i is P DMRS — i . In this case, the average P DMRS — i can be derived as: [0000] P _ DMRS   _   i = 3  P DMRS   _   i 3 = P DMRS   _   i , , i = 1 , 2 , ⋯   R P DMRS   _   i = P _ DMRS   _   i [0059] As shown in FIG. 8 , an OFDM symbol in a resource block contains 12 REs; the total number of REs used by DMRS is N=6; the multiplexing approach is a hybrid of CDM and FDM; and the EPRE for the DMRS at layer i is P DMRS — i . In this case, the average P DMRS — i can be derived as: [0000] P _ DMRS   _   i = 3  P DMRS   _   i 6 = P DMRS   _   i 2 , , i = 1 , 2 , ⋯   R P DMRS   _   i = 2  P _ DMRS   _   i [0060] As shown in FIG. 9 , a resource block contains 12 REs; the total number of REs used by DMRS is N=6; the multiplexing approach is FDM; and the EPRE for the DMRS at layer i is P DMRS — i . In this case, the average P DMRS — i can be derived as: [0000] P _ DMRS   _   i = 3  P DMRS   _   i 6 = P DMRS   _   i 2 , , i = 1 , 2 , ⋯   R P DMRS   _   i = 2  P _ DMRS   _   i [0061] It can be derived from above that: [0000] P DMRS — i = P DMRS — i +Δ R [0062] Herein, Δ R is an offset parameter determined by the DMRS distribution pattern, which reflects the offset of the EPRE for each DMRS RE with respect to the average EPRE for the DMRSs at each layer. [0063] P DMRS — i can be determined at the base station based on the EPRE for data symbols at each layer and the ratio between the average EPRE for the DMRS and the average EPRE for the data symbol: [0000] P DMRS — i =poweroffset+ P i (dB), i= 1, 2, . . . r [0000] where poweroffset is an offset between the average EPRE for data symbols at each layer, P i , and the average EPRE for the P DMRS — i , as signaled from the base station to the UE in a semi-static or static manner. Herein, P i is the average EPRE of the data symbols at layer i. As such, the EPRE for the DMRS can be denoted as: [0000] P DMRS — i =poweroffset+Δ R +P i (dB), i= 1, 2, . . . r [0064] It can be seen from the above equation that, as poweroffset and Δ R are both static or semi-static parameters, a fixed ratio can be maintained between the EPRE for each DMRS, P DMRS — i , and the energy of the data symbols at the corresponding layer, P i , such that P DMRS — i may vary synchronously with the change in the state of P i . [0065] Value of Poweroffset [0066] Poweroffset is a UE-related parameter. Specifically: for individual UEs in the MU-MIMO mode, their poweroffset values are different from one another; for a UE in the SU-MIMO mode, its individual layers have the same poweroffset value; and for UEs in the hybrid SU-MIMO/MU-MIMO mode, the individual [0070] UEs have poweroffset values which are different from one other; and the individual layers for the same UE have the same poweroffset value. [0071] In FIG. 9 , poweroffset<0 dB, which means that the average EPRE for the DMRS is smaller than the average EPRE for the data symbols, as shown in FIG. 9( a ). The relative magnitudes of the DMRS EPRE and the average EPRE for the data symbols are illustrated in FIG. 9( b ). [0072] In FIG. 10 , poweroffset=0 dB, which means that the average EPRE for the DMRS equals to the average EPRE for the data symbols, as shown in FIG. 10( a ). The relative magnitudes of the DMRS EPRE and the average EPRE for the data symbols are illustrated in FIG. 10( b ). [0073] Calculation of Δ R [0074] Within the same OFDM symbol in the bandwidth allocated for the UE, the ratio between the total number of REs occupied by the DMRS at each layer and total number of REs occupied by all the DMRSs within the bandwidth is 1/f, then [0000] Δ R =10 log f [0075] As shown in FIG. 7 , [0000] Δ R =10 log 1=0 (dB). [0076] As shown in FIGS. 8 , 9 and 10 , [0000] Δ R =10 log 2=3 (dB). [0077] Generally, r layers of data (r≧f) are spatially multiplexed in a single resource block: [0078] when f=1, the DMRSs of the respective spatially multiplexed layers of data multiplex the time-frequency channel resources in a CDM manner, as shown in FIG. 7 ; [0079] when 1<f<r, the DMRSs at the respective layers are located in f sub-carrier positions, i.e., r DMRSs are divided into f groups each corresponding to a different sub-carrier; the DMRSs of the respective layers of data multiplex the time-frequency channel resources in a hybrid FDM/CDM manner, as shown in FIGS. 9 and 10 ; and [0080] when f=r, all the DMRSs multiplex the time-frequency channel resources in a FDM manner, as shown in FIG. 8 . [0081] When the number of antennas at each of the base station side and the UE side is M=8 and the channel rank satisfies 4<r≦8, there may be a plurality of DMRS usage modes, as shown in FIGS. 4-6 . [0082] As shown in FIGS. 4 and 6 , [0000] Δ R =10 log 2=3 (dB), f= 2. [0083] As shown in FIG. 5 , [0000] Δ R =10 log 1=0 (dB), f= 1. [0084] In contrast to the scenario in FIG. 5 , the DMRS distribution pattern shown in FIG. 6 requires that the number of resource blocks (RBs) allocated by the base station for the UE must be even. [0085] As such, there can be a correspondence among Δ R , the rank R and the DMRS distribution pattern, as shown in FIG. 11 , in which: [0086] any channel rank R corresponds to a particular DMRS distribution pattern which in turn may correspond to one or more channel ranks R; [0087] any channel rank R corresponds to a particular offset parameter Δ R which in turn may correspond to one or more channel ranks R; and there is a one-to-one correspondence between the offset parameter Δ R and the DMRS distribution pattern. [0088] FIG. 12 shows a schematic diagram illustrating relative magnitudes between the DMRS EPRE and the EPRE for data symbols when R=2 and poweroffset=0 dB. [0089] FIG. 13 shows a schematic diagram illustrating relative magnitudes between the DMRS EPRE and the EPRE for data symbols when R=3 and poweroffset=0 dB. [0090] For correct symbol detection, the base station can notify the power offset value (poweroffset) between the DMRS and the data symbols in a semi-static or static manner. [0091] Mapping of Antenna Ports and SU-MIMO/MU-MIMO Signaling [0092] The DMRS distribution pattern can be classified into 3 categories in accordance with the different distribution patterns of DMRS for different channel ranks R, as shown in Table 2. Differences among the 3 categories of DMRS distribution patterns consist in: (1) system overhead for the individual patterns; (2) transmission approaches for DMRS; and (3) channel estimation approaches at the UE side. [0000] TABLE 2 Examples of DMRS DMRS Distribution Corresponding Distribution Pattern Channel Rank R Pattern DMRS R ≦ 2 FIG. 2 Distribution Pattern 1 DMRS 2 < R ≦ 4 FIG. 3 Distribution Pattern 2 DMRS 4 < R ≦ 8 FIGS. 4, 5 and 6 Distribution Pattern 3 [0093] The antenna ports for the individual DMRSs use the same DMRS sequence or have a one-to-one correspondence with the DMRS sequences. As such, the UE can conveniently acquire the DMRS sequence(s) for the individual DMRS antenna ports for channel estimation. [0094] The UE can acquire reference signal information required for channel estimation and symbol detection by any one of the following signaling approaches (Approach 1-5). [0095] Approach 1: The base station signals to the UE a current channel rank. If there is a one-to-one correspondence between the channel rank and the allocation of DMRS antenna port (see Table 3, for example), the UE can determine the individual DMRS antenna port(s) allocated by the base station and a corresponding DMRS sequence. [0000] TABLE 3 Channel Exemplary DMRS Antenna Rank R Port Numbering 1 {0} 2 {0, 1} 3 {0, 1, 2} 4 {0, 1, 2, 3} 5 {0, 1, 2, 3, 4} 6 {0, 1, 2, 3, 4, 5} 7 {0, 1, 2, 3, 4, 5, 6} 8 {0, 1, 2, 3, 4, 5, 6, 7} [0096] For example, when acquiring from the base station the current channel rank R=3, the UE can determine by referring to Table 3 that the DMRS antenna ports the base station allocates for the UE is {0,1,2}. [0097] Approach 2: The base station signals to the UE a current DMRS distribution pattern, a start numbering of the allocated DMRS antenna port and a current channel rank (or the number of layers) for the UE. Accordingly, the UE determines the currently allocated DMRS antenna port(s). In this approach, the base station sequentially allocates the numberings of DMRS antenna ports to the UE. [0098] Alternatively, the base station may signal the total number of layers transmitted over the channel resource currently used by the UE and the UE can determine the DMRS distribution pattern accordingly. [0099] Referring to FIG. 14 , for example, the base station signals that the current DMRS distribution pattern is 2 (corresponding to the numberings of antenna ports of {0,1,2,3}), the start numbering of the current DMRS antenna ports is 1 and the current channel rank (or the number of layers) for the UE is 2. Accordingly, the UE can determine the allocated DMRS antenna ports to be {1, 2}. In this case, it can be determined that the UE is in the hybrid SU-MIMO/MU-MIMO state. As another example, referring to FIG. 15 , the base station signals that the current DMRS distribution pattern is 3 (corresponding to the numberings of antenna ports of {0,1,2,3,4,5,6,7}), the start numbering of the current DMRS antenna ports is 1 and the current channel rank (or the number of layers) for the UE is 5. Accordingly, the UE can determine the allocated DMRS antenna ports to be {1,2,3,4,5}. [0100] Approach 3: The base station signals to the UE a current DMRS distribution pattern and bit information associated with the allocation of the respective DMRS antenna ports in that pattern. Accordingly, the UE determines the currently allocated DMRS antenna ports and then determines the current channel rank (or the number of layers) r for the UE based on the number of the allocated antenna ports. [0101] In this approach, the base station can allocate, in an arbitrary manner, the numberings of DMRS antenna ports to the UE. Herein, each antenna port uses a bit identifier. [0102] Alternatively, the base station may signal the total number of layers transmitted over the channel resource currently used by the UE and the UE can determine the DMRS distribution pattern accordingly. [0103] Referring to FIG. 16 , for example, the base station signals that the current DMRS distribution pattern is 2 (in which 4 bits are used to identify the allocation for each antenna port) and the bit information for the antenna port allocation is 1001 (in which “0” indicates an unallocated port and “1” indicates an allocated port). Accordingly, the UE determines the allocated DMRS antenna ports to be {0,3} and the channel rank of the UE itself to be r=2. [0104] Approach 4: The base station signals to the UE a current DMRS distribution pattern and the current channel rank (or the number of layers) for the UE. In this case, the UE calculates a start numbering of DMRS antenna port based on identification information associated with the UE itself, so as to determine the currently allocated DMRS antenna port(s). In this approach, the base station sequentially allocates the numberings of the DMRS antenna ports to the UE. [0105] Alternatively, the base station may signal the total number of layers transmitted over the channel resource currently used by the UE, and the UE can determine the DMRS distribution pattern accordingly. [0106] Referring to FIG. 17 , for example, if the base station signals that the current DMRS distribution pattern is 2 (corresponding to the numberings of antenna ports of {0,1,2,3}) and the current channel rank (or the number of layers) for the UE is 2. In this case, the UE calculates the start numbering of the DMRS antenna port as 1 based on its own Radio Network Temporary Identifier (RNTI) (e.g., the RNTI of the UE is 003A (hex), which is mapped by a function as F(003A)=1, where F is a mapping function shared between the base station and the UE), and accordingly, determines the allocated DMRS antenna ports to be {1,2}. At the same time, it can be determined that the UE is in the hybrid SU-MIMO/MU-MIMO state. [0107] Approach 5: The base station shares a DMRS allocation configuration table with the UE and signals to the UE an index number for a DMRS antenna port configuration in the table. In this case, the UE inquires the table based on the index number to determine the specific DMRS antenna port configuration information, the number of layers transmitted by the system for the UE (or the rank of the UE) as well as the total number of layers transmitted by the system over the channel resource used by the UE. [0108] For example, the Table 4 below is a DMRS antenna port configuration table incorporating all the possibilities for the SU-MIMO mode, the MU-MIMO mode and the hybrid thereof. The number of possible combinations can be greatly reduced by applying a certain constraints, so as to reduce the items in Table 4. Preferable constraints may include, for example: each UE in the hybrid SU-MIMO/MU-MIMO mode can multiplex at most two layers; and in the MU-MIMO or hybrid SU-MIMO/MU-MIMO mode, there can be at most 4 UEs. [0111] Table 4 below can be derived from the above two constraints (or, of course, either one of these two constraints or any other constraints). The actual physical time-frequency resource used by the DMRS antenna port(s) depends on the mapping between each DMRS antenna port and the physical time-frequency resource. [0112] The total channel rank in Table 4(a) indicates the total number of layers for all the users as multiplexed on the time-frequency channel resource used by the UE. [0113] Table 4(a) is an information table containing the total channel rank and the DMRS antenna port configuration for the UE. With this table, the UE can determine the current channel rank r of its own, the total channel rank R and the specific resource allocation information for the DMRS antenna port. [0114] Table 4(b) is an information table containing the DMRS distribution pattern and the DMRS antenna port configuration for the UE. With this table, the UE can determine the current channel rank r of its own and the specific allocation information for the DMRS antenna port. In this case, the UE cannot determine the total channel rank. [0000] TABLE 4(a) Total Channel DMRS Antenna Port Rank Configuration 1 1 {0} 2 1 {1} 3 2 {1} 4 2 {0} 5 2 {0, 1} 6 3 {0, 1, 2} 7 3 {0, 1} 8 3 {2} 9 3 {1} 10 3 {0} 11 4 {0, 1, 2, 3} 12 4 {0, 1} 13 4 {2, 3} 14 4 {3} 15 4 {2} 16 4 {1} 17 4 {0} 18 5 {0, 1, 2, 3, 4} 19 5 {0, 1} 20 5 {2, 3} 21 5 {4} 22 5 {3} 23 5 {2} 24 5 {1} 25 6 {0, 1, 2, 3, 4, 5} 26 6 {0, 1} 27 6 {2, 3} 28 6 {4, 5} 29 6 {5} 30 6 {4} 31 6 {3} 32 6 {2} 33 7 {0, 1, 2, 3, 4, 5, 6} 34 7 {0, 1} 35 7 {2, 3} 36 7 {4, 5} 37 7 {6} 38 7 {5} 39 7 {4} 40 7 {3} 41 8 {0, 1, 2, 3, 4, 5, 6, 7} 42 8 {0, 1} 43 8 {2, 3} 44 8 {4, 5} 45 8 {6, 7} 46 8 {7} 47 8 {6} 48 8 {5} 49 8 {4} [0000] TABLE 4(b) DMRS Antenna DMRS Distribution Port Pattern Configuration 1 1 {0} 2 {1} 3 {1} 4 {0} 5 {0, 1} 6 2 {0, 1, 2} 7 {0, 1} 8 {2} 9 {1} 10 {0} 11 {0, 1, 2, 3} 12 {0, 1} 13 {2, 3} 14 {3} 15 {2} 16 {1} 17 {0} 18 3 {0, 1, 2, 3, 4} 19 {0, 1} 20 {2, 3} 21 {4} 22 {3} 23 {2} 24 {1} 25 {0, 1, 2, 3, 4, 5} 26 {0, 1} 27 {2, 3} 28 {4, 5} 29 {5} 30 {4} 31 {3} 32 {2} 33 {0, 1, 2, 3, 4, 5, 6} 34 {0, 1} 35 {2, 3} 36 {4, 5} 37 {6} 38 {5} 39 {4} 40 {3} 41 {0, 1, 2, 3, 4, 5, 6, 7} 42 {0, 1} 43 {2, 3} 44 {4, 5} 45 {6, 7} 46 {7} 47 {6} 48 {5} 49 {4} [0115] It can be seen from the above Table 4(a) and Table 4(b), the base station can notify the configuration information for DMRS antenna port to the UE using 6-bit signaling (2 5 <49<2 6 ), including the total number of layers the system multiplexes on the resource used by the UE. According to Table 4(a), for example, if the UE reads bit information of 41, then the UE is in the SU-MIMO state, the number of layers transmitted for the UE is 8 and the DMRS antenna ports in use are {0,1,2,3,4,5,6,7}. Similarly, if the UE reads bit information of 20, then the DMRS antenna ports in use are {2,3}, the UE is in the hybrid SU-MIMO/MU-MIMO state and the number of layers transmitted for the UE is 2. [0116] If the base station signals to the UE the current DMRS distribution pattern, it is assumed by default that the UE has the information required for performing channel estimation on all the DMRS antenna ports in this DMRS distribution pattern. [0000] TABLE 5 DMRS Distribution Pattern DMRS Antenna Ports DMRS Distribution Pattern 1 {0, 1} DMRS Distribution Pattern 2 {0, 1, 2, 3} DMRS Distribution Pattern 3 {0, 1, 2, 3, 4, 5, 6, 7} [0117] Referring to Table 5, for example, if the base station signals that the current DMRS distribution pattern is 1, it is assumed by default that the UE has the information on the DMRS antenna ports {0,1}. If the base station signals that the current DMRS distribution pattern is 2, it is assumed by default that the UE has the information on any one of the DMRS antenna ports {0,1,2,3}. If the base station signals that the current DMRS distribution pattern is 3, it is assumed by default that the UE has the information on any one of the DMRS antenna ports {0,1,2,3,4,5,6,7}. [0118] If the base station signals to the UE that the total number of layer for all the users as transmitted on the channel resource used by the UE is R, it is assumed by default that the UE has the configuration information for the R DMRS antenna ports currently configured by the system (including the REs used by the individual DMRS antenna ports and the like) as well as the related information required for performing channel estimation on the R DMRS antenna ports. [0000] TABLE 6 Total Number of Layers for All The DMRS Antenna Users Port(s) 1 {0} 2 {0, 1} 3 {0, 1, 2} 4 {0, 1, 2, 3} 5 {0, 1, 2, 3, 4} 6 {0, 1, 2, 3, 4, 5} 7 {0, 1, 2, 3, 4, 5, 6} 8 {0, 1, 2, 3, 4, 5, 6, 7} [0119] Referring to Table 6, for example, if the base station signals that the current total number of layers for all the users is 1, the UEs have the information on the DMRS antenna port {0}. If the base station signals that the current total number of layers for all the users is 2, then the DMRS antenna ports the system configures for all the current UEs are {0,1} and the UEs have the related information required for performing channel estimation on these DMRS antenna ports. If the base station signals that the current total number of layer for all the users is 3, then the DMRS antenna ports the system configures for all the current UEs are {0,1,2} and the UEs have the related information required for performing channel estimation on these DMRS antenna ports. [0120] Herein, the information on the DMRS antenna port may contain DMRS sequence information, time-frequency resources and information on orthogonal sequence used by each antenna port. [0121] In the case where the base station signals the total number of layers for all the users, each user can determine whether it is in the SU-MIMO mode, the MU-MIMO mode or the hybrid SU-MIMO/MU-MIMO mode based on its own allocation information for the DRMS antenna port. In the MU-MIMO mode or the SU-MIMO/MU-MIMO mode, the UE can determine the information on the DMRS antenna port(s) of other UEs. [0122] With the above Approach 5, for example, if the base station signals to the UE that the current configuration information is 20, it can be determined from Table 4(a) that the DMRS antenna ports used by the UE are {2,3}, the total number of layers for all the users is 5 and thus the DMRS antenna ports possibly used by all the other UEs are {0,1,4}. [0123] According to the above Approach 5, if the base station signals to the UE that the current configuration information is 20, it can be determined from Table 4(b) that the DMRS antenna ports used by the UE are {2,3}, the total number of layers for all the users is 3 and thus the DMRS antenna ports possibly used by all the other UEs are {0,1,4,5,6,7}. [0124] If the time-frequency channel resources used by UEs in the multi-user mode do not completely overlap with each other, then, in all the frequency bands for all the UEs, a maximum value for the total number of layers transmitted from the system to all the UEs is R max and the total rank or the total number of layers R as notified by the system to the individual UEs takes a value of R max . Accordingly, if the system notifies to the individual UEs the DMRS distribution pattern, the DMRS distribution pattern corresponds to R max . [0125] The UE detects, in its own frequency band, a reception power or correlation for its unused DMRS antenna port to determine whether or not a DMRS antenna port is allocated to another UE. When the DMRS antenna port is determined as being allocated to another UE, the UE performs channel estimation on the DMRS antenna port to suppress or cancel interference from the another UE corresponding to the antenna port. [0126] As shown in FIG. 18 , the frequency band resources allocated for three UEs each in the MU-MIMO mode (i.e., UE 1, UE 2 and UE 3) are {Band-1, Band-2, Band-3, Band-4}, {Band-2, Band-3} and {Band-3, Band-4}, respectively. With such resource allocation, the total rank (or the number of layers) on the respective frequency bands are shown in Table 7, thereby R max =3 at Band-3. [0000] TABLE 7 Total Number of Layers Transmitted By Frequency Band System Band-1 1 Band-2 2 Band-3 3 Band-4 2 [0127] If the system signals to the UE 1, UE 2 and UE 3 that the total rank of the current channel is 3, then it can be known from Table 6 that the DMRS antenna ports possibly used by all the current users are {0,1, 2 }. It is assumed in accordance with Table 4(a) that the DMRS antenna port configuration information for the UE 1, UE 2 and UE 3 is 8, 9 and 10, respectively. In this case, the UE 1 can determine that the DMRS antenna ports used by all the other UEs are {0, 1}, and can thus determine, sequentially at the frequency bands Band-1, Band-2, Band-3 and Band-4, the usage of the DMRS antenna ports {0, 1} by the other UEs based on parameters such as reception power. In the case of correct determination, the UE 1 can suppress or cancel the interference from the other UEs at three frequency bands: Band-2, Band-3 and Band-4. The other UEs can operate in a similar way. [0128] As an alternative, if the system signals to the UE 1, UE 2 and UE 3 that the current DMRS distribution pattern is 2, then it can be known from Table 5 that the DMRS antenna ports possibly used by all the current UEs are {0,1,2,3}. It is assumed in accordance with Table 4(b) that the DMRS antenna port configuration information for the UE 1, UE 2 and UE 3 is 8, 9 and 10, respectively. In this case, the UE 1 can determine that the DMRS antenna ports used by all the other UEs are {0, 1, 3}, and can thus determine, sequentially at the frequency bands Band-1, Band-2, Band-3 and Band-4, the usage of the DMRS antenna ports {0, 1, 3} by the other UEs based on parameters such as reception power. In the case of correct determination, the UE 1 can suppress or cancel the interference from the other UEs at three frequency bands: Band-2, Band-3 and Band-4. The other UEs can operate in a similar way. [0129] The present invention has been described above with reference to the preferred embodiments thereof. It should be understood that various modifications, alternations and additions can be made by those who skilled in the art without departing from the spirits and scope of the present invention. Therefore, the scope of the present invention is not limited to the above particular embodiments but only defined by the claims as attached.
A user equipment receives, from the base station apparatus, bit information. The bit information indicates first information indicating one or more antenna ports and second information indicating a number of layers for downlink data symbols.
72,880
FIELD [0001] The present specification generally relates to photovoltaic modules, and more particularly to photovoltaic modules that include reinforcing members for reducing stresses in the photovoltaic modules. BACKGROUND [0002] Photovoltaic modules often use light energy (photons) from the sun to generate electricity through a photovoltaic effect. A thin film photovoltaic module typically consists of two pieces of glass that are laminated together using a thin sheet of polymeric material. One of the glass members has photovoltaic materials deposited onto its surface. Photovoltaic modules should be constructed to endure various environmental conditions that cause stresses in the glass members. Accordingly, reinforcing structures are needed for reducing stresses in the glass members. SUMMARY [0003] In one embodiment, a thin film photovoltaic module that is connectable to a terminal includes a first glass sheet defining a sun facing surface and a second glass sheet defining a back facing surface opposite the front side surface. The second glass sheet includes a feed-though opening extending through the second glass sheet. A photovoltaic material is between the first glass sheet and the second glass sheet. An encapsulant material is between the first glass sheet and the second glass sheet that bonds the first glass sheet and the second glass sheet together and seals the photovoltaic material from moisture. A conductor is electrically connected to the photovoltaic material at one end. The conductor passes through the feed-though opening. A reinforcing member is disposed on the sun facing surface of the first glass sheet. The reinforcing member has a footprint hanging over at least a portion of the feed-through opening. [0004] In another embodiment, a thin film photovoltaic module that is connectable to a terminal includes a first glass sheet defining a sun facing surface and a second glass sheet defining a back facing surface opposite the front side surface. The second glass sheet includes a feed-though opening extending through the second glass sheet. A photovoltaic material is between the first glass sheet and the second glass sheet. An encapsulant material is between the first glass sheet and the second glass sheet that bonds the first glass sheet and the second glass sheet together and seals the photovoltaic material from moisture. The feed-through opening defining an unbonded region between the first glass sheet and the second glass sheet. A conductor is electrically connected to the photovoltaic material at one end. The conductor passes through the feed-though opening. A reinforcing member is disposed on the sun facing surface and extends into the unbonded region of the first glass sheet. [0005] In another embodiment, a method of reducing bending stresses in a thin film photovoltaic module comprising a first glass sheet defining a sun facing surface, a second glass sheet defining a back facing surface opposite the front side surface and a photovoltaic material between the first glass sheet and the second glass sheet is provided. The method includes providing the second glass sheet with a feed-though opening extending through the second glass sheet through which a conductor passes. The first glass sheet and the second glass sheet are bonded together with an encapsulant material between the first glass sheet and the second glass sheet thereby sealing the photovoltaic material from moisture. A reinforcing member is disposed on the sun facing surface of the first glass sheet such that the reinforcing member has a footprint hanging over at least a portion of the feed-through opening. [0006] Additional features and advantages of the claimed subject matter will be set forth in the detailed description which follows, and in part, will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows, the claims, as well as the appended drawings. [0007] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate the various embodiments described herein, and together with the description serve to explain the principles and operations of the claimed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS [0008] FIG. 1 is a side section view of an embodiment of a photovoltaic module; [0009] FIG. 2 is a quarter section perspective view of the photovoltaic module of FIG. 1 ; [0010] FIG. 3 is a quarter section perspective view of the photovoltaic module of FIG. 1 ; [0011] FIG. 4 is a quarter section perspective view of the photovoltaic module of FIG. 1 with an embodiment of a reinforcing member; and [0012] FIG. 5 illustrates an exemplary reinforcing member footprint of the reinforcing member of FIG. 4 on a sun facing surface laid over an opening footprint of a feed-through opening on the sun facing surface. DETAILED DESCRIPTION [0013] Embodiments described herein generally relate to thin film photovoltaic modules including reinforcing features that serve to reduce stresses that occur in glass sheets, for example, due to an impact. For example, International Electrotechnical Commission (IEC) document 61646, “Thin-Film Terrestrial Photovoltaic (PV) Modules—Design Qualification and Type Approval,” incorporated herein by reference, states that a thin film photovoltaic module must withstand impacts by one-inch diameter ice balls projected in a direction perpendicular to the photovoltaic module face at a speed of 23 m/s (51 mph). The reinforcing features help reduce the stresses in the glass sheets due to such an impact to prevent any breakage. [0014] Referring to FIG. 1 , a section view of a photovoltaic module 10 includes a relatively thin glass sheet 12 (e.g., less than about one mm, such as 0.7 mm) forming a sun facing surface 14 . The glass sheet 12 may be a specialty glass commercially available from Corning Incorporated. The photovoltaic module 10 further includes a thicker glass sheet 16 (e.g., greater than one mm, such as 3.2 mm) forming a back facing surface 18 that faces opposite the sun facing surface 14 . The glass sheet 16 may be a soda lime glass that may or may not be heat strengthened. In another embodiment, the glass sheet 16 may be replaced with a specialty glass also commercially available from Corning Incorporated, which may be thinner than 3.2 mm. For example, the glass sheet 12 and the glass sheet 16 may have about the same thicknesses. Photovoltaic materials (represented by element 20 ) are located between the glass sheet 12 and the glass sheet 16 . In some embodiments, the photovoltaic materials are deposited on an internal side 22 of the glass sheet 12 . A central polymeric layer 24 , called the encapsulant or interlayer, may be provided between the glass sheets 12 and 16 . The encapsulant layer 24 may serve two purposes: First, it can bond the two glass sheets 12 and 16 together into one structural member. Second, the encapsulant layer 24 can seal the photovoltaic materials 20 that are sandwiched between the two glass sheets 12 and 16 from moisture ingress over the expected life of the photovoltaic module 10 , which can be 30 years or more. [0015] The encapsulant material used for thin film photovoltaic modules 10 may be ethylene vinyl acetate (EVA) or polyvinyl butyral (PVB), as examples. These materials may be in solid sheet form with a thickness of approximately 0.4 mm to 0.76 mm. The three components (glass with PV/encapsulant/cover glass) may be stacked and placed into an autoclave oven during formation of the photovoltaic module 10 . The assembly may be first heated to sufficient temperature to melt the encapsulant layer 24 and evacuated to remove air and moisture. A press force may be applied to the stacked assembly so that the melted encapsulant material fills void regions between the glass sheets 12 and 16 . The encapsulant layer 24 solidifies as the assembly is cooled. [0016] Referring to FIG. 2 , a quarter section of the photovoltaic module 10 is shown and may include conductors 26 and 28 (e.g., wires) are in contact with the photovoltaic materials 20 and are used to carry the power generated by the photovoltaic materials 20 to devices that process the power into a useable form. A feed-through opening 30 may be provided in a centralized region of the glass sheet 16 (as opposed to an edge of the glass sheet 16 ) so that the conductors 26 and 28 may pass out of the photovoltaic module 10 (e.g., to be connected to a terminal). The feed-through opening 30 may be provided in the centralized region of the glass sheet 16 such that the relatively delicate conductors 26 and 28 can be protected with a junction box or other protective cover. [0017] Providing a feed-through opening 30 through the glass sheet 16 provides an unbonded region 32 between the glass sheet 12 and the glass sheet 16 . For example, for a radiused opening sidewall 34 , the unbonded region 32 begins at an inner opening edge 36 where the glass sheet 16 is bonded to the glass sheet 12 . Referring briefly to FIG. 3 , a potting material 38 may be used to fill the feed through opening 30 through the glass sheet 16 . The potting material 38 may have material properties selected to support and stiffen the glass sheet 12 in the unbonded region 32 defined by the feed-through opening 30 to improve the reliability of the photovoltaic module 10 . [0018] As can be appreciated, presence of the unbonded region 32 and absence of the glass sheet 16 in this unbonded region 32 can leave the glass sheet 12 providing the sun facing surface 14 vulnerable to stresses, particularly impact stresses since the glass sheet 12 may take the brunt of the impact and bending loads at the unbonded region 32 . Referring now to FIG. 4 , a reinforcing member 40 is disposed on the sun facing surface 14 of the glass sheet 12 . The reinforcing member 40 covers at least a portion of the feed-through opening 30 , extending into the unbonded region 32 between the glass sheet 12 and the glass sheet 16 . The reinforcing member 40 may be a flat glass sheet material, for example, of specialty glass commercially available from Corning Incorporated. The thickness of both the glass sheet 12 and the reinforcing member 40 may be determined by economics and product reliability requirements. The thickness of the reinforcing member 40 may chosen to significantly increase the rigidity of the photovoltaic module 10 while keeping the reinforcing member thickness to a reasonably small value and therefore low cost and low profile height above the sun facing surface 14 of the glass sheet 12 . The thickness of the glass sheet 12 and that of the reinforcing member 40 may be about the same, such as about 0.7 mm. [0019] An adhesive layer 42 may be used to attach the reinforcing member 40 to the sun facing surface 14 of the glass sheet 12 . The adhesive material of the adhesive layer 42 may have a small thickness as well as a modulus of elasticity large enough that there is a relatively low amount of shear deformation occurring within the cross-section of the adhesive layer 42 . The large modulus of elasticity for the adhesive layer 42 may be selected such that the glass sheet 12 and the reinforcing member 42 act nearly as if they were one single piece of glass with a thickness equal to the sum of the glass sheet 12 and the reinforcing member 40 plus the thickness of the adhesive layer 42 . Even if the adhesive material selected has a relatively low modulus of elasticity, the assembly can behave as if it were two pieces of glass allowed to slide relative to each other, and the reinforcing member 40 can still act to stiffen the assembly and reduce the bending that occurs in the glass sheet due to an impact force, thereby improving reliability. [0020] FIG. 5 illustrates an exemplary reinforcing member footprint 50 of the reinforcing member 40 on the sun facing surface 14 laid over an opening footprint 52 of the feed-through opening 30 on the sun facing surface 14 . The reinforcing member footprint 50 should significantly overlap the opening footprint 52 over the entire area of the opening footprint 52 in order to adequately limit bending distortion of the glass sheet 12 upon an impact force applied at a location corresponding to a center C of the feed-through opening 30 . For example, the overlap distance may be at least 3 times the thickness of the reinforcing member 40 . In some embodiments, the reinforcing member footprint 50 may have an area that is larger than an area of the opening footprint 52 . In these embodiments, the reinforcing member footprint 50 may overlie the entire opening footprint 52 . [0021] When selecting the reinforcing member 40 and the adhesive layer 42 , various attributes may be considered. The resulting modulus of elasticity (Young's modulus) of the adhesive material after the material has cured may be considered. A high modulus of elasticity (e.g., of at least about 3 MPa) may be desired. The thicknesses of the reinforcing member 40 and the adhesive layer 42 may be kept small in order to keep the height of the reinforcement member 40 as compact as possible. Higher profiles of the reinforcing member 40 are more likely to be impacted during module installation, for example. Higher profiles of the reinforcing member 40 also tend to more readily collect debris when the photovoltaic module 10 is in use, thereby blocking sun exposure and reducing module efficiency. The adhesive strength may be as high as possible. The optical transmittance of the adhesive layer 42 (and the reinforcing member 40 ) should be as high as possible (e.g., a hemispherical transmittance of at least about 85 percent over an optical wavelength range of 400 nanometers to 1100 nanometers) in order to minimize loss of sun energy exposing the PV material. The photovoltaic module 10 may be mounted outdoors and can experience a variety of environmental conditions, and the potting material must withstand these conditions and still serves its functions for the life of the photovoltaic module 10 . The adhesive material may be selected to resist yellowing when exposed to UV light over long durations. As one example, the adhesive used to attach the reinforcing member 40 to the photovoltaic module 10 may be Dow Corning model PV-6100 which has excellent adhesive, durability, and energy transmission properties. The thickness of this adhesive layer 42 may be for example, 0.1 to 0.5 mm thick. [0022] The above-described thin film photovoltaic (PV) modules 10 include a feed-through opening 30 that serves the purpose of allowing electrical conductors to pass from the photovoltaic material layer externally to a point outside the module, in which an additional reinforcing member 40 (e.g., formed of glass) that is significantly larger than the diameter of the feed-through opening 30 is attached with an adhesive to the sun facing surface 14 of the glass sheet 12 . This reinforcing member 40 can serve to stiffen the sun side glass sheet 12 in the unbonded region of the feed-through opening, thereby reducing bending stresses that occur in the sun side glass when impacted with an ice ball (or hail) and subsequently improving the reliability of the module. The additional reinforcing member 40 and the adhesive layer 42 which is used to attach it to the glass sheet 12 both have optical transmitting properties such that a negligible reduction in sun power is delivered to the thin film PV materials. The tensile stress levels in the glass sheet 12 can be reduced by a factor of 10 . [0023] It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the specification cover the modifications and variations of the various embodiments described herein, provided such modification and variations come within the scope of the appended claims and their equivalents.
A thin film photovoltaic module that is connectable to a terminal includes a first glass sheet defining a sun facing surface and a second glass sheet defining a back facing surface opposite the front side surface. The second glass sheet includes a feed-though opening extending through the second glass sheet. A photovoltaic material is between the first glass sheet and the second glass sheet. An encapsulant material is between the first glass sheet and the second glass sheet that bonds the first glass sheet and the second glass sheet together and seals the photovoltaic material from moisture. A conductor is electrically connected to the photovoltaic material at one end. The conductor passes through the feed-though opening. A reinforcing member is disposed on the sun facing surface of the first glass sheet. The reinforcing member has a footprint hanging over at least a portion of the feed-through opening.
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CROSS-REFERENCE TO RELATED APPLICATIONS This is a continuation of application Ser. No. 09/192,313, filed Nov. 16, 1998, now U.S. Pat. No. 6,184,963; which is a continuation of application Ser. No. 08/924,737, filed Sep. 5, 1997, now U.S. Pat. No. 5,838,399; which was a continuation of application Ser. No. 08/610,148, filed Feb. 29, 1996, now U.S. Pat. No. 5,708,484; which was a divisional of application Ser. No. 08/457,577, filed Jun. 1, 1995, now U.S. Pat. No. 5,532,850; which was a divisional of application Ser. No. 08/277,434, filed Jul. 18, 1994, now U.S. Pat. No. 5,528,396; which was a divisional of application Ser. No. 07/910,455, filed Jul. 8, 1992, now U.S. Pat. No. 5,331,447; and which, in turn, was a continuation of application Ser. No. 07/205,185, filed Jun. 10, 1988, now U.S. Pat. No. 5,132,820, the entire disclosures of which are incorporated herein by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is generally directed to display devices and, more particularly, to active matrix liquid crystal display devices in which pixels (e.g., picture elements or picture cells) are formed by use of thin film transistors and pixel electrodes. 2. Description of the Invention An active matrix liquid crystal display device includes a liquid crystal display unit on which a plurality of pixels are arranged in matrix form. Each individual pixel on the liquid crystal display unit is disposed in each of intersection regions defined by two adjacent scanning signal lines (gate signal lines) and two adjacent image signal lines (drain signal lines). The plurality of scanning signal lines extending in the row-direction (horizontal direction) are arrayed in the column-direction, while the plurality of image signal lines extending in the column-direction (vertical direction), intersecting the scanning signal lines, are arrayed in the row-direction. The pixel is formed mainly of a liquid crystal in combination with a thin film transistor (TFT), a common transparent pixel electrode and a transparent pixel electrode which are disposed through the liquid crystal. The transparent pixel electrode and the thin film transistor are each provided for every pixel. The transparent pixel electrode is connected to a source electrode of the thin film transistor. A drain electrode of the thin film transistor is connected to the image signal lines, while a gate electrode is connected to the scanning signal lines. A typical arrangement is such that unnecessary incident light emerging from a panel front surface is shielded by a light shielding film formed on the upper portion of TFT, and beams of backlight which are not required are shielded by the non-transparent gate electrode. In accordance with a variety of experiments performed, the present inventors have found that sufficient light shielding effects cannot be obtained by a TFT gate electrode of an ordinary size. When the light strikes upon an amorphous semiconductor layer of the thin film transistor, electron-hole couplings are generated, thereby deteriorating OFF-characteristics of the transistor. Hence, it is required that the amorphous semiconductor layer be arranged so as not to undergo the irradiation of light as much as possible. The light for display is classified into two types: natural incident light (or light of a room lamp) emerging from the front surface of the liquid crystal display panel and incident backlight of a fluorescent lamp which emerges from the underside of the panel. The above-described liquid crystal display device tends to increase in the size of a pixel thereof, as the liquid crystal display unit is correspondingly increased in configuration. For instance, the size of pixel of the conventional liquid crystal display unit was 0.2×0.2 (mm 2 ). However, the present inventors have developed a liquid crystal display device having a pixel size of 0.32×0.32 (mm 2 ). In this type of liquid crystal display device, foreign substances such as dust or the like are intermixed in the liquid crystal display device in the manufacturing process, or the foreign substances are adhered to a mask for use with photolithography. If the foreign substances are present or intermixed in between the source electrode (or transparent pixel electrode) and the drain electrode of the thin film transistor, short-circuiting takes place between these electrodes, resulting in a so-called point defect in which the short-circuited pixel is deteriorated. If the foreign substances are likewise present or intermixed in between the source electrode (transparent pixel electrode) and the gate electrode of the thin film transistor, the same point defect is caused. From this phenomenon, the present inventors have found out such a problem that the point defect (e.g., a loss of pixel), inherent in the above-described liquid crystal display device, becomes conspicuous, as each individual pixel increases in size. Incidentally, the arrangement that a configuration of the gate electrode is made larger than the semiconductor layer has already been known in Japanese Patent Laid-Open Publication No. 17962/1985. However, even when simply increasing the size of the gate electrode, a parasitic capacitance between the gate electrode and the source electrode also increases, and a DC component applied to the liquid crystal due to scanning signals is increased. In all, the undesirable results become so prevalent that utilization is difficult. An example of an active matrix liquid crystal display device is described on, e.g., pp. 193 to 200 of NIKKEI ELECTRONICS issued on Dec. 15, 1986, published by Nikkei McGraw-Hill Co., Ltd. The following listings are exemplary of the pixel dividing technique in the active matrix liquid crystal display device: Japanese Patent Laid-Open Publication Nos. 49994/1982, 78388/1984, 97322/1985 and 77886/1986. SUMMARY OF THE INVENTION It is a primary object of the present invention to provide a liquid crystal display device capable of reducing deterioration in OFF-characteristics of a TFT due to light incident on the TFT. To this end, according to one aspect of the invention, there is provided a liquid crystal display device capable of improving the OFF-characteristics of the TFT and restraining a DC component applied to the liquid crystal. According to another aspect of the invention, there is provided, in the liquid crystal display device, a technique capable of diminishing a point defect which causes deterioration of pixels on a liquid crystal display unit. According to still another aspect of the invention, there is provided, in the liquid crystal display device, a technique capable of making it hard to visually perceive the point defect which appears on the liquid crystal display unit. According to a further aspect of the invention, there is provided, in the liquid crystal display device, a technique capable of decreasing the point defect which causes the deterioration of the pixels on the liquid crystal display unit and also reducing black scattering appearing on the liquid crystal display unit thereof. According to a still further aspect of the invention, there is provided, in the liquid crystal display device, a technique capable of accomplishing the above-described objects, decreasing a resistance value of scanning signal lines and reducing the point defect attributed to short-circuiting between a pixel electrode of the pixel and the scanning signal lines. Another object of the invention is to provide a technique capable of reducing the black scattering and preventing disconnection of the electrodes of a holding (or storage) capacitance element for diminishing the black scattering. Another object of the invention is to provide, in the liquid crystal display device, a technique capable of reducing the black scattering with a simple constitution. Another object of the invention is to provide, in the liquid crystal display device, a technique capable of reducing the DC component applied to the liquid crystal of the liquid crystal display unit and diminishing the black scattering. Another object of the invention is to provide, in the liquid crystal display device including color filters, a technique capable of reducing the point defect which appears on the liquid crystal display unit and ensuring positioning allowance dimensions with respect to each individual pixel on the liquid crystal display unit and each individual color filter for every color. Another object of the invention is to provide, in the liquid crystal display device, a technique capable of diminishing the point defect appearing on the liquid crystal display unit and decreasing the probability that the point defect or a linear defect occurs on the liquid crystal display unit. Another object of the invention is to provide, in the liquid crystal display device, a technique capable of diminishing the point defect appearing on the liquid crystal display unit and improving an area (an opening rate) of the pixel electrode of every pixel on the liquid crystal display unit. Another object of the invention is to provide, in the liquid crystal display device, a technique capable of enhancing resolution of a color picture. Another object of the invention is to provide a technique capable of accomplishing the above-described objects and reducing an area of wiring or eliminating a multilayered wiring structure. Another object of the invention is to provide, in the liquid crystal display device, a technique capable of reducing the deterioration of connection between the thin film transistor and the pixel electrode. Another object of the invention is to provide a liquid crystal display device capable of enhancing the contrast. The principal features of the present invention are described as follows: (1) A liquid crystal layer is sealed between a top-surface-side glass substrate (SUB 2 ) on which a common electrode (ITO 2 ) is formed and an underside glass substrate (SUB 1 ) on which a pixel electrode (ITO 1 ) and a TFT (TFT 1 ) are formed (FIGS. 1 and 2 ). Viewed from the liquid crystal layer, a gate electrode (GT) of the TFT is disposed in close proximity to the underside substrate (SUB 1 ), while a semiconductor layer (AS) is spaced away therefrom. The gate electrode (GT) has a large size which is sufficient to completely cover (when viewed from below) the semiconductor layer (AS). According to this constitution, OFF-characteristics of the TFT can be improved, because the incident backlight passing through the underside substrate (SUB 1 ) does not reach the semiconductor layer (AS) on account of its being shielded by the gate electrode (GT). (2) The pixels are disposed in intersection regions defined by two scanning signal lines and two image signal lines. The thin film transistor of the pixel selected by one of two scanning signal lines is split into a plurality of segments. The thus divided thin film transistor is connected to a plurality of segments into which the pixel electrode is split. A holding capacitance element is constructed in such a way that the divided pixel electrodes serve as one electrode thereof, and the other of two scanning signal lines serves as the other electrode thereof by using it as a capacitance electrode line. In this arrangement, only part of the divided portions of the pixel becomes the point defect. Otherwise, the point defect will spread over the entire pixel. It is therefore possible to diminish the point defect of the pixel and at the same time to improve a holding characteristic of a voltage applied to the liquid crystal due to the holding capacitance element, resulting in a drop in the amount of black scattering. Particularly, the divided pixels contribute to diminution in point defect derived from the short-circuit between the gate electrode and the source electrode or the drain electrode of the thin film transistor. Besides, the point defect attributed to the short-circuit between the pixel electrode and the other electrode of the holding capacitance element can be reduced. Consequently, the point defect created in part of the split portions of the pixels is small as compared with the area of the entire pixel, whereby it is hard to visually perceive the point defect. Light shielding effects are enhanced by broadening the gate electrode. On the other hand, there arises a reverse effect in which the DC component applied to the liquid crystal becomes a problem because of an increase in overlapping parasitic capacitance between the source electrode and the drain electrode. This reverse effect can, however, be reduced by virtue of the holding capacitor. (3) The scanning signal lines are composed of composite films obtained by superposing a plurality of conductive layers on each other. The gate electrode and the capacitance electrode line are each composed of single layered films each consisting of one conductive layer among the composite films. Based on this construction, in addition to the above-described effects, it is feasible to decrease a resistance value of the scanning signal lines and reduce the point defect due to the short-circuit between the pixel electrode and the scanning signal lines. (4) Formed between one electrode of the holding capacitance element and a dielectric film thereof is a base layer composed of a first conductive film and a second conductive film which is formed thereon and has a smaller specific resistance value and a smaller configuration than those of the first conductive film. The above-described one electrode is connected to the first conductive film exposed from the second conductive film of the base layer. Owing to this arrangement, it is possible to minimize the disconnection of one electrode of the holding capacitance element, because one electrode of the holding capacitance element can surely be bonded along a stepped portion caused by the other electrode thereof. (5) The capacitance electrode line of the first stage or the final stage is connected to the common pixel electrode of the pixel. In this arrangement, the capacitance electrode line of the first stage or the final stage and part of the conductive layer of an outside extension wire may be formed into one united body, and the common pixel electrode is connected to the outside extension wire. The scanning signal lines can therefore be connected to the common pixel electrode with a simple constitution. (6) The capacitance electrode line or the scanning signal line of the first stage is connected to the scanning signal line or the capacitance electrode line of the final stage. Based on this arrangement, the scanning signal lines and the capacitance electrode lines are all connected to a vertical scanning circuit, and hence a DC offset system (a DC cancel system) may be adopted. As a result, the DC component applied to the liquid crystal can be reduced, thereby increasing a life span of the liquid crystal. (7) In accordance with an embodiment III of the present invention which is illustrated in FIG. 15A, light shielding films 1 and 2 are provided to fill up gaps formed between the pixel electrodes ITO 1 through ITO 3 . In this embodiment III, the problem that the light such as backlight leaks out through the gaps between the pixel electrodes can be almost obviated. (8) In accordance with an embodiment IV of the present invention, light shielding films 3 and 4 are electrically connected to an adjacent scanning line GL. In the embodiment IV, capacitors may equivalently be formed between the light shielding films 1 and 2 (adjacent scanning line) and the respective divided pixel electrodes. These and other objects, features and advantages of the invention will become more apparent on reading the following detailed description with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a plan view illustrating the principal portion of one pixel on a liquid crystal display unit of an active matrix color liquid crystal display device in which embodiment I of the present invention is incorporated; FIG. 2 is a sectional view taken substantially along the line II—II of FIG. 1, illustrating the portion cut by this cutting-plane line and peripheral portions of a sealing portion; FIG. 3 is a plan view showing the principal portion of a liquid crystal display unit on which a plurality of pixels are disposed depicted in FIG. 1; FIGS. 4 to 6 are plan views each showing the principal portion in a predetermined process of manufacturing the pixels depicted in FIG. 1; FIG. 7 is a plan view illustrating the principal portion in a state where color filters are superposed on the pixels depicted in FIG. 3; FIG. 8A is a plan view illustrating the principal portion of one pixel on the liquid crystal display unit of the active matrix color liquid crystal display device in which an embodiment II of the present invention is incorporated, and FIG. 8B is a partially enlarged view thereof; FIG. 9 is an equivalent circuit diagram showing the liquid crystal display unit of the active matrix color liquid crystal display device in which the embodiments I and II of the present invention are incorporated; FIG. 10 is a plan view illustrating the principal portion of one pixel in a layout somewhat modified from that of the pixel depicted in FIG. 8; FIG. 11 is an equivalent circuit diagram of the pixel depicted in FIGS. 8 and 10, respectively; FIG. 12 is a time chart showing a driving voltage of a scanning signal line based on a DC offset system; FIGS. 13 and 14 are equivalent circuit diagrams each illustrating the liquid crystal display unit of the active matrix color liquid crystal display device in which the embodiment II of the present invention is incorporated; FIG. 15A is a plan view illustrating the principal portion of one pixel on the liquid crystal display unit of the active matrix color liquid crystal display device in which an embodiment III of the present invention is incorporated; and FIG. 15B is a plan view illustrating the principal portion of one pixel on the liquid crystal display unit of the color liquid crystal display device of the active matrix color liquid crystal device in which an embodiment IV of the present invention is incorporated. The constitution of the present invention will hereinafter be described in combination with one embodiment in which the present invention is applied to the active matrix liquid crystal display device. In all the accompanying drawings which illustrate the embodiments, the components having the same functions are marked with the like symbols, and their repetitive descriptions are therefore omitted herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS (Embodiment I) Turning attention now to FIG. 1 (a plan view of the principal portion), there is illustrated one pixel on a liquid crystal display unit of an active matrix color liquid crystal display device in which an embodiment I of the present invention is actualized. FIG. 2 shows a section cut by the cutting-plane line II—II of FIG. 1 . FIG. 3 (a plan view of the principal portion) illustrates the principal portion of the liquid crystal display unit on which a plurality of pixels are disposed depicted in FIG. 1 . As illustrated in FIGS. 1 through 3, in the liquid crystal display device, the pixel including a thin film transistor TFT and a transparent pixel electrode ITO is formed on an inside (on the side of a liquid crystal) surface of a lower transparent glass substrate SUB 1 . The lower transparent glass substrate SUB 1 is shaped with a thickness of, e.g., approximately 1.1 (mm). Each individual pixel is disposed in an intersection region (a region surrounded by four signal lines) defined by two adjacent scanning signal lines (gate signal lines or horizontal signal lines) GL and two adjacent image signal lines (drain signal lines or vertical signal lines) DL. As depicted in FIGS. 1 to 3 , the plurality of scanning signal lines GL extending in the row-direction are disposed (or arrayed) in the column-direction, while the plurality of image signal lines DL extending in the column-direction are disposed (or arrayed) in the row-direction. The thin film transistor TFT of every pixel is split into three (plural numbers) segments within the pixel, viz., this transistor TFT is composed of thin film transistors (divided thin film transistors) TFT 1 , TFT 2 and TFT 3 . All of the thin film transistors TFT 1 to TFT 3 are shaped to virtually have the same size (the width is equal to a channel length). Each of the divided thin film transistors TFT 1 to TFT 3 is formed mainly of a gate electrode GT, an insulating film GI, and an i-type (intrinsic conductive type in which deterministic impurities are not doped) amorphous Si semiconductor layer AS, and a source electrode SD 1 and drain electrode SD 2 . Note that the source/drain is originally determined by a bias polarity therebetween, but the source/drain is, it should be understood, interchangeable during the operation, because the polarity is reversed during the operation in a circuit of the titled device of this specification. In the following description, however, one is fixedly expressed as a source, and the other a drain for convenience. The gate electrode GT is, as fully illustrated in FIG. 4 (a plan view of the principal portion in a predetermined manufacturing process), formed to assume a T-shape (it branches off in the T-like configuration) in which to protrusively extend from the scanning signal line GL in the column-direction (e.g., a vertical direction in FIGS. 1 and 4 ). Namely, the gate electrode GT is arranged to extend virtually in parallel with the image signal line DL. The gate electrodes GT are also arranged to protrusively extend to regions in which the respective thin film transistors TFT 1 to TFT 3 are formed. The gate electrodes of the thin film transistors TFT 1 to TFT 3 are formed into one united body (as a common gate electrode) in continuation from the same scanning signal line GL. The gate electrode GT consists of a first single layered conductive film g 1 so as to minimize the possibility of forming a large stepped portion (i.e., a step-like configured protrusion) in the forming region of the thin film transistor TFT. The formation of the first conductive film g 1 involves the use of, for instance, a chromium (Cr) film having a thickness of approximately 1000 (Å) on the basis of sputtering. It can be observed from FIGS. 1, 2 and 5 that the gate electrode GT is shaped to be sufficiently larger than the semiconductor layer AS to completely cover this layer AS (when viewed from below). Where a backlight such as a fluorescent lamp or the like is provided underneath the substrate SUB 1 , the non-transparent Cr gate electrode GT overshadows the semiconductor layer AS, with the result that no backlight strikes upon the layer AS. Hence, a conductive phenomenon caused by the irradiation of light, i.e., the deterioration of OFF-characteristics, is not likely to occur. In connection with an original size of the gate electrode GT, this electrode GT has a minimum width (including an allowance for positioning the gate electrode and the source/drain electrodes) required to span the source/drain electrodes SD 1 and SD 2 ; and a length thereof which determines a channel width W depends upon a ratio with respect to a distance L (a channel length) between the source electrode and the drain electrode, i.e., such a length is conditional on a factor of W/L which determines a mutual conductance gm. The configuration of the gate electrode employed in this embodiment is, as a matter of course, more than the original one. If the gate electrode is put into consideration in terms of only a gate function and a light shielding function as well, the gate electrode and the line GL cooperate with a single layer to form one united body. In this case, as a non-transparent (or opaque) conductive material, Al containing Si, pure Al or Al containing Pd may be selected. The scanning signal line GL consists of a composite film of the first conductive film g 1 and the second conductive film g 2 superposed thereon. The first conductive film g 1 of the scanning signal line GL is formed in the same manufacturing process as that of the first conductive film g 1 of the gate electrode GT, and is also arranged to be integral therewith. Based on the sputtering technique, the second conductive film g 2 is formed of, e.g., an aluminum (Al) film which is 2000 to 4000 (Å) in thickness. The second conductive film g 2 serves to decrease a resistance value of the scanning signal line GL and is capable of increasing a velocity (a writing characteristic of information on the pixels) at which a signal on a scanning signal line is transmitted. The scanning signal line GL is arranged such that the second conductive film g 2 has a width smaller than that of the first conductive film g 1 . That is, the scanning signal line GL is formed so as to level the surface of an insulating film GI superposed thereon, because a stepped configuration of the side wall may be moderated. The insulating film GI serves as a gate insulating film for each of the thin film transistors TFT 1 to TFT 3 . The insulating films GI are disposed on the gate electrode GT and the scanning signal line GL. The formation of the insulating film GI involves the use of, e.g., a silicon nitride film having a thickness of 3000 (Å) or thereabouts on the basis of plasma CVD. As described above, the surfaces of the insulating films GI are levelled in the forming regions of the thin film transistors TFT 1 through TFT 3 and of the scanning signal lines GL. The i-type semiconductor layer AS is, as fully depicted in FIG. 5 (a plan view of the principal portion in a predetermined manufacturing process), employed as a channel forming region of each of the plurality of divided thin film transistors TFT 1 to TFT 3 . The i-type semiconductor layers AS of the plurality of divided thin film transistors TFT 1 to TFT 3 are formed into one united body within the pixel. Namely, each of the plurality of divided thin film transistors TFT 1 to TFT 3 of the pixel is formed in an insular region of one (common) i-type semiconductor layer AS. The i-type semiconductor layer AS is formed of an amorphous silicon film or a polycrystalline silicon film, the thickness of which is approximately 1800 (Å). The i-type semiconductor layer AS is formed in continuation from the Si 3 N 4 gate insulating film GI by the same plasma CVD device, changing supply gas components in such a manner that this layer AS is not exposed to the outside from the plasma CVD device. Similarly, d 0 (FIG. 2) and an N + layer in which p for ohmic contact is doped are successively formed with a thickness of about 400 (Å). Subsequent to this step, the substrate SUB 1 is taken out of the CVD device, the N + -layer d 0 and the i-layer AS are subjected to patterning to form independent insular portions shown in FIGS. 1, 2 and 5 by employing a photo-processing technique. Thus, by virtue of the arrangement that the i-type semiconductor layers AS of the plurality of divided thin film transistors TFT 1 to TFT 3 of the pixel are formed into one united body, the drain electrode SD 2 common to the thin film transistors TFT 1 to TFT 3 passes over the i-type semiconductor layer AS once (in fact, a step equivalent to the film thickness obtained by totaling the thicknesses of the first conductive layer g 1 , the N + -type semiconductor layer d 0 and the i-type semiconductor layer AS) from the drain electrode SD 2 to the i-type semiconductor layer AS. This contributes to a drop in the probability that the drain electrode SD 2 is disconnected, which further leads to a decrease in the possibility of causing the point defect. In the embodiment I, the point defect created in the pixel when the drain electrode SD 2 goes over the step of i-type semiconductor layer AS can be reduced by a factor of 3. Though different from the layout of the embodiment I, where the portion of the image signal line DL which has gone directly over the i-type semiconductor layer AS is formed as the drain electrode 2 , it is possible to diminish the probability that a linear defect is caused due to the disconnection when the image signal line DL (the drain electrode SD 2 ) goes over the i-type semiconductor layer AS. In other words, the i-type semiconductor layers AS of the plurality of divided thin film transistors TFT 1 to TFT 3 of the pixel are formed into one united body, whereby the image signal line DL (the drain electrode SD 2 ) goes over the i-type semiconductor layer AS only once (in fact, however, twice—the beginning and the end of such an action). The i-type semiconductor layer AS, as depicted in detail in FIGS. 1 and 5, extends to the intersection (a crossover) between the scanning signal line GL and the image signal line DL. The thus extended i-type semiconductor layer AS is intended to diminish the degree of short-circuiting between the scanning signal line GL and the image signal line DL at the intersection. The source electrode SD 1 and the drain electrode SD 2 of each of the plurality of divided thin film transistors TFT 1 through TFT 3 of the pixel are, as fully illustrated in FIGS. 1, 2 and 6 (a plan view of the principal portion in the predetermined manufacturing process), so disposed on the i-type semiconductor layer AS as to be spaced away from each other. The source electrode SD 1 and the drain electrode SD 2 may be interchangeable in terms of operation when the bias polarity of the circuit varies. Namely, as in the case of an FET, the thin film transistor TFT is of a bidirectional type. Each of the source electrode SD 1 and the drain electrode SD 2 is so arranged that a first conductive film d 1 , a second conductive film d 2 and a third conductive film d 3 are sequentially superposed from the lower layer contiguous to the N + -type semiconductor layer do. The first, second and third conductive films d 1 , d 2 and d 3 of the source electrode SD 1 are formed in the same process as that of the drain electrode SD 2 . The first conductive film d 1 is composed of a chromium film shaped by sputtering, the thickness of which is 500 to 1000 (Å) (approximately 600 (Å) in this embodiment). The chromium film has such properties that the stress increases, if the film thickness becomes large. Therefore, the thickness must fall within a range of about 2000 (Å). The chromium film has a favorable contact condition with respect to the N + -type semiconductor layer d 0 . The chromium film also performs a function to prevent aluminum contained in the second conductive film d 2 from diffusing into the N + -type semiconductor layer d 0 by forming a so-called barrier layer. In addition to the chromium film, the formation of the first conductive film d 1 may involve the use of a high melting point metal (Mo, Ti, Ta and W) film or a high melting point metal silicide (MoSi z , TiSi z , TaSi z and WSi z ) film. After the patterning has been effected on the first conductive film d 1 by the photo-processing, the N + -layer d 0 is removed by the same photo-processing mask or with the first conductive film d 1 serving as a mask. More specifically, the N + -layer do left on the i-layer AS except for the first conductive film dl is removed by self-alignment. At this time, the N + -layer d 0 is etched so that the portion equivalent to its thickness is all removed, and hence the surface of the i-layer AS is also etched to some extent. The extent to which the surface is etched may be controlled according to the etching time. Subsequently, the second conductive film d 2 is formed of aluminum with a thickness of 3000 to 4000 (Å) (approximately 3000 (Å) in this embodiment) by sputtering. The aluminum film is smaller in stress than the chromium film and can be formed thick. The aluminum film behaves to reduce resistance values of the drain electrode SD 2 and the image signal line DL. The second conductive film d 2 is arranged to increase the velocities at which the thin film transistor TFT functions and at which the signal of the image signal line DL is transmitted. Namely, the second conductive film d 2 is capable of improving the writing characteristic of the pixel. Excepting the aluminum film, the second conductive film d 2 may be formed of an aluminum film containing silicon (Si) and copper (Cu) as additives. After the second conductive film d 2 has undergone patterning based on the photo-processing technique, the third conductive film d 3 is composed of a transparent conductive film (ITO: a nesa film) having 1000 to 2000 (Å) (approximately 1200 (Å) in this embodiment) in thickness, which requires the sputtering process. The third conductive film d 3 constitutes not only the source electrode SD 1 , the drain electrode SD 2 and the image signal line DL but also the transparent pixel electrode ITO. The first conductive films dl of the source electrode SD 1 and of the drain electrode SD 2 are each shaped larger on the side of channel forming region than the upper second conductive film d 2 and the third conductive film d 3 as well. To be more specific, if there is created some deviation in mask alignment in the manufacturing process between the first, second and third conductive films d 1 , d 2 and d 3 , the first conductive film d 1 is arranged to become larger than the second and third conductive films d 2 and d 3 (the channel forming regions of the first, second and third conductive films d 1 , d 2 and d 3 may be on the line). The first conductive films d 1 of the source electrode SD 1 and the drain electrode SD 2 are each so formed as to prescribe the gate length L of the thin film transistor TFT. In the plurality of divided thin film transistors TFT 1 to TFT 3 of the pixel, each of the first conductive films d 1 of the source electrode SD 1 and the drain electrode SD 2 is shaped larger on the side of channel forming region than the second conductive film d 2 and the third conductive film d 3 as well. This arrangement permits the gate length L of the thin film transistor TFT to be defined by a dimension between the first conductive films d 1 of the source electrode SD 1 and of the drain electrode SD 2 . The spacing (the gate length L) between the first conductive films d 1 can be prescribed by processing accuracy (patterning accuracy), so that it is feasible to make uniform the gate length L of each of the thin film transistors TFT 1 to TFT 3 . The source electrode SD 1 is, as explained earlier, connected to the transparent pixel electrode ITO. The source electrode SD 1 is formed along the stepped portion (the step equivalent to the thickness obtained by totaling the thicknesses of the first conductive film g 1 , the N + -layer do and the i-type semiconductor layer AS) of the i-type semiconductor layer AS. More specifically, the source electrode SDl consists of: the first conductive film d 1 formed along the stepped portion of the i-type semiconductor layer AS; the second conductive film d 2 so formed thereon as to be smaller on the connecting-side to the transparent pixel electrode ITO than the first conductive electrode d 1 ; and the third conductive film d 3 which is exposed from the second conductive film d 2 and is connected to the first conductive electrode d 1 . The first conductive electrode d 1 of the source electrode SD 1 has a good bonding property with respect to the N + -type semiconductor layer do and is formed chiefly as a barrier layer against diffused matters from the second conductive film d 2 . The second conductive film d 2 of the source electrode SD 1 is formed sufficiently dimensioned to extend over the i-type semiconductor layer AS, because the chromium film of the first conductive film d 1 cannot be formed too thick due to an increase in stress and is incapable of surmounting the stepped portion of the i-type semiconductor layer AS. That is, the second conductive film d 2 is formed thick, thereby improving its step coverage. The second conductive film d 2 which can be formed thick contributes greatly to a reduction in resistance value of the source electrode SD 1 (this is the same with the drain electrode SD 2 as well as with the image signal line DL). The third conductive film d 3 is incapable of surmounting the stepped portion associated with the i-type semiconductor layer AS of the second conductive film d 2 , and it follows that the third conductive film d 3 is arranged to make a connection to the exposed first conductive film d 1 by reducing the size of the second conductive film d 2 . The first and third conductive films d 1 and d 3 each have a favorable bonding property, and the connecting portion therebetween is small. Hence, these two conductive films can be securely connected to each other. As discussed above, the source electrode SD 1 of the thin film transistor TFT is composed of at least the first conductive film dl serving as the barrier layer formed along the i-type semiconductor layer AS and the second conductive film d 2 which is formed on the upper portion of the first conductive film d 1 and has a smaller size and a smaller specific resistance value than those of the first conductive film d 1 . The first conductive film d 1 exposed from the second conductive film d 2 is connected to the third conductive film d 3 defined as the transparent pixel electrode ITO, whereby the thin film transistor TFT can be securely connected to the transparent pixel electrode ITO. It is therefore possible to reduce the point defect due to the disconnection. Besides, the source electrode SD 1 may involve the use of the second conductive film d 2 (an aluminum film) having a small resistance value by virtue of the barrier effects produced by the first conductive film d 1 , and this is conducive to a drop in resistance value. The drain electrode SD 2 is so formed as to be integral with the image signal line DL in the same manufacturing process. The drain electrode SD 2 assumes an L-like configuration wherein this electrode SD 2 protrudes in such a row-direction as to intersect the image signal line DL. The drain electrode SD 2 of each of the plurality of divided thin film transistors TFT 1 to TFT 3 of the pixel is connected to the same image signal line DL. The transparent pixel electrode ITO is provided in every pixel and constitutes one of the pixel electrodes of the liquid crystal display unit. The transparent pixel electrode ITO is split into three transparent pixel electrodes (divided transparent pixel electrodes) ITO 1 , ITO 2 and ITO 3 corresponding to the plurality of divided thin film transistors TFT 1 to TFT 3 , respectively. The transparent pixel electrode ITO 1 is connected to the source electrode SD 1 of the thin film transistor TFT 1 . The transparent pixel electrode IT 02 is connected to the source electrode SD 1 of the thin film transistor TFT 2 . The transparent pixel electrode ITO 3 is connected to the source electrode SD 1 of the thin film transistor TFT 3 . The transparent pixel electrodes ITO 1 through ITO 3 are, as in the case of the thin film transistors TFT 1 through TFT 3 , virtually of the same size. Each of the transparent pixel electrodes ITO 1 through IT 03 is so formed as to be integral with the i-type semiconductor layer AS of each of the thin film transistors TFT 1 to TFT 3 (the divided thin film transistors TFTs are concentrated on one portion), thus assuming the L-like configuration. As is obvious from the description given above, the thin film transistor TFT of the pixel disposed in each of the intersection regions defined by the two adjacent scanning signal lines GL and the two adjacent image signal lines DL is split into the plurality of thin film transistors TFT 1 to TFT 3 ; and the thus divided thin film transistors TFT 1 to TFT 3 are connected to the plurality of divided transparent pixel electrodes ITO 1 to ITO 3 . Owing to this arrangement, only part (for instance TFT 1 ) of the divided portions of the pixel would be associated to contributing to the point defect, and hence there is no point defect in a large proportion of the pixel (TFT 2 and TFT 3 are not associated with the point defect). Consequently, a magnitude of the point defect of the pixel can be reduced on the whole. The point defect created in part of the divided portions of the pixel is small as compared with the entire area thereof (the point defect is one-third the area of the pixel in this embodiment), whereby it is difficult to visually perceive the point defect. Each of the divided transparent pixel electrodes ITO 1 to ITO 3 of the pixel is formed virtually of the same size. A uniform area of the point defect in the pixel can be obtained because of this arrangement. Because each of the divided transparent pixel electrodes is formed virtually of the same size, it is feasible to make uniform both a liquid crystal capacitor (Cpix) provided by a combination of each of the transparent pixel electrodes ITO 1 to ITO 3 and the common transparent pixel electrode ITO, and a superposition capacitor (Cgs) given by superposition of the transparent pixel electrodes ITO 1 to ITO 3 on the gate electrodes GT, this superposition capacitance being added to each of the transparent pixel electrodes ITO 1 to ITO 3 . Each of the transparent pixel electrodes ITO 1 to ITO 3 can make uniform the liquid crystal capacitance and the superposition capacitance, and it is therefore possible to make the DC component uniform which is applied to liquid crystal molecules of the liquid crystal LC due to the superposition capacitance. When adopting a way of offsetting the DC component, scattering in the DC component applied to the liquid crystal of every pixel can be decreased. Protection films PSV 1 are provided on the thin film transistor TFT and the transparent pixel electrode ITO. The protection film PSV 1 is formed mainly for protecting the thin film transistor TFT from moisture or the like. The protection film PSV 1 should have high transparency and high moisture-resistant properties. The protection film PSV 1 is composed of, e.g., a silicon nitride film or a silicon oxide film formed by the plasma CVD, in which case the film thickness is approximately 8000 (Å). A light shielding film LS is disposed on the protection film PSV 1 on the thin film transistor TFT, with the result that the light emerging from the outside does not strike upon the i-type semiconductor layer AS serving as a channel forming region. The light shielding film LS is, as depicted in FIG. 1, disposed in the region surrounded by a dotted line. Based on sputtering, the light shielding film LS is formed of, e.g., an aluminum film or a chromium film having high light shielding properties, the thickness of which is about 1000 (Å). Therefore, it follows that the common semiconductor layer AS to the thin film transistors TFT 1 through TFT 3 is sandwiched in between the relatively large gate electrode GT and the light shielding films LS provided up and down so as not to be irradiated with the outside natural light or the beams of backlight. The light shielding film LS and the gate electrode GT are formed in a substantially similar configuration to the semiconductor layer AS, but are larger than this semiconductor layer AS. The light shielding film LS and the gate electrode GT are almost equal in size (the gate electrode GT is depicted smaller than the light shielding film LS to make the border line clear in the Figure). Note that a backlight lamp may be installed on the side of the substrate SUB 2 , while the substrate SUB 1 is provided as an observation side (an outside exposing side). In this case, the light shielding film LS functions as a light shielding member against the backlight, while the gate electrode GT behaves as a light shielding member against the natural light. The thin film transistor TFT is arranged such that when applying a positive bias to the gate electrode GT, a channel resistance between the source and the drain decreases, and if the bias becomes zero, the channel resistance increases. The thin film transistor TFT serves to control a voltage impressed on the transparent pixel electrode ITO. The liquid crystal LC is sealed in an air space formed between the lower transparent glass substrate SUB 1 and the upper transparent glass substrate SUB 2 , the liquid crystal being prescribed by a lower orientation film OR 11 and an upper orientation film OR 12 for orienting liquid crystal molecules. The lower orientation film OR 11 is formed on the upper portion of the protection film PSV 1 provided on the side of the lower transparent glass substrate SUB 1 . Sequentially laminated on the inside (on the side of liquid crystal) surface of the upper transparent glass substrate SUB 2 are a color filter FIL, the protection film PSV 2 , the common transparent pixel electrode (COM) ITO and the upper orientation film OR 12 . The common transparent pixel electrode ITO stands vis-a-vis with the transparent pixel electrode ITO provided in every pixel on the side of the lower transparent glass substrate SUB 1 , and cooperates with another adjacent common transparent pixel ITO to form one united body. This common transparent pixel electrode ITO is allowed to undergo impression of a common voltage Vcom. The common voltage Vcom is defined as an intermediate electric potential between a low level driving voltage Vdmin and a high level driving voltage Vdmax which are impressed on the image signal line DL. The color filter FIL is formed in such a manner that a dyeing base member formed of resin, e.g., acrylic resin is stained with dyestuffs. For every pixel, the color filter FIL is disposed in a position standing vis-a-vis with the pixel. The color filters FIL are allocated according to the dyeing. Namely, as in the case of a pixel, each individual color filter FIL is disposed in the intersection region defined by the two scanning signal lines GL and the two image signal lines DL. Each pixel is split into a plurality of segments in a filter of a predetermined color of the color filter FIL. The color filter FIL may be arranged in the following manner. The arrangement begins with formation of the dyeing base member on the surface of the upper transparent glass substrate SUB 2 . Excepting a red color filter forming region, the dyeing base member is then partly removed by the photolithography. Subsequent to this step, the dyeing base member is stained with a red dyestuff and is subjected to a bonding process, thus forming a red filter R. Next, a green filter G and a blue filter B are sequentially formed by performing the same processes. The respective color filters of the color filter FIL are formed in the intersection regions so that these filters face the individual pixels. The scanning signal lines GL and the image signal lines DL each exist between the respective color filters of the color filter FIL. Therefore, a space allowance, which corresponds to the presence of each signal line, for positioning can be ensured (a positioning margin can be enlarged). Moreover, when forming the individual color filters of the color filter FIL, a positioning space allowance between the different color filters can also be ensured. In accordance with this embodiment, the pixels are formed in the intersection regions defined by the two scanning signal lines GL and the two image signal lines DL. Each pixel is split into a plurality of segments, and the respective color filters of the color filter FIL are formed in such positions standing vis-a-vis with the thus divided pixels. In this constitution, the above-described point defect can be diminished in magnitude, and at the same time it is feasible to ensure the space allowance for positioning the respective pixels and the color filters. The protection film PSV 2 is designed for preventing the dyestuffs with which the color filter FIL is differently stained from permeating into the liquid crystal LC. The protection film PSV 2 is formed of, for example, transparent resinous material such as acrylic resin, epoxy resin and so on. The assembly of this liquid crystal display device involves the steps of separately forming layers on the side of lower transparent glass substrate SUB 1 and the upper transparent glass substrate SUB 2 , superposing the lower and upper transparent glass substrates SUB 1 and SUB 2 on each other, and sealing the liquid crystal LC therebetween. The plurality of pixels on the liquid crystal display unit are, as depicted in FIG. 3, arranged in the same row-direction as the direction in which the scanning signal lines GL extend, thus constituting pixel rows X 1 , X 2 , X 3 , X 4 . . . In each pixel of the pixel rows X 1 , X 2 , X 3 , X 4 . . . the positions in which the thin film transistors TFT 1 to TFT 3 and the transparent pixel electrodes ITO 1 to ITO 3 are disposed are the same. To be more specific, in each pixel of the pixel rows X 1 , X 3 . . . , the positions in which the thin film transistors TFT 1 through TFT 3 are disposed are set to the left, whereas the positions in which the transparent pixel electrodes ITO 1 through ITO 3 are disposed are set to the right. The individual pixels of the pixel rows X 2 , X 4 , . . . that are positioned at the stage subsequent to the pixel rows X 1 , X 3 , . . . in the column-direction and the pixel of the pixel rows X 1 , X 3 , . . . each exhibit a linear symmetry with respect to image signal line DL. In each pixel of the pixel rows X 2 , X 4 , . . . , the thin film transistors TFT 1 to TFT 3 are disposed on the right side, whereas the transparent pixel electrodes ITO 1 to ITO 3 are disposed on the left side. The pixels of the picture element rows X 2 , X 4 , . . . are each placed to shift (deviate) a distance equivalent to half of a pixel in the row-direction with respect to the pixels of the pixel rows X 1 , X 3 , . . . Supposing that the intervals between the pixels of the pixel row X are all set to 1.0 (1.0 pitch), the pixel interval is 1.0 in the next pixel row X, and hence the pixels deviate from those of the previous pixel row X with a 0.5 pixel interval (0.5 pitch) in the row-direction. The image signal lines DL disposed between the pixels and arrayed in the row-direction are such that each extends a distance equivalent to half of a pixel in the row-direction between the pixel rows. As discussed above, in the liquid crystal unit, the plurality of pixels in which the thin film transistor TFT and the transparent pixel electrode ITO are disposed respectively in the same positions are arranged in the row-direction, thus constituting the pixel row X. The pixels of the next pixel row X and the pixels of the preceding pixel row are linearly symmetric with respect to the image signal line DL. The pixels of the next pixel row are disposed to shift a distance in the row-direction equivalent to half of a pixel with respect to the pixels of the previous pixel row. As illustrated in FIG. 7 (a plan view of the principal portion in a state where the pixels and the color filters are superposed on each other), it is therefore possible to provide a 1.5 pixel interval (1.5 pitch) between each of the pixels of the previous pixel row X in which predetermined color filters are formed (for instance, the pixels of the pixel row X 3 in which the red filters are formed) and each of the pixels of the next pixel row X in which the same color filters are formed (for example, the pixels of the pixel row X 4 in which the red filters are formed). The pixels of the pixel row X of the previous pixel row X are disposed invariably at the 1.5 picture element intervals from the pixels of the closest next pixel row in which the same color filters are formed. The color filter FIL is allowed to take a triangular arrangement of RGB. This triangular arrangement of RGB of the color filter FIL is capable of enhancing conditions under which the respective colors are mixed. Hence, a resolution of color image can be improved. Between the pixel rows X, the image signal line DL extends a distance half of a pixel in the row-direction, whereby this image signal line DL does not intersect the adjacent image signal line DL. This eliminates the necessity of leading round the image signal line DL, resulting in a decrease in occupied area thereof. It is therefore feasible to eliminate both a detour of the image signal line DL and the multilayered wiring structure. Directing attention to FIG. 9 (an equivalent circuit diagram of the liquid crystal display unit), there is illustrated a construction of a circuit of the liquid crystal display. In FIG. 9, the symbols YiG, Yi+1G, . . . indicate the image signal lines DL connected to the pixels in which green filters G are formed. The symbols YiB, Yi+1B, . . . represent the image signal lines DL connected to the pixels in which the blue filters B are formed. The symbols Yi+1R, Yi+2R, . . . denote the image signal lines DL connected to the pixels in which the red filters R are formed. These image signal lines DL are selected by an image signal driving circuit. The symbol Xi denotes the scanning signal line GL for selecting the pixel row X 1 depicted in FIGS. 3 and 7. Similarly, the symbols Xi+1, Xi+2, . . . indicate the scanning signal lines GL for selecting the pixel rows X 2 , X 3 , . . . . These scanning signal lines GL are connected to a horizontal scanning circuit. Referring to FIG. 2, the central part thereof illustrates one pixel in section; the left part thereof illustrates a section, in which the outside extension wire is provided, of the left fringes of the transparent glass substrates SUB 1 and SUB 2 ; and the right part thereof illustrates a section, in which no outside extension wire is provided, of the right fringes of the transparent glass substrates SUB 1 and SUB 2 . Sealing materials SL shown on the right and left sides of FIG. 2 are designed for sealing the liquid crystal LC. The sealing materials SL are provided along the entire fringes of the transparent glass substrates SUB 1 and SUB 2 except for a liquid crystal sealing port (not illustrated). The sealing material SL is formed of, e.g., epoxy resin. The common transparent pixel electrode ITO on the side of the upper transparent glass substrate SUB 2 is connected leastwise at one portion to the outside extension wire formed of a silver paste material SIL on the side of the lower transparent glass substrate SUB 1 . The outside extension wire is formed in the same process as those of the gate electrode GT, the source electrode SD 1 and the drain electrode SD 2 . Formed inside the sealing materials SL are layers of the orientation films OR 11 and OR 12 , the transparent pixel electrode ITO, the common transparent pixel electrode ITO, the protection films PSV 1 and PSV 2 and the insulating film GI. Polarization plates POL are placed on the outer surfaces of the lower and upper transparent glass substrates SUB 1 and SUB 2 . (Embodiment II) The embodiment II of the present invention is characterized by the following points: an opening rate of each pixel on the liquid crystal display unit of the liquid crystal display device is improved; and the point defect and the black scattering of the liquid crystal display unit are reduced by decreasing the DC component applied to the liquid crystals. FIG. 8A (a plan view of the principal portion) illustrates one pixel on the liquid crystal display unit of the liquid crystal display device in which the embodiment II of the present invention is incorporated. FIG. 8B is a view enlarged three times as large as the portion (TFT 3 and its peripheral portion), shown in FIG. 8A, surrounded by a bold solid frame line B on the lower left side in the Figure. The liquid crystal display device of the embodiment II is arranged in such a way that the i-type semiconductor layer As in each individual pixel on the liquid crystal display unit is, as illustrated in FIGS. 8A and 8B, provided for each of the thin film transistors TFT 1 through TFT 3 . Namely, each of the plurality of divided thin film transistors TFT 1 through TFT 3 is formed in an independent insular region of the i-type semiconductor layer AS. In the thus constituted pixel, the thin film transistors TFT 1 to TFT 3 can be equally allocated in the column-direction in which the image signal lines DL extend. Consequently, it is feasible to shape each of the transparent pixel electrodes ITO 1 to ITO 3 in a rectangular configuration and to connect them, respectively, to the thin film transistors TFT 1 to TFT 3 . The transparent pixel electrodes ITO 1 to ITO 3 (each assuming the rectangular configuration) serve to reduce an area of space (an area corresponding to the region indicated by the oblique line shown in FIG. 8A is diminished) in the column-direction between the continuous transparent pixel electrode ITO within the pixel. As a result, the improvement can be obtained in regard to the area (an opening rate). As encircled by a dotted line marked with the symbol A, in FIG. 8A, a variation in configuration of each of the transparent pixel electrodes ITO 1 to ITO 3 is made by using a line inclined at a certain angle to the scanning signal line GL or the image signal line DL (for example, a line inclined at an angle of 45°). Each of the transparent pixel electrodes ITO 1 to ITO 3 is capable of reducing the area of space between the transparent pixel electrodes ITO as compared with a case where the configuration is varied by a line orthogonal to or parallel with the scanning signal line GL or the image signal line DL. Hence, the opening rate can be improved. Each of the transparent pixel electrodes ITO 1 to ITO 3 is superposed on the scanning signal line GL of the next stage in the column-direction both on the side connected to the thin film transistor TFT and on the side opposite thereto. As in the case of the gate electrode GT of the respective thin film transistors TFT 1 to TFT 3 , this superposition is effected by causing the scanning signal line GL of the next stage to branch off in a T-like shape, which is contiguous to the scanning signal line GL (the scanning signal line GL for selecting the pixel) for selecting its gate electrode GT. The thus diverged scanning signal line GL is, as in the case of the gate electrode of the thin film transistor TFT, composed of a single layer of the first conductive film (chromium film) g 1 . By virtue of the above-described superposition, there is constituted a holding capacitance element (an electrostatic capacitance element) Cadd wherein each of the transparent pixel electrodes ITO 1 to ITO 3 is employed as one electrode, and the portion diverged from the scanning signal line of the next stage which serves as a capacitor electrode line is used as the other electrode. A dielectric film of the holding capacitance element Cadd is formed of the same layer as that of the insulating film used as a gate insulating film of the thin film transistor TFT. As in the embodiment I, the gate electrode GT is formed larger than the semiconductor layer AS. In this embodiment, however, the thin film transistors TFT 1 to TFT 3 are formed for every semiconductor layer AS, and hence a relatively large pattern is formed per thin film transistor TFT. Simultaneously, a connection to the diverged gate wire GL (g 1 ) is made. FIG. 10 (a plan view illustrating the principal portion of one pixel in another example) shows another layout of the holding capacitance element Cadd. Referring to FIG. 11 (an equivalent circuit diagram), there is depicted an equivalent circuit of the pixel shown in FIGS. 8 and 10. The holding capacitance element Cadd depicted in FIG. 10 exhibits an increment in the holding capacitance by an enhancing of the superposition of each of the transparent pixel electrodes ITO 1 to ITO 3 on the diverged portion (the other electrode of the holding capacitance element Cadd) of the capacitance electrode line. Fundamentally, the holding capacity element Cadd shown in FIG. 10 is identical with the holding capacitance element Cadd illustrated in FIG. 8 . In FIG. 11, as in the previous case, the symbol Cgs represents the amount of superposition associated with the source electrode SD 1 and the gate electrode GT of the thin film transistor TFT. The dielectric film of the superposition quantity Cgs is defined as the insulating film GI. The symbol Cpix designates a liquid crystal capacitor provided between the transparent pixel electrode ITO (PIX) and the common transparent pixel electrode ITO (COM). The dielectric film of the liquid crystal capacitor Cpix includes the liquid crystal LC, the protection film PSV 1 and the orientation films OR 11 and OR 12 . The symbol V1c denotes a mid-point potential. The holding capacitance element Cadd behaves to reduce the influence of a gate potential variation ΔVg on the midpoint potential (a pixel electrode potential) V1c. This will be expressed by the following formula: Δ V 1 c= ( Cgs /( Cgs+Cadd+Cpix )×Δ Vg where ΔV1c is the amount of variation in the mid-point potential due to ΔVg. This variation quantity ΔV1c is the cause of the DC component applied to the liquid crystal. A value of the variation quantity can be reduced as the holding capacitor Cadd is increased. The holding capacitance Cadd also has a function to increase the time of electric discharge, whereby the image information after turning OFF the thin film transistor is unaltered. The reduction in the DC component applied to the liquid crystal LC permits both improvement of life span of the liquid crystal LC and diminution in so-called seizing wherein the preceding image still subsists when changing over the liquid crystal display picture. As discussed in the embodiment I, the gate electrode GT is large enough to completely cover the semiconductor layer AS, and the area of overlap of the source electrode SD 1 with the drain electrode SD 2 increases correspondingly. Hence, a reverse effect is yielded in which the parasitic capacitor Cgs increases, and the mid-point potential V1c tends to be adversely influenced by the gate (scanning) signal Vg. This negative influence can, however, be obviated by providing the holding capacitor Cadd. In the liquid crystal display device including the pixels disposed in the intersection regions defined by the two scanning signal lines GL and by the two image signal lines DL, the thin film transistor TFT of the pixel selected by any one of the two scanning signal lines is split into a plurality of segments. The thus divided thin film transistors TFT 1 through TFT 3 are connected to the plurality of transparent pixel electrodes (ITO 1 through ITO 3 ) in which the transparent pixel electrode ITO is split. Formed for each of the thus divided transparent pixel electrodes ITO 1 through ITO 3 is the holding capacitance element Cadd in which the pixel electrode ITO serves as one electrode, and the other scanning signal line GL of the two scanning signal lines, which is defined as the capacitance electrode line, serves as the other electrode. In this arrangement, as explained earlier, only part of the divided portions of the pixel becomes the point defect, and hence no point defect is caused in a large proportion of the pixel. It is therefore possible to reduce the magnitudes of the point defect and the DC component applied to the liquid crystal due to the holding capacitance element Cadd. This further leads to the improvement in the life span of the liquid crystal LC. Especially, the division of pixel contributes to a reduction in magnitude of the point defect caused from a short-circuit between the source electrode SD 1 or the drain electrode SD 2 and the gate electrode GT of the thin film transistor TFT. In addition, it is feasible to diminish the point defect which would be attributed to a short-circuit between each of the transparent pixel electrodes ITO 1 to ITO 3 and the other electrode (the capacitance electrode line) of the holding capacitance element Cadd. The latter point defect is decreased in magnitude by a factor of 3 in this embodiment. As a result, the point defect produced in part of the divided portions of the pixel is smaller than the entire area of the pixel, whereby the point defect is hard to be seen. The holding capacity of the holding capacitance element Cadd is set to a value which is 4 to 8 times the liquid crystal capacitor Cpix (4.Cpix<Cadd<8.Cpix) and 8 to 32 times the superposition capacitor Cgs (8.Cgs<Cadd<32.Cgs). The scanning signal line GL is composed of the composite layer obtained by superposing the second conductive film (aluminum film) g 2 on the first conductive film (chromium film) g 1 . The other electrode of the holding capacitance element Cadd, viz., the diverged portion of the capacitance electrode line, is formed of the single layer film consisting of a single layer of the first conductive film 9 of the composite film. Consequently, this arrangement is capable of decreasing the resistance value of the scanning signal line GL and enhancing the writing characteristic. Moreover, one electrode (transparent pixel electrode ITO) of the holding capacitance element Cadd can securely be bonded to the upper portion of the insulating film GI along the stepped portion based on the other electrode of the holding capacitance element, thereby reducing the probability that one electrode of the holding capacitance element Cadd is to be disconnected. The other electrode of the holding capacitance element Cadd is constituted by a single layer of the first conductive film g 1 , but the second conductive film g 2 defined as the aluminum film is not formed. By virtue of this arrangement, it is possible to prevent the short-circuit, which is due to the hillock of the aluminum film, between one electrode and the other electrode of the holding capacitance element Cadd. Formed between each of the transparent pixel electrodes ITO 1 to ITO 3 which are superposed to constitute the holding capacitance element Cadd and the diverged portion of the capacitance electrode line is an insular region composed of the first conductive film d 1 and the second conductive film d 2 as in the case of the source electrode SD 1 , with the result that the transparent pixel electrode ITO is not disconnected when surmounting the stepped portion of the diverged portion. This insular region is shaped as small as possible so as not to diminish the area (opening rate) of the transparent pixel electrode ITO. Disposed between one electrode of the holding capacitance element Cadd and the insulating film GI employed as a dielectric film thereof is a base layer consisting of the first conductive film d 1 and the second conductive film d 2 formed on this first conductive film d 1 , this second conductive film d 2 having a smaller size and a smaller specific resistance value than those of the first conductive film d 1 . One electrode (a third conductive film d 3 ) is connected to the first conductive film d 1 exposed from the second conductive film d 2 of the above-mentioned base layer, thereby making it possible to securely bond one electrode of the holding capacitance element Cadd along the stepped portion caused by the other electrode of the holding capacitance element Cadd. Therefore, the probability of an internal disconnection at the stepped portion of one electrode of the holding capacitance element Cadd can be reduced. FIG. 13 (an equivalent circuit diagram showing the liquid crystal display unit) illustrates a construction of the liquid crystal display unit of the liquid crystal display device in which the transparent pixel electrode ITO of the pixel is provided with the holding capacitance element. The construction of the liquid crystal display unit is based on repetitions of a unit fundamental pattern including the pixel, the scanning signal line GL and the image signal line DL. The scanning signal line GL of the final stage (or the scanning signal line of the first stage) used as a capacitance electrode line is, as depicted in FIG. 13, connected to the common transparent pixel electrode (Vcom) ITO. The common transparent pixel electrode ITO is, as illustrated in FIG. 2, connected to the outside extension wire through the silver paste material SIL on the fringe of the liquid crystal display device. Besides, some conductive layers (g 1 and g 2 ) of the outside extension wire are formed in the same manufacturing process as that of the scanning signal line GL. As a result, this facilitates a connection between the scanning signal line GL (capacitance electrode line) of the final stage and the common transparent pixel electrode ITO. As explained earlier, since the capacitance electrode line of the final stage is connected to the common transparent pixel electrode (Vcom) ITO of the pixel, the capacitance electrode line of the final stage can be so formed as to be integral with part of the conductive layers of the outside extension wire. Furthermore, the common transparent pixel electrode ITO is connected to the outside extension wire, and the capacitance electrode line of the final stage is thereby connected to the common transparent pixel electrode ITO with a simple arrangement. Based on the DC offset system (DC cancel system) disclosed in Japanese Patent Application No. 62-95125 for which the present inventors applied on Apr. 20, 1987, corresponding to U.S. Pat. No. 4,955,697, the liquid crystal display device is capable of reducing the DC component applied to the liquid crystal LC, as shown in FIG. 12 (a time chart), by controlling the driving voltage of the scanning signal line DL. Referring to FIG. 12, the symbol Vi represents a driving voltage of an arbitrary scanning signal line GL, and Vi+1 designates a driving voltage of the scanning signal line GL of the next stage. The symbol Vee indicates a driving voltage Vdmin which assumes a low level is impressed on the scanning signal line GL, and Vdd indicates a driving voltage Vdmax which assumes a high level is impressed on the scanning signal line GL. Voltage variation quantities V 1 to V 4 of the mid-point potential (see FIG. 11) at the respective timings t=t 1 to t 4 are given such as: t=t 1 : ΔV 1=−( Cgs/C )· V 2 t=t 2 : ΔV 2=+( Cgs/C )·( V 1 +V 2)−( Cadd/C )· V 2 t=t 3 : ΔV 3=−( Cgs/C )·( V 1 +Cadd/C )·( V 1+ V 2) t=t 4 : ΔV 4=−( Cadd/C )· V 1 However, a total pixel capacitance: C=Cgs+Cpix+Cadd. If a sufficient driving voltage impressed on the scanning signal line GL is provided (see “Notes” given below), the DC voltage applied to the liquid crystal LC is expressed such as: Δ V 3+ V 4=( Cadd·V 2− Cgs ·V 1)/ C, hence, Cadd·V 2= Cgs·V =0 Then, the DC voltage applied to the liquid crystal LC comes to zero. “Notes”: A variation quantity of a scanning line Vi exerts an influence on the mid-point potential V1c at the timings t 1 and t 2 . However, the mid-point potential V1c becomes equal to the image signal potential through a signal line Xi during a period of t 2 to t 3 (sufficient writing of the image signal). The potential applied to the liquid crystal is substantially contingent upon a potential immediately after turning OFF the thin film transistor TFT (a TFT OFF-period is sufficiently longer than a TFT ON-period). Therefore, when calculating the DC component applied to the liquid crystal, a period of t 1 to t 3 may be almost ignored, and what should be considered here is the potential just after the thin film transistor TFT has been turned OFF, i.e., the influence produced at the transition between the timings t 3 and t 4 . It is to be noted that the polarity of the image signal Vi is inverted per frame or per line, and the DC component associated with the image signal itself is zero. Based on the DC offset system, an amount of decrease caused by the lead-in of the mid-point potential V1c due to the superposition capacitor Cgs is made to rise by the driving voltage impressed on the scanning signal line GL (capacitance electrode line) of the next stage as well as on the holding capacitance element Cadd, and the DC component applied to the liquid crystal LC can be minimized. This permits the liquid crystal display device to improve the life span of the liquid crystal LC. As a matter of course, where the gate GT increases in configuration to enhance the light shielding effects, a value of the holding capacitor Cadd may be incremented correspondingly. Adoption of this DC offset system may necessitate a step of, as shown in FIG. 14 (an equivalent circuit diagram illustrating the liquid crystal unit), connecting the scanning signal line GL (or the capacitance electrode line) of the first stage to the capacitance electrode line (or the scanning signal line GL) of the final stage. In FIG. 14, only four scanning signal lines are illustrated for convenience. In fact, however, several hundred pieces of scanning signal lines are disposed. The scanning signal line of the first stage is connected to the capacitance electrode line of the final stage through an inside wire in the liquid crystal display unit or the outside extension wire. In the liquid crystal display device, as described above, the scanning signal lines GL and the capacitance electrode lines are all connected to a horizontal scanning circuit by connecting the scanning signal lines of the first stage to the capacitance electrode lines of the final stage. Hence, the DC offset system (DC cancel system) is allowed to be utilized. As a result, the DC component applied to the liquid crystal LC can be reduced, thereby improving the life span of the liquid crystal. The present invention made by the present inventors has concretely been described so far on the basis of the illustrative embodiments. The present invention is not, however, limited to the above-described precise embodiments. As a matter of course, various changes or modifications may be effected therein without departing from the spirit or the scope of the invention. For example, in accordance with the present invention, each individual pixel on the liquid crystal display unit of the liquid crystal display device can be split into two or four segments. If the number of divided segments of the pixel becomes too large, it follows that the opening rate goes down. As explained earlier, it is therefore adequate that the pixel be split into two or four segments. Even if the pixel is not divided, however, the light shielding effects can be obtained. The foregoing embodiment has presented a reverse stagger structure in which the formation is performed in the order of gate electrode→gate insulating film→semiconductor layer→source and drain electrodes. However, another reverse stagger structure in which the up-and-down relation or the sequence of formations are opposite to the former ones is also available in this invention. (Embodiment III) Referring to FIG. 15A, there is shown an improvement of the embodiment of FIG. 8 A. The modified point is that light shielding films 1 and 2 are formed between the divided pixel electrodes. The light shielding films 1 and 2 are formed of layers each assuming the same level as that of the first conductive film g 1 employed for the scanning line GL and the electrode of the capacitor Cadd and the gate electrode GT. However, the light shielding films 1 and 2 are formed separately from the capacitor electrode and the gate electrode, and are electrically arranged to be in a floating state. Provided that for instance, the photomask or the etching process is deteriorated due to undesirable conditions in the manufacturing process, no deterioration is created even when the light shielding films are short-circuited to either the gate electrode GT or the capacitor electrode owing to the foregoing floating state. According to this embodiment, there are obtained the light shielding effects equal to the backlight shielding effects associated with the gate electrode. It is possible to considerably restrict an amount of light leaking from gaps formed between the divided pixel electrodes ITO 1 to ITO 3 . In addition, the black display becomes more clear than ever before, and this leads to enhancement of contrast. (Embodiment IV) The different point of an embodiment IV from the embodiment of FIG. 15A is that light shielding films 3 and 4 are formed in continuation (electrically connected to) from the scanning signal line GL or the electrode of the capacitor Cadd. In this embodiment, the light shielding films 3 and 4 are short-circuited to the gate electrode GT for the reason of the above-described manufacturing process, in which case the two scanning lines are also short-circuited. The embodiment III is superior to this embodiment in terms of eliminating such an undesirable condition. However, the following points are more advantageous than the embodiment III. (1) The scanning signal line GL is formed in continuation from its diverged line (capacitance electrode), which makes a spacing therebetween unnecessary. Consequently, the amount of leaked light can be further restricted. (2) In combination with the light shielding effects, the capacitor Cadd described in the embodiment relative to the light can equivalently be formed between the pixel electrode and the adjacent scanning line; or alternatively a value of capacitance thereof can be increased. Therefore, if the value of auxiliary capacitor Cadd is kept constant, the opening rate becomes greater than in the embodiment III, whereby the display becomes brighter. Note that a total superposition area of the divided pixel electrodes ITO 1 to ITO 3 and of the light shielding films 3 and 4 is made invariable in order to substantially equalize the values of respective auxiliary capacitors Cadd. The superposition area of the two light shielding films 3 and 4 and of the middle pixel electrode ITO 2 overlapped with these light shielding films 3 and 4 is almost half that of the pixel electrodes ITO 1 and ITO 3 provided at both ends. As discussed above, in the embodiments III and IV, the light leaking from the gaps between the divided pixels in the case of taking no measure is shielded by the light shielding films provided therebetween. Hence, there is yielded an effect of enhancing the contrast.
There are disclosed various types of TFT active matrix liquid crystal display devices and method of fabrication thereof in which a pixel is divided into three parts, a capacitor is added to each pixel, light shielding is applied to each TFT, and the matrix is driven by a DC cancelling technique.
79,906
BACKGROUND OF THE INVENTION Sorting of refuse into various categories, such as clear and colored glass, metals, plastics, etc., not only is recognized as an environmentally commendable practice but is fast becoming a legal mandate in many areas. It has resulted in a proliferation of new devices for facilitating the refuse sorting process particularly in residential households. Various multiple compartment refuse containers have been proposed, such as those in U.S. Pat. Nos. 4,834,262 and 4,834,253 and earlier in U.S. Pat. No. 3,893,615, and simpler forms presumably not patented are commercially available. All have one aspect in common and that is that they present multiple refuse-receiving compartments to the user which are of fixed size. The types of refuse requiring sorting, however, are not generated in equal amounts. One household may produce several times the volume of colored glass bottles as it does aluminum cans. Another may generate waste plastic in only a fraction of the volume of clear glass refuse. Prior art multiple compartment refuse containers occupy a total space in which one compartment may be totally filled with cans while next to it another compartment of equal size is inefficiently filled only to a fraction of its capacity with plastic bottles. It is the principal object of this invention to provide refuse bag holding means of a total volume which is substantially less than the total volume of the bags if all were filled to capacity. Put another way it is the purpose of the invention to reduce the size of a multiple compartment refuse container as much as possible such that bags holding refuse of large volume can expand as needed at the expense of bags which need only minimal space to receive refuse generated in lesser volume. STATEMENT OF THE INVENTION A refuse bag support system is provided by the invention for sorting and storing refuse of various types and volumes in a plurality of side-by-side bags. The support means includes a plurality of arms each with means for releasably supporting an edge portion of a bag opening. Bag-holding means are provided of a total volume which is substantially less than the total volume of the bags if all were filled to capacity. The arms are mounted in pairs on the bag holding means with one bag gripped by each pair of arms. Displacement means are included for selectively moving the arms of each pair thereof apart for widening the opening of the associated bag and toward one another for narrowing that opening. In all forms of the invention the bag-holding means may be an open-top container and underlying means, such as the bottom of the bag-holding means, may be included for carrying the weight of the bag contents and relieving the arms of that weight. The arms may be rigid or flexible. If the arms are rigid they may be pivotably mounted on a central hub and slidable along an upper periphery of the structure so that the arms of each pair may be displaced angularly apart for widening the opening of the associated bag and angularly toward one another for narrowing that opening. Alternatively rigid arms of each pair may be substantially parallel and span opposed edges of a box-like bag-holding structure so as to be selectively slidable at their ends along the edges of the structure to displace the arms apart for widening the opening of the associated bag and toward one another for narrowing that opening. If the arms are flexible they may be releasably secured at their ends side-by-side in diametrically opposite locations on a circular periphery of the bag-holding structure and be longer than the diameter of the periphery, so as to snap between two positions, one wherein the arms of a given adjacent pair are bowed apart to open the associated bag and the other wherein teh arms of a given pair are bowed together to close the associated bag. In all forms of the invention the total volume of the bag holding means is substantially less than the total volume of the bags if all were filled to capacity. The bags holding refuse of large volume then expand as needed at the expense of bags which need only minimal space to receive refuse generated in lesser volume. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a pictorial view of that embodiment of the invention wherein the bag supporting arms are angularly displacable with respect to one another; FIG. 2 is a fragmentary vertical section taken along the line 2--2 of FIG. 1; FIG. 3 is an exploded pictorial view of one pair of the arms and associated bag of the embodiment of FIG. 1; FIG. 4 is a pictorial view of the embodiment of the invention wherein the bag supporting arms are parallel and linearly displacable with respect to one another; FIG. 5 is an enlarged fragmentary pictorial view of one arm of one pair of the arms and associated bag of the embodiment of FIG. 4; FIG. 6 is a pictorial view of that embodiment of the invention wherein the bag supporting arms are flexible and can be snapped between bowed apart and bowed together positions; FIG. 7 is an exploded pictorial view of one pair of the arms and associated bag of the embodiment of FIG. 6; FIG. 8 is an enlarged fragmentary section taken along the line 8--8 of FIG. 6 with the arms removed and showing slots in the container periphery for holding the ends of the arms; FIG. 9 is a top plan view of the embodiment of FIG. 6 showing all of the bag supporting arms in their bowed together position closing the associated bags; and FIG. 10 is a top plan view of the embodiment of FIG. 6 showing one of the pairs of arms in the bowed apart position holding the associated bag open. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring first to the embodiment of FIGS. 1 to 3, the apparatus of the invention includes a substantially cylindrical open-top container 10 of generally conventional form, typically of plastic material. The open top of the container 10 may be closed by a suitable conventional lid which is optional and therefore not here shown. The object is to incorporate plastic refuse bags in the container 10 in a manner such that bags holding refuse of large volume can expand as needed at the expense of bags which need only minimal space to receive refuse generated in lesser volume. In this embodiment four plastic bags 11A, 11B, 11C and 11D are illustrated in the container 10. The total volume of the container 10 is substantially less than the total volume of the bags 11A to 11D if all were filled to capacity. The bag 11A is shown in FIG. 3 in association with a pair or rigid arms 12A and 12B typically formed of an appropriately bent still metal rod. The rigid arms 12A and 12B are equipped with means for releasably gripping an edge portion of the opening of the bag 11A. In this embodiment the gripping means are respective conventional resilient plastic channel elements 13A and 13B which are force-fitted down over the associated edge portion of the bag 11A and underlying arm as shown in FIG. 3. Each of the bags 11B to 11D has a pair of arms associated with it similar to the arms 12A and 12B associated with the bag 11A, and each pair of such arms is also equipped with gripping means similar to the channel elements 13A and 13B. As shown in FIG. 2 the container 10 includes a circular upper periphery position 15 and a bottom 16. An axial post 17 is appropriately mounted at 17A at the center of the bottom 16 of the container 10. The top of the post 17 is substantially in the plane of the circular upper periphery of the container 10 and supports a hub 18. The hub device 18 includes a journal 19 concentrically surrounding the top portion of the post 17 and fixed to it at its lower end. A removable cap 20 is releasably secured in concentric position to the top end of the post 17. Alternatively the hub could be mounted at the end of a bracket cantilevered from the periphery portion 15 rather than on the top of the post 17. In FIGS. 2 and 3 the arm 12B is shown to include a right-angle end segment 21 which is fitted downwardly into the space between the journal 19 and the top portion of the post 17 when the cap 20 is removed. All of the other rigid arms of this embodiment include an end segment similar to the end segment 21. At the opposite end of the arm 12B is a crooked portion 22 which overlies and is in slideable engagement with the upper periphery 15 of the container 10 when the angled end segment 21 is in place within the journal 19. All of the arms in this embodiment include an outer end portion similar to the crooked portion 22. When all of the rigid arms and the cap 20 are in place as shown in FIG. 2, the inner end of each arm is pivotably mounted on the hub 18 and the other end of each arm is slideable along the upper peripher 15 of the container 10. In use edge portions of the bags 11A to 11B are releasably gripped by a pair of the adjacent arms and their channel elements, such as the arms 12A and 12B and their associated channel elements 13A and 13B of FIG. 3. The bottom 16 of the container 10 carries the weight of the bag contents and relieves the arms of that weight. Various types of refuse are selectively placed in the respective bags. For example, bottles 25 may be placed in the bag 11A, cans 26 may be placed in the bag 11B and refuse of some other type 27 may be placed in the bag 11C. In this example a relatively large volume of cans 26 is shown to have been placed in the bag 11B as compared to the lesser volume of refuse 27 placed in the bag 11C. Therefore the pair of arms associated with the bag 11B are displaced angularly apart to widen the opening of that bag and the pair of arms associated with the bag 11C are displaced angularly toward one another to narrow its opening. The bag 11B holding refuse of relatively large volume can then expand as needed at the expense of the bag 11C which need only occupy minimal space in the container 10 to recieve its refuse 27 generated in lesser volume. When one or more of the bags 11A to 11D is filled it may be selectively removed and replaced with an empty bag. Turning now to FIGS. 4 and 5 an embodiment of the invention is shown which in principle is the same as that of the embodiment of FIGS. 1 to 3. The difference in structure in the embodiment of FIGS. 4 to 5 is that the container 30 is not substantially cylindrical but instead is an open-top box-like container. Again, an appropriate lid may be provided if desired. The box-like container 30 may be formed of telescopic sections 31 and 31A which can expand or contract the size of the container 30 to accommodate various numbers of bags. Suitable tracks 32A and 32B are provided along each side of the inner section 31 of the telescopic container 30 to guide the sections during their relative movement. Only two bags 33 and 34 are shown in FIG. 4 thereof. It is to be understood that in the preferred operation of this apparatus more bags will be included so that during use they are side-by-side and occupy the entire inner volume of the container 30. Each of the bags is associated with a pair of rigid arms such as the arms 35A and 35B associated with the bag 33. As shown in FIG. 5 the arm 35A is of generally triangular lateral cross section for rigidity and may include a finger aperture 36 for easy gripping. It may also include suitable indicia in words 37 or pictures 38 indicating the type of refuse to be deposited in the associated bag 33. The opposite ends of the rigid arm 35A include triple flanges 40A and 40B each of which defines a pair of downwardly directed slots. The opposite outer pairs of slots are adapted to fit over the upper parallel opposed edges 41A and 41B of the outer telescopic container section 31A and the inner pair of slots are adapted to fit over the upper edges 42A and 42B of the inner telescopic section 31 of the container. Thus the rigid arm 35A can be used with either one of the telescopic sections 31 or 31A. The rigid arm 35A also includes means for releasably gripping edge portions of the opening of the bag 33. This could be a rod and asociated channel element as in the embodiment of FIGS. 1 to 3 but for illustration of possible options the embodiment of FIGS. 4 and 5 is shown with gripping means comprising a resilient channel 45 having side flanges which are biased together at their outer edges and which can be pried apart manually to receive and pinch an edge portion of the bag 33. It is to be understood that all of the rigid arms in the embodiment of FIGS. 4 and 5 are of a construction similar to that described above in connection with the rigid arm 35A. It is also to be understood as in the previous embodiment that the bag holding container 30, even in its expanded form, has a total volume which is substantially less than the total volume of the bags it is designed to contain if all were filled to capacity. The arms of each pair are substantially parallel as shown in FIG. 4, they span the opposed edges 41A-41B and 42A-42B of the structure and they are selectively slidable at their ends along the edges of the structure to displace the parallel arms of each pair apart for widening the opening of the associated bag and toward one another for narrowing that opening. The operation of the embodiment of FIGS. 4 and 5 is similar to that of FIGS. 1 to 3 in that the bags holding a type of refuse of large volume can expand as needed at the expense of bags which need only minimal space to receive refuse generated in lesser volume. Also as in the previous embodiment the bottom of the container 30 carries the weight of the bag contents and releives the arms of that weight. Turning now to the embodiment of FIGS. 6 to 10 a container 50 is provided which is very similar to the container 10 of the embodiment of FIGS. 1 to 3 in that it is substantially cylindrical and open-topped. Again, a lid may be provided. The container 50 includes a substantially circular upper periphery 51 which includes slots 52A and 52B at diameterically opposite locations on the circular periphery 51. A plurality of flexible arms are provided each with means for releasably supporting an edge portion of a bag opening. A pair of such arms 53A and 53B are shown in FIG. 7 associated with a bag 54. The arms 53A and 53B and all others like them in this embodiment may be formed of strips of flexible plastic. At the opposite ends of each arm are a pair of outer and inner probruberances 54A and 54B. The arms are releasably secured at their ends side-by-side in the diametrically opposite locations on the circular periphery 51 simply by sliding the arm ends down into the slots so that the protruberances 54A and 54B restrain each arm end portion against movement radial to the periphery 51. Alternative means for releasably fitting the ends of the arms in place include forming an eyelet in each end of each arm and fitting it down over the upstanding fingers on the periphery 51 shown in FIG. 8 which define the slots 52A. Each of the flexible arms in the embodiment of FIGS. 6 to 10 is substantially longer than the diameter of the periphery 51 as is clearly shown in FIGS. 6, 9 and 10. Since the arms are flexible they can be snapped between two positions, one wherein the arms of a given adjacent pair are bowed apart and the other wherein the arms of an adjacent pair are bowed together. Each time a given arm is moved from one such position to the next it snaps over dead center and as it does so is briefly of a somewhat S-configuration. The bag 54 in FIG. 7 is shown to include a pair of open-ended seams 60A and 60B on its edge portions through which the respective arms 53A and 53B are inserted when the bag 54 is placed within the container 50. This is only one optional means for releasably supporting the edge portion of the opening of the bag 54. Adaptations of the releasable supporting means of the embodiments of FIGS. 1 to 3 or of FIGS. 4 and 5 may also be employed. The bottom of the container 50 carries the weight of the contents of the bag 54 and relieves the releasable supporting means of that weight. In FIG. 9 all of the pairs of flexible arms and their associated bags are shown bowed together so that the openings of all the bags are held closed. In FIGS. 6 and 10 the first pair of adjacent flexible arms are shown bowed apart thereby opening the associated bag to receive refuse. In operation each bag may be selectively accessed in turn by snapping one or more of the pairs of flexible arms over dead center until the desired opened bag is reached. As in the two prior embodiments the total volume of the container 50 is substantially less than the total volume of the bags it contains if all were filled to capacity. The bags holding refuse of large volume can expand as needed at the expense of bags which need only minimal space to receive refuse generated in lesser volume. When "bags" are referred to herein and in the following claims it is intended to mean not only conventional plastic refuse bags but also other flexible containers such as sling-like elements for holding appropriately shaped refuse similar in a sense to slings used for carrying small amounts of firewood, or accordion-like elements which may expand or contract or even materials of stretchable or extensible or telescopic capability. It is also to be understood that the invention is not to be limited to containers such as 10, 30 and 50 which fully enclose bags. Open frameworks are also to be included in the bag-holding means of the invention. Indicia such as the words 37 or pictures 38 may be incorporated in the embodiments of FIGS. 1 to 3 and FIGS. 6 to 10 by appropriate means, just as in the embodiment of FIGS. 4 and 5. The scope of the invention is to be determined by the following claims rather than be the foregoing description of preferred embodiments.
A refuse bag support system for sorting and storing refuse of varying types and volume in a bag-holding structure of a total volume which is substantially less than the total volume of side-by-side bags therein if all were filled to capacity, including a pair of arms holding each bag which are movable apart to widen the associated bag opening and movable together to narrow it.
18,013
CROSS REFERENCE TO RELATED APPLICATION [0001] This is a continuation of U.S. application Ser. No. 09/336,689, filed Jun. 21, 1999, which is a continuation of U.S. application Ser. No. 08/770,728, filed Dec. 19, 1996, now U.S. Pat. No. 5,914,761, issued Jun. 22, 1999, which is a continuation of U.S. application Ser. No. 08/308,157, filed Sep. 20, 1994, now U.S. Pat. No. 5,600,464, issued Feb. 4, 1997, the subject matter of which is incorporated by reference herein. BACKGROUND OF THE INVENTION [0002] The present invention relates to a liquid crystal display device having a high picture quality and in which residual image is substantially eliminated. [0003] In a conventional liquid crystal display device, two facing transparent electrodes formed respectively on each of two substrates are used as the electrodes for driving the liquid crystal layer. In such a device, a display method represented by a twisted nematic display has been adopted, wherein the crystal display operates by being supplied with an electric field having approximately a vertical direction to the substrate boundary planes. On the other hand, in arrangements wherein the electric field has approximately a parallel direction to the substrates, methods utilizing a pair of comb-like electrodes are disclosed, for example, in JP-B-63-21907 and WO91/10936. In these cases, the electrodes are not necessarily transparent, since opaque metallic electrodes having high conductivity are used. However, the above-mentioned publications do not provide any teachings concerning liquid crystal material, oriented film and insulating film, which are necessary for obtaining high picture quality when driving the display system, in which the electric field is supplied to the liquid crystal in an approximately parallel direction to the substrate plane (hereinafter referred to as an in-plane switching system), with an active matrix driving method or a simple matrix driving method. [0004] When a character or a drawing is displayed in a display plane, an image of the character or the drawing remains for a while in the display plane even after erasing, and sometimes it causes an uneven display known as an afterimage. The afterimage is a common problem which causes deterioration of image quality for both the display method wherein the electric field is supplied in a perpendicular direction and the display method involving the in-plane switching system. Especially, in case of the in-plane switching system, the afterimage is generated more easily than the case wherein the electric field is generated perpendicularly to the substrate plane. SUMMARY OF THE INVENTION [0005] The object of the present invention is to provide a liquid crystal display device providing a high picture quality and in which the problems of residual image is substantially eliminated. [0006] In order to solve the above described problems, the inventors realized the invention explained hereinafter. [0007] As a first feature, a liquid crystal display (hereinafter called a liquid crystal display device of an in-plane switching system) is provided, wherein: [0008] display picture elements are composed of electrodes on a substrate; [0009] an orienting film for a liquid crystal layer is formed on the substrate directly or via an insulating layer; [0010] the substrate is arranged so as to face another transparent substrate on which another orienting film is formed; [0011] the liquid crystal layer is held between the above two substrates; [0012] the electrodes are formed so as to generate an electric field which is applied to the liquid crystal layer in a direction parallel to the substrate; [0013] the electrodes are connected to external control means; and [0014] a polarizer for changing the optical characteristics of the liquid crystal layer is provided, wherein [0015] a brightness recovering time of no greater than five minutes is obtained, where the brightness recovering time is the time until the brightness of a displayed portion that has been displayed for 30 minutes and is turned off returns to the background brightness. [0016] In the liquid crystal display device of an in-plane switching system, the display picture elements are composed of scanning signal electrodes and image signal electrodes. Further, provision of picture element electrodes and active elements are desirable, but, this condition is not essential to the present invention. [0017] Here, the orienting film refers to a film having a function to orient the liquid crystal. The insulating film refers to a film for electrically insulating, however, the film concurrently can have a function to protect an electrode. [0018] As a second feature of this invention, a liquid crystal display device of an in-plane switching system is provided, wherein [0019] the necessary time for recovering brightness is less than five minutes, and [0020] respective products (∈ r ρ) LC , (∈ r ρ) AF , and/or (∈ r ρ) PAS ) of a specific dielectric constant ∈ r and a specific resistivity ρ of the liquid crystal layer (abbreviated as LC), the orienting film (abbreviated as AF), and/or the insulating film (abbreviated as PAS) are in a range of 1×10 9 Ω·cm−8×10 15 Ω·cm. [0021] Here, the dielectric constant of the liquid crystal layer ∈ r is an average dielectric constant expressed by the following equation: ∈ r =(∈∥+2∈⊥)/3 [0022] where, ∈∥ is the dielectric constant in a molecular major axis direction, and ∈⊥ is the dielectric constant in a molecular minor axis direction. [0023] When ∈ r ρ is less than 1×10 9 Ω·cm, the device can not maintain its insulating property and a sufficient voltage keeping rate. [0024] As a third feature of this invention, a liquid crystal display device of an in-lane switching system is provided, wherein the necessary time for recovering brightness is less than five minutes, and respective values of surface resistance of the orienting film and/or the insulating film are in a range of 3×10 11 Ω/□−2.5×10 18 Ω/□. [0025] When the values of surface resistance are less than 3×10 11 Ω/□, the device can not maintain its insulating property and voltage keeping rate. [0026] As a fourth feature of this invention, a liquid crystal display device of an in-plane switching system is provided, wherein respective products ((∈ r ρ) LC , (∈ r ρ) AF , and/or (∈ r ρ) PAS ) of a specific dielectric constant ∈ r and a specific resistivity ρ of the liquid crystal layer, the orienting film, and/or the insulating film mutually have an approximately similar value. [0027] As a fifth feature of this invention, a liquid crystal display device similar to the fourth feature is provided, wherein [0028] the respective products are in a range of 1×10 9 Ω·cm−8×10 15 Ω·cm. [0029] As a sixth feature of this invention, a liquid crystal display device of an in-plane switching system is provided, wherein [0030] a ratio of the maximum value to the minimum value of respective products ((∈ r ρ) LC , (∈ r ρ) AF , and/or (∈ r ρ) PAS ) of a specific dielectric constant ∈ r and a specific resistivity ρ of the liquid crystal layer, the orienting film, and/or the insulating film is equal to or greater than 1 and equal to or less than 100. [0031] As a seventh feature of this invention, a liquid crystal display device of an in-plane switching system provided, wherein [0032] respective products ((∈ r ρ) LC , (∈ r ρ) AF , and/or (∈ r ρ) PAS ) of a specific dielectric constant ∈ r and a specific resistivity ρ of the liquid crystal layer, the orienting film, and/or the insulating film have a relationship expressed by the following equations (1) to (3). 0.1≦(∈ r ρ) LC /(∈ r ρ) AF ≦10  (1) 0.1≦(∈ r ρ) LC /(∈ r ρ) PAS ≦10  (2) 0.1≦(∈ r ρ) AF /(∈ r ρ) PAS ≦10  (3) [0033] As an eighth feature of this invention, a liquid crystal display device of an in-plane switching system is provided, wherein [0034] the sum of the film thickness of the orienting film and the insulating film on the substrate 1 is in a range 0.5-3 μm. [0035] As a ninth feature of this invention, a liquid crystal display device according to any of the first to eighth features is provided wherein the device is provided with [0036] an input means for information; [0037] a means for calculating or processing the information; [0038] a device for outputting the calculated or processed information; [0039] a memory device; and [0040] an internal power source. [0041] In the liquid crystal display device of the present invention, the thickness of the insulating film is preferably in a range of 0.4-2 μm. [0042] Further, in the liquid crystal display device of the present invention, the orienting film is preferably made of an organic material, and the insulating film is preferably made of an inorganic material. Furthermore, the orienting film is preferably made of an organic material, and the insulating film preferably has a double layer structure made of an inorganic material and an organic material. [0043] Further, in the liquid crystal display device of the present invention, the orienting film is preferably made of an organic material and the insulating film is preferably made of an inorganic material, and the orienting film made of an organic material is preferably thicker than the insulating material made of an inorganic material. [0044] Further, both of the orienting film and the insulating film are preferably composed of an organic material, and both of the orienting film and the insulating film are preferably composed of the same material. Furthermore, one side of a plane of the orienting film which abuts the liquid crystal is flat. [0045] In order to realize a color display having a high picture quality, a color filter is preferably provided on either one of the substrates, and an insulator is preferably inserted between the color filter and the liquid crystal layer. Further, a film having a function to flatten steps on the color filter is preferably composed of an organic material, and a film composed of an inorganic material is preferably formed on the film composed of organic material. Furthermore, the orienting film is preferably formed on the substrate having a color filter by the intermediary of a layer composed of inorganic material. BRIEF DESCRIPTION OF THE DRAWINGS [0046] FIGS. 1 ( a )- 1 ( b ) are schematic diagrams for explaining the operation of the liquid crystal in a liquid crystal display device supplied with in-plane switching to the substrate according to the present invention; [0047] [0047]FIG. 2 is a schematic diagram indicating angles formed by the orienting direction of a molecular longitudinal axis on a boundary plane to an electrical field direction, and by the transmitting axis of a polarizer to the electrical field direction in the liquid crystal display device supplied with a horizontal electric field to the substrate according to the present invention; [0048] FIGS. 3 ( a ) to 3 ( c ) are a plan view and side and front cross sections, respectively, of a picture element unit; [0049] FIGS. 4 ( a ) to 4 ( c ) are a plan view and side and front cross sections, respectively, of a picture element unit; [0050] FIGS. 5 ( a ) to 5 ( c ) are a plan view and side and front cross sections, respectively, of a picture element unit; [0051] FIGS. 6 ( a ) to 6 ( c ) are a plan view and side and front cross sections, respectively, of a picture element unit; [0052] [0052]FIG. 7 is a schematic diagram indicating a typical example of system composition in the liquid crystal display device according to the present invention; [0053] FIGS. 8 ( a ) to 8 ( c ) are schematic illustrations indicating refraction law of electric force line, and variation of horizontal electric field strength in a liquid crystal layer depending on relative dielectric constant and thickness of the layer in respective layers; [0054] [0054]FIG. 9( a ) is a graph indicating relationships among the maximum value of products ∈ρ of respective specific resistivity ρ and specific dielectric constant ∈ and residual image characteristics of a liquid crystal, an insulating film, and an orienting film; [0055] [0055]FIG. 9( b ) is a graph indicating relationships among the ratio of the maximum value and the minimum value of products ∈ρ of respective specific resistivity ρ and specific dielectric constant ∈ and residual image characteristics of a liquid crystal, an insulating film, and an orienting film; [0056] [0056]FIG. 10( a ) is a graph indicating a relationship between a sum of film thickness of the insulating film and the orienting film, and results of residual image evaluation; [0057] [0057]FIG. 10( b ) is a graph indicating a relationship between a sum of film thickness of the insulating film and the orienting film, and transmission factor; and [0058] FIGS. 11 ( a ) and 11 ( b ) are model graphs indicating relationships between a charging process and a discharging process of electric charge, and residual image characteristics. DESCRIPTION OF THE INVENTION [0059] Hereinafter, a principle of operation of an in-plane switching system, wherein an electric field is supplied in a direction parallel to a substrate, is explained, and subsequently, the operation of the present invention is explained. [0060] First of all, an angle φ P , which is the angle formed between the polarized light transmitting axis 11 of a polarizer and the direction of the electric field 9 , and an angle φ LC , which is an angle formed between the direction of the liquid crystal major axis(optical axis) 10 in the vicinity of the liquid crystal boundary and the direction of the electric field 9 , are shown in FIG. 2. The polarizer and the liquid crystal boundary exist in pairs at each of an upper side and a lower side, respectively. [0061] Therefore, the angles are expressed as φ P1 , φ P2 , φ LC1 , and φ LC2 , if necessary. FIG. 2 corresponds to a front view of FIGS. 1 ( a ) to 1 ( d ), which is explained later. [0062] FIGS. 1 ( a ) and 1 ( b ) are side cross sections indicating liquid crystal operation in a liquid crystal panel of the present invention, and FIGS. 1 ( c ) and 1 ( d ) are front views of the respective FIGS. 1 ( a ) to 1 ( d ). In FIG. 1, the active elements are omitted. Further, in accordance with the present invention, stripe-shaped electrodes are provided so as to form a plurality of picture elements, but, only one picture element is shown in FIGS. 1 ( a ) to 1 ( d ). A side cross section of a cell under no voltage is shown in FIG. 1( a ), and the front view of FIG. 1( a ) is shown in FIG. 1( c ). Linear signal electrodes 3 , 4 , and a common electrode 5 are formed at the inside of one 10 pair of transparent substrates 1 , an insulating film 7 is provided on the substrates and the electrodes, and an orienting film 8 is supplied and processed for orientation on the insulating film 7 . A liquid crystal composition is held between the substrates. A bar-shaped liquid crystal molecule 12 is oriented so as to have a small angle to a longitudinal direction of the stripe-shaped electrodes, that is 45 degrees <φ LC φ<135 degrees, or, −45 degrees <φ LC <−135 degrees, when no electric field is supplied. An example is explained hereinafter in which an orienting direction of the liquid crystal molecule at the upper and the lower boundaries is parallel, that is φ LC1 =φ LC2 . Further, dielectric anisotropy of the liquid crystal composition is assumed as positive. [0063] Next, when an electric field 9 is supplied, the liquid crystal molecule changes its orienting direction to the 25 direction of the electric field as shown in FIGS. 1 ( b ) and 1 ( d ). Therefore, optical transmission becomes changeable by applying an electric field when a polarizer 2 is arranged at a designated angle 11 . As explained above, in accordance with the present invention, a display giving contrast becomes possible without the transparent electrodes. The dielectric anisotropy of the liquid crystal composition is assumed as positive in the present description, but negative anisotropy is also usable. In a case of the negative anisotropy, the liquid crystal molecule is oriented at a first oriented condition so as to have a small angle, φ LC , to a vertical direction to the longitudinal direction of the stripe-shaped electrodes, that is −45 degrees <φ LC <45 degrees, or, 135 degrees <φ LC <225 degrees. [0064] In FIGS. 1 ( a ) to 1 ( d ), an example wherein a common electrode is in a different layer from the signal electrode and the picture element electrode is shown, but the common electrode can be in the same layer with the signal electrode and the picture element electrode. A typical example of a picture element structure in which the common electrode is in the same layer with the picture element electrode is shown in FIGS. 3 ( a ) to 3 ( c ), and typical examples of a picture element structure in which the common electrodes are in different layers from the picture element electrodes are shown in FIGS. 4 ( a )- 4 ( c ) and 5 ( a )- 5 ( c ). Further, even if the common electrode is not provided, the scanning electrode can be given the same function as the common electrode. However, the gist of the present invention explained hereinafter is in insulating materials for composing the liquid crystal element, and is applicable to various electrode structures and thin film transistor structures. [0065] As explained above, a liquid crystal display device having a high picture quality and in which residual images are substantially eliminated can be obtained by making a necessary time for recovering the brightness of the display device, after displaying an identical drawing pattern for 30 minutes, less than five minutes. The residual images are induced when polarization is generated in the liquid crystal layer, the orienting film, or the insulating film for any reason. Therefore, the residual images can be reduced concretely, as explained in the second feature, by making respective products ((∈ r ρ) LC , (∈ r ρ) AF , and/or (∈ r ρ) PAS ) of a specific dielectric constant ∈ r and a specific resistivity ρ of the liquid crystal layer, the orienting film, and/or the insulating film, respectively, equal to or less than 8×10 15 Ω·cm, because any accumulated electric charge can be relaxed quickly. A model graph indicating the principle of residual image reduction in the above case is shown in FIG. 11( a ). That means, the residual image can be reduced because the relaxing speed is fast even if an electric charge has accumulated, and the electric charge is discharged quickly. Further, the residual image can be reduced by decreasing the accumulated electric charge, as shown in FIG. 11( b ), even if the relaxing speed is slow. Therefore, the residual image problem can be eliminated by making the surface resistance of the orienting film and/or the insulating film equal to or less than 2.5×10 18 Ω/□ in order to decrease any accumulating electric charge, as stated in the third feature. Furthermore, as stated in the fourth, sixth, and seventh features, the residual image can be reduced further by substantially equalizing products of specific dielectric constant ∈ r and specific resistivity ρ of the liquid crystal layer, the orienting film, and the insulating layer. As described previously, the residual image is induced when polarization is generated in the liquid crystal layer, the orienting film, or the insulating film for any reason. And, the polarization in the respective layer and films interfere with each other, so that the polarization generated in the orienting film generates a secondary polarization in the liquid crystal layer. [0066] For instance, if any polarization remains in the orienting film in a relaxation process of polarization of the liquid crystal layer, the polarization in the orienting film affects the ability of the liquid crystal layer to prevent the relaxation of the polarization in the liquid crystal layer. Accordingly, in order to promote the relaxation generated in the respective layer or films without interference, respective relaxation times must be equal. The inventors of the present invention found that the above described principle can be established significantly using a method wherein the electric field is supplied in a direction parallel to the substrate, that is, when using the in-plane switching method. In the in-plane switching method, electric equivalent circuits corresponding to the respective liquid crystal layer, the insulating film, and the orienting film are connected in parallel. [0067] Therefore, for instance, when a product (∈ r ρ) of specific dielectric constant ∈ r and specific resistivity ρ for the orienting film or the insulating film is larger than that for the liquid crystal layer, a residual voltage in the orienting film or the insulating film is supplied to the liquid crystal layer as an extra voltage, and consequently, a residual image is induced. Furthermore, in consideration that the resistance R can be expressed by the equation, R=ρd/S (where ρ: specific resistivity, d: length in the direction of the electric field, S: vertical cross section area to the electric field), the in-plane switching system has a significantly larger resistance in the element structure than the method wherein the electric field is supplied to the substrate perpendicularly. That means that the residual direct current component in the in-plane switching system is remarkably large. In the above described case, a combination of the fourth features, the sixth feature or the seventh feature with the second feature as the fifth feature makes it possible to relax the accumulated charge in a short time without causing initial interference in the liquid crystal layer, the orienting film, and/or the insulating film in the course of relaxing the accumulated charge. [0068] Therefore, the combination is an effective means for reducing the residual image. [0069] The above principle can be established in the in-plane switching system regardless of whether a simple matrix driving method or an active matrix driving method is employed. [0070] Further, the resistance components of the orienting film and the insulating film at each of the picture elements can be decreased by making the sum of the thicknesses of a film having a function to orient liquid crystal (orienting film) and a film having functions to insulate electrically and to protect the electrode group(insulating film) fall within a range of from 0.5 μm to 3 μm, desirably from 0.7 μm to 2.8 μm. Actually, the thickness of the insulating film is desirably selected in a range from 0.4 μm to 2 μm as described above in order to deduce additional effects of the steps on the substrate whereon the electrode group is mounted. As explained previously, in a method wherein the direction of the electric field supplied to the liquid crystal is approximately parallel to the substrate plane, electric equivalent circuits corresponding to the respective liquid crystal layer, the insulating film, and the orienting film are connected in parallel. [0071] Accordingly, a voltage which has remained in the orienting film and the insulating film is supplied directly to the liquid crystal layer. Considering the fact that residual images are generated by supplying a residual voltage in the orienting film and the insulating film to the liquid crystal layer, the residual voltage in the orienting film and the insulating film can be reduced, and an excessive voltage supplied to the liquid crystal layer can be eliminated by decreasing resistance components equivalent to the orienting film and the insulating film at each of the picture elements. In order to decrease the resistance components in the orienting film and the insulating film, the film thicknesses of the orienting film and the insulating film must be increased for purposes of enlarging the cross sectional area perpendicular to the direction of the electric field. [0072] The insulating film can be formed with a reliable inorganic material, and the orienting film can be formed with an organic material. Further, the insulating film can be formed in a double layer structure which is composed of an inorganic material layer and a relatively easily shapable organic material layer. [0073] [0073]FIG. 8( a ) is a schematic illustration indicating variation in the line of electric force in a liquid crystal layer depending on the magnitude of the dielectric constant in each of the layers. The smaller the dielectric constants in the orienting film and the insulating film are as compared to the dielectric constant of the liquid crystal layer, the more ideal will be the in-plane switching. [0074] Accordingly, an electric field component horizontal to the substrate plane can be utilized effectively by replacing a layer of inorganic material with a layer of organic material having as low a dielectric constant as possible. Further, the above effect can be realized by making the insulating film with an organic material. Furthermore, fabricating the insulating film and the orienting film with the same material realizes a high efficiency in a manufacturing process. In order to improve picture quality in a liquid crystal display device, flattening the surface plane of the orienting film abutting on the liquid crystal is important. By the flattening, steps at the surface plane can be eliminated, and light leakage can be suppressed by making effects of rubbing uniform all through the surface plane . [0075] In order to realize a color display using the in-plane switching system, it is necessary that only the insulating film be inserted between a color filter and the liquid crystal layer. In this regard, a conductive body existing in the interval between the color filter and the liquid crystal destroys a horizontal electric field. [0076] Generally, an organic material, such as an epoxy resin, is used as a flattening film for a color filter, and transparent electrodes are provided on the flattening film. However, since the transparent electrodes are not necessary in the in-plane switching system, as stated previously, the flattening film contacts directly with the orienting film. In this case, printability of the orienting film sometimes causes troubles. Therefore, a layer of inorganic material, such as silicon nitride, provided on an upper portion of the flattening film is effective in improving printability. The color filter is not necessarily provided on facing plane s of the substrates whereon the electrodes group existed; rather, preciseness of alignment can be improved by providing the color filter on the substrate plane whereon the active elements and electrodes group are mounted. Detailed Description of the Embodiments [0077] Embodiment 1 [0078] FIGS. 3 ( a ) to 3 ( c ) indicate a structure of an electrode for a picture element unit forming a first embodiment of the present invention. A scanning signal electrode 13 made of aluminum was formed on a polished glass substrate, and the surface of the scanning signal electrode was coated with alumina film, i.e. anodic oxide film of aluminum. A gate silicon nitride (gate SiN) film 6 and an amorphous silicon (a-Si) film 14 were formed so as to cover the scanning signal electrode, and a n-type a-Si film, a picture element electrode 4 and an image signal electrode 3 were formed on the a-Si film. Further, a common electrode 5 was provided in the same layer as the picture element electrode 4 and the image signal electrode 3 . The picture element electrode 4 and the signal electrode 3 had a structure, as shown in FIG. 3, parallel to the strip-shaped common electrode 5 and crossing across the scanning signal electrode 13 , and a thin film transistor 15 and a group of metallic electrodes were formed at one end of the substrate. In accordance with the above structure, an electric field 9 could be supplied between the picture element electrode 3 and the common electrode 5 at one end of the substrate in a direction approximately parallel to substrate plane . All of the electrodes on the substrate were made of aluminum. But any metallic material having a low electric resistance, such as chromium, copper, and others, can be used. The number of the picture elements was 40(×3)×30 (i.e. n=120, m=30), and the pitches of the picture elements were 80 μm in width (i.e. between common electrodes) and 240 μm in length (i.e. between gate electrodes). The width of the common electrode 5 was made 12 μm, which was narrower than the gap between adjacent common electrodes, in order to secure a large opening fraction. Three strip-shaped color filters respectively for red (R), green (G), and blue (B) were provided on a substrate facing the substrate having a thin film transistor. On the color filters, transparent resin was laminated in order to flatten the surface of the color filter. As material for the above transparent resin, an epoxy resin was used. Further, an orienting controlling film made of polyamide group resin was applied on the transparent resin. A driving LSI was connected to the panel, as shown in FIG. 7, a vertical scanning circuit 20 and an image signal driving circuit 21 were connected to the TFT substrate, and the active matrix was driven by a scanning signal voltage, an image signal voltage and a timing signal supplied from a power source circuit and a controller 22 . [0079] The directions of the upper and the lower boundary planes were approximately parallel mutually, and formed an angle of 15 degrees (φ LC1 =φ LC2 =15°) to the direction of the supplied electric field (FIG. 2). A gap d was kept by holding dispersed spherical polymer beads between the substrates at 6.5 μm interval under a liquid crystal filled condition. The panel was held between two polarizers (made by Nitto Denko Co., G1220DU), the polarizing light transmitting axis of one polarizer was selected as approximately parallel to a rubbing direction, i.e. φ P1 =15°, and the axis of the other polarizer was selected as perpendicular to the rubbing direction, i.e. φ P2 =−75°. Accordingly, normal closed characteristics were obtained. [0080] Between the substrates, a liquid crystal ZLI-2806 (made by Merck Co.) containing trans, trans-4,4′dipentyl-trans-1,1′dicyclohexane-4-carbonitrile for a main component having a negative dielectric anisotropy Δ∈ was held. The liquid crystal had a specific resistivity of 5.1×10 11 Ωcm and an average specific dielectric constant of 6.5. While, silicon nitride(SiN) was used as for an insulating film, and its specific resistivity was 2.5×10 13 Ωcm and specific dielectric constant was 8. As for an orienting film, a polyamide orienting film made from 2,2-bis[4-(p-aminophenoxy) phenylpropane and pyromellitic acid dianhydride was used, and its specific resistivity was 7.5×10 13 Ωcm and its average specific dielectric constant was 2.9. Accordingly, respective products (∈ r ρ) of specific resistivity ρ and specific dielectric constant ∈ r of the liquid crystal layer, the insulating film, and the orienting film, respectively, was less than 8×10 15 Ωcm and the ratio of the maximum value and the minimum value of the three bodies, ((∈ r ρ) max /(∈ r ρ) min ), was less than 100. [0081] The residual image was evaluated by visual observation with five rankings. An identical figure pattern was displayed for thirty minutes, and samples were classified by necessary time for recovering brightness after switching off the display. Samples were evaluated and classified as follows. [0082] Sample of rank 5 was the one which necessitated more than five minutes for recovering brightness, rank 4 was from one minute to less than five minutes, rank 3 was from 30 seconds to less than one minute, rank 2 was less than 30 seconds but generation of any residual image was felt, and rank 1 was no residual image at all. [0083] The sample in the embodiment 1 was evaluated as rank 1 because no residual image was observed at all. [0084] The present invention relates to use of a specific dielectric constant and specific resistivity for the insulating material composing the element, and accordingly, the present invention is applicable to various structures of electrodes and TFTs. [0085] Embodiment 2 [0086] FIGS. 4 ( a ) to 4 ( c ) indicate a structure of an electrode for a picture element unit forming a second embodiment of the present invention. A scanning signal electrode 13 and a common electrode 5 made of aluminum was formed on a polished glass substrate, and the surface of the scanning signal electrode was coated with an alumina film, i.e. anodic oxide film of aluminum. A gate silicon nitride (gate SiN) film 6 was formed so as to cover the scanning signal electrode 13 and the common electrode 5 . Subsequently, an amorphous silicon (a-Si) film 14 and an n-type a-Si film on the a-Si film were formed. Further, a picture element electrode 4 and a signal electrode 3 were formed. Accordingly, the picture element electrode 4 and the common electrode 5 were in different layers mutually. The picture element electrode had an H-shaped structure, as shown in FIG. 4, and the common electrode 5 had a cruciform structure, a part of each of the electrodes had a structure functioning as capacitance elements. In accordance with the above structure, an electric field could be supplied between the picture element electrode 4 and the common electrode 5 at one end of the substrate in a direction approximately parallel to the substrate plane. All of the electrodes on the substrate were made of aluminum; however, any metallic material having low electric resistance, such as chromium, copper, and others, can be used. The number of picture elements was 320×160, and the pitches of the picture elements were 100 μm in width (i.e. between signal electrodes) and 300 μm in length (i.e. between scanning electrodes). Driving transistors were connected to the panel as shown in FIG. 7, a vertical scanning circuit 20 and an image signal driving circuit 21 were connected to the TFT substrate, and the active matrix was driven by a scanning signal voltage, an image signal voltage and a timing signal supplied from a power source circuit and a controller 22 . [0087] The directions of the upper and the lower boundary planes were approximately parallel mutually, and formed an angle of 105 degrees (φ LC1 =φ LC2 =105°) to a direction of the supplied electric field (FIG. 2). A gap d was kept by holding dispersed spherical polymer beads between the substrates at a 4.2 μm interval under a liquid crystal filled condition. The panel was held between two polarizers (made by Nitto Denko Co., G1220DU), the polarizing light transmitting axis of one polarizer was selected as approximately parallel to a rubbing direction, i.e. φ P1 =105°, and the axis of the other polarizer was selected as perpendicular to the rubbing direction, i.e. φ P2 =15°. Accordingly, normal closed characteristics were obtained. [0088] Between the substrates there was disposed a liquid crystal of which the main component was a compound containing three fluoro groups at terminals having a positive dielectric anisotropy Δ∈. The liquid crystal had a specific resistivity of 5.0×10 14 Ωcm and an average specific dielectric constant of 6.1. Silicon nitride (SiN) was used as for an insulating film, and its specific resistivity was 3.0×10 14 Ωcm and specific dielectric constant was 8. As for an orienting film, a polyamide orienting film made from 2,2-bis[4-(p-aminophenoxy) phenylpropane and pyromellitic acid dianhydride was used, and its specific resistivity was 1.0×10 14 Ωcm and its average specific dielectric constant was 2.9. [0089] Accordingly, respective products (∈ r ρ) of specific resistivity ρ and specific dielectric constant ∈ r of the liquid crystal layer, the insulating film, and the orienting film, respectively, were less than 8×10 15 Ωcm and the ratio of the maximum value and the minimum value of the three bodies, ((∈ r ρ) max /(∈ r ρ) min ), was less than 100. [0090] The active matrix type liquid crystal display device as obtained above was evaluated as rank 1 in the evaluation of residual image, and no residual image was observed at all. [0091] Embodiment 3 [0092] The composition of this embodiment is the same as embodiment 2 except for the following matters. [0093] The insulating film had a double layer structure composed of an inorganic silicon nitride (SiN) layer and an organic epoxy resin layer, and a compound, RN-718 (made by Nissan Chemical Co.), was applied on the insulating film having two layers as an orienting film. The insulating film had a specific resistivity of 9.1×10 13 Ωcm and a specific dielectric constant of 3.1. And, the liquid crystal had a specific resistivity of 1.0×10 12 Ωcm and a specific dielectric constant of 6.1. [0094] Accordingly, respective products (∈ r ρ) of specific resistivity ρ and specific dielectric constant ∈ r of the liquid crystal layer, the insulating film, and the orienting film, respectively, were less than 8×10 15 Ωcm, and the ratio of the maximum value and the minimum value of the three bodies, ((∈ r ρ) max /(∈ r ρ) min ), was less than 100. [0095] The active matrix type liquid crystal display device as obtained above was evaluated as rank 1 in the evaluation of residual image, and no residual image was observed at all. [0096] Embodiment 4 [0097] FIGS. 5 ( a ) to 5 ( c ) indicate a structure of the electrode for a picture element unit forming the fourth embodiment of the present invention. A thin film transistor element 15 comprises a picture element electrode 4 , a signal electrode 3 , a scanning electrode 13 and amorphous silicon member 14 . A common electrode 5 was in the same layer as the scanning electrode 13 and was formed by making a pattern from the same metallic layer. Further, the picture element electrode 4 and the signal electrode 3 were also formed by making a pattern from the same metallic layer. A capacitative element was formed of a structure holding a gate silicon nitride (gate SiN) film 6 with the picture element electrode 4 and the common electrode 5 in a region connecting two common electrodes 5 . The picture element electrode 4 is arranged between two common electrodes 5 , as shown in the front cross section taken along line A-A′ (FIG. 5 b ). Pitches of the picture elements were 69 μm in width (i.e. between signal wiring electrodes) and 207 μm in length (i.e. between scanning wiring electrodes). The width of the respective electrodes was 10 μm. While, in order to secure a large opening fraction, the widths of the picture element electrode independently formed for a picture element unit and a portion extended to a longitudinal direction of the signal wiring electrode of the common electrode were made narrow, such as 5 μm and 8 μm, respectively. In order to realize as large an opening fraction as possible, the common electrode and the signal electrode were somewhat overlapped (1 μm) via the insulating film. Accordingly, a black matrix structure 16 , wherein shading was provided only in a direction along the scanning wiring electrode, was formed. Consequently, a gap between the common electrode 5 and the picture element electrode 4 became 20 μm, and the length of the opening in a longitudinal direction became 157 μm, and a large opening fraction, such as 44.0%, was obtained. The number of picture elements was 320×160 with 320 signal wiring electrodes and 160 wiring electrodes. Driving transistors were connected to the panel as shown in FIG. 7, a vertical scanning circuit 20 and an image signal driving circuit 21 were connected to the TFT substrate, and the active matrix was driven by a scanning signal voltage, an image signal voltage and a timing signal supplied from a power source circuit and a controller 22 . [0098] The insulating film was composed of a single layer made of an organic epoxy resin, and a compound, RN-718 (made by Nissan Chemical Co.), was applied on the insulating film as an orienting film. In this case, the insulating film had a specific resistivity of 1.5×10 12 Ωcm and a specific dielectric constant of 3.0. The orienting film had a specific resistivity of 4.0×10 13 Ωcm and its specific dielectric constant was 3.1. The liquid crystal had a specific resistivity of 1.5×10 13 Ωcm and its specific dielectric constant was 6.1. [0099] Accordingly, respective products (∈ r ρ) of specific resistivity p and specific dielectric constant ∈ r of the liquid crystal layer, the insulating film, and the orienting film, respectively, was less than 8×10 15 Ωcm, and the ratio of the maximum value and the minimum value of the three bodies, ((∈ r ρ) max /(∈ r ρ) min ), was less than 100 . [0100] The active matrix type liquid crystal display device as obtained above was evaluated as rank 1 in the evaluation of residual image, and no residual image was observed at all [0101] Embodiment 5 [0102] The composition of this embodiment is the same as embodiment 4 except for the following matters. [0103] A color filter was formed in the insulating film. First, a silicon nitride (SiN) layer was formed, and subsequently, the color filter was provided by printing. Further, epoxy resin was applied in order to flatten the surface. Then, a compound, RN-718 (made by Nissan Chemical Co.), was applied on the insulating film as an orienting film. The insulating film of the present embodiment had a specific resistivity of 4.4×10 11 Ωcm and a specific dielectric constant of 3.9. The orienting film had a specific resistivity of 4.9×10 13 Ωcm and a specific dielectric constant of 3.1. And, the liquid crystal had a specific resistivity of 1.6×10 13 Ωcm and a specific dielectric constant of 6.1. [0104] Accordingly, respective products (∈ r ρ) of specific resistivity ρ and specific dielectric constant ∈ r of the liquid crystal layer, the insulating film, and the orienting film, respectively, were less than 8×10 15 Ωcm and the ratio of the maximum value and the minimum value of the three bodies, ((∈ r ρ) max / (∈ r ρ) min ), was less than 100. [0105] The active matrix type liquid crystal display device as obtained above was evaluated as rank 1 in the evaluation of residual image, and no residual image was observed at all. [0106] Embodiment 6 [0107] The composition of this embodiment is the same as embodiment 5 except for the following matters. [0108] In order to increase the flatness of the orienting film plane abutting on the liquid crystal, the thickness of the orienting film was set five times, 5000 Å, that of the thickness (1000 Å) used in the above embodiment 5. Therefore, the flatness of the plane was increased, steps on the plane were decreased, and lapping treatment was performed uniformly. Consequently, light leakage at the step portion was eliminated. [0109] The active matrix type liquid crystal display device as obtained above was evaluated as rank 1 in the evaluation of residual image, no residual image was observed at all, and contrast was improved over that of the embodiment 5. [0110] Embodiment 7 [0111] The composition of this embodiment is the same as embodiment 6 except for the following matters. [0112] The printability of the polyamide orienting film on the epoxy resin layer is not necessarily preferable. Therefore, a silicon nitride (SiN) film, an inorganic material film, was formed on the epoxy resin, which was effective to flatten the color filter and as an insulating film. In accordance with the above treatment, the printability of the orienting film was improved. [0113] The active matrix type liquid crystal display device as obtained above was evaluated as rank 1 in the evaluation of residual image, since no residual image was observed at all, contrast was improved over that of the embodiment 5, printability of the orienting film was improved, and the production yield was increased. [0114] Embodiment 8 [0115] The composition of this embodiment is the same as embodiment 4 except for the following matters. [0116] A color filter was formed in the insulating film. First, a silicon nitride (SiN) layer was formed, and subsequently, the color filter was provided by printing. Further, an epoxy resin was applied in order to flatten the surface. Then, a compound, RN-718 (made by Nissan Chemical Co.), was applied on the insulating film as an orienting film. The insulating film of the present embodiment had a specific resistivity of 4.4×10 11 Ωcm and a specific dielectric constant of 3.9. The orienting film had a specific resistivity of 4.9×10 13 Ωcm and a specific dielectric constant of 3.1. And, the liquid crystal had a specific resistivity of 1.6×10 13 Ωcm and a specific dielectric constant of 6.1. [0117] Accordingly, respective products (∈ r ρ) of specific resistivity ρ and specific dielectric constant ∈ r of the liquid crystal layer, the insulating film, and the orienting film, respectively, were less than 8×10 15 Ωcm and the ratio of the maximum value and the minimum value of the three bodies, ((∈ r ρ) max /(∈ r ρ) min ), was less than 100. [0118] The active matrix type liquid crystal display device as obtained above was evaluated as rank 1 in the evaluation of residual image, and no residual image was observed at all. [0119] Embodiment 9 [0120] FIGS. 6 ( a ) to 6 ( c ) indicate a structure of an electrode for a picture element unit forming the ninth embodiment of the present invention. In the present embodiment, thin film transistors were not provided for the picture element units. A scanning signal electrode 13 and a signal electrode 3 were in different layers mutually. Each of the electrodes were connected respectively to a scanning circuit driver and an image signal circuit driver, and the matrix was driven in a simple time-shared manner. [0121] The directions of the upper and the lower boundary planes were approximately parallel mutually, and formed an angle of 105 degrees (φ LC1 =φ LC2 =105°) to the direction of the supplied electric field (FIG. 2). A gap d was kept by holding dispersed spherical polymer beads between the substrates at a 4.2 μm interval under a liquid crystal filled condition. The panel was held between two polarizers (made by Nitto Denko Co., G1220DU), the polarizing light transmitting axis of one polarizer was selected as approximately parallel to a rubbing direction, i.e. φ P1 =105°, and the axis of the other polarizer was selected as perpendicular to the rubbing direction, i.e. φ P2 =15°. Accordingly, normal closed characteristics were obtained. [0122] In this embodiment, a liquid crystal, of which the main component was a trifluoro compound containing three fluoro groups at the terminals, having a specific resistivity of 1.0×10 14 Ωcm and an average specific dielectric constant of 6.1, was used. While, silicon nitride (SiN) was used for an insulating film, and its specific resistivity was 1.0×10 12 Ωcm and specific dielectric constant was 8. As for an orienting film, a polyamide orienting film made from 2,2-bis [4-(p-aminophenoxy) phenylpropane and pyromellitic acid dianhydride was used, and its specific resistivity was 2.2×10 13 Ωcm and its average specific dielectric constant was 2.9. [0123] Accordingly, respective products (∈ r ρ) of specific resistivity ρ and specific dielectric constant ∈ r of the liquid crystal layer, the insulating film, and the orienting film were less than 8×10 15 Ωcm and the ratio of the maximum value and the minimum value of the three bodies, ((∈ r ρ) max /(∈ r ρ) min ), was less than 100. [0124] The active matrix type liquid crystal display device as obtained above was evaluated as rank 1 in the evaluation of residual image, and no residual image was observed at all. [0125] Embodiment 10 [0126] The composition of this embodiment is the same as embodiment 1 except for the following matters. [0127] The liquid crystal had a specific resistivity of 2.0×10 11 Ωcm and an average specific dielectric constant of 6.5. Silicon nitride (SiN) was used for the insulating film, and its specific resistivity was 3.0×10 13 Ωcm and its specific dielectric constant was 8. As for the orienting film, a polyamide orienting film made from 2,2-bis [4-(p-aminophenoxy) phenylpropane and pyromellitic acid dianhydride was used, and its specific resistivity was 1.0×10 13 Ωcm and its average specific dielectric constant was 2.9. [0128] Accordingly, respective products (∈ r ρ) of specific resistivity ρ and specific dielectric constant ∈ r of the liquid crystal layer, the insulating film, and the orienting film were less than 8×10 15 Ωcm. [0129] The active matrix type liquid crystal display evaluation of residual image, and the residual image time was within five minutes. [0130] Embodiment 11 [0131] The composition of this embodiment is the same as embodiment 2 except for the following matters. [0132] The liquid crystal had a specific resistivity of 2.0×10 14 Ωcm and an average specific dielectric constant of 6.1. Silicon dioxide (SiO 2 ) was used for the insulating film, and its specific resistivity was 1.0×10 13 Ωcm and its specific dielectric constant was 8. As for the orienting film, a polyamide orienting film made from 2,2-bis [4-(p-aminophenoxy) phenylpropane and pyromellitic acid dianhydride was used, and its specific resistivity was 2.0×10 12 Ωcm and its average specific dielectric constant was 2.9. [0133] Accordingly, respective products (∈ r ρ) of specific resistivity ρ and specific dielectric constant ∈ r of the liquid crystal layer, the insulating film, and the orienting film were less than 8×10 15 Ωcm. The active matrix type liquid crystal display device as obtained above was evaluated as rank 4 in the evaluation of residual image, and the residual image time was within five minutes. [0134] Embodiment 12 [0135] The composition of this embodiment is the same as embodiment 2 except for the following matters. [0136] The liquid crystal had a specific resistivity of 2.0×10 13 Ωcm and an average specific dielectric constant of 6.1. Silicon nitride (SiN) was used as for the insulating film, and its specific resistivity was 1.0×10 15 Ωcm and its specific dielectric constant was 8. The orienting film was formed with a compound RN-718 (made by Nissan Chemical Co.), and its specific resistivity was 3.2×10 12 Ωcm and its average specific dielectric constant was 3.1. [0137] Accordingly, respective products (∈ r ρ) of specific resistivity ρ specific dielectric constant ∈ r of the liquid crystal layer, the insulating film, and the orienting film were less than 8×10 15 Ωcm. The active matrix type liquid crystal display device as obtained above was evaluated as rank 4 in the evaluation of residual image, and the residual image time was within five minutes. [0138] Embodiment 13 [0139] FIGS. 5 ( a ) to 5 ( c ) indicate a structure of an electrode for a picture element unit forming the thirteenth embodiment of the present invention. A thin film transistor 15 was composed of a picture element electrode 4 , a signal electrode 3 , a scanning electrode 13 , and an amorphous silicon member 14 . A common electrode 5 was in a same layer with the scanning electrode 13 , and a pattern was made of the same metal layer. Further, the picture element electrode and the signal electrode were formed by a pattern made of the same metal. A capacitance element is formed as a structure wherein a gate silicon nitride (gate SiN) film 6 is inserted between the picture element electrode 4 and the common electrode 5 in a region where the two common electrodes 5 are connected. The picture element electrode 4 is arranged between the two common electrodes 5 as shown as a plan cross section taken along line A-A′ in FIG. 5( b ). The picture element has pitches of 69 μm in the horizontal direction (i.e. between signal wiring electrodes) and 207 μm in the vertical direction (i.e. between scanning wiring electrodes). The width of all of the electrodes is 10 μm. [0140] While, in order to improve an opening fraction, the signal wiring electrode of the picture element electrode 4 , formed independently for a picture element unit, and the common electrode 5 , in a direction along a longitudinal direction of the signal wiring electrode, had a somewhat narrower width at an extended portion, and were, respectively, 5 μm and 8 μm. In order to realize a larger opening fraction as possible, the common electrode 5 and the signal electrode 3 were overlapped somewhat (1 μm) through intermediary of the insulating film. [0141] Accordingly, a black matrix structure 16 wherein light was shielded only in a direction along the scanning wiring electrode was adopted. In accordance with the above described features, a gap between the common electrode became 20 μm, the longitudinal length of the opening became 157 μm, and consequently, a large opening fraction, such as 44.0%, was obtained. [0142] The number of picture elements was 320×160 with 320 signal wiring electrodes and 160 wiring electrodes. [0143] A driving LSI was connected to the panel, as shown in FIG. 7, a vertical scanning circuit 20 and an image signal driving circuit 21 were connected to the TFT substrate, and the active matrix was driven by a scanning signal voltage, an image signal voltage and a timing signal supplied from a power source circuit and a controller 22 . [0144] In this embodiment, an insulating film 0.4 μm thick was formed with silicon nitride (SiN). As for the orienting film, a polyamide orienting film made from 4, 4′-diaminodiphenylether and pyromellitic acid dianhydride was used. The thickness of the orienting film was 0.1 μm, and accordingly, the total thickness of the insulating film and the orienting film was 0.5 μm. [0145] Between the substrates, a nematic liquid crystal composition having a positive dielectric anisotropy Δ∈ of 4.5 and birefringence Δn of 0.072 (589 nm, 20° C.) was inserted. [0146] The direction of the upper and the lower boundary plane s were approximately parallel mutually, and formed an angle of 95 degrees (φ LC1 =φ LC2 =95°) to the direction of the supplied electric field. A gap d was kept by holding dispersed spherical polymer beads between the substrates at a 4.5 μm interval under a liquid crystal filled condition. Therefore, Δn·d is 0.324 μm. The panel was held between two polarizers (made by Nitto Denko Co., G1220DU), the polarizing light transmitting axis of one polarizer was selected as approximately parallel to the rubbing direction, i.e. φ P1 − 95°, and the axis of the other polarizer was selected as perpendicular to the rubbing direction, i.e. φ P2 −5°. Accordingly, normal closed characteristics were obtained. [0147] The residual image of the active matrix liquid crystal display device obtained in the above explained manner was evaluated as rank 1 , as shown in FIG. 10( a ), and no residual image was observed at all. Further, the transparency of the insulating film and the orienting film maintained a more than 90% transmission factor, as shown in FIG. 10( b ). The transparency was evaluated by the transmission factor at 400nm. [0148] Embodiment 14 [0149] The composition of this embodiment is the same as embodiment 13 except for the following matters. [0150] In this embodiment, silicon dioxide (SiO 2 ) was used for the insulating film, and its thickness was 1.2 μm. As for the orienting film, a polyamide orienting film made from 4, 4′-diaminodiphenylether and pyromellitic acid dianhydride was used. The thickness of the orienting film was 0.3 μm, and accordingly, the total thickness of the insulating film and the orienting film was 1.5 μm. [0151] The residual image of the active matrix liquid crystal display device obtained in the above manner was evaluated as rank 1 , as shown in FIG. 10( a ), and no residual image was observed at all. Further, the transparency of the insulating film and the orienting film maintained a more than 90% transmission factor, as shown in FIG. 10( b ). [0152] Embodiment 15 [0153] The composition of this embodiment is the same as embodiment 13 except for the following matters. [0154] In this embodiment, the orienting film had a double layer structure comprising inorganic silicon nitride (SiN) and organic epoxy resin. The thickness of the silicon nitride layer and the epoxy resin layer was 1.0 μm and 0.6 μm, respectively. Further, as for the orienting film, an orienting film composition RN-718 (made by Nissan Chemical Co.) was used, and its thickness was 0.2 μm. Accordingly, the total thickness of the insulating film and the orienting film was 1.8 μm. [0155] The residual image of the active matrix liquid crystal display device obtained in the above manner was evaluated as rank 1 , as shown in FIG. 10( a ), and no residual image was observed at all. Further, the transparency of the insulating film and the orienting film maintained a more than 90% transmission factor, as shown in FIG. 10( b ). [0156] Embodiment 16 [0157] The composition of this embodiment is the same as embodiment 13 except for the following matters. [0158] In this embodiment, the orienting film had a double layer structure comprising inorganic silicon nitride (SiN) and an organic epoxy resin. The thickness of the silicon nitride layer and the epoxy resin layer was 0.3 μm and 1.5 μm, respectively. Further, as for the orienting film, an orienting film composition RN-718 (made by Nissan Chemical Co.) was used, and its thickness was 0.2 μm. Accordingly, the total thickness of the insulating film and the orienting film was 2.0 μm. [0159] The residual image of the active matrix liquid crystal display device obtained in the above manner was evaluated as rank 1 , as shown in FIG. 10( a ), and no residual image was observed at all. Further, transparency of the insulating film and the orienting film maintained a more than 90% transmission factor, as shown in FIG. 10( b ). [0160] Embodiment 17 [0161] The composition of this embodiment is the same as embodiment 13 except for the following matters. [0162] In this embodiment, silicon dioxide (SiO 2 ) was used for the insulating film, and its thickness was 0.2 μm. As for the orienting film, a polyamide orienting film made from 4, 4′-diaminodiphenylether and pyromellitic acid dianhydride was used. The thickness of the orienting film was 2.0 μm, and accordingly, the total thickness of the insulating film and the orienting film was 2.2 μm. [0163] The residual image of the active matrix liquid crystal display device obtained in the above manner was evaluated as rank 1 , as shown in FIG. 10( a ), and no residual image was observed at all. Further, the transparency of the insulating film and the orienting film maintained a more than 90% transmission factor, as shown in FIG. 10( b ). [0164] Embodiment 18 [0165] The composition of this embodiment is the same as embodiment 13 except for the following matters. [0166] In this embodiment, an epoxy resin was used as the insulating film, and its thickness was 1.8 μm. As for the orienting film, a polyamide orienting film made from 2,2-bis [4-(p-aminophenoxy) phenylpropane and pyromellitic acid dianhydride was used, and its thickness was 0.5 μm. Accordingly, the total thickness of the insulating film and the orienting film was 2.3 μm. [0167] The residual image of the active matrix liquid crystal display device obtained in the above manner was evaluated as rank 1 , as shown in FIG. 10( a ), and no residual image was observed at all. Further, the transparency of the insulating film and the orienting film maintained a more than 90% transmission factor, as in FIG. 10( b ). [0168] Embodiment 19 [0169] The composition of this embodiment is the same as embodiment 13 except for the following matters. [0170] In this embodiment, the insulating film and the orienting film were made of the same material. That means, a polyamide orienting film made from 2,2-bis [4-(p-aminophenoxy) phenylpropane and pyromellitic acid dianhydride, which has both the functions of an insulating film and an orienting film, as applied was 2.8 μm thick. [0171] The residual image of the active matrix liquid crystal display device obtained in the above manner was evaluated as rank 1 , as shown in FIG. 10( a ), and no residual image was observed at all. Further, transparency of the insulating film and the orienting film maintained a more than 90% transmission factor, as shown in FIG. 10( b ). [0172] Embodiment 20 [0173] The composition of this embodiment is the same as embodiment 13 except for the following matters. [0174] A color filter was formed in the insulating film. First, a silicon nitride (SiN) film was formed, and the color filter was provided on the silicon nitride film by printing. Further, an epoxy resin was applied in order to flatten the film surface. Subsequently, the orienting film was formed by applying an orienting film composition RN-718 (made by Nissan Chemical Co.). [0175] The thickness of the silicon nitride layer and the epoxy resin layer was 0.3 μm and 1.5 μm, respectively. Further, the orienting film composition as applied was 0.2 μm thick. [0176] The residual image of the active matrix liquid crystal display device obtained in the above manner was evaluated as rank 1 , as shown in FIG. 10( a ), and no residual image was observed at all. Further, the transparency of the insulating film and the orienting film maintained a more than 90% transmission factor, as shown in FIG. 10( b ). [0177] Embodiment 21 [0178] The composition of this embodiment is the same as embodiment 20 except for the following matters. [0179] In order to make the orienting film surface abutting to the liquid crystal more flat, the epoxy resin layer was made 0.3 μm thick and the orienting film composition Rn-718 as applied was 0.7 μm thick. Accordingly, the flatness of the surface was improved, and a lapping treatment was performed more uniformly because of decreased steps at the surface. As a result, light leakage was eliminated. [0180] The residual image of the active matrix liquid crystal display device obtained in the above manner was evaluated as rank 1 , as shown in FIG. 10( a ), and no residual image was observed at all. Further, the contrast was increased over that of the embodiment 17. [0181] Embodiment 22 [0182] The composition of this embodiment is the same as embodiment 20 except for the following matters. [0183] The printability of the polyamide orienting film on the epoxy resin layer is not necessarily preferable. Therefore, inorganic silicon nitride (SiN) film 0.3 μm thick was formed on an epoxy resin layer 1.5 μm thick, which was applied for flattening of the color filter and as an insulating film. Therefore, the printability of the orienting film was improved. At that time, the orienting film composition RN-718 as applied was 0.1 μm thick. [0184] The residual image of the active matrix liquid crystal display device obtained in the above manner was evaluated as rank 1 , as shown in FIG. 10( a ), since no residual image was observed at all, and the contrast was increased over that of the embodiment 17, and the production yield was increased by improvement of the printability of the orienting film. [0185] Embodiment 23 [0186] FIGS. 6 ( a ) to 6 ( c ) indicate a structure of an electrode for a picture element unit forming the twenty third embodiment of the present invention. In this embodiment, thin film transistors were not provided for the picture element units. A scanning signal electrode 13 and a signal electrode 3 were in different layers mutually. Each of the electrodes were connected respectively to a scanning circuit driver and an image signal circuit driver, and the matrix was driven in a simple time-shared manner. [0187] The directions of the upper and the lower boundary plane s were approximately parallel mutually, and formed an angle of 105 degrees (φ LC1 =φ LC2 =105°) to the direction of the supplied electric field (FIG. 2). A gap d was kept by holding dispersed spherical polymer beads between the substrates at a 4.2 μm interval under a liquid crystal filled condition. The panel was held between two polarizers (made by Nitto Denko Co., G1220DU), the polarizing light transmitting axis of one polarizer was selected as approximately parallel to a rubbing direction, i.e. φ P1 =105°, and the axis of the other polarizer was selected as perpendicular to the rubbing direction, i.e. φ P2 =15°. Accordingly, normal closed characteristics were obtained. [0188] As for the orienting film, a silicon nitride (SiN) film 0.7 μm thick was formed. And, an orienting film of RN-422 (made by Nissan Chemical Co.) was formed 0.9 μm thick on the insulating film. [0189] The active matrix type liquid crystal display device as obtained above was evaluated as rank 1 in the evaluation of residual image, and no residual image was observed at all. Further, the transparency of the insulating film and the orienting film maintained a more than 90% transmission factor, as shown in FIG. 10( b ). [0190] Embodiment 24 [0191] The composition of this embodiment is the same as embodiment 10 except for the following matters. [0192] In this embodiment, a silicon nitride (SiN) film was used as for the insulating film, and its thickness was 0.3 μm. As for the orienting film, a polyamide orienting film made from 4,4′-diaminodiphenylether and pyromellitic acid dianhydride was used. The thickness of the orienting film was 0.1 μm, and accordingly, the total thickness of the insulating film and the orienting film was 0.4 μm. [0193] The residual image of the active matrix liquid crystal display device obtained in the above manner was evaluated as rank 3 , as shown in FIG. 10( a ), and the residual image time was within five minutes. Further, transparency of the insulating film and the orienting film maintained a more than 90% transmission factor, as shown in FIG. 10( b ). [0194] Organic films used in the present invention for the insulating film and the orienting film are not restricted by the organic polymers described in the embodiments. In addition to polyamide and epoxy group polymers, polyesters, polyurethanes, polyvinyl alcohols, polyamides, silicones, acrylates, olefin-sulfon group polymers, and the like can be used regardless of the photosensitivity. Further, surface treating agents, for instance, such as amino group silane coupling agents as γ-aminopropyl triethoxysilane, δ-aminopropyl methyldiethoxysilane, and N-β(aminoethyl)γ-aminopropyl trimethoxysilane, epoxy group silane coupling agents, titanate coupling agents, aluminum alcoholates, aluminum chelates, and zirconium chelates can be mixed or reacted with the organic polymers. But, the present invention is not restricted to the above examples. [0195] Further, material for the inorganic film is not restricted only to silicon nitride and silicon dioxide, but also germanium nitride, germanium oxide, aluminum nitride, and aluminum oxide can be used. However, the present invention is not restricted to the above examples. COMPARATIVE EXAMPLE 1 [0196] The composition of the embodiment used is the same as embodiment 2 except for the following matters. [0197] The liquid crystal had a specific resistivity of 2.0×10 14 Ωcm and an average specific dielectric constant of 6.1. Silicon nitride (SiN) was used for the insulating film, and its specific resistivity was 6×10 15 Ωcm and its specific dielectric constant was 8. As for the orienting film, a polyamide orienting film made from 2,2-bis[4(p-aminophenoxy) phenylpropane and pyromellitic acid dianhydride was used, and its specific resistivity was 2.0×10 12 Ωcm and its average specific dielectric constant was 2.9. [0198] Accordingly, respective products (∈ r ρ) of specific resistivity ρ specific dielectric constant ∈ r of the liquid crystal layer and the orienting film were less than 8×10 15 Ωcm, but the product (∈ r ρ) of specific resistivity ρ and specific dielectric constant ∈ r of the insulating film was larger than 8×10 15 Ωcm. [0199] The active matrix type liquid crystal display device as obtained above was evaluated as rank 5 in the evaluation of residual image, and the residual image time was beyond five minutes. [0200] COMPARATIVE EXAMPLE 2 [0201] The composition of the embodiment used is the same as embodiment 2 except for the following matters. [0202] The liquid crystal had a specific resistivity of 6.3×10 12 Ωcm and an average specific dielectric constant of 6.1. Silicon nitride (SiN) was used for the insulating film, and its specific resistivity was 2×10 15 Ωcm and its specific dielectric constant was 8. As for the orienting film, a polyamide orienting film made from 2,2-bis[4-(p-aminophenoxy) phenylpropane and pyromellitic acid dianhydride was used, and its specific resistivity was 5.5×10 12 Ωcm and its average specific dielectric constant was 2.9. [0203] Accordingly, respective products (∈ r ρ) of specific resistivity ρ specific dielectric constant ∈ r of the liquid crystal layer and the orienting film were less than 8×10 15 Ωcm, but product (∈ r ρ) of specific resistivity ρ specific dielectric constant ∈ r of the insulating film was larger than 8 ×10 15 Ωcm. [0204] The active matrix type liquid crystal display device as obtained above was evaluated as rank 5 in the evaluation of residual image, and the residual image time was beyond five minutes. [0205] COMPARATIVE EXAMPLE 3 [0206] The composition of the embodiment used is the same as embodiment 10 except for the following matters. [0207] In the present example, silicon nitride (SiN) was used for the insulating film, and its thickness was 2.1 μm. As for the orienting film, a polyamide orienting film made from 4, 4″-diaminodiphenylether and pyromellitic acid dianhydride was used. The thickness of the orienting film was 1.0 μm, and accordingly, the total thickness of the insulating film and the orienting film was 3.1 μm. [0208] The residual image of the active matrix liquid crystal display device obtained in the above manner was evaluated as rank 1 , as shown in FIG. 10( a ), but the transparency of the insulating film and the orienting film was less than 90% transmission factor, as shown in FIG. 10( b ). [0209] COMPARATIVE EXAMPLE 4 [0210] The composition of the embodiment used is the same as embodiment 10 except for the following matters. [0211] In the present example, silicon nitride (SiN) was used as for the insulating film, and its thickness was 0.1 μm. As for the orienting film, RN-718 was used. The thickness of the orienting film was 0.1 μm, and accordingly, the total thickness of the insulating film and the orienting film was 0.2 μm. [0212] The active matrix type liquid crystal display device as obtained above was evaluated as rank 5 in the evaluation of residual image, and the residual image time was beyond five minutes. [0213] In accordance with the present invention, a liquid crystal display device having a high picture quality and in which a residual image is substantially eliminated can be obtained by making the brightness recovering time within five minutes after displaying same figure and/or character pattern for 30 minutes.
A liquid crystal display device having a pair of substrates, at least one of which is transparent, a liquid crystal layer interposed between the pair of substrates, an electrode structure formed on one of the pair of substrates for generating an electric field in said liquid crystal layer, the electrode structure including at least one common electrode and at least one pixel electrode, a gate insulating film formed on the one common electrode, an insulation layer formed on the gate insulating film and an orientation film formed on the insulation layer. A sum of thickness of the gate insulating film, the insulation layer and the orientation film is no greater than about 2.8 μm.
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CLAIM OF PRIORITY [0001] This Application claims priority under 35 U.S.C. §119(e) from earlier filed U.S. Provisional Application Ser. No. 61/479,619, filed Apr. 27, 2011, by Richard Holloway and Luke Schwandt, the entirety of which is incorporated herein by reference. BACKGROUND [0002] 1. Field of the Invention [0003] The present device relates to the field of conveyor devices, particularly escalators and moving walkways that include a moving handrail. [0004] 2. Background [0005] Conveyor devices such as escalators and moving walkways are a common sight in large stores, malls, airports, public transit stations, and other buildings. Most of these devices have a handrail that moves in sync with the stairs or belt on which people stand. The handrails are touched by many users of the conveyor device, and each user can transfer germs, viruses, dirt, grime, and/or other undesirable elements to the handrails. The germs or other elements left behind on the handrails can be transferred to other users who touch the handrails, leading to the transmission of diseases. [0006] In the wake of growing concern over the spread of germs and viruses in public areas and the knowledge that handrails are often not routinely cleaned or disinfected, users sometimes avoid touching handrails. While this practice can decrease the chances of disease transmission, a user who avoids holding on to a handrail when on a moving conveyance can be at risk of becoming unbalanced or even falling, possibly injuring themselves in the process. [0007] To combat the issues caused by germs in public areas, many facilities have installed hand sanitizer dispensers at various convenient locations. Although hand sanitizer dispensers can be a useful in helping people to keep their hands clean, people may not always take the time to use them or go out of their way to apply hand sanitizer. Some people carry personal bottles of sanitizer with them, but, again, may forget to use them. [0008] As an alternative to sanitizing one's hands, frequently touched surfaces can be sanitized before people touch them. This can prevent the spread of diseases by killing germs and viruses before they reach a person's hands and are then subsequently transferred to other persons and surfaces. While sanitizing frequently touched surfaces can be effective, it can be onerous and/or labor intensive to constantly sanitize such surfaces manually. [0009] What is needed is a device that can automatically and continuously sanitize a moving handrail to aid in the prevention of germ and virus transmission and to encourage users to hold on to handrails for support. BRIEF DESCRIPTION OF THE DRAWINGS [0010] FIG. 1 depicts a side view of an embodiment of a moving handrail sanitizing device. [0011] FIG. 2 depicts a close up isometric view of an embodiment of the moving handrail sanitizing device. [0012] FIG. 3 depicts an embodiment of a sanitizer container. [0013] FIG. 4A depicts an isometric view of an embodiment of an applicator. [0014] FIG. 4B depicts a side view of an embodiment of a sponge. [0015] FIG. 5 depicts an exploded view of a first exemplary embodiment of an applicator. [0016] FIG. 6 depicts a second exemplary embodiment of an applicator. [0017] FIG. 7 depicts a third exemplary embodiment of an applicator. [0018] FIG. 8 depicts a fourth exemplary embodiment of an applicator. [0019] FIG. 9 depicts an embodiment of the support structure. [0020] FIG. 10 depicts embodiments of the moving handrail sanitizing device in use. DETAILED DESCRIPTION [0021] FIG. 1 depicts a side view of an embodiment of a moving handrail sanitizing device 100 . FIG. 2 depicts a close up isometric view of an embodiment of the moving handrail sanitizing device 100 . A moving handrail sanitizing device 100 can comprise a sanitizer container 102 and an applicator 104 . A connector 106 can couple the sanitizer container 102 with the applicator 104 . The applicator 104 can apply sanitizing substance 108 to a moving handrail 110 . The handrail 110 can be a handrail that moves in conjunction with a conveyor device, such as an escalator, moving walkway, or any other type of conveyance. In some embodiments, the moving handrail sanitizing device 100 can further comprise a support structure 112 . [0022] FIG. 3 depicts an embodiment of a sanitizer container 102 . The sanitizer container 102 can be an apparatus configured to house a portion of a sanitizing substance 108 . The sanitizing substance 108 can be a cleansing agent capable of cleaning and/or disinfecting the handrail 110 . In some embodiments, the sanitizing substance 108 can be a disinfectant, antiseptic, and/or antimicrobial substance. By way of a non-limiting example, the sanitizing substance 108 can be an alcohol-based cleansing agent. In some embodiments, the sanitizing substance 108 can be a liquid. In other embodiments, the sanitizing substance 108 can be a gel, foam, aerosol, or be in any other known and/or convenient state. [0023] In some embodiments, the sanitizer container 102 can be comprised of walls 114 that can define a compartment 116 capable of holding a portion of the sanitizing substance 108 , such as a tank, reservoir, basin, or any other type of vessel. In other embodiments, the sanitizer container 102 can be a receptacle configured to accept a separate body that contains a portion of the sanitizing substance 108 , such as a cartridge, bottle, or any other type of housing. In some embodiments, the sanitizer container 102 can be substantially cuboid in shape. In other embodiments the sanitizer container 102 can be cylindrical, spherical, conical, or have any other known and/or convenient geometry. [0024] In some embodiments, the sanitizing container 102 can comprise one or more clear portions 118 , such as a window. The clear portions 118 can allow the level of sanitizing substance 108 within the sanitizing container 102 to be viewed. In other embodiments, the sanitizing container 102 can comprise a sensor 119 that can automatically monitor the level of sanitizing substance 108 within the sanitizing container 102 and/or be triggered when the level of sanitizing substance 108 reaches a predetermined level. The sensor 119 can send a signal to one or more indicators 188 , as described below with reference to FIG. 9 . In still other embodiments, the entire sanitizing container 102 can be comprised of a clear or translucent material, such that the level of sanitizing substance 108 within the sanitizing container 102 can be viewed. [0025] The sanitizer container 102 can comprise at least one container inlet 120 . The container inlet 120 can be an ingress configured to allow sanitizing substance 108 to enter the sanitizing container 102 . In some embodiments, the container inlet 120 can be an aperture that can be closed with a threaded cap 122 . In other embodiments, the container inlet 120 can be an open top, a hinged lid, a screw top, or any other open and/or closable aperture through which a portion of the sanitizing substance 108 can enter the sanitizer container 102 . [0026] In some embodiments, the sanitizing substance 108 can be poured and/or placed directly into the sanitizer container 102 through the container inlet 120 . In other embodiments in which the sanitizing substance 108 is packaged in a separate body such as a cartridge, bottle, or other housing, the body can be inserted into the sanitizer container 102 through the container inlet 120 . [0027] The sanitizer container 102 can also comprise at least one container outlet 124 . The container outlet 124 can be an egress configured to allow sanitizing substance 108 to exit the sanitizing container 102 . In some embodiments, the container outlet 124 can be a nozzle. In other embodiments, the container outlet 124 can be a valve, tap, spigot, aperture, or any other mechanism through which a portion of sanitizing substance 108 can exit the sanitizer container 102 . In some embodiments, the container outlet 124 can be located at the bottom of the sanitizer container 102 , such that the sanitizing substance 108 flows by gravity through the container outlet 124 . In some of these embodiments, the sanitizer container 102 can have one or more sloped portions at its bottom, such that the sanitizing substance 108 is funneled by gravity toward the container outlet 124 . In alternate embodiments, the sanitizing container 102 can comprise a pump which can operate to transport the sanitizing substance 108 to a container outlet 124 located at any convenient location on the sanitizer container 102 . [0028] In some embodiments, the sanitizing container 102 can comprise one or more attachment points 126 . The attachment points 126 can be protrusions and/or apertures configured to allow the sanitizing container 102 to be coupled with the support structure 112 . [0029] Returning to FIGS. 1 and 2 , the connector 106 can convey the sanitizing substance 108 from the sanitizer container 102 to the applicator 104 . In some embodiments, the connector 106 can be a hose. By way of a non-limiting example, a hose connector 106 can be an at least partially flexible tubular member having a substantially circular cross-section. In other embodiments, the connector 106 can be a duct, tube, pipe, cylinder, channel, conduit, or any other type of connection capable of conveying the sanitizing substance 108 . One end of the connector 106 can be coupled with the container outlet 124 . In some embodiments in which the connector 106 is a hose, the container outlet 124 can be a barbed nozzle configured to retain one end of the hose positioned around the nozzle. In alternate embodiments, the connector 106 and the container outlet 124 can have corresponding connections that enable the connector 106 and container outlet 124 to be coupled with one another, such as a threaded screw-on connection. [0030] In some embodiments, the connector 106 can comprise one or more valves 128 . The valves 128 can be control elements capable of regulating and/or ceasing the flow of the sanitizing substance 108 through the connector 106 . In some embodiments, one or more valves 128 can be located substantially at the center of the connector 106 . In other embodiments, one or more valves 128 can be located at the proximal end of the connector 106 , at the distal end of the connector 106 , or at any other convenient location on the connector 106 . In some embodiments, the valve 128 can comprise a handle that can be manually operated to regulate the flow of the sanitizing substance 108 . In alternate embodiments, the valve 128 and/or the connector 106 can comprise one or more sensors 129 configured to monitor the flow of the sanitizing substance 108 and/or regulate the flow of the sanitizing substance 108 . The sensors 129 can send a signal to one or more indicators 188 , as described below with reference to FIG. 9 . [0031] In alternate embodiments, the sanitizer container 102 can be directly coupled with the applicator 104 , such that no connector 106 is needed to convey the sanitizing substance 108 from the sanitizer container 102 to the applicator 104 . [0032] FIG. 4A depicts an isometric view of an embodiment of an applicator 104 . The applicator 104 can be an apparatus configured to apply the sanitizing substance 108 to a moving handrail 110 . In some embodiments, the applicator can comprise a sponge 130 . The sponge 130 can be any type of known and/or convenient synthetic or natural sponge that can absorb sanitizing substance 108 and/or apply sanitizing substance 108 to a handrail 110 . By way of a non-limiting example, the sponge 130 can be an elastomeric, porous polymer. The sponge 130 can have substantially the same width or be wider than the width of a handrail 110 . [0033] FIG. 4B depicts a side view cross section of an embodiment of a sponge 130 . In some embodiments comprising a sponge 130 , the sponge 130 can comprise one or more sensors 131 . The sensors 131 can be embedded into the sponge 130 at a predetermined height. As the sponge 130 applies the sanitizing substance 108 to the handrail 110 , the contact with the moving handrail 110 can wear down the sponge 130 . The sensors 131 can be activated when the top of the sponge 130 is worn down to the predetermined height, such that the sensors 131 come into contact with the moving handrail 110 . The sensors 131 can send a signal to one or more indicators 188 , as described below with reference to FIG. 9 . [0034] In alternate embodiments, the applicator 104 can comprise a sprayer configured to spray the sanitizing substance 108 on a handrail 110 . In still other embodiments, the applicator 104 can comprise a brush, squeegee, pad, cloth, or any other cleaning tool capable of applying the sanitizing substance 108 to a handrail 110 . [0035] The applicator 104 can comprise an applicator inlet 132 . The applicator inlet 132 can be an ingress configured to allow sanitizing substance 108 to enter the applicator 104 . The applicator inlet 132 can be coupled with the connector 106 and be configured to receive the sanitizing substance 108 conveyed by the connector 106 . In some embodiments, the applicator inlet 132 can be formed substantially similarly to the container outlet 124 . In some embodiments, the applicator inlet 132 can be a nozzle. In other embodiments, the applicator inlet 132 can be a valve, tap, spigot, aperture, or any other mechanism through which a portion of sanitizing substance 108 can enter the applicator 104 . In some embodiments in which the connector 106 is a hose, the applicator inlet 132 can be a barbed nozzle configured to retain one end of the hose positioned around the nozzle. In alternate embodiments, the connector 106 and the applicator inlet 132 can have corresponding connections that enable the connector 106 and applicator inlet 132 to be coupled with one another, such as a threaded screw-on connection. [0036] In some embodiments, the applicator 104 can comprise a rising mechanism 134 . The rising mechanism 134 can be configured to apply a force to the applicator 104 , such that the applicator 104 can maintain sufficient contact between the applicator 104 and the exterior surface of the moving handrail 110 when desired. In some embodiments, the rising mechanism 134 can be one or more springs. In other embodiments, the rising mechanism 134 can be one or more pistons, motorized arms, scissor lifts, robotic arms, or any other device capable of applying a force to the applicator 104 such that the applicator 104 contacts the handrail 110 . [0037] In some embodiments, the rising mechanism 134 can apply constant force to the applicator 104 such that the applicator 104 is in constant contact with the handrail 110 . In other embodiments, the rising mechanism 134 can selectively apply force to the applicator 104 , such that the applicator 104 only comes into contact with the handrail 110 intermittently and/or when desired. In alternate embodiments, the rising mechanism 134 can be absent, such as in embodiments with applicators 104 comprising sprayers that do not need to be in contact with the handrail 110 . [0038] FIG. 5 depicts an exploded view of a first exemplary embodiment of an applicator 104 . In this embodiment, the applicator 104 can be a sponge assembly. The sponge assembly can comprise a tray 536 , a sponge 130 , and a base 538 . The tray 536 can comprise a tray floor 540 and tray walls 542 extending away from the tray floor 540 at the edges of the tray floor 540 , such that the tray 536 has an open top. The sponge 130 can be coupled with and/or rest on the tray floor 540 between the tray walls 542 . In some embodiments, the sponge 130 can be removably coupled with the tray 536 , such that the sponge 130 can be replaced when desired. The applicator inlet 132 can be coupled with the tray 536 , such that the sanitizing substance 108 received by the applicator 104 can pool into the tray 536 and be absorbed by the sponge 130 . The base 538 can comprise a base floor 544 and base walls 546 extending away from the base floor 544 at the edges of the base floor 544 , such that the base 538 has an open top. The base walls 546 can be spaced farther apart than the tray walls 542 , such that the tray 536 can at least partially fit inside the open top of the base 538 . [0039] In some embodiments, one or more tray walls 542 and/or base walls 546 can have grooves 548 indented into the tops of the tray walls 542 and/or base walls 546 . The grooves 548 can be shaped as arcs substantially similar to the arc of a cross section of a handrail 110 , such that the handrail 110 can come into contact with the sponge 130 housed within the tray 536 without impacting the tray walls 542 and/or base walls 546 . [0040] The rising mechanism 134 in this first exemplary embodiment can be one or more springs 550 coupled with the base floor 544 . The springs 550 can be oriented toward the underside of the tray floor 540 when the tray 536 is positioned inside the base 538 , such that the springs 550 apply a force to the underside of the tray 536 that tends to push the tray 536 away from the base 538 . The base 538 and the tray 536 can be coupled with one another through a sliding mechanism 552 . The sliding mechanism 552 can allow the tray 540 to move vertically with respect to the base 538 while keeping the base 538 and the tray 536 substantially fixed relative to one other horizontally. In some embodiments, the sliding mechanism 552 can comprise one or more protrusions 554 extending from the exterior of the tray walls 542 and one or more corresponding notches 556 in the interior of the base walls 546 , such that the protrusions 554 can be fit into the notches 556 . In other embodiments, the sliding mechanism 552 can comprise one or more protrusions 554 extending from the interior of the base walls 546 and one or more corresponding notches 556 in the exterior of the tray walls 542 , such that the protrusions 554 can be fit into the notches 556 . In still other embodiments, the tray 536 and the base 538 can be coupled with gliders, sliders, or any other mechanism that allows vertical movement of the tray 536 relative to the base 538 . The base walls 546 can comprise an inlet notch 558 and/or aperture positioned to allow the applicator inlet 132 coupled with the tray 556 to move with the tray 536 without impacting the base walls 546 as the tray 536 moves relative to the base 538 . [0041] FIG. 6 depicts a second exemplary embodiment of an applicator 104 . In this second exemplary embodiment, the applicator 104 can comprise a tray 636 , a sponge 130 , and one or more pistons 660 . The tray 636 can comprise a tray floor 640 and tray walls 642 extending away from the tray floor 640 at the edges of the tray floor 640 , such that the tray 636 has an open top. The sponge 130 can be coupled with and/or rest on the tray floor 640 between the tray walls 642 . In some embodiments, the sponge 130 can be removably coupled with the tray 636 , such that the sponge 130 can be replaced when desired. In some embodiments, tray walls 642 can have grooves 648 indented into the tops of the tray walls 642 . The grooves 648 can be shaped as arcs substantially similar to the arc of a cross section of a handrail 110 , such that the handrail 110 can come into contact with the sponge 130 housed within the tray 636 without impacting the tray walls 642 . The applicator inlet 132 can be coupled with the tray 636 , such that the sanitizing substance 108 received by the applicator 104 can pool into the tray 636 and be absorbed by the sponge 130 . [0042] The rising mechanism 134 in this second exemplary embodiment can be the pistons 660 . Each piston 660 can comprise a piston shaft 662 . In some embodiments, the pistons 660 can be pneumatic cylinders. The tray 636 can be coupled with the top of the piston shaft 662 . In some embodiments, the piston 660 can be coupled with a canister 664 . In some embodiments, the canister 664 can be filled with a gas or liquid. By way of a non-limiting example, the canister 664 can be an air compressor. The gas or liquid can flow between the canister 664 and the piston 660 through tubes 666 . The movement of the gas or liquid between the canister 664 and the piston 660 can cause the piston shaft 662 to move up and down, causing the tray 636 to rise and fall. [0043] In some embodiments, the piston 660 can operate to directly maintain the pressure of the applicator 104 against the handrail 110 . In other embodiments, the piston 660 can be coupled with the embodiment of the applicator 104 shown in FIG. 5 , such that the piston 660 can move the applicator 104 into a position proximate to the handrail 110 and the springs 550 can maintain the pressure of the applicator 104 against the handrail 110 . [0044] FIG. 7 depicts a third exemplary embodiment of an applicator 104 . In this third exemplary embodiment, the applicator 104 can comprise a tray 736 , a sponge 130 , and a scissor lift 768 . The tray 736 can comprise a tray floor 740 and tray walls 742 extending away from the tray floor 740 at the edges of the tray floor 740 , such that the tray 736 has an open top. The sponge 130 can be coupled with and/or rest on the tray floor 740 between the tray walls 742 . In some embodiments, the sponge 130 can be removably coupled with the tray 736 , such that the sponge 130 can be replaced when desired. In some embodiments, tray walls 742 can have grooves 748 indented into the tops of the tray walls 742 . The grooves 748 can be shaped as arcs substantially similar to the arc of a cross section of a handrail 110 , such that the handrail 110 can come into contact with the sponge 130 housed within the tray 736 without impacting the tray walls 742 . The applicator inlet 132 can be coupled with the tray 736 , such that the sanitizing substance 108 received by the applicator 104 can pool into the tray 736 and be absorbed by the sponge 130 . [0045] The rising mechanism 134 in this third exemplary embodiment can be the scissor lift 768 . The scissor lift 768 can comprise a first arm 770 , a second arm 772 , a track 774 , and at least one motor assembly 776 . The tray 736 can be coupled with the first arm 770 and the second arm 772 . The first arm 770 and second arm 772 can be coupled with one another at a hinge 778 at substantially the midpoint of both arms 770 772 . The track 774 can be coupled with the support structure 112 . In some embodiments, the track 774 can be a series of grooves. In other embodiments, the track 774 can be rails, paths, slots, or any other type of track. The motor assembly 776 can comprise a motor 780 and one or more wheels 782 . The wheels can be configured to interact with the track 774 . The motor can be configured to power the wheels 782 . In some embodiments, the base of the first arm 770 can be coupled with the support structure 112 and the base of the second arm 772 can be coupled with the motor assembly 776 . In alternate embodiments, the base of the first arm 770 can be coupled with a first motor assembly 776 and the base of the second arm 772 can be coupled with a second motor assembly 776 . [0046] In operation, the motor 780 can turn the wheels 782 to move the motor assemblies 776 along the track 774 , thereby moving the base of the second arm 772 relative to the base of the first arm 770 . The movement of the base of the second arm 772 relative to the base of the first arm 770 can cause the angle between the first arm 770 and second arm 772 to change, thereby causing the tray 736 to rise and fall. In some embodiments, one or more of the first arm 770 , the second arm 772 , the tray 736 , the support structure 112 and/or the motor assembly 776 can be hingeably coupled with one another, such that the components of the scissor lift 768 can move relative to one another. [0047] In some embodiments, the scissor lift 768 can operate to directly maintain the pressure of the applicator 104 against the handrail 110 . In other embodiments, the scissor lift 768 can be coupled with the embodiment of the applicator 104 shown in FIG. 5 , such that the scissor lift 768 can move the applicator 104 into a position proximate to the handrail 110 and the springs 550 can maintain the pressure of the applicator 104 against the handrail 110 . [0048] FIG. 8 depicts a fourth exemplary embodiment of an applicator 104 . In this fourth exemplary embodiment, the applicator 104 can comprise a spray nozzle 884 . The applicator inlet 132 can be coupled with the spray nozzle 884 , such that the sanitizing substance 108 received by the applicator 104 can be sprayed through the spray nozzle 884 towards the handrail 110 . [0049] FIG. 9 depicts an embodiment of the support structure 112 . The support structure 112 can be a housing that at least partially encloses the sanitizer container 102 , applicator 104 , and connector 106 . The sanitizer container 102 and/or the applicator 104 can be coupled with the support structure 112 . In some embodiments, the sanitizer container 102 can be mounted on the interior of the support structure 112 at a location higher than the applicator 104 , such that gravity can aid the conveyance of the sanitizing substance 108 from the sanitizer container 102 to the applicator 104 through the connector 106 . [0050] The support structure can have one or more access points 186 . In some embodiments, the access points 186 can be hinged doors and/or covers that can be opened to access the interior of the support structure 112 . In other embodiments, the access points 186 can be removable portions of the support structure 112 . In some embodiments, the access points 186 can be locked and require a key to be opened. [0051] In some embodiments, the support structure 112 can comprise one or more indicators 188 visible from the exterior of the support structure 112 . In some embodiments, indicators 188 can be lights, signs, screens, or any other type of display that can convey information. By way of a non-limiting example, the indicators 188 can indicate when maintenance of the moving handrail sanitizing device 100 is needed. In some embodiments, the indicators 188 can be in communication with one or more sensors in the applicator 104 , connector 106 and/or sanitizer container 102 , such as the sensors 119 , 129 and 131 . The sensors can inform the indicators 188 when the level of sanitizing substance 108 is too low, when the sponge 130 is worn out, when a leak is detected in the connector 106 , or when any other malfunction, status, or predetermined condition is detected within the moving handrail sanitizing device 100 . [0052] In some embodiments, the exterior of the support structure 112 can comprise one or more placards 190 . The placards 190 can comprise text and/or images to convey information such as product names, brand names, model numbers, maintenance information, or any other desired information. [0053] In some embodiments, one or more scrapers 192 can be coupled with the support structure 112 at a location proximate to the path of the moving handrail 110 , such that edges of the scraper 192 are proximal to the external surface of the moving handrail 110 . The scrapers 192 can be capable of deflecting and/or removing pieces of debris on the external surface of the moving handrail 110 . In some embodiments, the scrapers 192 can be elongated, substantially rectangular members. In other embodiments the scrapers 192 can extend around the lateral edges of a moving handrail 110 . In still other embodiments, the scrapers 192 can be wipers, brushes, squeegees, wedges, or have any other known and/or convenient geometry capable of deflecting and/or removing pieces of debris. In some embodiments, the scrapers 192 can be positioned at an angle relative to the external surface of the moving handrail 110 . In some embodiments, the scrapers 192 can be positioned on the interior of the support structure 112 . In alternate embodiments, the scrapers 192 can be integral with the support structure 112 and/or positioned on the exterior of the support structure 112 . By way of a non-limiting example, the support structure 112 can be shaped such that the opening through which the moving handrail 110 enters the support structure 112 has minimal clearance, such that the exterior of the support structure 112 functions as a scraper 192 by deflecting debris as the handrail 110 enters the interior of the support structure 112 . [0054] FIG. 10 depicts embodiments of the moving handrail sanitizing device 100 in use. In operation, the moving handrail sanitizing device 100 can be positioned at a desired location on the path of a moving handrail 110 . In some embodiments, the moving handrail sanitizing device 100 can be placed at one end of a moving handrail 110 at a point in which the handrail 110 is moving downward and around a turning point 1094 . By way of a non-limiting example, a moving handrail sanitizing device 100 a can be placed such that the handrail 110 can enter the support structure 112 a after the handrail has passed turning point 1094 a when the handrail is moving in a substantially counterclockwise direction. The applicator 104 a can apply the sanitizing substance 108 to the handrail 110 , and the handrail 110 can have time to dry as it moves toward turning point 1094 b. By way of another non-limiting example, a moving handrail sanitizing device 100 b can be placed such that the handrail 110 can enter the support structure 112 b after the handrail has passed turning point 1094 b when the handrail is moving in a substantially clockwise direction. The applicator 104 b can apply the sanitizing substance 108 to the handrail 110 , and the handrail 110 can have time to dry as it moves toward turning point 1094 a. In other embodiments, the moving handrail sanitizing device 100 can be positioned at a point in which the handrail 110 is moving in any direction. The applicator 104 can be positioned below the handrail 110 , on the side of the handrail 110 , horizontally, vertically, at an angle, or at any other desired position or orientation. [0055] In alternate embodiments, the moving handrail sanitizing device 100 can be configured to sanitize moving elements that are not handrails. By way of a non-limiting example, an embodiment could be positioned on the underside of a moving belt device, such as, but not limited to, a conveyor belt at a grocery store checkout. [0056] In some embodiments, the applicator 104 can continually apply the sanitizing substance 108 to the moving handrail 110 . In alternate embodiments, the applicator 104 can intermittently apply the sanitizing substance 108 to the moving handrail 110 . In some embodiments with intermittent application of sanitizing substance 108 , the moving handrail sanitizing device 100 can comprise an automatic timer 1096 . The automatic timer 1096 can be configured to control the applicator 104 and/or the rising mechanism 134 such that sanitizing substance 108 can be applied to the handrail 110 at predetermined intervals and/or for predetermined periods of time. In other embodiments with intermittent application of sanitizing substance 108 , the moving handrail sanitizing device 100 can comprise a counter mechanism 1098 . The counter mechanism 1098 can count how many times a certain section of the moving handrail 110 has passed by the counter mechanism 1098 . The counter mechanism 1098 can be configured to control the applicator 104 and/or the rising mechanism 134 such that sanitizing substance 108 can be applied to the handrail 110 after a predetermined number of handrail revolutions have occurred and/or application of sanitizing substance 108 can cease after a predetermined number of handrail revolutions have occurred. In still other embodiments, the moving handrail sanitizing device 100 can comprise a power switch 1100 configured to turn the moving handrail sanitizing device 100 on and off. [0057] Although the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, the invention as described and hereinafter claimed is intended to embrace all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims.
A device for cleaning and sanitizing a moving handrail, such as those found on escalators and moving walkways. The device can automatically and continuously sanitize a handrail as it moves past or through the device, thereby preventing the spread of germs and viruses and encouraging users to make contact with the handrail for safety reasons without worrying about disease transmission.
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BACKGROUND OF THE INVENTION The present invention relates to self-service fuel pumping stations where the pump can be operated by a number of parties, each of whom has an individual operating key or card. In recent years, self-service fuel pumping stations have become increasingly popular. Not only is there a savings in that the station does not have to be attended during normal working hours, but there is the advantage that fuel can be made available on a seven day a week, 24 hour basis. In a typical self-service station, there are a number of subscribers, each of whom has an individual access key or card to operate the fuel pump. The fuel pump itself is provided with a number of key slots, one for each of the subscribers who has access to the station, or a single card reader. When an individual wishes to pump fuel, he first inserts his key or card into the particular key slot which is assigned to him. When he turns the key, power is supplied to the fuel pump to cause it to operate. The person then takes the nozzle to the tank to be filled, inserts the nozzle in the tank opening, and operates the nozzle valve to cause fuel to flow into the tank. So that there can be an accounting for each subscriber for the fuel he pumps, there is an individual counter or meter for each key slot. Each counter keeps a total of the fuel pumped due to operation of its related key slot and the subscriber is billed periodically in accordance with the reading on the counter. One of the problems of such self-service stations is the possibility of the person pumping fuel without this being registered on the counter. This generally occurs where there is a malfunctioning of the pulsing device, either through a mechanical or electrical failure of the component or from deliberate tampering with the pulsing device. As a precaution, many self-service stations have the pumping unit equipped with a timer which causes an automatic shut off of the pump if the pulsing device does not operate. This occurs in the following manner. When the person initially inserts his individual key or card to cause the pump to operate, the timing device is triggered. This timing device is also responsive to the pulsing device, and if the timer does not detect the pulses from the pulsing device within a predetermined time period beginning from the insertion of the key or card, the timing device shuts off the pump. However, the time period from the insertion of the key or card to the sensing of the pulses cannot be made too short. For example, let's take the typical situation where a person might be filling the tank of a vehicle. The person first inserts his key, then takes the nozzle from the pump, walks to the location of the tank opening in the vehicle, loosens the gas cap, and then begins pumping. The present time period of the timing device must allow for the amount of time that it takes to perform the steps. Otherwise the person has the annoyance of the premature shut off. A more serious situation is where the inlet to the tank is possibly on an upper part of the vehicle so that the person must climb on top of the vehicle to fill the tank. Therefore, the timing device is usually made to respond where there is a lapse of about sixty seconds from the delivery of power to the pump and the sensing of the pulses. Even with the timing device, it is possible for the person to obtain substantial amounts of fuel without this being registered on the counter by "milking" the pump. First, let's assume that the pulsing device in inoperable, either by tampering or accidental failure of some component. The person inserts his key and immediately starts pumping fuel. After about sixty seconds, the timing device shuts off the pump. The person leaves the nozzle in the tank inlet, and removes the key from the slot. After a short period of time during which the timing device automatically resets itself (e.g. about one second), the person again inserts the key into his individual slot and then immediately opens the valve at the nozzle to pump more gas for a period of about sixty seconds. These steps are repeated a number of times until a substantial amount of fuel has been "milked" from the tank, all of this being accomplished without any recording on the counter. Thus the setting of the timing device is a compromise, and as a practical matter not at all the best compromise. It must be set for a sufficiently long period of time to permit the person to begin pumping fuel without a premature shut off. Yet it is desirable to have it short enough to prevent the "milking". It is to this problem that the present invention is directed. A search of the patent literature discloses a number of patents relating generally to self-service pumping stations. For example, U.S. Pat. No. 3,099,366, Reilly, discloses a system where there are individual meter read-outs, total meter read-outs, and also meter tickets to be checked against the meter readings. Magnetic counters are activated by electrical pulses. Other systems are shown in U.S. Pat. No. 2,712,885, Winship; U.S. Pat. No. 2,995,275, Brice; and U.S. Pat. No. 3,497,107, Tatsuno. U.S. Pat. No. 3,510,630, Ryan et al, provides an accounting system for such a self-service station where different types of fuel are taken from different sources at the station. In view of the foregoing, it is an object of the present invention to provide an apparatus and method to effectively prevent any substantial amount of fuel being taken from the self-service station without this being recorded, and also to permit fuel to be delivered conveniently without premature shut off. SUMMARY OF THE INVENTION The apparatus of the present invention is adapted to deliver fluid, such as liquid fuel, at a self-service station where there is a record made of the fuel delivered. The apparatus comprises a pump that pumps fluid from a fluid source to a nozzle means. There is selectively operable switch means to cause the pump to operate and counting means responsive to fluid flow in a manner to record the same. Also, there is flow detecting means to detect fluid flow to the nozzle. Shut off control means is connected to the flow detecting means and to the counting means so as to detect a condition where the flow detecting means detects flow to the nozzle and the counting means is not operating to record flow. Upon occurrence of such a condition, there is a shut off of fluid flow to the nozzle. Thus, the fluid is not delivered where there is not a recording of the fluid delivered. Specifically, the shut off control means comprises timing means to detect a time interval extending from a beginning of fluid flow to operation of the counting means. The shut off means shuts off the fluid flow where the time interval exceeds a predetermined time limit. Further, the shut off control means in the specific configuration shown herein comprises a shut off switch to interrupt flow of power to the pump. There is also a flow switch responsive to the detecting means and operatively connected to the timing means in a manner that activation of the flow switch by the flow detecting means initiates operation of the timing means. As shown herein, the timing means comprises a capacitor arranged to provide a shut off signal at a predetermined voltage level. The flow switch is connected to the capacitor means and to a voltage source to cause the capacitor to be charged to the predetermined voltage level upon operation of the flow switch in response to fluid flow. There is a capacitor discharge means to reduce the charge on the capacitor. This capacitor discharge means is connected to the counting means to reduce the charge on the capacitor in response to operation of the counting means. In the method of the present invention, apparatus such as that described above is provided. The method comprises detecting fluid flow to the nozzle, and then detecting operation of the counting means. The fluid flow is shut off under circumstances where fluid flow is detected, but there is not a detection of operation of the counting means. This is accomplished by initiating operation of a timing device upon detection of fluid flow to the nozzle so as to provide a measure of a time interval beginning with initiation of the fluid flow. At the end of the time interval, the fluid flow is shut off under circumstances where detection of operation of the counting means does not take place before expiration of the time interval. Specifically, the time interval is provided by charging the capacitor by connecting the capacitor to a voltage source upon detection of fluid flow to the nozzle. The charge on the capacitor is reduced upon detecting of operation of the counting means. However, under circumstances where the capacitor reaches the predetermined voltage level, a shut off signal from the capacitor is initiated to shut off fluid flow to the nozzle. Other features of the invention will become apparent from the following detailed description. FIG. 1 is a front elevational view of a pumping unit of a pumping station incorporating the present invention; FIG. 2 is a schematic drawing of the apparatus of the present invention, and FIG. 3 is a circuit diagram showing the main components of the timer, flow switch and shut off switch. DESCRIPTION OF THE PREFERRED EMBODIMENT It is believed that a clearer understanding of the present invention will be attained by first describing the main components of a self-service pumping station, second the automatic shut off system of a typical prior art station, and finally the system of the present invention. In FIG. 1, there is shown a single pumping unit 10 suitable for use in the present invention. This comprises a housing structure 12 on top of which is the key lock control panel 14 having a plurality of key slots 16. Located in the lower part of the housing 12 is the pump and motor unit 18. This unit 18 draws in fuel from a supply tank through a line 20 and pumps the fuel upwardly through a second line 22. The fuel in line 22 passes through a strainer 24, thence through a flow meter 26, and then through a third line 28. The line 28 connects to a hose 30 wound on a reel 32. The discharge end of the hose 30 connects to a nozzle 34 having a manually controlled valve 36. Connected to the flow meter 26 is a register 38 having therein a rotating element that responds to flow through the meter 26. A pulser 40 is connected to the register 38 in a manner to deliver a pulse for each revolution of the rotating element in the register 38. Thus, the pulses delivered from the pulser 40 are proportional to the volume of flow through the meter 26. The pulser 40 in turn has an operative connection to a junction box 42 that interconnects with the key lock control panel 14. It is to be understood that all of the components 10-42 described immediately above currently exist in the prior art. Reference is now made to FIG. 2 which is a schematic drawing of a circuit to illustrate the operation of the circuitry of a typical self-service pumping station. In the schematic of FIG. 2, for ease of explanation, the various switches, which in the existing apparatus would be transistor components, are shown in FIG. 2 simply as relays. The individual key lock switches are designated 46, and for purposes of illustration, only four of these key lock switches 46 have been shown herein, these being designated 46A, 46B, 46C and 46D. There is a shut off relay 48 which is normally in the position shown in FIG. 2. When any one of the key lock switches 46A-46D is closed, current flows from the positive voltage source at 50, through the relay contacts 48, to cause the motor relay 52 to close. This in turn delivers power to the motor and pump unit 18 to cause the pump to operate. However, until the nozzle valve 36 is opened, the pump does not actually deliver any fuel. If the pump is a centrifugal pump, the pump simply rotates without delivering fuel. If the pump is a positive displacement pump, the fuel flows through a bypass, and no fuel is delivered. Also, when any one of the key lock switches 46A-46D is closed, current is caused to flow through the coil of a timing relay 54 to cause it to close. Thus, current flows from the gound terminal 56 through a variable resistor 58, thence through a resistor 60 to charge the upper plate 62 of a capacitor C1- with respect to the lower plate 64 which is connected to a positive voltage source 66. When the upper plate 62 of the capacitor C1 reaches a predetermined threshold or avalanche voltage, it causes current to flow through a zener diode Z1 to cause current to flow through the coil of a relay 66 and thus cause it to close. This in turn causes current to flow through the coil of the shut off relay 48 and move the switch of the relay 48 to its up position, where the relay 48 remains locked in its upper position as long as the relay contact 54 remains closed. The principal effect of moving the relay 48 to its up position is to interrupt current through the coil of the relay 52 so that the relay contacts 52 open. This shuts off the motor and the pump. As long as the key lock switch 46 remains closed, the shut off relay 48 remains in its up position so that the motor and pump 18 will not operate. However, when the key is removed from the lock so as to open the switch 46, the relay contacts 54 open to de-energize the relay 48 and permit its contacts to move to its bottom position as shown in FIG. 2. Then, one of the key lock switches 46A-46D can again be closed by inserting the appropriate key to close one of the key lock switches 56A-56D to close the power relay 52. However, in accordance with the explanation above, if the charge on the capacitor C1 is permitted to build up to a sufficient level, there will again be a shut off of the motor and pump due to the action of the shut off relay 48. The charge on the capacitor C1 is kept at a sufficiently low level by operation of the pulsing device 40, and this will be described immediately below. Let it be assumed that one of the key lock switches 46A-46D has been closed to cause the motor and pump 18 to begin operating. Let it further be assumed that very shortly after inserting the key in the lock to close one of the switches 46A-46D, the person begins pumping fuel into his fuel tank. This causes the flow meter 26 to rotate, with each rotation of the flow meter 26 momentarily closing a reed switch 68 for each revolution for the flow meter 26. The flow meter 26 could have, for example, a rotating magnetic element which closes the switch 68 each time it passes in proximity thereto. Each time the reed switch closes, it momentarily closes the relay 70. Each time the relay 70 is closed momentarily, it accomplishes two things. First, it causes a current pulse to travel through one of the coils 72A-72D which has its related key lock switch 46A-46D closed. This in turn activates the counter 74A ro record the pulse. As indicated previously, the counters 74A-74D are read periodically to determine the amount of fuel delivered by closing a particular key lock so that the individual customer or user could be billed accordingly. In addition, the momentary closing of the pulsing relay 70 provides a path from the upper plate 62 of the capacitor C1 through a resistor R1, through a diode D1 to the positive terminal 76. The result is that even though the current flow through the variable resistor 58 and resistor 60 begins to charge the upper plate 62, the pulser 40 causes a discharge of the capacitor C1 to the positive terminal 76. Let us now apply this to the typical situation where the person has inserted the key into one of the slots to close one of the key lock switches 46A-46D. Simultaneously, the motor relay 52 and the relay contacts 54 close so that current is simultaneously delivered to the motor to cause it to turn and current is also delivered through resistor 58 and resistor 60 to charge the capacitor C1. Let it further be assumed that the variable resistor 58 is set so that in approximately sixty seconds the upper plate 62 becomes sufficiently negative (relative to the positively charged lower plate 64) to reach the avalanche voltage of the zener diode Z1 to close the relay 66 and cause the shut off relay 48 to move to its up position. However, prior to the passage of that sixty second interval, the person has begun pumping fuel. Then, the flow through the meter 26 causes the pulsing device 40 to operate to in turn cause periodic momentary closure of the reed switch to cause periodic closure of the pulsing relay 70. This charges the capacitor 62 so that the shut off relay 48 remains in its position shown in FIG. 2. However, when the person finally finishes pumping fuel, the pulses from the pulsing device 40 cease, and the charge on the capacitor C1 begins to build up. This would then cause the shut off relay 48 to operate in the manner described above. At such time that the person removed his key from the slot, the key lock switch 46A-46D (whichever one is closed) now opens. This causes the relay 54 to open, which in turn causes the shut off relay 48 to move to its down position (as shown in FIG. 2). The charge on the capacitor C1 is discharged to the positive terminal 75, and the apparatus is now in a condition to be operated by a subsequent user who would insert his key in the appropriate slot. As indicated previously, if the pulsing device 40 becomes inoperative for some reason, the apparatus can still be "milked" by pumping fuel during the time interval that it takes to charge the capacitor to the appropriate level. This is done by inserting the key in the slot to close one of the switches 46A-46D and immediately start pumping fuel (within a second or two). After the sixty second interval when the shut off mechanism operates, the person removes his key so that the shut off mechanism is reset, again inserts his key and begins pumping. As indicated previously, it is to be understood that the circuitry described with reference to FIG. 2 is a simplified diagram merely to illustrate the operating principles of the prior art device. The prior art device as it actually exists is shown in FIG. 3, and this will be described immediately below, incorporating the novel features of the present invention. In describing the components of FIG. 3, there will first be a recitation of the components which correspond closely to those already described in reference to FIG. 2, these being: the power relay 52, the key lock switch 46A, the coil 72A, the counter 74A, the pulsing device 40, the reed switch 68, the capacitor C1, resistor R1 and R2, diode D1, ground terminal 56, variable resistor 58, fixed resistor 60, zener diode Z1, shut off relay 48, positive terminal 50. It is to be understood that the relays 54, 66 and 76 do not exist in the apparatus in FIG. 3, and the functions of those relays 54, 66 and 76 are carried out by transistors. Also, even though only one key lock switch 46A is shown, it is to be understood that a large number of such switches are provided, one for each customer using the self-service pumping system. When the key lock switch 46A is closed, current flows from the positive terminal 50 through the shut off relay 48, through the twenty-two ohm resistor R2, through the power relay 52, through diode D2 through the key switch 46A to ground, thus causing the motor pump unit 18 to operate. At the same time, current flows through the two voltage dividing resistors R3 and R4 to provide a less positive voltage to be applied to the base of transistor Q1. Transistor Q1 conducts through the two voltage dividing resistors R5 and R6 to apply base current to the transistor Q2 to cause it to be conductive and provide a current path from the ground terminal 56 through the transistor Q2, through the variable resistor 58, through the resistor 66 to begin charging the upper plate of the capacitor C1. The lower plate 64 of the capacitor C1 is connected to the positive terminal 66, and as the upper plate of the capacitor C1 continues to become charged less positively, it eventually reaches the threshold of avalanche voltage of the zener diode Z1. When the charge on the capacitor C1 becomes sufficiently high, the zener diode conducts to turn on the transistor Q3, which in turn causes transistor Q4 to conduct, which in turn causes transistor Q5 to conduct. Since the emitter of the transistor Q5 is connected to the positive voltage source 66, there is a current path from the collector of the transistor Q5 to the terminal 80, thence through the coil of the shut off relay 48 through the transistor Q2 to the ground terminal at 56. This causes the switch of the relay 48 to move to its up position (where it remains locked as long as transistor Q2 remains conductive) and shut off the current path through the resistor R2 and through the power relay 52. This in turn permits the power relay 52 to open so as to shut off the motor. With the relay 48 in its up position, and with the transistor Q2 still conducting, current continues to flow through the transistor Q2 and through the relay 48 to keep the relay 48 in its up position (i.e. its shut off position). When the key is removed from the slot to open the switch 46A, the transistor Q2 becomes nonconductive to interrupt current through the relay coil 48 and permit the relay 48 to move to its down position as shown in FIG. 3. To describe now the operation of the pulsing device 40 and its associated components, each time the reed switch 68 closes, it passes a current pulse through the voltage dividing resistors R7 and R8 to cause a current pulse to travel through the capacitor C2 which is in turn transmitted to the base of the switching transistor Q6. When the transistor Q6 becomes conductive, it transmits base current to the transistor Q7 which sends an amplified signal to the bases of transistors Q8 and Q9. Transistor Q8 is in turn connected to a totalizer 82, which keeps a total of all pulses, so that the total flow of fuel through the system can be recorded. (The totalizer 82 and transistor Q8 are optional features.) When the transistor Q9 becomes conductive for the duration of the current pulse, it causes a current pulse to travel from the positive voltage source 66 through the low impedence resistor R9 through the diode D3, through the individual counter coil 72A and thence through the key lock switch 46A to ground. This causes the current pulses to be recorded on the counter 74A. In addition, when the transistor Q9 becomes conductive, the collector terminal of the transistor Q9 reaches a high positive level, rather close to the level of the positive voltage terminal 72, thus for the duration of the pulse, the upper plate of the capacitor C1 discharges through the resistor R1 and diode D1 to the collector terminal of the transistor Q9. From the above description it becomes apparent that each time the reed switch 68 conducts, it activates the transistors Q6, Q7 and Q9 to cause a current pulse to go to the counter 72. Also, for the duration of the pulse, the upper plate of the capacitor C1 discharges through the collector of the transistor Q9. The transistor Q10 is arranged to be conductive when there is more than one key switch 46A-46D closed. However, since the operation of transistor Q10 is not critical to the present invention, its operation will not be discussed herein. It is to be emphasized that the components described thus far with reference to FIG. 3 already exist in a typical prior art self-service system. In practice, the variable resistor 58 must be set at a level so that the time period during which the capacitor C1 charges to the shut off level is sufficiently long to prevent premature shut off. To describe now the components of the present invention, there is provided a flow switch 90 which is made responsive to actual flow of fuel from the motor pump unit 18. This flow switch could be placed, for example, at either of the pipes 22 or 28 in a manner that the switch 90 closes when there is flow through the pipe 22 or 28. The flow switch 90 is connected through leads 92 and 94 to open terminals 96 and 98 in the line between the variable resistor 58 and the fixed resistor 60. Further, let it be assumed that the variable resistor 58 is moved from a higher resistance setting to a very low resistive setting. With the flow switch 90 now being inserted between the terminals 96 and 98 as described above, let us again review the operation of the circuitry shown in FIG. 3. Upon closing of the switch 46A, current begins to flow through the path from the terminal 50, through the shut off relay 48, through resistor R2, through the power relay 52, through diode D2, and through switch 46A to ground. The pump immediately begins pumping, but no fuel is yet delivered. At the same time, upon closing of the switch 46A, the transistors Q1 and Q2 become conductive. However, since the flow switch 90 is open, no current flows from the transistor Q2 through the variable resistor 58. Thus, the capacitor C1 is not being charged. Let it now be assumed that there is some malfunction in the pulsing device 40, or some malfunction in the transistors Q6, Q7 and Q9, or their associated components, so that pulses are not delivered to the transistor Q9 to make it conductive. In this situation, the power relay 52 shall remain closed for an indefinite period of time, as long as the key lock switch 46A remains closed. As soon as the fuel valve 36 is opened so that fuel flows through the pipe, two things occur. First, the pulsing device 40 begins transmitting pulses to the transistor Q9. Second, the flow switch 90 closes so as to connect the contacts 96 and 98, so that the capacitor C1 begins to become charged at a preset rate through 58. However, the capacitor C1 does not become charged sufficiently to reach the avalanche voltage of the zener diode Z1 and trigger the shut off mechanism, since the capacitor C1 discharges with each pulse that causes the transistor Q9 to be conductive. Let us know take a situation where the pulsing device 40 is inoperative for one reason or another, and fuel begins to flow. In this instance, the capacitor C1 is charged with relative rapidity to the avalanche voltage of the zener diode Z1 to trigger the shut off mechanism. This makes it very difficult to "milk" the pump. When the flow valve 36 is opened, there is flow of fuel for about two seconds, after which the capacitor C1 becomes charged and shuts off the pump. The shut off relay 48 remains in the shut off position as long as the key remains in the slot to keep the key lock switch 46A closed. The person then has to remove the key, wait for the shut off mechanism to become reset and then reinsert the key in the slot. When the person can only pump for about two seconds before there is another shut off. The inconvenience and length of time involved is generally sufficient to dissuade most people from attempting to "milk" the pump. On the other hand, let's take the situation where the person places his key in the slot and is then rather slow in beginning to pump the fuel. Since the flow switch 90 remains open, the capacitor C1 is not being charged. Thus, even if the person is delayed to an unusual extent before beginning to pump fuel, he does not have the inconvenience of the premature shut off. Yet if that person attempts to "milk" the pump, the shut off mechanism reacts rapidly enough to shut down the pump very quickly.
A self-service station where a number of parties, each having an individual operating key or card, can pump gas from a single pump by inserting the key or card into a matching slot to activate the pump. When the fuel begins to flow to the discharge nozzle, a pulsing device is activated to register on a counter the amount of fuel pumped. To prevent pumping of fuel under circumstances where the pulsing device is not operating, there is a timer that shuts off the pump if the pulsing device does not become operative after a certain period of time. The timer is arranged with a flow responsive switch so that the time period is measured from the time fuel actually begins to flow to the time that the pulsing device starts to operate. This permits the time period to be made relatively short to minimize the pumping of fuel without recording the same on the counter.
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CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation-in-part of U.S. patent application Ser. No. 10/731,729 filed Dec. 9, 2003, the content of which is incorporated by reference. BACKGROUND OF INVENTION [0002] 1. Field of Invention [0003] The present invention generally relates to fibers, methods of making fibers and to products made thereof. More particularly, the present invention relates to polypropylene fibers that can comprise syndiotactic polypropylene. [0004] 2. Background of the Art [0005] Polypropylene has found employment in a wide variety of applications. Examples of uses include nonwoven fabrics such as spun bonded, melt blown, thermally bonded and carded staple fibers uses for applications such as diaper components and medical fabrics where properties such as bulk and softness are important. Polypropylene fibers have found commercial use in synthetic carpets, geotextiles, textile fabrics and the like. While polypropylene fibers have found wide application as carpet yarns, polypropylene-fibers may lack the elasticity and resiliency of other carpet fiber polymers, for example, nylon. When loads such as furniture legs rest on polypropylene carpets for an extended period are removed, they may leave their impression on the carpet in the form of packed carpet fibers. Poor resiliency prevents the packed fibers from returning back to their original configuration, which may be referred to as elastic recovery. [0006] Bicomponent fibers may comprise a first polymer component and a second component, with each component fused to the other along the fiber axis. The first and second components may be configured as core and sheath, side by side, tipped, (micro) denier and mixed fibers, and are generally produced utilizing a specially equipped fiber spinning machine. Examples of bicomponent fibers include nylon and polyurethane, and polypropylene and polyethylene copolymers. SUMMARY OF THE INVENTION [0007] In one aspect, the invention is a bicomponent fiber including a first component and a second component fused together in a side-by-side arrangement wherein the first component includes a syndiotactic polypropylene homopolymer and the second component includes an ethylene propylene random copolymer. [0008] In another aspect, the invention is a method of making a fiber include extruding a first fiber component and a second fiber component and fusing together the first component and the second component into a side-by-side arrangement to form a bicomponent fiber wherein the first component comprises a syndiotactic polypropylene homopolymer and the second component comprises an ethylene-propylene random copolymer. [0009] In still another aspect, the invention is an article of manufacture comprising bicomponent fibers made by a method of making a fiber include extruding a first fiber component and a second fiber component and fusing together the first component and the second component into a side-by-side arrangement to form a bicomponent fiber wherein the first component comprises a syndiotactic polypropylene homopolymer and the second component comprises an ethylene-propylene random copolymer. [0010] Another aspect of the present invention is a nonwoven fabric including at least 5 wt % of a bicomponent fiber of ethylene-propylene random copolymer and syndiotactic polypropylene, the bicomponent fiber being in a side-by-side arrangement, wherein the bicomponent fiber exhibits shrinkage upon exposure to a heat source resulting in an increase in bulk for the fiber. DETAILED DESCRIPTION OF THE INVENTION [0011] The fibers of the present invention may be bicomponent fibers comprising syndiotactic polypropylene as a first component and ethylene-propylene random copolymers (EPRC) as a second component. Syndiotactic and isotactic are terms that describe the steric configuration of polypropylene. For example, the isotactic structure is typically described as having the methyl groups attached to the tertiary carbon atoms of successive monomeric units on the same side of a hypothetical plane through the main chain of the polymer, e.g., the methyl groups are all above or all below the plane. Using the Fischer projection formula, the stereochemical sequence of isotactic polypropylene is described as follows: [0012] Another way of describing the structure is through the use of NMR spectroscopy. Bovey's NMR nomenclature for an isotactic pentad is . . . mmmm . . . with each “m” representing a “meso” dyad or successive methyl groups on the same side of the plane. As known in the art, any deviation or inversion on the structure of the chain lowers the degree of isotacticity and crystallinity of the polymer. [0013] In contrast to the isotactic structure, syndiotactic polymers are those in which the methyl groups attached to the tertiary carbon atoms of successive monomeric units in the chain lie on alternate sides of the plane of the polymer. Using the Fischer projection formula, the structure of a syndiotactic polymer is designated as: [0014] In NMR nomenclature, this pentad is described as . . . rrrr . . . in which each “r” represents a “racemic” dyad, i.e. successive methyl group on alternate sides of the plane. The percentage of r dyads in the chain determines the degree of syndiotacticity of the polymer. Syndiotactic polymers are crystalline and like the isotactic polymers are insoluble in xylene. This crystallinity distinguishes both syndiotactic and isotactic polymers from an atactic polymer which is soluble in xylene. [0015] The syndiotactic polypropylenes suitable for use in the blends of the present invention and methods of making such syndiotactic polypropylenes are well know to those of skill in the polyolefin art. Such materials may be prepared using, for example, Ziegler-Natta and metallocene catalysts. Examples of suitable syndiotactic polypropylenes, methods of and catalysts for their making may be found in U.S. Pat. Nos. 3,258,455, 3,305,538, 3,364,190, 4,852,851, 5,155,080, 5,225,500, 5,334,677 and 5,476,914, all herein incorporated by reference. [0016] Metallocene catalysts may be characterized generally as coordination compounds incorporating one or more cyclopentadienyl (Cp) groups (which may be substituted or unsubstituted, each substitution being the same or different) coordinated with a transition metal through n bonding. [0017] The Cp substituent groups may be linear, branched or cyclic hydrocarbyl radicals. The cyclic hydrocarbyl radicals may further form other contiguous ring structures, including, for example indenyl, azulenyl and fluorenyl groups. These additional ring structures may also be substituted or unsubstituted by hydrocarbyl radicals, such as C 1 to C 20 hydrocarbyl radicals. [0018] A specific example of a metallocene catalyst is a bulky ligand metallocene compound generally represented by the formula: [L] m M[A] n where L is a bulky ligand, A is a leaving group, M is a transition metal and m and n are such that the total ligand valency corresponds to the transition metal valency. For example m may be from 1 to 3 and n may be from 1 to 3. [0019] The metal atom “M” of the metallocene catalyst compound, as described throughout the specification and claims, may be selected from Groups 3 through 12 atoms and lanthanide Group atoms in one embodiment; and selected from Groups 3 through 10 atoms in a more particular embodiment, and selected from Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in yet a more particular embodiment; and selected from Groups 4, 5 and 6 atoms in yet a more particular embodiment, and Ti, Zr, Hf atoms in yet a more particular embodiment, and Zr in yet a more particular embodiment. The oxidation state of the metal atom “M” may range from 0 to +7 in one embodiment; and in a more particular embodiment, is +1, +2, +3, +4 or +5; and in yet a more particular embodiment is +2, +3 or +4. The groups bound the metal atom “M” are such that the compounds described below in the formulas and structures are electrically neutral, unless otherwise indicated. [0020] The bulky ligand generally includes a cyclopentadienyl group (Cp) or a derivative thereof. The Cp ligand(s) form at least one chemical bond with the metal atom M to form the “metallocene catalyst compound”. The Cp ligands are distinct from the leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution/abstraction reactions. [0021] Cp typically includes 7-bonded and/or fused ring(s) or ring systems. The ring(s) or ring system(s) typically include atoms selected from group 13 to 16 atoms, for example, carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron, aluminum and combinations thereof, wherein carbon makes up at least 50% of the ring members. Non-limiting examples include cyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl, tetrahydroindenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or “H 4 Ind”), substituted versions thereof, and heterocyclic versions thereof. [0022] Cp substituent groups may include hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, aryls, acyls, aroyls, alkoxys, aryloxys, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and combinations thereof. More particular non-limiting examples of alkyl substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all their isomers, for example tertiary-butyl, isopropyl, and the like. Other possible radicals include substituted alkyls and aryls such as, for example, fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboron for example; and disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, Group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide. Other substituents R include olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example 3-butenyl, 2-propenyl, 5-hexenyl and the like. In one embodiment, at least two R groups, two adjacent R groups in one embodiment, are joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron and combinations thereof. Also, a substituent group R group such as 1-butanyl may form a bonding association to the element M. [0023] Each anionic leaving group is independently selected and may include any leaving group, such as halogen ions, hydrides, C 1 to C 12 alkyls, C 2 to C 12 alkenyls, C 6 to C 12 aryls, C 7 to C 20 alkylaryls, C 1 to C 12 alkoxys, C 6 to C 16 aryloxys, C 7 to C 18 alkylaryloxys, C 1 to C 12 fluoroalkyls, C 6 to C 12 fluoroaryls, and C 1 to C 12 heteroatom-containing hydrocarbons and substituted derivatives thereof; hydride, halogen ions, C 1 to C 6 alkylcarboxylates, C 1 to C 6 fluorinated alkylcarboxylates, C 6 to C 12 arylcarboxylates, C 7 to C 18 alkylarylcarboxylates, C 1 to C 6 fluoroalkyls, C 2 to C 6 fluoroalkenyls, and C 7 to C 18 fluoroalkylaryls in yet a more particular embodiment; hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl, fluoromethyls and fluorophenyls in yet a more particular embodiment; C 1 to C 12 alkyls, C 2 to C 12 alkenyls, C 6 to C 12 aryls, C 7 to C 20 alkylaryls, substituted C 1 to C 12 alkyls, substituted C 6 to C 12 aryls, substituted C 7 to C 20 alkylaryls and C 1 to C 12 heteroatom-containing alkyls, C 1 to C 12 heteroatom-containing aryls and C 1 to C 12 heteroatom-containing alkylaryls in yet a more particular embodiment; chloride, fluoride, C 1 to C 6 alkyls, C 2 to C 6 alkenyls, C 7 to C 18 alkylaryls, halogenated C 1 to C 6 alkyls, halogenated C 2 to C 6 alkenyls, and halogenated C 7 to C 18 alkylaryls in yet a more particular embodiment; fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- and trifluoromethyls) and fluorophenyls (mono-, di-, tri-, tetra- and pentafluorophenyls) in yet a more particular embodiment; and fluoride in yet a more particular embodiment. [0024] Other non-limiting examples of leaving groups include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., —C 6 F 5 (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF 3 C(O)O — ), hydrides and halogen ions and combinations thereof. Other examples of leaving groups include alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like. In one embodiment, two or more leaving groups form a part of a fused ring or ring system. [0025] L and A may be bridged to one another. A bridged metallocene, for example may, be described by the general formula: XCp A Cp B MA n wherein X is a structural bridge, Cp A and Cp B each denote a cyclopentadienyl group, each being the same or different and which may be either substituted or unsubstituted, M is a transition metal and A is an alkyl, hydrocarbyl or halogen group and n is an integer between 0 and 4, and either 1 or 2 in a particular embodiment. [0026] Non-limiting examples of bridging groups (X) include divalent hydrocarbon groups containing at least one Group 13 to 16 atom, such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom and combinations thereof; wherein the heteroatom may also be C 1 to C 12 alkyl or aryl substituted to satisfy neutral valency. The bridging group may also contain substituent groups as defined above including halogen radicals and iron. More particular non-limiting examples of bridging group are represented by C 1 to C 6 alkylenes, substituted C 1 to C 6 alkylenes, oxygen, sulfur, R 2 C═, R 2 Si═, —Si(R) 2 Si(R 2 )—, R 2 Ge═, RP═ (wherein “═” represents two chemical bonds), where R is independently selected from the group hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted Group 15 atoms, substituted Group 16 atoms, and halogen radical; and wherein two or more Rs may be joined to form a ring or ring system. In one embodiment, the bridged metallocene catalyst component has two or more bridging groups (X). [0027] Other non-limiting examples of bridging groups include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-tetramethylethylene, dimethylsilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl, di(i-propyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di(t-butylphenyl)silyl, di(p-tolyl)silyl and the corresponding moieties, wherein the Si atom is replaced by a Ge or a C atom; dimethylsilyl, diethylsilyl, dimethylgermyl and/or diethylgermyl. [0028] In another embodiment, the bridging group may also be cyclic, and include 4 to 10 ring members or 5 to 7 ring members in a more particular embodiment. The ring members may be selected from the elements mentioned above, and/or from one or more of B, C, Si, Ge, N and O in a particular embodiment. Non-limiting examples of ring structures which may be present as or part of the bridging moiety are cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene and the corresponding rings where one or two carbon atoms are replaced by at least one of Si, Ge, N and O, in particular, Si and Ge. The bonding arrangement between the ring and the Cp groups may be cis-, trans-, or a combination thereof. [0029] The cyclic bridging groups may be saturated or unsaturated and/or carry one or more substituents and/or be fused to one or more other ring structures. If present, the one or more substituents are selected from the group hydrocarbyl (e.g., alkyl such as methyl) and halogen (e.g., F, Cl) in one embodiment. The one or more Cp groups which the above cyclic bridging moieties may optionally be fused to may be saturated or unsaturated and are selected from the group of those having 4 to 10 ring members, more particularly 5, 6 or 7 ring members (selected from the group of C, N, O and S in a particular embodiment) such as, for example, cyclopentyl, cyclohexyl and phenyl. Moreover, these ring structures may themselves be fused such as, for example, in the case of a naphthyl group. Moreover, these (optionally fused) ring structures may carry one or more substituents. Illustrative, non-limiting examples of these substituents are hydrocarbyl (particularly alkyl) groups and halogen atoms. [0030] In one embodiment, the metallocene catalyst includes CpFlu Type catalysts (e.g., a metallocene incorporating a substituted Cp fluorenyl ligand structure) represented by the following formula: X(CpR n 1 R m 2 )(FIR p 3 ) wherein Cp is a cyclopentadienyl group, Fl is a fluorenyl group, X is a structural bridge between Cp and Fl, R 1 is a substituent on the Cp, n is 1 or 2, R 2 is a substituent on the Cp at a position which is proximal to the bridge, m is 1 or 2, each R 3 is the same or different and is a hydrocarbyl group having from 1 to 20 carbon atoms with R 3 being substituted on a nonproximal position on the fluorenyl group and at least one other R 3 being substituted at an opposed nonproximal position on the fluorenyl group and p is 2 or 4. [0031] In yet another aspect, the metallocene catalyst includes bridged mono-ligand metallocene compounds (e.g., mono cyclopentadienyl catalyst components). In this embodiment, the at least one metallocene catalyst component is a bridged “half-sandwich” metallocene catalyst. In yet another aspect of the invention, the at least one metallocene catalyst component is an unbridged “half sandwich” metallocene. [0032] Described another way, the “half sandwich” metallocenes above are described in U.S. Pat. No. 6,069,213, U.S. Pat. No. 5,026,798, U.S. Pat. No. 5,703,187, and U.S. Pat. No. 5,747,406, including a dimer or oligomeric structure, such as disclosed in, for example, U.S. Pat. No. 5,026,798 and U.S. Pat. No. 6,069,213, which are incorporated by reference herein. [0033] Non-limiting examples of metallocene catalyst components consistent with the description herein include: cyclopentadienylzirconiumA n , indenylzirconiumA n , (1-methylindenyl)zirconiumA n , (2-methylindenyl)zirconiumA n , (1-propylindenyl)zirconiumA n , (2-propylindenyl)zirconiumA n , (1-butylindenyl)zirconiumA n , (2-butylindenyl)zirconiumA n , methylcyclopentadienylzirconiumA n , tetrahydroindenylzirconiumA n , pentamethylcyclopentadienylzirconiumA n , cyclopentadienylzirconiumA n , pentamethylcyclopentadienyltitaniumA n , tetramethylcyclopentyltitaniumA n , (1,2,4-trimethylcyclopentadienyl)zirconiumA n , dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(cyclopentadienyl)zirconiumA n , dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2,3-trimethylcyclopentadienyl)zirconiumA n , dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2-dimethylcyclopentadienyl)zirconiumA n , dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(2-methylcyclopentadienyl)zirconiumA n , dimethylsilylcyclopentadienylindenylzirconiumA n , dimethylsilyl(2-methylindenyl)(fluorenyl)zirconiumA n , diphenylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(3-propylcyclopentadienyl)zirconiumA n , dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(3-t-butylcyclopentadienyl)zirconiumA n , dimethylgermyl(1,2-dimethylcyclopentadienyl)(3-isopropylcyclopentadienyl)zirconiumA n , dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(3-methylcyclopentadienyl)zirconiumA n , diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconiumA n , diphenylmethylidenecyclopentadienylindenylzirconiumA n , isopropylidenebiscyclopentadienylzirconiumA n , isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconiumA n , isopropylidene(3-methylcyclopentadienyl)(9-fluorenyl)zirconiumA n , ethylenebis(9-fluorenyl)zirconiumA n , mesoethylenebis(1-indenyl)zirconiumA n , ethylenebis(1-indenyl)zirconiumA n , ethylenebis(2-methyl-1-indenyl)zirconiumA n , ethylenebis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumA n , ethylenebis(2-propyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumA n , ethylenebis(2-isopropyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumA n , ethylenebis(2-butyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumA n , ethylenebis(2-isobutyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumA n , dimethylsilyl(4,5,6,7-tetrahydro-1-indenyl)zirconiumA n , diphenyl(4,5,6,7-tetrahydro-1-indenyl)zirconiumA n , ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconiumA n , dimethylsilylbis(cyclopentadienyl)zirconiumA n , dimethylsilylbis(9-fluorenyl)zirconiumA n , dimethylsilylbis(1-indenyl)zirconiumA n , dimethylsilylbis(2-methylindenyl)zirconiumA n , dimethylsilylbis(2-propylindenyl)zirconiumA n , dimethylsilylbis(2-butylindenyl)zirconiumA n , diphenylsilylbis(2-methylindenyl)zirconiumA n , diphenyisilylbis(2-propylindenyi)zirconiumA n , diphenylsilylbis(2-butylindenyl)zirconiumA n , dimethylgermylbis(2-methylindenyl)zirconiumA n , dimethylsilylbistetrahydroindenylzirconiumA n , dimethylsilylbistetramethylcyclopentadienylzirconiumA n , dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconiumA n , diphenyIsilyl(cyclopentadienyl)(9-fluorenyl)zirconiumA n , diphenylsilylbisindenylzirconiumA n , cyclotrimethylenesilyltetramethylcyclopentadienylcyclopentadienylzirconiumA n , cyclotetramethylenesilyltetramethylcyclopentadienylcyclopentadienylzirconiumA n , cyclotrimethylenesilyl (tetramethylcyclopentadienyl )(2-methylindenyl)zirconiumA n , cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(3-methylcyclopentadienyl)zirconiumA n , cyclotrimethylenesilylbis(2-methylindenyl)zirconiumA n , cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2,3,5-trimethylclopentadienyl)zirconiumA n , cyclotrimethylenesilylbis(tetramethylcyclopentadienyl)zirconiumA n , dimethylsilyl(tetramethylcyclopentadieneyl)(N-tertbutylamido)titaniumA n , biscyclopentadienylchromiumA n , biscyclopentadienylzirconiumA n , bis(n-butylcyclopentadienyl)zirconiumA n , bis(n-dodecyclcyclopentadienyl)zirconiumA n , bisethylcyclopentadienylzirconiumA n , bisisobutylcyclopentadienylzirconiumA n , bisisopropylcyclopentadienylzirconiumA n , bismethylcyclopentadienylzirconiumA n , bisnoxtylcyclopentadienylzirconiumA n , bis(n-pentylcyclopentadienyl)zirconiumA n , bis(n-propylcyclopentadienyl)zirconiumA n , bistrimethylsilylcyclopentadienylzirconiumA n , bis(1,3-bis(trimethylsilyl)cyclopentadienyl)zirconiumA n , bis(1-ethyl-2-methylcyclopentadienyl)zirconiumA n , bis(1-ethyl-3-methylcyclopentadienyl)zirconiumA n , bispentamethylcyclopentadienylzirconiumA n , bispentamethylcyclopentadienylzirconiumA n , bis(1-propyl-3-methylcyclopentadienyl)zirconiumA n , bis(1-n-butyl-3-methylcyclopentadienyl)zirconiumA n , bis(1-isobutyl-3-methylcyclopentadienyl)zirconiumA n , bis(1-propyl-3-butylcyclopentadienyl)zirconiumA n , bis(1,3-n-butylcyclopentadienyl)zirconiumA n , bis(4,7-dimethylindenyl)zirconiumA n , bisindenylzirconiumA n , bis(2-methylindenyl)zirconiumA n , cyclopentadienylindenylzirconiumA n , bis(n-propylcyclopentadienyl)hafniumA n , bis(n-butylcyclopentadienyl)hafniumA n , bis(n-pentylcyclopentadienyl)hafniumA n , (n-propylcyclopentadienyl)(n-butylcyclopentadienyl)hafniumA n , bis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumA n , bis(trimethylsilylcyclopentadienyl)hafniumA n , bis(2-n-propylindenyl)hafniumA n , bis(2-n-butylindenyl)hafniumA n , dimethylsilylbis(n-propylcyclopentadienyl)hafniumA n , dimethylsilylbis(n-butylcyclopentadienyl)hafniumA n , bis(9-n-propylfluorenyl)hafniumA n , bis(9-n-butylfluorenyl)hafniumA n , (9-n-propylfluorenyl)(2-n-propylindenyl)hafniumA n , bis(1-n-propyl-2-methylcyclopentadienyl)hafniumA n , (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafniumA n , dimethylsilyltetramethylcyclopentadienylcyclopropylamidotitaniumA n , dimethylsilyltetramethylcyclopentadienylcyclobutylamidotitaniumA n , dimethylsilyltetramethylcyclopentadienylcyclopentylamidotitaniumA n , dimethylsilyltetramethylcyclopentadienylcyclohexylamidotitaniumA n , dimethylsilyltetramethylcyclopentadienylcycloheptylamidotitaniumA n , dimethylsilyltetramethylcyclopentadienylcyclooctylamidotitaniumA n , dimethylsilyltetramethylcyclopentadienylcyclononylamidotitaniumA n , dimethylsilyltetramethylcyclopentadienylcyclodecylamidotitaniumA n , dimethylsilyltetramethylcyclopentadienylcycloundecylamidotitaniumA n , dimethylsilyltetramethylcyclopentadienylcyclododecylamidotitaniumA n , dimethylsilyltetramethylcyclopentadienyl(sec-butylamido)titaniumA n , dimethylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titaniumA n , dimethylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titaniumA n , dimethylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titaniumA n , methylphenylsilyltetramethylcyclopentadienylcyclopropylamidotitaniumA n , methylphenylsilyltetramethylcyclopentadienylcyclobutylamidotitaniumA n , methylphenylsilyltetramethylcyclopentadienylcyclopentylamidotitaniumA n , methylphenylsilyltetramethylcyclopentadienylcyclohexylamidotitaniumA n , methylphenylsilyltetramethylcyclopentadienylcycloheptylamidotitaniumA n , methylphenylsilyltetramethylcyclopentadienylcyclooctylamidotitaniumA n , methylphenylsilyltetramethylcyclopentadienylcyclononylamidotitaniumA n , methylphenylsilyltetramethylcyclopentadienylcyclodecylamidotitaniumA n , methylphenylsilyltetramethylcyclopentadienylcycloundecylamidotitaniumA n , methylphenylsilyltetramethylcyclopentadienylcyclododecylamidotitaniumA n , methylphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titaniumA n , methylphenylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titaniumA n , methylphenyisilyi(tetramethylcyclopentadienyl)(n-decylamido)titaniumA n , methylphenylsilyi(tetramethylcyclopentadienyl)(n-octadecylamido)titaniumA n , diphenylsilyltetramethylcyclopentadienylcyclopropylamidotitaniumA n , diphenylsilyltetramethylcyclopentadienylcyclobutylamidotitaniumA n , diphenylsilyltetramethylcyclopentadienylcyclopentylamidotitaniumA n , diphenylsilyltetramethylcyclopentadienylcyclohexylamidotitaniumA n , diphenylsilyltetramethylcyclopentadienylcycloheptylamidotitaniumA n , diphenylsilyltetramethylcyclopentadienylcyclooctylamidotitaniumA n , diphenylsilyltetramethylcyclopentadienylcyclononylamidotitaniumA n , diphenylsilyltetramethylcyclopentadienylcyclodecylamidotitaniumA n , diphenylsilyltetramethylcyclopentadienylcycloundecylamidotitaniumA n , diphenylsilyltetramethylcyclopentadienylcyclododecylamidotitaniumA n , diphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titaniumA n , diphenylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titaniumA n , diphenylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titaniumA n , diphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titaniumA n , and derivatives thereof. [0182] As used herein, the term “metallocene activator” is defined to be any compound or combination of compounds, supported or unsupported, which may activate a single-site catalyst compound (e.g., metallocenes, Group 15 containing catalysts, etc.) Typically, this involves the abstraction of at least one leaving group (A group in the formulas/structures above, for example) from the metal center of the catalyst component. The catalyst components of the present invention are thus activated towards olefin polymerization using such activators. Embodiments of such activators include Lewis acids such as cyclic or oligomeric polyhydrocarbylaluminum oxides and so called non-coordinating ionic activators (“NCA”), alternately, “ionizing activators” or “stoichiometric activators”, or any other compound that may convert a neutral metallocene catalyst component to a metallocene cation that is active with respect to olefin polymerization. [0183] More particularly, it is within the scope of this invention to use Lewis acids such as alumoxane (e.g., “MAO”), modified alumoxane (e.g., “TIBAO”), and alkylaluminum compounds as activators, to activate desirable metallocenes described herein. MAO and other aluminum-based activators are well known in the art. Non-limiting examples of aluminum alkyl compounds which may be utilized as activators for the catalysts described herein include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like. [0184] Ionizing activators are well known in the art and are described by, for example, Eugene You-Xian Chen & Tobin J. Marks, Cocatalysts for Metal - Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure - Activity Relationships 100(4) CHEMICAL REVIEWS 1391-1434 (2000). Examples of neutral ionizing activators include Group 13 tri-substituted compounds, in particular, tri-substituted boron, tellurium, aluminum, gallium and indium compounds, and mixtures thereof (e.g., tri(n-butyl)ammonium tetrakis(pentafluorophenyl)boron and/or trisperfluorophenyl boron metalloid precursors). The three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides. In one embodiment, the three groups are independently selected from the group of halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof. In another embodiment, the three groups are selected from the group alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls), and combinations thereof. In yet another embodiment, the three groups are selected from the group alkyls having 1 to 4 carbon groups, phenyl, naphthyl and mixtures thereof. In yet another embodiment, the three groups are selected from the group highly halogenated alkyls having 1 to 4 carbon groups, highly halogenated phenyls, and highly halogenated naphthyls and mixtures thereof. By “highly halogenated”, it is meant that at least 50% of the hydrogens are replaced by a halogen group selected from fluorine, chlorine and bromine. In yet another embodiment, the neutral stoichiometric activator is a tri-substituted Group 13 compound comprising highly fluorided aryl groups, the groups being highly fluorided phenyl and highly fluorided naphthyl groups. [0185] Illustrative, not limiting examples of ionic ionizing activators include trialkyl-substituted ammonium salts such as: triethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, tri(n-butyl)ammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-tri-fluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammoniumtetra(o-tolyl)boron, and the like; N,N-dialkylanilinium salts such as: N,N-dimethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-2,4,6-pentamethylaniliniumtetraphenylboron and the like; dialkyl ammonium salts such as: diisopropylammoniumtetrapentafluorophenylboron, dicyclohexylammoniumtetraphenylboron and the like; triaryl phosphonium salts such as: triphenylphosphoniumtetraphenylboron, trimethylphenylphosphoniumtetraphenylboron, tridimethylphenylphosphoniumtetraphenylboron and the like, and their aluminum equivalents. [0208] In yet another embodiment, an alkylaluminum may be used in conjunction with a heterocyclic compound. The ring of the heterocyclic compound may include at least one nitrogen, oxygen, and/or sulfur atom, and includes at least one nitrogen atom in one embodiment. The heterocyclic compound includes 4 or more ring members in one embodiment, and 5 or more ring members in another embodiment. [0209] The heterocyclic compound for use as an activator with an alkylaluminum may be unsubstituted or substituted with one or a combination of substituent groups. Examples of suitable substituents include halogen, alkyl, alkenyl or alkynyl radicals, cycloalkyl radicals, aryl radicals, aryl substituted alkyl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or any combination thereof. The substituents groups may also be substituted with halogens, particularly fluorine or bromine, or heteroatoms or the like. [0210] Non-limiting examples of hydrocarbon substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example tertiary butyl, isopropyl, and the like. Other examples of substituents include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl or chlorobenzyl. [0211] In one embodiment, the heterocyclic compound is unsubstituted. In another embodiment one or more positions on the heterocyclic compound are substituted with a halogen atom or a halogen atom containing group, for example a halogenated aryl group. In one embodiment the halogen is selected from the group consisting of chlorine, bromine and fluorine, and selected from the group consisting of fluorine and bromine in another embodiment, and the halogen is fluorine in yet another embodiment. [0212] Non-limiting examples of heterocyclic compounds utilized in the activator of the invention include substituted and unsubstituted pyrroles, imidazoles, pyrazoles, pyrrolines, pyrrolidines, purines, carbazoles, and indoles, phenyl indoles, 2,5,-dimethylpyrroles, 3-pentafluorophenylpyrrole, 4,5,6,7-tetrafluoroindole or 3,4-difluoropyrroles. [0213] In one embodiment, the heterocyclic compound described above is combined with an alkyl aluminum or an alumoxane to yield an activator compound which, upon reaction with a catalyst component, for example a metallocene, produces an active polymerization catalyst. Non-limiting examples of alkylaluminums include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-iso-octylaluminum, triphenylaluminum, and combinations thereof. [0214] Other activators include those described in WO 98/07515 such as tris (2, 2′, 2″-nonafluorobiphenyl) fluoroaluminate, which is incorporated by reference herein. Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations. Other activators include aluminum/boron complexes, perchlorates, periodates and iodates including their hydrates; lithium (2,2′-bisphenyl-ditrimethylsilicate)4T-HF; silylium salts in combination with a non-coordinating compatible anion. Also, methods of activation such as using radiation, electrochemical oxidation, and the like are also contemplated as activating methods for the purposes of rendering the neutral metallocene-type catalyst compound or precursor to a metallocene-type cation capable of polymerizing olefins. Other activators or methods for activating a metallocene-type catalyst compound are described in for example, U.S. Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775. [0215] In general, the activator and catalyst component(s) are combined in mole ratios of activator to catalyst component from 1000:1 to 0.1:1 in one embodiment, and from 300:1 to 1:1 in a more particular embodiment, and from 150:1 to 1:1 in yet a more particular embodiment, and from 50:1 to 1:1 in yet a more particular embodiment, and from 10:1 to 0.5:1 in yet a more particular embodiment, and from 3:1 to 0.3:1 in yet a more particular embodiment, wherein a desirable range may include any combination of any upper mole ratio limit with any lower mole ratio limit described herein. When the activator is a cyclic or oligomeric poly(hydrocarbylaluminum oxide) (e.g., “MAO”), the mole ratio of activator to catalyst component ranges from 2:1 to 100,000:1 in one embodiment, and from 10:1 to 10,000:1 in another embodiment, and from 50:1 to 2,000:1 in a more particular embodiment. When the activator is a neutral or ionic ionizing activator such as a boron alkyl and the ionic salt of a boron alkyl, the mole ratio of activator to catalyst component ranges from 0.5:1 to 10:1 in one embodiment, and from 1:1 to 5:1 in yet a more particular embodiment. [0216] More particularly, the molar ratio of Al/metallocene-metal (Al from MAO) ranges from 40 to 500 in one embodiment, ranges from 50 to 400 in another embodiment, ranges from 60 to 300 in yet another embodiment, ranges from 70 to 200 in yet another embodiment, ranges from 80 to 175 in yet another embodiment; and ranges from 90 to 125 in yet another embodiment, wherein a desirable molar ratio of Al(MAO) to metallocene-metal “M” may be any combination of any upper limit with any lower limit described herein. [0217] The activators may or may not be associated with or bound to a support, either in association with the catalyst component (e.g., metallocene) or separate from the catalyst component, such as described by Gregory G. Hlatky, Heterogeneous Single - Site Catalysts for Olefin Polymerization 100(4) CHEMICAL REVIEWS 1347-1374 (2000). [0218] Metallocene Catalysts may be supported or unsupported. Typical support materials may include talc, inorganic oxides, clays and clay minerals, ion-exchanged layered compounds, diatomaceous earth compounds, zeolites or a resinous support material, such as a polyolefin. [0219] Specific inorganic oxides include silica, alumina, magnesia, titania and zirconia, for example. The inorganic oxides used as support materials may have an average particle size of from 30 microns to 600 microns, or from 30 microns to 100 microns, a surface area of from 50 m 2 /g to 1,000 m 2 /g, or from 100 m 2 /g to 400 m 2 /g, a pore volume of from 0.5 cc/g to 3.5 cc/g, or from 0.5 cc/g to 2 cc/g. [0220] Desirable methods for supporting metallocene ionic catalysts are described in U.S. Pat. Nos. 5,643,847; 09,184,358 and 09,184,389, which are incorporated by reference herein. The methods generally include reacting neutral anion precursors that are sufficiently strong Lewis acids with the hydroxyl reactive functionalities present on the silica surface such that the Lewis acid becomes covalently bound. [0221] When the activator for the metallocene supported catalyst composition is a NCA, desirably the NCA is first added to the support composition followed by the addition of the metallocene catalyst. When the activator is MAO, desirably the MAO and metallocene catalyst are dissolved together in solution. The support is then contacted with the MAO/metallocene catalyst solution. Other methods and order of addition will be apparent to those skilled in the art [0222] Those skilled in the art will appreciate that modifications in the above generalized preparation method may be made without altering the outcome. Therefore, it will be understood that additional description of methods and means of preparing the catalyst are outside of the scope of the invention, and that it is only the identification of the prepared catalysts, as defined herein, that is necessarily described herein. [0223] The syndiotactic polypropylene utilized in the present invention may comprise at least 70 percent syndiotactic molecules. In alternate embodiments of the invention the syndiotactic polypropylene utilized in the present invention comprises at least 75 percent syndiotactic molecules, at least 80 percent syndiotactic molecules and at least about 83 percent syndiotactic molecules. It may be desirable to have the syndiotactic polypropylene utilized in the present invention comprising substantially all syndiotactic molecules. [0224] In alternate embodiments of the invention the syndiotactic polypropylenes utilized generally comprise in the range of about 83 to about 95 percent syndiotactic molecules, in the range of about 85 to about 95 percent syndiotactic molecules and it may be desirable to be in the range of about 89 to about 95 percent syndiotactic molecules. [0225] The syndiotactic polypropylenes utilized in the present invention generally have a melt flow rate in the range of about 4 to about 2000 dg/min. For use in some woven applications, the syndiotactic polypropylenes may have a melt flow rate in the range of about 4 to about 40 dg/min, and it may be desirable for the MFR to be in the range of about 4 to about 30 dg/min. For use in some non-woven applications, the syndiotactic polypropylenes may have a melt flow rate in the range of about 30 to about 2000 dg/min. It should be noted that the polypropylene homopolymers useful herein may include small amounts of ethylene, usually much less than 1 percent by weight. [0226] Examples of commercially available syndiotactic polypropylene homopolymers are polymers known as EOD 93-06 and EOD 93-07 are available from Total Petrochemicals. [0227] The EPRC may be an isotactic propylene copolymer, a syndiotactic propylene copolymer, or a blend of isotactic and syndiotactic propylene copolymers. The EPRC comprises a random EPRC which, in one embodiment, is prepared using a metallocene catalyst to have a melt-flow rate of from about 20 to about 100 g/10 minutes at 230° C./2.1 Kg. [0228] In another embodiment, the EPRC is prepared using a Ziegler-Natta catalyst. Desirably, the EPRC prepared having a melt flow rate of from about 0.5 to 6 g/10 minutes at 230° C./2.1 Kg and then is compounded with visbreaking materials, such as peroxides, to have a melt-flow rate of from about 25 to 100 g/10 minutes at 230° C./2.1 Kg. [0229] The EPRCs may have a monomodal molecular weight distribution or a multimodal molecular weight distribution, for example a bimodal molecular weight distribution. The EPRC may contain from 0.1 to up to 3 wt % ethylene. The EPRC may be a random block copolymer, but desirably is a substantially non-block random copolymer as is produced in metallocene catalyzed copolymer processes. [0230] The bicomponent fibers of the present invention may comprise a syndiotactic polypropylene component and an EPRC component with each component fused to the other along the fiber axis. The bicomponent fibers of the present invention may be any type of bicomponent fiber. Non-limiting examples of bicomponent fibers that may be utilized in the present invention include various embodiments of side-by-side fibers. [0231] The first component of the bicomponent fiber of the present invention will generally comprise in the range of about 20 to about 80 weight percent of the fiber. The second component will generally comprise in the range of about 80 to 20 weight percent of the fiber based on the weight of the first component and the second component. [0232] Where fiber shrinkage is desired, it may be desirable to utilize fibers having EPRC/sPP components in the side/side arrangement. The shrinkage of bicomponent fibers may be increased or decreased by adding more or less of sPP, respectively. Possible end use applications for this high shrinkage fiber may include a nonwoven textile material, a diaper, a feminine hygiene product, a drape, a gown, a mask, a glove, or an absorbent pad. The components may comprise differing physical characteristics that may alter the appearance of the article or application, such as for example, each of the components comprise a different color, thereby blending the two colors throughout a carpet material by way of each individual fiber. [0233] The high-shrinkage EPRC/sPP fibers may be used as a replacement for acrylic fibers in many end uses including non-woven fabrics. The bicomponent fiber may be blended at a level of 30-50% with the standard product. On exposure to a heat source, such as heated water or air, the high-bulk bicomponent fibers shrink so that bulk is developed in the standard, non-shrinkable portion of the carpet. Typically the heat source will be at least 100° C., and may be at temperatures of at least 120° C. It may be desirable to have the heat source between 110° C. and 150° C. [0234] The heat source may be a variety of means such as, for example, heated air, steam, heated drums, etc. The temperature of the heat source is related to 1) the heat transfer coefficient of the heating medium (air, water, steam), 2) the diameter of the fibers, 3) the residence time during which the fiber is heated, and 4) the relative melting points for the two materials of the bicomponent fibers. The melting points of the materials may vary, for example, sPP may range from about 110° C. to about 130° C., versus EPRC that may range from about 160 to 166° C. The bulk temperature of the fibers may be used as a process control parameter. It is desirable to keep the bulk temperature of the fibers below the melting point of the EPRC component, for example less than 163° C. or in alternate embodiments less than 160° C., less than 150° C., or less than 140° C. [0235] The fibers of the invention are believed to be useful as substitutes for prior art fibers. Non-limiting examples of suitable applications include nonwoven fabrics. [0236] The fibers of the invention have improved softness in comparison to polypropylene homopolymer fibers. This can be an advantage in applications such as diapers where a nonwoven fabric prepared using the invention is in contact with skin, particularly sensitive areas of the body. One useful embodiment of the fibers of the present invention are staple fibers wherein the fibers are stretched when prepared and then chopped into lengths of up to about 4 inches for use in applications such as non-woven fabrics. In another embodiment, a bicomponent fiber of the invention may function as a binding fiber where the bicomponent fiber is heated in the presence of other fibers above the softening point of at least one of the two components of the bicomponent fiber. The softened portion of the bicomponent fiber may then serve to bind the other fibers together in one embodiment, or compatibilize fibers in another embodiment. [0237] The components of a bicomponent fiber may be joined in a symmetric or asymmetric arrangement. Generally, the spinning of bicomponent fibers involves coextrusion of two different polymers to form several single filaments. Bicomponent fiber extrusion equipment may be utilized to bring together the two component melt streams in a desired predetermined arrangement. Such bicomponent fiber extrusion equipment is known in the art. [0238] The fibers of the present invention may optionally also contain conventional ingredients as are known to those of skill in the art. Non-limiting examples of such conventional ingredients include, antistatic agents, antioxidants, crystallization aids, colorants, dyes, flame retardants, fillers, impact modifiers, release agents, oils, other polymers, pigments, processing agents, reinforcing agents, stabilizers, UV resistance agents, antifogging agents, wetting agents and the like. Desirably primary antioxidants, process stabilizers, and catalyst neutralizers may be incorporated into the bicomponent fibers of the invention.
Bicomponent fibers of syndiotactic polypropylene and ethylene-propylene random copolymer, can be prepared. The bicomponent fibers may exhibit self-crimp properties and high shrinkage characteristics.
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REFERENCE TO A RELATED APPLICATION The present application is a continuation of our copending application Ser. No. 07/483,968 filed Feb. 15, 1990, now abandoned, which in turn is a continuation of our copending application Ser. No. 07/347,654 filed May 5, 1989, now abandoned, the entire disclosures of which applications are relied on and incorporated herein by reference. INTRODUCTION AND BACKGROUND The present invention relates to a finely divided silica with high structure, a method of preparing the silica and the use of the silica as a delustering agent in films of the paint, lacquer, varnish and enamel type. It is known that the delustering capacity of a silica depends on various factors such as e.g. the type of silica, the particle size, the refraction index and also on the vehicle system. Particle form and particle-size distribution of the secondary particles as well as the total effective specific particle volume are of particular significance. A number of other requirements are placed on delustering silicas in addition to high efficiency, expressed by the reduction of the degree of glossiness in comparison to a non-matte paint film. Thus, for example, the drying behavior of the film coatings should not be adversely affected, no excessive thickening of the paint coating system should occur and the scratch resistance of the film coatings should not be lowered by the silica added. The behavior in suspension of the silica is an important point. The tendency of silica to settle and to form hard sediment which can only be stirred up again with difficulty can be prevented or at least improved by a number of measures. Thus, for example, DE-AS 15 92 865 describes the impregnation of silica during the preparation process by means of wax emulsions. The addition of synthetic silica as delustering agent is known. See for example the publications: ______________________________________ EPO-Patent 0,008,613 German Patent 24 14 478 German DAS 17 67 332 German OLS 16 69 123 German DAS 15 92 865.______________________________________ Numerous methods of preparing synthetic silica are also known (cf. Ferch in "Chem.-Ing.-Techn." 48, pp. 922-33 (1976)). According to German Patent 24 14 478, aerogel-like delustering agents can be obtained by the structuring of pyrogenically prepared silica. To this end, pyrogenic silica is moistened with alkaline adjusted water, ground and dried. This procedure of preparing delustering agents is complicated and expensive. The delustering agent according to German Patent 24 14 478 is an excellent delustering agent. However, it has the disadvantage that it thickens the film compositions too heavily. A solvent must therefore be added in addition for working with a spray gun to facilitate application of the films to a surface to be coated. A wax-coated precipitated silica acid is prepared according to the process described in DE-PS 15 92 865 and is used as delustering agent. This delustering agent has the disadvantage, however, that the paints prepared with it exhibit an undesirable blue bloom on dark surfaces. SUMMARY OF THE INVENTION It is an object of the present invention to provide a finely divided precipitated silica of high structure with certain desired characteristics and especially to achieve a great savings of solvent while retaining the desired delustering action. Another object of the invention is to prepare a waxcoated delustering agent which does not exhibit a blue bloom and has a better delustering action. In more particular detail, an object of the present invention is to provide finely divided precipitated silica with a high structure and the following characteristics: ______________________________________BET surface (DIN 66132) between 150 and 350 m.sup.2 /gStamping density (DIN 53194) between 60 and 120 g/lDBP number between 3.0 and 4.0 ml/gParticle size distribution at least 70% from 1 to 6 μm(measured with a Coultercounter)(The determination isperformed according toDE-PS 17 67 332, column 2,lines 30-64.)______________________________________ In order to determine the particle size with a Coulter counter, approximately 0.5 g silica acid are dispersed in 50 ml isotonic solution of common salt (0.5% NaCl and 0.089% Na 4 P 2 O 7 . 10 M 2 O in distilled water) with a magnetic stirrer and subsequently treated for 1 minute with supersonics (200 watts). This suspension is added to 200 ml isotonic solution of common salt and agitated. A measuring capillary tube is immersed into the agitated suspension and an electric field is applied thereto. When the particles pass through the measuring capillary tube, the electric field is varied as a function of the particle size. It is still a further object of the invention to provide a method for preparing finely divided precipitated silica with a high structure processing the following characteristics: ______________________________________BET surface (DIN 66 132) of 150 to 350 m.sup.2 /gStamping density (DIN 53 194) between 60 and 120 g/lDBP number between 3.0 and 4.0 ml/gParticle size distribution at least 70% from 1 to 6 μm.______________________________________ The method of the invention is characterized by forming a mixture of water and sodium silicate which is then heated under agitation to a temperature of 70° to 80° C. Concentrated sulfuric acid is then dosed into this mixture until half of the alkali (sodium) present has been neutralized. The reaction mixture is treated by a shearing unit and, optionally, the temperature raised at the same time to 86°±5° C. Concentrated sulfuric acid is added after a waiting period of 30 to 120 minutes at a rather high rate of addition until the pH of the silica suspension produced is 3.0 to 3.5. The silica suspension is optionally diluted with water and the coarse portion optionally separated by a centrifugal pump and a hydrocyclone. The silica is filtered off by known filter devices and the resulting silica filter cake is washed free of sulfate. Then, the silica filter cake is redispersed with the addition of water using an agitator unit to form a suspension with a solid content of 80±10 g/l. Alkyl dimethylbenzyl ammonium chloride is optionally added to this suspension, and the suspension obtained in this manner is spray-dried. The recovered dried product can then be ground, if desired. DETAILED DESCRIPTION OF THE INVENTION In carrying out the present invention, silica particles are prepared with particle diameters in a particle-size range of 1 to 6 μm. Particles smaller that 1 μm are ineffective for delustering purposes and generally cause an undesirable thickening of the film vehicle. On the other hand, particles which are too large result in a disadvantageous roughness of the surface in the film coating. The object is to control appropriate sizes during the precipitation reaction and to retain chosen particle sizes by suitable measures until the finished product is obtained. In order to assure that all particles find the same conditions of growth, the entire charge of water glass starting material is put into a receiver at the beginning of the process for production. The addition of sulfuric acid is performed in two steps. In the first step, the addition of acid is measured in such a manner that the silica begins to flocculate after the end of the first stage of the addition of the acid. During this growth phase, in order to prevent an excessive particle growth, shearing is performed in addition to the agitation. The addition of acid remains interrupted until the desired particle spectrum has been achieved. Subsequently, the remaining alkali content of the water glass is neutralized in a second stage, during which shearing is continued. After a slightly acidic pH has been achieved, the precipitation reaction is terminated. The concentrated sulfuric acid used for purposes of the present invention is conventional and, for example, is in the range of D=1.75 to 1.85 and 90 to 97% by weight. The silica suspension is worked up and conditioned in the customary manner. There is the possibility that hard and coarse particles are produced in the course of the reaction by local excess acidifying. These undesired particles can be removed from the suspension with the aid of a hydrocyclone. The filtration of the suspension is performed e.g. with a plate-and-frame press in which the filter cake is washed free of sulfate. The washed filter cake is redispersed in water, a cationic tenside is optionally added and the product is then spray-dried. The cationic tenside (surfactant) brings about a displacement of the water from the particle surface thereby even in the aqueous phase, which suppresses to a great extent the shrinking process which takes place during the drying process. In this manner, it is possible to prevent the particles from clumping together to rather large, solid formations during drying. Depending on the desired degree of fineness, the silica can be used as is or additionally ground. As a result of the procedure described herein, a light grinding is sufficient, that is, only little grinding energy need be expended in order to disagglomerate the particles again. The precipitated silica of the present invention can be used as delustering agent in a wide variety of film coatings such as paints, varnishes, lacquers and the like. It has the advantage that no additional solvent need be used. In order to improve the sedimenting behavior of the silica products in coating film compositions, an impregnation with emulsions is carried out in accordance with the disclosure of DE-PS 15 92 865, incorporated herein by reference. A still further object of the invention is to provide a precipitated silica which is coated by an emulsion and prepared from the precipitated silica in accordance with the present invention. In this aspect of the invention, the coating can take place according to the known method of DE-PS 15 92 865 which corresponds to U.K. Patent 1,236,775, the entire disclosure of which is relied on and incorporated by reference. The coated precipitated silica exhibits a carbon content of 1 to 8% by weight in addition to the same physical and chemical characteristic data of the uncoated precipitated silica. In one embodiment of the invention, the precipitated silica can be coated by a silicon oil emulsion. This precipitated silica can be used as delustering agent in paints, varnishes, lacquers and the like. In a further particular embodiment of the invention, the precipitated silica can be coated by a polyethylene wax emulsion. This precipitated silica product can be used as delustering agent in paints, varnishes, lacquers and the like. It is especially advantageous that the precipitated silica coated with the wax emulsion does not generate a blue bloom in the paint surfaces. All manner of film forming components can be combined with the delustering agents of the invention. The following examples serve to illustrate the details of the present invention. The method of the invention is carried out in known apparatuses. The core of the precipitation apparatus used herein is a hard-rubberized, double-jacketed vessel with a volume of 120 liters which is provided with an agitator mechanism. Potential agitators suitable for the invention are e.g. anchor mixers, straight-arm paddle agitators or turbines. The reaction vessel can be heated with oil as heat carrier and thermostatted via the double jacket. A discharge pipe or tube is fixed to the bottom of the reaction vessel which pipe comprises a branch line in front of the bottom discharge valve. This branch runs to a shearing unit (Dispax reactor) with which the content of the reaction vessel can be rotated. The rotated precipitation suspension can be reintroduced into the top of the reaction vessel via the pipeline fixed to the pressure side of the shearing unit. The addition of water glass takes place either via a dosing pump from a storage vessel or directly from a vat by a vat pump. The sulfuric acid is dosed from a storage vessel by a dosing pump. The precipitation suspension is pumped for filtration with the aid of a positive-displacement pump into a plate-and-frame press on which the filter cake produced is washed free of sulfate with water. The washed filter cake is either placed on metal sheets and dried in a drying oven or is dispersed in water and spray-dried. The dried silica can be subsequently ground. The product dried in a drying oven must generally be pre-ground in a toothed-disk mill before the fine grinding by means of a pin mill or air-jet mill. The spray-dried product can either be used directly or subjected to a fine grinding. The efficiency of the non-coated precipitation silica prepared according to Examples 1-6 is compared in a black baking varnish with the product prepared according to DE-PS 24 14 478. In addition to the solvent requirement, the degree of glossiness according to Lange at a reflection angle of 60° and the grindometer value according to Hegman are evaluated. For the determination of the degree of glossiness, which is a measure for the delustering power of the tested delustering silica, the gloss meter according to B. Lange, which is often used in Germany, is used. The Lange gloss meter uses an angle of 45° as incident and reflection angle. The measured degrees of glossiness are indicated in percents. The smaller their value, the better the delustering capacity of the silica tested, or, in other words, the less delustering agent needs to be used in order to achieve a quite specific degree of gloss. The determination of grindometer value is carried out with the aid of a grindometer. The grindometer value, which is measured in μ, is a measure for the coarsest particles located in the finished, sprayable film composition mixture after the delustered silica has been stirred in. It can be related to the formation of specks in the dry paint film. The feared and undesired "spray grain" can be recognized with the aid of the grindometer. The paint used has the following composition: 7.5 parts by weight paint prepaste Tack® 1 47 parts by weight fatty-acid modified alkyd resin 60% in xylene (Alftalat AR 481 m) 24 parts by weight melamine resin Maprenal MF 800 55% in isobutanol 6 parts by weight butanol 10.5 parts by weight xylene 1 part by weight silicon oil Baysilon paint additive OL 17 1% in xylene. 2.6 parts by weight product are worked in at a time. The working in is carried out by ten-minute agitation with a wing agitator at 2000 rpms. The paint is sprayed onto metal sheets in a dry layer approximately 30 μm thick, air-dried and annealed 30 min. at 180° C. The values determined can be gained from table 2 below. Example 1 66 kg Water and 21 kg soda water glass (d=1.35 g/cm 3 ; ratio SiO 2 :Na 2 O=3.3) are added into the precipitation vessel and the mixture heated under agitation to 75° C. Concentrated sulfuric acid (d=1.83) is dosed into the precipitation mixture at a rate of 1.45 l/h. After 25 minutes of precipitation time, the shearing unit (Dispax reactor) is switched on. Shortly after the end of the addition of acid, silica begins to flocculate and the temperature of the precipitation is raised to 85° C. The supply of acid is interrupted for 20 minutes (waiting stage). After 50 minutes, the further addition of acid takes place with 1.8 l/h over a period of 15 minutes. The silica suspension produced exhibits a pH of 3.4 thereafter. The shearing unit is then cut off. The suspension is diluted with 28 l water and conveyed by means of a centrifugal pump with 4.5 bars supply pressure onto a hydrocyclone. The ratio of coarse material suspension to fine material suspension is 1:12. The fine material suspension is passed over a plate-and-frame press and washed sulfate-free. The washed filter cake is redispersed using an Ultra-Turrax with the addition of water in such a manner that a suspension of 80 g/l is produced. An alkyl dimethylbenzyl ammonium chloride (BARQUAT®) is added to the suspension, so that 0.8 g/l active substance is present in the suspension. This suspension runs through a sieve with a mesh size of 120 μm, which retains coarse foreign particles. The suspension is spray-dried immediately thereafter. The atomization takes place by means of a two-fluid nozzle. The dried product has the following physical and chemical properties: ______________________________________pH (DIN 53200) 6.0Water content (DIN) 4.8%Specific surface (DIN 66132) 272 m.sup.2 /gDBP absorption (ml/g) 3.7Stamping density (DIN 53194) 87 g/lParticle size distribution(Coulter counter)<1 μm 5%1-6 μm 84%>6 μm 11%______________________________________ EXAMPLES 2-5 Precipitated silica is prepared as described in Example 1 with the sole difference that the time of the interruption of the addition of acid (equal to the waiting stage) is varied. The physical and chemical data of the silica products obtained are ser forth in Table 1 below. EXAMPLE 6 A precipitated silica is prepared as described in Example 1. In contrast to Example 1, the heating to 85° C. during the second phase of the addition of acid is eliminated. The waiting stage is 30 minutes. The physical and chemical data of the precipitated silica obtained in this was set forth in Table 1 below. EXAMPLE 7 A precipitated silica is prepared as described in Example 1. In contrast to Example 1, the waiting stage is 60 minutes. After the end of precipitation, 3.4 kg of an emulsion of silicon oil are added into the precipitated silica suspension. The emulsion is prepared as follows: 0.24 parts by weight Emulan AF are dissolved in 80 parts by weight water. 20 parts by weight Baysilon oil® AC 3031 are added under dispersion with an Ultra-Turrax. The work-up of the precipitated silica suspension takes place as described in Example 1. The spray-dried precipitated silica is subsequently ground in an air-jet mill. The physical and chemical data for this product are set forth in Table 3 below. EXAMPLE 8 (Coating With Polyethylene Wax Emulsion) A precipitated silica is prepared as described in Example 1. The waiting stage is 90 minutes. 45 l of the fine material suspension obtained is compounded with 625 g of a wax emulsion under agitation. The wax emulsion is prepared in an autoclave which can be heated with vapor and is provided with a dispenser. 4.8 parts by weight of an alkyl polyglycol ether (Marlowet® GFW) are first dissolved in 81.0 parts by weight water at approximately 100° C. Then, 14.2 parts by weight low-pressure polyethylene wax are added and heated to 130° C. When 130° C. has been reached, the dispenser is turned on and the mixture dispersed for 30 minutes. During this time, the temperature is maintained between 130° C. and 140° C. After the dispenser has been turned off and the mixture cooled off to approximately 110° C., the finished emulsion is discharged. The polyethylene wax used is characterized by the following characteristics: ______________________________________Average molecular weight 1000Solidification point 100-104° C.Drop point 110-117° C.Density (g/cm.sup.3) 0.93.______________________________________ The precipitated silica suspension is worked up as described in Example 1. The spray-dried precipitated silica is then ground in an air-jet mill. The physical and chemical data for this product are set forth in Table 3 below. EXAMPLE 9 (Coating With Polyethylene Wax Emulsion) A precipitated silica is prepared as described in Example 1. The waiting stage is 90 minutes. 45 l of the fine material suspension obtained is compounded with 860 g of a wax emulsion under agitation. The wax emulsion is prepared in an autoclave which can be heated with vapor and is provided with a dispenser apparatus. 4.8 parts by weight of an alkyl polyglycol ether (Marlowet® GFW) are first dissolved in 81.0 parts by weight water at approximately 100° C. Then, 14.2 parts by weight low-pressure polyethylene wax are added and heated to 130° C. When 130° C. has been reached, the dispenser is turned on and the mixture dispersed for 30 minutes. During this time, the temperature is maintained between 130° C. and 140° C. After the dispenser apparatus has been turned off and the mixture cooled off to approximately 110° C., the finished emulsion is discharged. The polyethylene wax used has the following characteristics: ______________________________________Average molecular weight 2700Solidification point 92-96° C.Drop point 102-110° C.Density (g/cm.sup.3) 0.92.______________________________________ The precipitated silica suspension is worked up as described in Example 1. The spray-dried precipitated silica is then ground in an air-jet mill. The physical and chemical data are set forth in Table 3 below. EXAMPLE 10 The technical applications capabilities of the precipitated silicas obtained according to examples 7,8 and 9 are compared in three test-paint formulations with a delustering agent prepared according to DE-PS 15 92 865. The data is compiled in Table 4 below. The determination of the degree of glossiness is performed with gloss-measuring devices according to Lange and Gardner (ASTM D 523-53 T). According to Lange, the incidence and reflection angles are 45°, according to Gardner 60° and 85°. The grindometer value is determined according to ISO 1524 in black stoving lacquer. The text-paint formulations and the method of procedure are described below. A) Black stoving lacquer ______________________________________ parts by wt.______________________________________Paint prepaste TACK ® 1 7.5Alkydal ® R 40/60% in xylene 47.0Maprenal ® MF 800/55% in isobutanol 24.0Butanol 5.0Ethyl glycol 3.0Xylene 8.5Butyl glycol 3.0Baysilon ® oil OL 17 1% in xylene 2.0.______________________________________ 5 g precipitated silica as the delustering agent are stirred into 100 g paint with a wing agitator at 2000 rpms for 8 minutes. The viscosity of the mixture is set with xylene to a discharge time of 20 seconds (Ford beaker, DIN 4 mm nozzle). The paint is sprayed onto metal sheets in a dry layer approximately 30 m thick, air-dried and annealed 30 min. at 180° C. B) Polyester paint (UP paint) ______________________________________ parts by wt.______________________________________Roskydal ® 500 A 36.0Roskydal ® tix 18 4.0Tert. butyl catechol 1% in monostyrene 0.5Aerosil ® 200 0.3Barite, ground 20.0Bayer titanium R-FD-1 10.5Green pigment 600 1.5Baysilon ® oil OL 17 1% in toluene 2.0Ethyl acetate 6.0Monostyrene 18.4Octa-Soligen cobalt in toluene (2.2% Co) 0.8.______________________________________ 6.5 g precipitated silica as the delustering agent are added to 100 g of this paint mixture before processing and dispersed 8 minutes at 2000 rpms with a wing agitator. The viscosity of the mixture is adjusted with ethyl acetate to a run-off time of 20 seconds (Ford beaker, DIN 4 mm-nozzle). The paint mixture is applied in layer thicknesses of approximately 80 μm. C) DD paint ______________________________________ parts by wt.______________________________________Desmophen ® 800 10.0Desmophen ® 1700 20.0NC-Chips E 730 4.0Butyl acetate 98% 18.0Ethyl glycol acetate 22.8Butoxyl 5.0Shellsol ® A 20.0Baysilon oil OL 17 10% in xylene 0.2.______________________________________ 10.8 g delustering agent and 36 g Desmodur® L/75% in ethyl acetate are added to 100 g of the above mixture and dispersed 8 minutes at 2000 rpms with a wing agitator. The mixture is adjusted with ethyl acetate to a run-out time of 18 seconds (DIN beaker, 4 mm nozzle according to DIN 53211). The application is performed in layer thicknesses of 30-40 μm. Table 4 shows that a distinct improvement of the delustering action can be determined in all test paint formulations over the state of the art. TABLE 1__________________________________________________________________________Waiting Water Specific StampingStage Content surface DBP density Grain-size distributionTime pH DIN 55921 DIN 66132 absorption DIN 53194 (Coulter counter)(min.) DIN 53200 (%) (m.sup.2 /g) (ml/g) (g/l) <1 μm 1-6 μm >6 μm__________________________________________________________________________Example 1 20 6.0 4.8 272 3.7 87 5 84 11Example 2 30 6.0 5.3 300 3.8 80 7 85 8Example 3 45 5.2 5.7 239 3.7 82 10 85 5Example 4 60 5.8 6.4 244 3.4 86 15 84 1Example 5 90 5.9 3.9 278 3.8 76 15 83 2Example 6 30 6.4 7.7 316 3.8 103 3 84 13__________________________________________________________________________ TABLE 2__________________________________________________________________________ Parts by wt. Viscosity Solvent per DIN 4 mm processing Grindometer 5 = % gloss 60°Product sec. consistency value in μm length__________________________________________________________________________From Example 1 33 1.5 50 38.5From Example 2 33 1.5 37 40.5From Example 3 32 -- 28 42.5From Example 4 38 4.5 30 38.5From Example 5 31 -- 28 47.0From Example 6 33 -- 47 38.0Reference product 39 5.5 40 38.5according to DE-PS24 14 478__________________________________________________________________________ TABLE 3__________________________________________________________________________ Water Specific Stamping Content surface DBP density pH DIN 55921 DIN 66132 absorption DIN 53194 Carbon DIN 53200 (%) (m.sup.2 /g) (ml/g) (/gl/) content (%)__________________________________________________________________________From Example 7 6.2 4.7 250 3.7 64 1.7From Example 8 6.7 4.9 213 3.5 83 3.5From Example 9 6.7 4.9 203 3.6 79 4.0__________________________________________________________________________ TABLE 4__________________________________________________________________________ Black Stoving Varnish UP paint DD paint Grindometer Gloss 45° Gloss 45° Gloss 40° Gloss 85° Gloss 45° Gloss 60° Gloss 85°Product value in μm Lange Lange Gardner Gardner Lange Gardner Gardner__________________________________________________________________________From Example 7 28 2.5 17 26 49 5.5 9 18From Example 8a 30 2.5 8 13 22 6.5 10 17From Example 8b 30 2.5 13.5 21 40 4.5 9 13Delustering 26 4.5 44.5 59 86 22.5 36 68agent accordingto DE-PS 15 92 865__________________________________________________________________________ The trade designations used in the examples have the following meanings: ______________________________________Paint prepaste Tack ® 1Product Composition (% by wt.)______________________________________Carbon black paste 1 18 pigment carbon black of class HCC 36 alkyd resin based on soya bean 46 solventAlftalat AR 481 mCharacteristic: Short or medium oily, drying alkyd resins.Areas of application: Stoving varnishes and stoving first coats for metallic surfaces. Acid-hardening paints. Nitrocellulose combination paints.______________________________________ Alftalat AR 481 m______________________________________Composition of the100% resin (approximate)Oil content (triglyceride) 48%Phthalic acid anhydride 39%ViscosityRun-out time 4, DIN 53211/29° C. s 50-7023° C. s 40-60Dynamic viscosityDIN 53177/20° C. mPa · s 215-30023° C. mPa · s 175-250Color valueIodine color value DIN 6162 mg I/100 cm.sup.3 <15Gardner color standard <7ASTM D 1544Acid value mg KOH/g 25DIN 53402Density (delivered form) g/cm.sup.3 approx. 1.0220° C.Content of non-volatile % approx. 60portionsDIN 53216 (2 g + 2 cm.sup.3toluene/1 h 125° C.)Flash point (delivered form) °C. approx. 27DIN 53213______________________________________ Maprenal MF 800 Characteristic: Non-plasticizied, isobutyl-etherified melamine formaldehyde resins. ______________________________________ Maprenal MF 8 800______________________________________Viscosity (delivered form)Run-out time 4, DIN 53211/20° C. s 60-9023° C. s 50-80Dynamic viscosityDIN 53177/20° C. mPa · s 250-43023° C. mPa · s 220-360Color value (delivered form)Iodine color value DIN 6162 mg I/100 cm.sup.3 <1Gardner color standard <1ASTM D 1544Acid value mg KOH/g <1DIN 53402Density g/cm.sup.3 approx 0.9920° C.Gasoline compatibility cm.sup.3 /1 g 5-10(n-heptane)DIN 53 187melamine resin(delivered form)Content of non-volatile % approx. 55components (delivered form)DIN 53216 (2 g + 2 cm.sup.3)Butanol/1 h 120° C.)Flash point (delivered form) ° C. approx. 31DIN 53 213______________________________________ Baysilone paint additive OL 17 Polyether-modified methyl polysiloxane ______________________________________Delivery tolerances: appearance clear, yellowish iodine color max. 3 value, DIN 6162 viscosity, DIN 53015 650-850 mPa · s 23° C.Other characteristic density, DIN 53217 1.025-1.050 g/mldata: 20° C. flash point, approx. 80 C. DIN 51758 surface tension, DIN 53914, 23° C. approx. 21 mN/m with Harkins-Jordan correction refractive index, 1.447-1.451 23° C.Solubility: gasoline hydrocarbons u/l benzene hydrocarbons l alcohols l esters l ketones l glycol ethers l glycol ether acetates l explanations: l = soluble u = insoluble______________________________________ Baysilon oil® AC 3031 Chemical characterization polysiloxane diol ______________________________________Physical data______________________________________Melting temperature <-60° C. (setting point)Softening temperatureBoiling temperature above approx. 130° C.Decomposition temperature °C.pH approx. 7-8 (at 20 g/l water)Solubility in water insoluble at 20° C.Intrinsic odor distinct intrinsic odorState (20° C.) liquidVapor pressure (20° C.) <100 mbarsDensity (20° C.) 0.98 g/ml______________________________________ ______________________________________Emulan AF______________________________________Chemical medium-highly ethoxylated fattycharacter alcohol, non-ionicSolubility Dissolves well and usually also(at 25° C., 10%) clear in mineral oils, fatty oils, molten paraffins and fats. Dissolves clear in most organic solvents.Chemical character fatty alcohol ethoxylateConsistency like soft wax(room temperature)Acid value (DIN 53402) pract. 0Saponification value pract. 0(DIN 53 401)pH (1% aqueous solution 6-7.5or dispersion)Active substance pract. 100%contentDensity (c/cm.sup.3) approx. 0.91(20° C.)(DIN 53757) (50° .C)Viscosity (mPa · s) --(20° C.) (DIN 53015)Melting point approx. 42° C.Solidification point --Drop point (DGF M-III-3) --Flash point (DIN 51758) approx. 190° C.HLB value (W. C. Griffin) approx. 11Chief active tendency oil in water(Emulsion type)Solubility tendency in mineral oil and polar organic media______________________________________Alkydal R 40______________________________________Short-oily alkyd resin based on ricin oilOil content/triglyceride approx. 40%Phthalic acid anhydride approx. 38%Density/20° C. approx. 1.13 g/cm.sup.3OH content 2.5%Delivery toleranceIodine color number/50% max. 5solutionAcid value/solvent-free 20-30Viscosity/20° C. delivery form 3500-4500 mPa · s (cP)Flash point approx. 27° C.______________________________________Roskydal 500 A______________________________________Unsaturated polyester resin (glossy polyester), reactive,hardens hardDelivery tolerance.sup.1Non-volatile portion 74-77%Hazen color max. 100Acid value/delivery form 10-20Viscosity/20° C. 2200 . . . 2600 mPa · sOther data:Density/20° C. approx. 1.12 g/cm.sup.3Flash point approx. 37° C.______________________________________ .sup.1 test methods according to DIN 58184 Roskydal tix 18 Thixotropic, unsaturated polyester resin (paraffin type), reactive ______________________________________ Supply tolerance.sup.2______________________________________Non-volatile portion 49 . . . 53%Iodine color value max. 2Acid value/delivery form max. 15Viscosity 20° C. thixotropic flow behaviorFlash point approx. 32° C.______________________________________ .sup.2 test methods according to DIN 53184 __________________________________________________________________________Bayertitan R-FD-1 Brightening Rel. Oil Number Capacity according Scattering Density [adsorption] to Reynolds Power according Additional according to according to according to toBayertitan % TiO.sub.2 Components DIN 53 199 DIN 53 192 DIN 53 165 DIN 53 193__________________________________________________________________________F-FD-1 96 Al.sub.2 O.sub.3 19 1900 750 112 4 ·__________________________________________________________________________ ______________________________________Green pigment 6001 Green pigment 6001______________________________________Color index No. 77 335Color index pigment 19Chemical composition Co--Al--Ti--Ni Zn oxideOil number (1) g/100 g 20Drying loss (2) % max. 0.5Stamping density (3) g/l 1600Sieve residue (4) % max. 0.1Color strength (7) --Covering capacity 190value (8) %Particle size (TEM) m 0.15-2.0Density (9) g/cm.sup.3 5.0Water-soluble max. 0.5portion (10) %Spec. surface (11) m.sup.2 /g --pH (12) 8.5-9.5Heat resistance °C. >500Light resistance/ 8full shade (13)TiO.sub.2 mixture 1:1 8TiO.sub.2 mixture 1:10 8Weather resistance/ very goodfull shadeAcid resistance very goodAlkali resistance goodLime resistance goodSolvent resistance very goodMigration resistance very good______________________________________ Explanation of the footnotes: (1) according to DIN ISO 787/V, ASTM D 281 or JIS K 5101/9 (2) according to DIN ISO 787/II, ASTM D 280 or JIS K 5101/21. In the case of VOSSEN blue, the reweighing is performed immediately after removal of the specimen from the drying oven in a hot state. (3) according to DIN ISO 787/XI of JIS K 5101/18 (4) Cd, Co and Ti pigments according to DIN 53 195 (0.045 μm sieve) VOSSEN blue according to DIN ISO 787/XVIII, (0.040 sieve) [sic], ASTM D 1714 or JIS K 5101 20 (5) according to ISO 787/I (6) according to ISO 787/XVI (7) according to DIN 53 204 and DIN 53234 (8) soft in PVC, TiO2 RN 56 = 100% (9) according to DIN ISO 787/X or JIS K 5101/17 (10) according to DIN ISO 787/III or JIS K 51010/22 (11) according to DIN 66 131 (12) according to DIN ISO 787/IX, ASTM D 1208 or JIS K 5101/24 (13) according to DIN 54 003 or JIS K 5101/15 Octa-Solingen cobalt Octa-Solingen cobalt is a dry substance which contains 16% Co in addition to 2-n ethyl hexanoic acid (C 8 H 16 O 2 ). ______________________________________Desmophen 800______________________________________Heavily branched polyester containing hydroxyl groups.Characteristic valuesDelivery form 100% approx. 85%Hydroxyl content: approx. 8.8% approx. 7.5%Acid value: <4 <4Color value according 7-10* 3-8*to DIN 6162:Flash point accordingto DIN 51 758: >200° C. --to DIN-EN 53 -- approx. 49° C.Density at 20° C. 1.14 g/cm.sup.3 approx. 1.11 g/cm.sup.3according to DIN 51 757:Viscosity 900 ± 100 900 ± 100(velocity gradient mPas** mPas**D 150 s.sup.-1) at 20° C.: 725 ± 75 725 ± 75Water content: <0.15% <0.15%______________________________________ *50% in ethyl glycol acetate **70% in ethyl glycol acetate Aerosil® 200 Aerosil® 200 is a pyrogenically prepared silicic acid with the following physical and chemical characteristic values: ______________________________________Surface according to BET m.sup.2 /g 200 ± 25Average size of the primary nanometer 12particlesStamping density (1) g/l approx. 50Drying loss (2) (2 h at 105° C.) % <1.5upon leaving the worksAnnealing loss (2)(6) % <1(2 h at 1000° C.)pH (3) (in 4% aqueous 3.6-4.3dispersion)SiO.sub.2 (5) % >99.8Al.sub.2 O.sub.3 (5) % >0.05Fe.sub.2 O.sub.3 (5) % >0.003TiO.sub.2 (5) % >0.03HCl (5) % >0.025Sieve residue (4) according % >0.05to Mocker (45 m)______________________________________ Technical Data of the Aerosil Standard Types 1) according to DIN 53 194 2) according to DIN 55 921 3) according to DIN 53 200 4) according to DIN 53 580 5) in relation to the substance annealed 2 hours at 1000° C. 6) in relation to the substance dried 2 hours at 105° C. 7) HCl content is a component of the annealing loss ______________________________________Desmophen 1700______________________________________Linear polyester containing hydroxyl groupsCharacteristic dataHydroxyl content: approx. 1.2%Equivalent weight: approx. 1418Color value according to DIN 6162*: max. 5Flash point according to DIN 51758: >200° C.Density at 20° C. according to DIN 53217: approx. 1.19 g/cm.sup.3Viscosity at 23° C.** 575 ± 75 mPa · s(velocity gradient D ≈ 190 s.sup.-1)Water content: >0.15%______________________________________ *50% in ethyl glycol acetate **70% in ethyl glycol acetate NC-Chips E 730 NC-Chips E 730 is a collodion cotton [c.c. (wool), pyrocellulose, soluble nitrocellulose, pyroxyline] Shellsol® A Shellsol® A is a carbon solvent rich in aromatic hydrocarbons with the following data: ______________________________________Boiling limits °C. ASTM D 107/86 160-182Density at 12° C. ASTM D-1298 0.874Flash point °C. AP IP 170 PM ASTM D-93 47Evaporation number (ether = 1) DIN 53 170 46 ##STR1## 1.499Color (Saybolt) ASTM D-156 +30Viscosity 25° C. mm.sup.2 /s ASTM D-445 0.810Aniline [cloud] point ° C. = mixes ASTM D 611 15Kauri-butanol value ASTM D-1133 90Aromatic hydrocarbon content vol. % ASTM D-1319 19Surface tension at 20° C. mN/m ASTM D-971 29.5______________________________________ Desmodur L Aromatic polyisocyanate ______________________________________ 75% delivery 67% deliveryCharacteristic data form form______________________________________NCO content*: approx. 13% approx. 11.6%Equivalent weight: approx. 323 approx. 362Color value according max. 5 max. 5to DIN 6162*:Flash point according approx. +1° C. approx. -38° C.to DIN 53 213:Density at 20° C. approx. 1.17 approx. 1.15 g/cm.sup.3according to DIN 53217: g/cm.sup.3Viscosity at 23° C. 1500 ± 400 1500 ± 400(mPa · s)*Monomeric diisocyanate >0.5% >0.5%content______________________________________ *Delivery specification The term "DIN" stands for German industrial standard. As will be apparent from the above, many different film forming components such as synthetic resins and mixtures with or without pigments are suitable for combination with the finely divided precipitated silica delustering agent of this invention. Further modifications and variations will be apparent to those skilled in the art and are intended to be encompassed by the claims appended hereto. German priority application P 38 15 670.9-41 is incorporated and relied on herein.
Finely divided precipitated silica for use as a delustering agent with high structure and a ______________________________________ BET surface (DIN 66 132) of 150 to 350 m 2 /gStamping density (DIN 53 194) between 60 and 120 g/lDBP absorption number between 3.0 and 4.0 ml/gParticle size distribution at least 70% from 1 to 6 μm______________________________________ can be prepared by heating a mixture of water and sodium silicate under agitation to a temperature of 70° to 80° C., adding concentrated sulfuric acid into this mixture until half of the alkali present has been neutralized, shearing the reaction mixture and optionally raising the temperature at the same time to 86°±5° C. Concentrated sulfuric acid is added after a period of 30 to 120 minutes at a rather high rate until the pH of the silica suspension produced is 3.0 to 3.5. The resulting silica suspension is ultimately filtered off by known filter devices, the silica filter cake washed free of sulfate, and a dry product is ultimately obtained.
44,428
[0001] This is a continuation-in-part of an allowed application, Ser. No. 09/356,549, filed on Jul. 19, 1999, which is a division of Ser. No. 09/046,834, filed on Mar. 25, 1998, now U.S. Pat. No. 6,051,246, which claims foreign priority based on a Taiwan application, 86103892, filed on Mar. 28, 1997, now abandoned. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] This invention relates to a novel antimicrobial filter and a filtration process employing said filter. More specifically, it relates to a water treatment process comprising filtering water through a bed of sand which is coated with antimicrobial chemicals that kill and prevent the growth of bacteria. [0004] 2. Prior Art [0005] Antimicrobial metals have been known to be incorporated into paints and fibers for industrial or home applications. Organic quaternary ammonium silane has been shown to have anti-algae properties. The following patents show the use of silver, copper, and zinc in antimicrobial substances, and the use of organosilicon compounds. [0006] U.S. Pat. No. 3,865,728 discloses an organosilicon compound coated on a fibrous substrate and then heated to 65-100 degrees C. The resulting product is used for control of algae in aquarium tanks. [0007] U.S. Pat. No. 5,147,686 discloses an antimicrobial powder made by coating a titanium oxide substrate with antimicrobial metals including copper, zinc or alloys of Cu—Zn, Cu—Ag, Cu—Al, Cu—Sn or a combination of these metals. The composition is useful against various microorganisms such as E. Coli, Salmonella typhimurium, and others. The coated substrate is fired at 400 degrees C. The powder form of this product is intended to be incorporated into a resin. [0008] U.S. Pat. No. 5,151,122 relates to an antibacterial ceramic material. Various ceramics such as zeolite or alumina or clay are described as being fired at temperatures as high as 1200-1300 degrees C. so as to lock in the absorbed antibacterial metals such as silver, copper, or zinc. The patent further suggests that the product can be added to a resin which can be molded into any shape. [0009] U.S. Pat. No. 5,415,775 relates to an ultrafiltration membrane consisting of alumina and titanium dioxide which has been sintered at 1000-1500 degrees C. and then coated with metal oxide. The membrane exhibits anti-bacterial properties. [0010] U.S. Pat. Nos. 5,618,762, 5,503,840, and 5,595,750 variously show Ag, Cu, Zn. Pt, Cd, Cr as antibacterial components including protective coatings. [0011] None of the above patents addresses the problem of keeping water in reservoirs, cooling tower basins, public baths, and fish farms clear of harmful micro-organisms including algae or bacteria. In addition to its antimicrobial properties, the filter of the present invention is economical and shows high efficacy due to the small particle size structure of the sand which provides sufficient antimicrobial sites per unit volume and prolonged antimicrobial efficacy in flowing water due to strong adhesion of the antimicrobial components on the substrate, without any adverse environmental effects such as are encountered when chemical pesticides, bactericides or herbicides are used. [0012] The object of this invention is to provide antimicrobial filters having coated thereon a metal composition such as silver or copper, or coated with an organic quaternary ammonium salt according to a specific process capable of eliminating harmful microbes such as E. coli, Salmonella typhimurium, and Saccharomycetes such as Saccharomyces cerevisiae, Candida albicans; Algae groups, such as Blue Green Algae, Brown Algae, and Green Algae, and Bacteria such as Chaetomium globosum, Penicillium funiculosum including Legionella pneumophila. Another object is to provide a process for treating water with inexpensive filter media which have been treated with the antimicrobial substances of this invention. Such filter media are easily handled and can be changed as frequently as necessary to eliminate harmful microbes. The method of filtering water can be carried out in commercially available equipment. The coated sand can be filled in a water container or encased in a container formed by a mesh screen whose mesh openings are smaller than the sand particles. The container can then be replaced when the chemical coating is spent. These objects of the invention will become apparent from the following description. [0013] This embodiment of the invention is more economical than the honey-comb shaped substrate of applicant's above-mentioned application. The coatings of sand with silver or copper may be based on the method described in the prior application except for the elimination of calcining aids in both organic and inorganic coatings. [0014] In this invention, the sand treated with antibacterial substances removes suspended solids and eliminates bacteria and prevents their growth in the water. SUMMARY OF THE INVENTION [0015] The organic antimicrobial component is a quaternary ammonium salt having the formula: [0016] wherein m+n is 16 to 19, m is 1 to 6, and n is 13 to 17; or m+n is 20 to 23, m is 4 to 11 and n is 9 to 17 X is halogen; and Y is a hydrolyzable radical or hydroxy group. The inorganic antimicrobial components are silver or copper. These antimicrobial metal components are individually coated on sand with appropriate metals, and the coated sands are used as filter media either singly or in combination including inorganic-coated sand, to clean water. BRIEF DESCRIPTION OF THE DRAWING [0017] [0017]FIG. 1 shows the survival rate of the bacteria in accordance with the invention of an organic antimicrobial coating on a honeycomb-shaped substrate. DETAILED DESCRIPTION OF THE INVENTION [0018] Sand having a particle size corresponding to 10-20 mesh screens is impregnated with 1% by weight of silver nitrate solution, or 1% by weight of copper nitrate solution, respectively. The coated sand at is then calcined at 500 degrees C. for about 4 hours. The calcined coated sand is then washed in an ultrasonic cleaner to ensure that no loose chemicals adhere to the sand particles. [0019] The coating processes for the quaternary ammonium salts are described below. In addition, the organically coated sand is tested with bromophenol blue to ensure the coated sand is quantitatively indicating the presence of quaternary ammonium salt. A blue color indicates that the ammonium salt is at full strength. This is a reliable and convenient quality control method. [0020] Quaternary ammonium orgnanosiloxane salt (herein referred to as quaternary ammonium salt) used as algicide by coating on a fibrous material as shown in U.S. Pat. Nos. 3,817,452 and 3,865,728 forms no part of this invention. Rather, this invention provides a new method of preparing an antimicrobial filter. Moreover, the filter kills not only algae but also bacteria. [0021] In the process of coating the sand, the quaternary ammonium salt is dissolved in water to form a moiety of —Si(OH) 3 and the sand is soaked in the solution. The moiety of the quaternary ammonium salt reacts with the sand, SiO 2 , thereby forming a strong bond. 3-(Trimethoxysilyl)-propyidimethyloctadecyl ammonium chloride is representative of the group of silyl quaternary ammonium salts that may be used in the instant application. [0022] It has been found that in the process of making the organic antimicrobial filter of this invention, a special calcining aid may be used to enhance the adhesion or bonding of the quaternary ammonium salt to the substrate. The calcining aid is aluminum oxide with high pore surface per unit volume, such as Boehmite, which is available from Condea Corporation in Germany. Other calcining aids can be SiO 2 or SiO 2 Al 2 O 3 . [0023] In the preparation of the organic antimicrobial filter, aluminum oxide may be mixed with water in the ratio of 1:1 to 1:10 by weight. An acid such as nitric, hydrochloric, or oxalic acid is added to adjust the pH to 3-6. After the mixture is ground to a gelatinous solution, the sand is immersed in the gelatinous solution. This calcining-aid-coated sand is then calcined at 400 to 1500° C., preferably at 500 to 800° C. [0024] Quaternary ammonium salt is dissolved in a solvent selected from the group consisting of water, alcohols, ketones, esters, hydrocarbons, and chlorinated hydrocarbons in a concentration of about 0.05 to 20%, preferably 0.3 to 0.6% by weight. Water is the preferred solvent. The calcined sand prepared as described above is impregnated with the quaternary ammonium salt solution until it is saturated or until 50% of the solution is absorbed. The impregnated sand is then dried at 50 to 200° C., preferably at 60 to 150° C. to form the organic antimicrobial filter. Drying time depends on the amount of sand used. In a simplified process, the sand is directly placed in the 0.3 wt % of quaternary ammonium salt to saturate the sand and then dried at about 150° C. [0025] The antimicrobial filter of this invention may be placed in circulating water such as cooling tower water, to kill microbes. They may be placed in circulating air in air conditioning systems to sterilize the air. After a period of use, the filter may be regenerated by flushing with clean water or vibrated with a ultrasonic device and using a blower to remove any accumulated debris and cleaned by reversing the flow of water. [0026] The following examples illustrate the preparation of the antimicrobial articles of this invention and their efficacy. EXAMPLE 1 Preparation of the Inorganic Antimicrobial Filter [0027] Prepare a solution of 1 part by weight of the metal composition Ag NO3 and 99 parts by weight water. 10 mesh sand is added to the solution to be impregnated till saturation. Excess solution is drained. The coated substrate is calcined at 800-900° C. [0028] Prepare a solution of 1 parts by weight of the metal composition Cu(NO3)2.3H 2 O and 99 parts by weight water. 10 mesh sand is added to the solution to be impregnated till saturation. Excess solution is drained. The coated substrate is calcined at 800-900° C. Process of Producing Organic Antimicrobial Filter [0029] Into 100 ml. of 0.3 wt. % aqueous solution of 3-(trimethoxysilyl)propyldimthyloctadecyl ammonium chloride, there is dipped 100 grams of sand substrate to soak until saturated. At least 50% of the solution should be absorbed. The soaked substrate is dried at 100° C. for about 30 minutes to allow chemical bonding to occur. [0030] The inorganic coated sand may be mixed with the organic coated sand. Also the water flow may be reversed, with the water coming from bottom of the water tank, passing upward through the coated sand filter and leaving the water tank from the top. The reversed flow is intended to increase the contact with the filter and create more turbulent flow. [0031] Any tank fitted with inlet and outlet pipes may be used to implement the cleaning process of this invention. Provisions should be made to facilitate the change of antimicrobial sand. Alternatively, the antimicrobial sand may be enclosed in a wire mesh case whose mesh openings are smaller than the sand particles. [0032] It has been established in U.S. Pat. No. 6,051,246, this applicants' prior invention, the efficacy of the quaternary ammonium salt coated on a honey-comb shaped substrate as follows: [0033] Example 7 in its entirety of U.S. Pat. No. 6,051,248 is incorporated by reference. FIG. 1 shows the survival rate of each type of bacteria. Legionelia pneumophila dies within 10 minutes in contact with the antimicrobial article. E. coli dies after 40 minutes and Salmonella typhimurium after about 60 minutes. The control show the same rate of survival of Legionelia pneumophila as first inoculated. The efficacy of quaternary ammonium salt on sand should have the same effect. Following are the test for the efficacy of the coated sand filter. EXAMPLE 2 Test for Efficacy of Antimicrobial Filters [0034] Four samples of sand, each containing 5 g: [0035] sand without coating (Control); sand coated with quaternary ammonium salt (A); sand coated with copper compound (B) and sand coated with silver compound (C). All the coating is done according the above described processes. followed by washing with water to remove any loose chemical adhering on the surface. E. coli culture was incubated over night and diluted 100 times with nutrient. The diluted E. coli is evenly distributed into four 20-ml tubes. Add the four samples respectively into each correspondingly marked tube and Incubate at 37 degree C. with shaker for sufficient time to allow the bacteria to grow. [0036] Each tube is inserted into a spectrophotometer to study the growth rate of E. coli and expressed as O.D (A600)., optical density. sample control A B C O.D. 1.46 0.44 0.91 0.32 [0037] In conclusion, the filtration process using the antimicrobial filter improves the quality of water many folds. It indicates the filter with the silver compound is the most effective antimicrobial filter.
A water treating system utilizes antimicrobial sand filter for killing bacteria and preventing microbial growth. Said antimicrobial sand filter consists of organic quaternary ammonium salt and inorganic metal compound.
13,806
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a division of U.S. application Ser. No. 12/807,740 filed Sep. 13, 2010, which is a division of U.S. application Ser. No. 12/291,820 filed Nov. 13, 2008, now U.S. Pat. No. 7,819,170, which is a continuation of U.S. application Ser. No. 10/875,978 filed Jun. 23, 2004, now U.S. Pat. No. 7,472,740, which claims the benefit of U.S. provisional application No. 60/482,229, filed Jun. 24, 2003. The disclosures of all these prior applications are incorporated herein by this reference. FIELD OF THE INVENTION This invention relates to a method and apparatus for casting composite metal ingots, as well as novel composite metal ingots thus obtained. BACKGROUND OF THE INVENTION For many years metal ingots, particularly aluminum or aluminum alloy ingots, have been produced by a semi-continuous casting process known as direct chill casting. In this procedure molten metal has been poured into the top of an open ended mould and a coolant, typically water, has been applied directly to the solidifying surface of the metal as it emerges from the mould. Such a system is commonly used to produce large rectangular-section ingots for the production of rolled products, e.g. aluminum alloy sheet products. There is a large market for composite ingots consisting of two or more layers of different alloys. Such ingots are used to produce, after rolling, clad sheet for various applications such as brazing sheet, aircraft plate and other applications where it is desired that the properties of the surface be different from that of the core. The conventional approach to such clad sheet has been to hot roll slabs of different alloys together to “pin” the two together, then to continue rolling to produce the finished product. This has a disadvantage in that the interface between the slabs is generally not metallurgically clean and bonding of the layers can be a problem. There has also been an interest in casting layered ingots to produce a composite ingot ready for rolling. This has typically been carried out using direct chill (DC) casting, either by simultaneous solidification of two alloy streams or sequential solidification where one metal is solidified before being contacted by a second molten metal. A number of such methods are described in the literature that have met with varying degrees of success. In Binczewski, U.S. Pat. No. 4,567,936, issued Feb. 4, 1986, a method is described for producing a composite ingot by DC casting where an outer layer of higher solidus temperature is cast about an inner layer with a lower solidus temperature. The disclosure states that the outer layer must be “fully solid and sound” by the time the lower solidus temperature alloy comes in contact with it. Keller, German Patent 844 806, published Jul. 24, 1952 describes a single mould for casting a layered structure where an inner core is cast in advance of the outer layer. In this procedure, the outer layer is fully solidified before the inner alloy contacts it. In Robinson, U.S. Pat. No. 3,353,934, issued Nov. 21, 1967 a casting system is described where an internal partition is placed within the mould cavity to substantially separate areas of different alloy compositions. The end of the baffle is designed so that it terminates in the “mushy zone” just above the solidified portion of the ingot. Within the “mushy zone” alloy is free to mix under the end of the baffle to form a bond between the layers. However, the method is not controllable in the sense that the baffle used is “passive” and the casting depends on control of the sump location—which is indirectly controlled by the cooling system. In Matzner, German patent DE 44 20 697, published Dec. 21, 1995 a casting system is described using a similar internal partition to Robinson, in which the baffle sump position is controlled to allow for liquid phase mixing of the interface zone to create a continuous concentration gradient across the interface. In Robertson et al, British patent GB 1,174,764, published 21 Dec. 1965, a moveable baffle is provided to divide up a common casting sump and allow casting of two dissimilar metals. The baffle is moveable to allow in one limit the metals to completely intermix and in the other limit to cast two separate strands. In Kilmore et al., WO Publication 2003/035305, published May 1, 2003 a casting system is described using a barrier material in the form of a thin sheet between two different alloy layers. The thin sheet has a sufficiently high melting point that it remains intact during casting, and is incorporated into the final product. Takeuchi et al., U.S. Pat. No. 4,828,015, issued May 9, 1989 describes a method of casting two liquid alloys in a single mould by creating a partition in the liquid zone by means of a magnetic field and feeding the two zones with separate alloys. The alloy that is fed to the upper part of the zone thereby forms a shell around the metal fed to the lower portion. Veillette, U.S. Pat. No. 3,911,996, describes a mould having an outer flexible wall for adjusting the shape of the ingot during casting. Steen et al., U.S. Pat. No. 5,947,184, describes a mould similar to Veillette but permitting more shape control. Takeda et al., U.S. Pat. No. 4,498,521 describes a metal level control system using a float on the surface of the metal to measure metal level and feedback to the metal flow control. Odegard et al., U.S. Pat. No. 5,526,870, describes a metal level control system using a remote sensing (radar) probe. Wagstaff, U.S. Pat. No. 6,260,602, describes a mould having a variably tapered wall to control the external shape of an ingot. It is an object of the present invention to produce a composite metal ingot consisting of two or more layers having an improved metallurgical bond between adjoining layers. It is further object of the present invention to provide a means for controlling the interface temperature where two or more layers join in a composition ingot to improve the metallurgical bond between adjoining layers. It is further object of the present invention to provide a means for controlling the interface shape where two or more alloys are combined in a composite metal ingot. It is a further object of the present invention to provide a sensitive method for controlling the metal level in an ingot mould that is particularly useful in confined spaces. SUMMARY OF THE INVENTION One embodiment of the present invention is a method for the casting of a composite metal ingot comprising at least two layers formed of one or more alloys compositions. The method comprises providing an open ended annular mould having a feed end and an exit end wherein molten metal is added at the feed end and a solidified ingot is extracted from the exit end. Divider walls are used to divide the feed end into at least two separate feed chambers, the divider walls terminating above the exit end of the mould, and where each feed chamber is adjacent at least one other feed chamber. For each pair of adjacent feed chambers a first stream of a first alloy is fed to one of the pair of feed chambers to form a pool of metal in the first chamber and a second stream of a second alloy is fed through the second of the pair of feed chambers to form a pool of metal in the second chamber. The first metal pool contacts the divider wall between the pair of chambers to cool the first pool so as to form a self-supporting surface adjacent the divider wall. The second metal pool is then brought into contact with the first pool so that the second pool first contacts the self-supporting surface of the first pool at a point where the temperature of the self-supporting surface is between the solidus and liquidus temperatures of the first alloy. The two alloy pools are thereby joined as two layers and cooled to form a composite ingot. Preferably the second alloy initially contacts the self-supporting surface of the first alloy when the temperature of the second alloy is above the liquidus temperature of the second alloy. The first and second alloys may have the same alloy composition or may have different alloy compositions. Preferably the upper surface of the second alloy contacts the self-supporting surface of the first pool at a point where the temperature of the self-supporting surface is between the solidus and liquidus temperatures of the first alloy. In this embodiment of the invention the self-supporting surface may be generated by cooling the first alloy pool such that the surface temperature at the point where the second alloy first contacts the self-supporting surface is between the liquidus and solidus temperature. Another embodiment of the present invention comprises a method for the casting of a composite metal ingot comprising at least two layers formed of one or more alloys compositions. This method comprises providing an open ended annular mould having a feed end and an exit end wherein molten metal is added at the feed end and a solidified ingot is extracted from the exit end. Divider walls are used to divide the feed end into at least two separate feed chambers, the divider walls terminating above the exit end of the mould, and where each feed chamber is adjacent at least one other feed chamber. For each pair of adjacent feed chambers a first stream of a first alloy is fed to one of the pair of feed chambers to form a pool of metal in the first chamber and a second stream of a second alloy is fed through the second of the pair of feed chambers to form a pool of metal in the second chamber. The first metal pool contacts the divider wall between the pair of chambers to cool the first pool so as to form a self-supporting surface adjacent the divider wall. The second metal pool is then brought into contact with the first pool so that the second pool first contacts the self-supporting surface of the first pool at a point where the temperature of the self-supporting surface is below the solidus temperature of the first alloy to form an interface between the two alloys. The interface is then reheated to a temperature between the solidus and liquidus temperature of the first alloy so that the two alloy pools are thereby joined as two layers and cooled to form a composite ingot. In this embodiment the reheating is preferably achieved by allowing the latent heat within the first or second alloy pools to reheat the surface. Preferably the second alloy initially contacts the self-supporting surface of the first alloy when the temperature of the second alloy is above the liquidus temperature of the second alloy. The first and second alloys may have the same alloy composition or may have different alloy compositions. Preferably the upper surface of the second alloy contacts the self-supporting surface of the first pool at a point where the temperature of the self-supporting surface is between the solidus and liquidus temperatures of the first alloy. The self-supporting surface may also have an oxide layer formed on it. It is sufficiently strong to support the splaying forces normally causing the metal to spread out when unconfined. These splaying forces include the forces created by the metallostatic head of the first stream, and expansion of the surface in the case where cooling extends below the solidus followed by re heating the surface. By bringing the liquid second alloy into first contact with the first alloy while the first alloy is still in the semi-solid state or, and in the alternate embodiment, by ensuring that the interface between the alloys is reheated to a semi-solid state, a distinct but joining interface layer is formed between the two alloys. Furthermore, the fact that the interface between the second alloy layer and the first alloy is thereby formed before the first alloy layer has developed a rigid shell means that stresses created by the direct application of coolant to the exterior surface of the ingot are better controlled in the finished product, which is particularly advantageous when casting crack prone alloys. The result of the present invention is that the interface between the first and second alloy is maintained, over a short length of emerging ingot, at a temperature between the solidus and liquidus temperature of the first alloy. In one particular embodiment, the second alloy is fed into the mould so that the upper surface of the second alloy in the mould is in contact with the surface of the first alloy where the surface temperature is between the solidus and liquidus temperature and thus an interface having met this requirement is formed. In an alternate embodiment, the interface is reheated to a temperature between the solidus and liquidus temperature shortly after the upper surface of the second alloy contacts the self-supporting surface of the first alloy. Preferably the second alloy is above its liquidus temperature when it first contacts the surface of the first alloy. When this is done, the interface integrity is maintained but at the same time, certain alloy components are sufficiently mobile across the interface that metallurgical bonding is facilitated. If the second alloy is contacted where the temperature of the surface of the first alloy is sufficiently below the solidus (for example after a significant solid shell has formed), and there is insufficient latent heat to reheat the interface to a temperature between the solidus and liquidus temperatures of the first alloy, then the mobility of alloy components is very limited and a poor metallurgical bond is formed. This can cause layer separation during subsequent processing. If the self-supporting surface is not formed on the first alloy prior to the second alloy contacting the first alloy, then the alloys are free to mix and a diffuse layer or alloy concentration gradient is formed at the interface, making the interface less distinct. It is particularly preferred that the upper surface of the second alloy be maintained a position below the bottom edge of the divider wall. If the upper surface of the second alloy in the mould lies above the point of contact with the surface of the first alloy, for example, above the bottom edge of the divider wall, then there is a danger that the second alloy can disrupt the self supporting surface of the first alloy or even completely re-melt the surface because of excess latent heat. If this happens, there may be excessive mixing of alloys at the interface, or in some cases runout and failure of the cast. If the second alloy contacts the divider wall particularly far above the bottom edge, it may even be prematurely cooled to a point where the contact with the self-supporting surface of the first alloy no longer forms a strong metallurgical bond. In certain cases it may however be advantageous to maintain the upper surface of the second alloy close to the bottom edge of the divider wall but slightly above the bottom edge so that the divider wall can act as an oxide skimmer to prevent oxides from the surface of the second layer from being incorporated in the interface between the two layers. This is particularly advantageous where the second alloy is prone to oxidation. In any case the upper surface position must be carefully controlled to avoid the problems noted above, and should not lie more than about 3 mm above the bottom end of the divider. In all of the preceding embodiments it is particularly advantageous to contact the second alloy to the first at a temperature between the solidus and coherency temperature of the first alloy or to reheat the interface between the two to a temperature between the solidus and coherency temperature of the first alloy. The coherency point, and the temperature (between the solidus and liquidus temperature) at which it occurs is an intermediate stage in the solidification of the molten metal. As dendrites grow in size in a cooling molten metal and start to impinge upon one another, a continuous solid network builds up throughout the alloy volume. The point at which there is a sudden increase in the torque force needed to shear the solid network is known as the “coherency point”. The description of coherency point and its determination can be found in Solidification Characteristics of Aluminum Alloys Volume 3 Dendrite Coherency Pg 210. In another embodiment of the invention, there is provided an apparatus for casting metal comprising an open ended annular mould having a feed end and an exit end and a bottom block that can fit within the exit end and is movable in a direction along the axis of the annular mould. The feed end of the mould is divided into at least two separate feed chambers, where each feed chamber is adjacent at least one other feed chamber and where the adjacent feed chambers are separated by a temperature controlled divider wall that can add or remove heat. The divider wall ends above the exit end of the mould. Each chamber includes a metal level control apparatus such that in adjacent pairs of chambers the metal level in one chamber can be maintained at a position above the lower end of the divider wall between the chambers and in the other chamber can be maintained at a different position from the level in the first chamber. Preferably the level in the other chamber is maintained at a position below the lower end of the divider wall. The divider wall is designed so that the heat extracted or added is calibrated so as to create a self-supporting surface on metal in the first chamber adjacent the divider wall and to control the temperature of the self-supporting surface of the metal in the first chamber to lie between the solidus and liquidus temperature at a point where the upper surface of the metal in the second chamber can be maintained. The temperature of the self-supporting layer can be carefully controlled by removing heat from the divider wall by a temperature control fluid being passed through a portion of the divider wall or being brought into contact with the divider wall at its upper end to control the temperature of the self-supporting layer. A further embodiment of the invention is a method for the casting of a composite metal ingot comprising at least two different alloys, which comprises providing an open ended annular mould having a feed end and an exit end and means for dividing the feed end into at least two separate, feed chambers, where each feed chamber is adjacent at least one other feed chamber. For each pair of adjacent feed chambers, a first stream of a first alloy is fed through one of the adjacent feed chambers into said mould, a second stream of a second alloy is fed through another of the adjacent feed chambers. A temperature controlling divider wall is provided between the adjacent feed chambers such that the point on the interface where the first and second alloy initially contact each other is maintained at a temperature between the solidus and liquidus temperature of the first alloy by means of the temperature controlling divider wall whereby the alloy streams are joined as two layers. The joined alloy layers are cooled to form a composite ingot. The second alloy is preferably brought into contact with the first alloy immediately below the bottom of the divider wall without first contacting the divider wall. In any event, the second alloy should contact the first alloy no less than about 2 mm below the bottom edge of the divider wall but not greater than 20 mm and preferably about 4 to 6 mm below the bottom edge of the divider wall. If the second alloy contacts the divider wall before contacting the first alloy, it may be prematurely cooled to a point where the contact with the self-supporting surface of the first alloy no longer forms a strong metallurgical bond. Even if the liquidus temperature of the second alloy is sufficiently low that this does not happen, the metallostatic head that would exist may cause the second alloy to feed up into the space between the first alloy and the divider wall and cause casting defects or failure. When the upper surface of the second alloy is desired to be above the bottom edge of the divider wall (e.g. to skim oxides) it must in all cases be carefully controlled and positioned as close as practical to the bottom edge of the divider wall to avoid these problems. The divider wall between adjacent pairs of feed chambers may be tapered and the taper may vary along the length of the divider wall. The divider wall may further have a curvilinear shape. These features can be used to compensate for the different thermal and solidification properties of the alloys used in the chambers separated by the divider wall and thereby provide for control of the final interface geometry within the emerging ingot. The curvilinear shaped wall may also serve to form ingots with layers having specific geometries that can be rolled with less waste. The divider wall between adjacent pairs of feed chambers may be made flexible and may be adjusted to ensure that the interface between the two alloy layers in the final cast and rolled product is straight regardless of the alloys used and is straight even in the start-up section. A further embodiment of the invention is an apparatus for casting of composite metal ingots, comprising an open ended annular mould having a feed end and an exit end and a bottom block that can fit inside the exit end and move along the axis of the mould. The feed end of the mould is divided into at least two separate feed chambers, where each feed chamber is adjacent at least one other feed chamber and where the adjacent feed chambers are separated by a divider wall. The divider wall is flexible, and a positioning device is attached to the divider wall so that the wall curvature in the plane of the mould can be varied by a predetermined amount during operation. A further embodiment of the invention is a method for the casting of a composite metal ingot comprising at least two different alloys, which comprises providing an open ended annular mould having a feed end and an exit end and means for dividing the feed end into at least two separate, feed chambers, where each feed chamber is adjacent at least one other feed chamber. For adjacent pairs of the feed chambers, a first stream of a first alloy is fed through one of the adjacent feed chambers into the mould, and a second stream of a second alloy is fed through another of the adjacent feed chambers. A flexible divider wall is provided between adjacent feed chambers and the curvature of the flexible divider wall is adjusted during casting to control the shape of interface where the alloys are joined as two layers. The joined alloy layers are then cooled to form a composite ingot. The metal feed requires careful level control and one such method is to provide a slow flow of gas, preferably inert, through a tube with an opening at a fixed point with respect to the body of the annular mould. The opening is immersed in use below the surface of the metal in the mould, the pressure of the gas is measured and the metallostatic head above the tube opening is thereby determined. The measured pressure can therefore be used to directly control the metal flow into the mould so as to maintain the upper surface of the metal at a constant level. A further embodiment of the invention is a method of casting a metal ingot which comprises providing an open ended annular mould having a feed end and an exit end, and feeding a stream of molten metal into the feed end of said mould to create a metal pool within said mould having a surface. The end of a gas delivery tube is immersed into the metal pool from the feed end of mould tube at a predetermined position with respect to the mould body and an inert gas is bubbled through the gas delivery tube at a slow rate sufficient to keep the tube unfrozen. The pressure of the gas within the said tube is measured to determine the position of the molten metal surface with respect to the mould body. A further embodiment of the invention is an apparatus for casting a metal ingot that comprises an open-ended annular mould having a feed end and an exit end and a bottom block that fits in the exit end and is movable along the axis of the mould. A metal flow control device is provided for controlling the rate at which metal can flow into the mould from an external source, and a metal level sensor is also provided comprising a gas delivery tube attached to a source of gas by means of a gas flow controller and having an open end positioned at a predefined location below the feed end of the mould, such that in use, the open end of the tube would normally lie below the metal level in the mould. A means is also provided for measuring the pressure of the gas in the gas delivery tube between the flow controller and the open end of the gas delivery tube, the measured pressure of the gas being adapted to control the metal flow control device so as to maintain the metal into which the open end of the gas delivery tube is placed at a predetermined level. This method and apparatus for measuring metal level is particularly useful in measuring and controlling metal level in a confined space such as in some or all of the feed chambers in a multi-chamber mould design. It may be used in conjunction with other metal level control systems that use floats or similar surface position monitors, where for example, a gas tube is used in smaller feed chambers and a feed control system based on a float or similar device in the larger feed chambers. In one preferred embodiment of the present invention there is provided a method for casting a composite ingot having two layer of different alloys, where one alloy forms a layer on the wider or “rolling” face of a rectangular cross-sectional ingot formed from another alloy. For this procedure there is provided an open ended annular mould having a feed end and an exit end and means for dividing the feed end into separate adjacent feed chambers separated by a temperature controlled divider wall. The first stream of a first alloy is fed though one of the feed chambers into the mould and a second stream of a second alloy is fed through another of the feed chambers, this second alloy having a lower liquidus temperature than the first alloy. The first alloy is cooled by the temperature controlled divider wall to form a self-supporting surface that extends below the lower end of the divider wall and the second alloy is contacted with the self-supporting surface of the first alloy at a location where the temperature of the self-supporting surface is maintained between the solidus and liquidus temperature of the first alloy, whereby the two alloy streams are joined as two layers. The joined alloy layers are then cooled to form a composite ingot. In another preferred embodiment the two chambers are configured so that an outer chamber completely surrounds the inner chamber whereby an ingot is formed having a layer of one alloy completely surrounding a core of a second alloy. A preferred embodiment includes two laterally spaced temperature controlled divider walls forming three feed chambers. Thus, there is a central feed chamber with a divider wall on each side and a pair of outer feed chambers on each side of the central feed chamber. A stream of the first alloy may be fed through the central feed chamber, with streams of the second alloy being fed into the two side chambers. Such an arrangement is typically used for providing two cladding layers on a central core material. It is also possible to reverse the procedure such that streams of the first alloy are feed through the side chambers while a stream of the second alloy is fed through the central chamber. With this arrangement, casting is started in the side feed chambers with the second alloy being fed through the central chamber and contacting the pair of first alloys immediately below the divider walls. The ingot cross-sectional shape may be any convenient shape (for example circular, square, rectangular or any other regular or irregular shape) and the cross-sectional shapes of individual layers may also vary within the ingot. Another embodiment of the invention is a cast ingot product consisting of an elongated ingot comprising, in cross-section, two or more separate alloy layers of differing composition, wherein the interface between adjacent alloys layers is in the form of a substantially continuous metallurgical bond. This bond is characterized by the presence of dispersed particles of one or more intermetallic compositions of the first alloy in a region of the second alloy adjacent the interface. Generally in the present invention the first alloy is the one on which a self-supporting surface is first formed and the second alloy is brought into contact with this surface while the surface temperature is between the solidus and liquidus temperature of the first alloy, or the interface is subsequently reheated to a temperature between the solidus and liquidus temperature of the first alloy. The dispersed particles preferably are less than about 20 μm in diameter and are found in a region of up to about 200 μm from the interface. The bond may be further characterized by the presence of plumes or exudates of one or more intermetallic compositions of the first alloy extending from the interface into the second alloy in the region adjacent the interface. This feature is particularly formed when the temperature of the self-supporting surface has not been reduced below the solidus temperature prior to contact with the second alloy. The plumes or exudates preferably penetrate less than about 100 μm into the second alloy from the interface. Where the intermetallic compositions of the first alloy are dispersed or exuded into the second alloy, there remains in the first alloy, adjacent to the interface between the first and second alloys, a layer which contains a reduced quantity of the intermetallic particles and which consequently can form a layer which is more noble than the first alloy and may impart corrosion resistance to the clad material. This layer is typically 4 to 8 mm thick. This bond may be further characterized by the presence of a diffuse layer of alloy components of the first alloy in the second alloy layer adjacent the interface. This feature is particularly formed in instances where the surface of the first alloy is cooled below the solidus temperature of the first alloy and then the interface between first and second alloy is reheated to between the solidus and liquidus temperatures. Although not wishing to be bound by any theory, it is believed that the presence of these features is caused by formation of segregates of intermetallic compounds of the first alloy at the self supporting surface formed on it with their subsequent dispersal or exudation into the second alloy after it contacts the surface. The exudation of intermetallic compounds is assisted by splaying forces present at the interface. A further feature of the interface between layers formed by the methods of this invention is the presence of alloy components from the second alloy between the grain boundaries of the first alloy immediately adjacent the interface between the two alloys. It is believed that these arise when the second alloy (still generally above its liquidus temperature) comes in contact with the self-supporting surface of the first alloy (at a temperature between the solidus and liquidus temperature of the first alloy). Under these specific conditions, alloy component of the second alloy can diffuse a short distance (typically about 50 μm) along the still liquid grain boundaries, but not into the grains already formed at the surface of the first alloy. If the interface temperature in above the liquidus temperature of both alloys, general mixing of the alloys will occur, and the second alloy components will be found within the grains as well as grain boundaries. If the interface temperature is below the solidus temperature of the first alloy, there will be not opportunity for grain boundary diffusion to occur. The specific interfacial features described are specific features caused by solid state diffusion, or diffusion or movement of elements along restricted liquid paths and do not affect the generally distinct nature of the overall interface. Regardless how the interface is formed, the unique structure of the interface provides for a strong metallurgical bond at the interface and therefore makes the structure suitable for rolling to sheet without problems associated with delamination or interface contamination. In yet a further embodiment of the invention, there is a composite metal ingot, comprising at least two layers of metal, wherein pairs of adjacent layers are formed by contacting the second metal layer to the surface of the first metal layer such that the when the second metal layer first contacts the surface of the first metal layer the surface of the first metal layer is at a temperature between its liquidus and solidus temperature and the temperature of the second metal layer is above its liquidus temperature. Preferably the two metal layers are composed of different alloys. Similarly in yet a further embodiment of the invention, there is a composite metal ingot, comprising at least two layers of metal, wherein pairs of adjacent layers are formed by contacting the second metal layer to the surface of the first metal layer such that the when the second metal layer first contacts the surface of the first metal layer the surface of the first metal layer is at a temperature below its solidus temperature and the temperature of the second metal layer is above its liquidus temperature, and the interface formed between the two metal layers is subsequently reheated to a temperature between the solidus and liquidus temperature of the first alloy. Preferably the two metal layers are composed of different alloys. In one preferred embodiment, the ingot is rectangular in cross section and comprises a core of the first alloy and at least one surface layer of the second layer, the surface layer being applied to the long side of the rectangular cross-section. This composite metal ingot is preferably hot and cold rolled to form a composite metal sheet. In one particularly preferred embodiment, the alloy of the core is an aluminum-manganese alloy and the surface alloy is an aluminum-silicon alloy. Such composite ingot when hot and cold rolled to form a composite metal brazing sheet that may be subject to a brazing operation to make a corrosion resistant brazed structure. In another particularly preferred embodiment, the alloy core is a scrap aluminum alloy and the surface alloy a pure aluminum alloy. Such composite ingots when hot and cold rolled to form composite metal sheet provide for inexpensive recycled products having improved properties of corrosion resistance, surface finishing capability, etc. In the present context a pure aluminum alloy is an aluminum alloy having a thermal conductivity greater than 190 watts/m/K and a solidification range of less than 50° C. In yet another particularly preferred embodiment the alloy core is a high strength non-heat treatable alloy (such as an Al—Mg alloy) and the surface alloy is a brazeable alloy (such as an Al—Si alloy). Such composite ingots when hot and cold rolled to form composite metal sheet may be subject to a forming operation and used for automotive structures which can then be brazed or similarly joined. In yet another particularly preferred embodiment the alloy core is a high strength heat treatable alloy (such as an 2xxx alloy) and the surface alloy is a pure aluminum alloy. Such composite ingots when hot and cold rolled form composite metal sheet suitable for aircraft structures. The pure alloy may be selected for corrosion resistance or surface finish and should preferably have a solidus temperature greater than the solidus temperature of the core alloy. In yet another particularly preferred embodiment the alloy core is a medium strength heat treatable alloy (such as an Al—Mg—Si alloy) and the surface alloy is a pure aluminum alloy. Such composite ingots when hot and cold rolled form composite metal sheet suitable for automotive closures. The pure alloy may be selected for corrosion resistance or surface finish and should preferably have a solidus temperature greater than the solidus temperature of the core alloy. In another preferred embodiment, the ingot is cylindrical in cross-section and comprises a core of the first alloy and a concentric surface layer of the second alloy. In yet another preferred embodiment, the ingot is rectangular or square in cross-section and comprises a core of the second alloy and a annular surface layer of the first alloy. BRIEF DESCRIPTION OF THE DRAWINGS In the drawings which illustrate certain preferred embodiments of this invention: FIG. 1 is an elevation view in partial section showing a single divider wall; FIG. 2 is a schematic illustration of the contact between the alloys; FIG. 3 is an elevation view in partial section similar to FIG. 1 , but showing a pair of divider walls; FIG. 4 is an elevation view in partial section similar to FIG. 3 , but with the second alloy having a lower liquidus temperature than the first alloy being fed into the central chamber; FIGS. 5 a , 5 b and 5 c are plan views showing some alternative arrangements of feed chamber that may be used with the present invention; FIG. 6 is an enlarged view in partial section of a portion of FIG. 1 showing a curvature control system; FIG. 7 is a plan view of a mould showing the effects of variable curvature of the divider wall; FIG. 8 is an enlarged view of a portion of FIG. 1 illustrating a tapered divider wall between alloys; FIG. 9 is a plan view of a mould showing a particularly preferred configuration of a divider wall; FIG. 10 is a schematic view showing the metal level control system of the present invention; FIG. 11 is a perspective view of a feed system for one of the feed chambers of the present invention; FIG. 12 is a plan view of a mould showing another preferred configuration of the divider wall; FIG. 13 is a microphotograph of a section through the joining face between a pair of adjacent alloys using the method of the present invention showing the formation of intermetallic particles in the opposite alloy; FIG. 14 is a microphotograph of a section through the same joining face as in FIG. 13 showing the formation of intermetallic plumes or exudates; FIG. 15 is a microphotograph of a section through the joining face between a pair of adjacent alloys processed under conditions outside the scope of the present invention; FIG. 16 is a microphotograph of a section through the joining face between a cladding alloy layer and a cast core alloy using the method of the present invention; FIG. 17 is a microphotograph of a section through the joining face between a cladding alloy layer and a cast core alloy using the method of the present invention, and illustrating the presence of components of core alloy solely along grain boundaries of the cladding alloy at the joining face; FIG. 18 is a microphotograph of a section through the joining face between a cladding alloy layer and a cast core alloy using the method of the present invention, and illustrating the presence of diffused alloy components as in FIG. 17 ; and FIG. 19 a microphotograph of a section through the joining face between a cladding alloy layer and a cast core alloy using the method of the present invention, and also illustrating the presence of diffused alloy components as in FIG. 17 . DESCRIPTION OF THE PREFERRED EMBODIMENTS With reference to FIG. 1 , rectangular casting mould assembly 10 has mould walls 11 forming part of a water jacket 12 from which a stream of cooling water 13 is dispensed. The feed portion of the mould is divided by a divider wall 14 into two feed chambers. A molten metal delivery trough 30 and delivery nozzle 15 equipped with an adjustable throttle 32 feeds a first alloy into one feed chamber and a second metal delivery trough 24 equipped with a side channel, delivery nozzle 16 and adjustable throttle 31 feeds a second alloy into a second feed chamber. The adjustable throttles 31 , 32 are adjusted either manually or responsive to some control signal to adjust the flow of metal into the respective feed chambers. A vertically movable bottom block unit 17 supports the embryonic composite ingot being formed and fits into the outlet end of the mould prior to starting a cast and thereafter is lowered to allow the ingot to form. As more clearly shown with reference to FIG. 2 , in the first feed chamber, the body of molten metal 18 gradually cools so as to form a self-supporting surface 27 adjacent the lower end of the divider wall and then forms a zone 19 that is between liquid and solid and is often referred as a mushy zone. Below this mushy or semi-solid zone is a solid metal alloy 20 . Into the second feed chamber is fed a second alloy liquid flow 21 having a lower liquidus temperature than the first alloy 18 . This metal also forms a mushy zone 22 and eventually a solid portion 23 . The self-supporting surface 27 typically undergoes a slight contraction as the metal detaches from the divider wall 14 then a slight expansion as the splaying forces caused, for example, by the metallostatic head of the metal 18 coming to bear. The self-supporting surface has sufficient strength to restrain such forces even though the temperature of the surface may be above the solidus temperature of the metal 18 . An oxide layer on the surface can contribute to this balance of forces. The temperature of the divider wall 14 is maintained at a predetermined target temperature by means of a temperature control fluid passing through a closed channel 33 having an inlet 36 and outlet 37 for delivery and removal of temperature control fluid that extracts heat from the divider wall so as to create a chilled interface which serves to control the temperature of the self supporting surface 27 below the lower end of the divider wall 35 . The upper surface 34 of the metal 21 in the second chamber is then maintained at a position below the lower edge 35 of the divider wall 14 and at the same time the temperature of the self supporting surface 27 is maintained such that the surface 34 of the metal 21 contacts this self supporting surface 27 at a point where the temperature of the surface 27 lies between the solidus and liquidus temperature of the metal 18 . Typically the surface 34 is controlled at a point slightly below the lower edge 35 of the divider wall 14 , generally within about 2 to 20 mm from the lower edge. The interface layer thus formed between the two alloy streams at this point forms a very strong metallurgical bond between the two layers without excessive mixing of the alloys. The coolant flow (and temperature) required to establish the temperature of the self-supporting surface 27 of metal 18 within the desired range is generally determined empirically by use of small thermocouples that are embedded in the surface 27 of the metal ingot as it forms and once established for a given composition and casting temperature for metal 18 (casting temperature being the temperature at which the metal 18 is delivered to the inlet end of the feed chamber) forms part of the casting practice for such an alloy. It has been found in particular that at a fixed coolant flow through the channel 33 , the temperature of the coolant exiting the divider wall coolant channel measured at the outlet 37 correlates well with the temperature of the self supporting surface of the metal at predetermined locations below the bottom edge of the divider wall, and hence provides for a simple and effective means of controlling this critical temperature by providing a temperature measuring device such as a thermocouple or thermistor 40 in the outlet of the coolant channel. FIG. 3 is essentially the same mould as in FIG. 1 , but in this case a pair of divider walls 14 and 14 a are used dividing the mouth of the mould into three feed chambers. There is a central chamber for the first metal alloy and a pair of outer feed chambers for a second metal alloy. The outer feed chambers may be adapted for a second and third metal alloy, in which case the lower ends of the divider walls 14 and 14 a may be positioned differently and the temperature control may differ for the two divider walls depending on the particular requirements for casting and creating strongly bonded interfaces between the first and second alloys and between the first and third alloys. As shown in FIG. 4 , it is also possible to reverse the alloys so that the first alloy streams are fed into the outer feed chambers and a second alloy stream is fed into the central feed chamber. FIG. 5 shows several more complex chamber arrangements in plan view. In each of these arrangements there is an outer wall 11 shown for the mould and the inner divider walls 14 separating the individual chambers. Each divider wall 14 between adjacent chambers must be positioned and thermally controlled such that the conditions for casting described herein are maintained. This means that the divider walls may extend downwards from the inlet of the mould and terminate at different positions and may be controlled at different temperatures and the metal levels in each chamber may be controlled at different levels in accordance with the requirements of the casting practice. It is advantageous to make the divider wall 14 flexible or capable of having a variable curvature in the plane of the mould as shown in FIGS. 6 and 7 . The curvature is normally changed between the start-up position 14 ′ and steady state position 14 so as to maintain a constant interface throughout the cast. This is achieved by means of an arm 25 attached at one end to the top of the divider wall 14 and driven in a horizontal direction by a linear actuator 26 . If necessary the actuator is protected by a heat shield 42 . The thermal properties of alloys vary considerably and the amount and degree of variation in the curvature is predetermined based on the alloys selected for the various layers in the ingot. Generally these are determined empirically as part of a casting practice for a particular product. As shown in FIG. 8 the divider wall 14 may also be tapered 43 in the vertical direction on the side of the metal 18 . This taper may vary along the length of the divider wall 14 to further control the shape of the interface between adjacent alloy layer. The taper may also be used on the outer wall 11 of the mould. This taper or shape can be established using principals, for example, as described in U.S. Pat. No. 6,260,602 (Wagstaff) and will again depend on the alloys selected for the adjacent layers. The divider wall 14 is manufactured from metal (steel or aluminum for example) and may in part be manufactured from graphite, for example by using a graphite insert 46 on the tapered surface. Oil delivery channels 48 and grooves 47 may also be used to provide lubricants or parting substances. Of course inserts and oil delivery configurations may be used on the outer walls in manner known in the art. A particular preferred embodiment of divider wall is shown in FIG. 9 . The divider wall 14 extends substantially parallel to the mould sidewall 11 along one or both long (rolling) faces of a rectangular cross section ingot. Near the ends of the long sides of the mould, the divider wall 14 has 90° curves 45 and is terminated at locations 50 on the long side wall 11 , rather than extending fully to the short side walls. The clad ingot cast with such a divider wall can be rolled to better maintain the shape of the cladding over the width of the sheet than occurs in more conventional roll-cladding processes. The taper described in FIG. 8 may also be applied to this design, where for example, a high degree of taper may be used at curved surface 45 and a medium degree of taper on straight section 44 . FIG. 10 shows a method of controlling the metal level in a casting mould which can be used in any casting mould, whether or not for casting layered ingots, but is particularly useful for controlling the metal level in confined spaces as may be encountered in some metal chambers in moulds for casting multiple layer ingots. A gas supply 51 (typically a cylinder of inert gas) is attached to a flow controller 52 that delivers a small flow of gas to a gas delivery tube with an open end 53 that is positioned at a reference location 54 within the mould. The inside diameter of the gas delivery tube at its exit is typically between 3 to 5 mm. The reference location is selected so as to be below the top surface of the metal 55 during a casting operation, and this reference location may vary depending on the requirements of the casting practice. A pressure transducer 56 is attached to the gas delivery tube at a point between the flow controller and the open end so as to measure the backpressure of gas in the tube. This pressure transducer 56 in turn produces a signal that can be compared to a reference signal to control the flow of metal entering the chamber by means known to those skilled in the art. For example an adjustable refractory stopper 57 in a refractory tube 58 fed in turn from a metal delivery trough 59 may be used. In use, the gas flow is adjusted to a low level just sufficient to maintain the end of the gas delivery tube open. A piece of refractory fibre inserted in the open end of the gas delivery tube is used to dampen the pressure fluctuations caused by bubble formation. The measured pressure then determines the degree of immersion of the open end of the gas delivery tube below the surface of the metal in the chamber and hence the level of the metal surface with respect to the reference location and the flow rate of metal into the chamber is therefore controlled to maintain the metal surface at a predetermined position with respect to the reference location. The flow controller and pressure transducer are devices that are commonly available devices. It is particularly preferred however that the flow controller be capable of reliable flow control in the range of 5 to 10 cc/minute of gas flow. A pressure transducer able to measure pressures to about 0.1 psi (0.689 kPa) provides a good measure of metal level control (to within 1 mm) in the present invention and the combination provides for good control even in view of slight fluctuations in the pressure causes by the slow bubbling through the open end of the gas delivery tube. FIG. 11 shows a perspective view of a portion of the top of the mould of the present invention. A feed system for one of the metal chambers is shown, particularly suitable for feeding metal into a narrow feed chamber as may be used to produce a clad surface on an ingot. In this feed system, a channel 60 is provided adjacent the feed chamber having several small down spouts 61 connected to it which end below the surface of the metal. Distribution bags 62 made from refractory fabric by means known in the art are installed around the outlet of each down spout 61 to improve the uniformity of metal distribution and temperature. The channel in turn is fed from a trough 68 in which a single down spout 69 extends into the metal in the channel and in which is inserted a flow control stopper (not shown) of conventional design. The channel is positioned and leveled so that metal flows uniformly to all locations. FIG. 12 shows a further preferred arrangement of divider walls 14 for casting a rectangular cross-section ingot clad on two faces. The divider walls have a straight section 44 substantially parallel to the mould sidewall 11 along one or both long (rolling) faces of a rectangular cross section ingot. However, in this case each divider wall has curved end portions 49 which intersect the shorter end wall of the mould at locations 41 . This is again useful in maintaining the shape of the cladding over the width of the sheet than occurs in more conventional roll-cladding processes. Whilst illustrated for cladding on two faces, it can equally well be used for cladding on a single face of the ingot. FIG. 13 is a microphotograph at 15× magnification showing the interface 80 between an Al—Mn alloy 81 (X-904 containing 0.74% by weight Mn, 0.55% by weight Mg, 0.3% by weight Cu, 0.17% by weight, 0.07% by weight Si and the balance Al and inevitable impurities) and an Al—Si alloy 82 (AA4147 containing 12% by weight Si, 0.19% by weight Mg and the balance Al and inevitable impurities) cast under the conditions of the present invention. The Al—Mn alloy had a solidus temperature of 1190° F. (643° C.) and a liquidus temperature of 1215° F. (657° C.). The Al—Si alloy had a solidus temperature of 1070° F. (576° C.) and a liquidus temperature of 1080° F. (582° C.). The Al—Si alloy was fed into the casting mould such that the upper surface of the metal was maintained so that it contacted the Al—Mn alloy at a location where a self-supporting surface has been established on the Al—Mn alloy, but its temperature was between the solidus and liquidus temperatures of the Al—Mn alloy. A clear interface is present on the sample indicating no general mixing of alloys, but in addition, particles of intermetallic compounds containing Mn 85 are visible in an approximately 200 μm band within the Al—Si alloy 82 adjacent the interface 80 between the Al—Mn and Al—Si alloys. The intermetallic compounds are mainly MnAl 6 and alpha-AlMn. FIG. 14 is a microphotograph at 200× magnification showing the interface 80 of the same alloy combination as in FIG. 13 where the self-surface temperature was not allowed to fall below the solidus temperature of the Al—Mn alloy prior to the Al—Si alloy contacting it. A plume or exudate 88 is observed extending from the interface 80 into the Al—Si alloy 82 from the Al—Mn alloy 81 and the plume or exudate has a intermetallic composition containing Mn that is similar to the particles in FIG. 13 . The plumes or exudates typically extend up to 100 μm into the neighbouring metal. The resulting bond between the alloys is a strong metallurgical bond. Particles of intermetallic compounds containing Mn 85 are also visible in this microphotograph and have a size typically up to 20 μm. FIG. 15 is a microphotograph (at 300× magnification) showing the interface between an Al—Mn alloy (AA3003) and an Al—Si alloy (AA4147) but where the Al—Mn self-supporting surface was cooled more than about 5° C. below the solidus temperature of the Al—Mn alloy, at which point the upper surface of the Al—Si alloy contacted the self-supporting surface of the Al—Mn alloy. The bond line 90 between the alloys is clearly visible indicating that a poor metallurgical bond was thereby formed. There is also an absence of exudates or dispersed intermetallic compositions of the first alloy in the second alloy. A variety of alloy combinations were cast in accordance with the process of the present invention. The conditions were adjusted so that the first alloy surface temperature was between its solidus and liquidus temperature at the upper surface of the second alloy. In all cases, the alloys were cast into ingots 690 mm×1590 mm and 3 metres long and then processed by conventional preheating, hot rolling and cold rolling. The alloy combinations cast are given in Table 1 below. Using convention terminology, the “core” is the thicker supporting layer in a two alloy composite and the “cladding” is the surface functional layer. In the table, the First Alloy is the alloy cast first and the second alloy is the alloy brought into contact with the self-supporting surface of the first alloy. TABLE 1 First Alloy Second Alloy Casting Casting L-S temper- L-S temper- Location Range ature Location range ature Cast and alloy (° C.) (° C.)) and alloy (° C.) (° C.) 051804 Clad 0303 660-659 664-665 Core 3104 654-629 675-678 030826 Clad 1200 657-646 685-690 Core 2124 638-502 688-690 031013 Clad 0505 660-659 692-690 Core 6082 645-563 680-684 030827 Clad 1050 657-646 695-697 Core 6111 650-560 686-684 In each of these examples, the cladding was the first alloy to solidify and the core alloy was applied to the cladding alloy at a point where a self-supporting surface had formed, but where the surface temperature was still within the L-S range given above. This may be compared to the example above for brazing sheet where the cladding alloy had a lower melting range than the core alloy, in which case the cladding alloy (the “second alloy”) was applied to the self supporting surface of the core alloy (the “first alloy”). Micrographs were taken of the interface between the cladding and the core in the above four casts. The micrographs were taken at 50× magnification. In each image the “cladding” layer appears to the left and the “core” layer to the right. FIG. 16 shows the interface of Cast #051804 between cladding alloy 0303 and core alloy 3104. The interface is clear from the change in grain structure in passing from the cladding material to the relatively more alloyed core layer. FIG. 17 shows the interface of Cast #030826 between cladding alloy 1200 and core alloy 2124. The interface between the layers is shown by the dotted line 94 in the Figure. In this figure, the presence of alloy components of the 2124 alloy are present in the grain boundaries of the 1200 alloy within a short distance of the interface. These appear as spaced “fingers” of material in the Figure, one of which is illustrated by the numeral 95 . It can be seen that the 2124 alloy components extend for a distance of about 50 μm, which typically corresponds to a single grain of the 1200 alloy under these conditions. FIG. 18 shows the interface of Cast #031013 between cladding alloy 0505 and core alloy 6082 and FIG. 19 shows the interface of Cast #030827 between cladding alloy 1050 and core alloy 6111. In each of these Figures the presence of alloy components of the core alloy are gain visible in the grain boundaries of the cladding alloy immediately adjacent the interface.
A composite metal ingot, comprising at least two layers of differing alloy composition, wherein pairs of adjacent layers consisting of a first alloy and a second alloy are formed by applying the second alloy in a molten state to the surface of the first alloy while the surface of the first alloy is at a temperature between solidus and liquidus temperatures of the first alloy to form an interface there between, wherein the second alloy is a high or medium strength heat treatable aluminum alloy, and further wherein one or more alloy components from the second alloy are present within grain boundaries of the first alloy adjacent said interface.
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TECHNICAL FIELD [0001] This invention relates to the isolation and purification of a saxitoxin-binding polypeptide, saxiphilin, and to methods, assays and devices for the detection, concentration, purification and extraction of saxitoxin which employ purified saxiphilin. In particular the invention relates to an economical, robust, high throughput assay which does not require the use of radioactively-labelled reagents, and which is suitable for use in the field. BACKGROUND OF THE INVENTION [0002] Paralytic shellfish poisoning caused by ingestion of fish, crustaceans or molluscs containing toxins derived from dinoflagellates is a world-wide problem resulting in severe human illness, which often results in death. The poisoning is caused by paralytic shellfish toxins (PSTs) which are the family of toxins related to the archetypal molecule saxitoxin (STX). In addition, blooms of toxic freshwater algae can contaminate water supplies with the same neurotoxins that cause paralytic shellfish poisoning. This toxin contaminated water can have dire consequences for humans, livestock and wildlife. [0003] The general structure of PSTs is as follows: R 1 R 2 R 3 R 4 STX H H H CONH 2 dcSTX H H H H B1 H H H CONHSO 3 − B2 OH H H CONHSO 3 − C1 H H OSO 3 − CONHSO 3 − C2 H OSO 3 − H CONHSO 3 − C3 OH H OSO 3 − C CONHSO 3 − C4 OH OSO 3 − H CONHSO 3 − neoSTX OH H H CONH 2 dcNeoSTX OH H H H GTX2 H H OSO 3 − CONH 2 GTX3 H OSO 3 − H CONH 2 GTX1 OH H H CONH 2 GTX4 OH OSO 3 − H CONH 2 [0004] This family of toxins can be divided into three broad categories: the saxitoxins, which are highly potent neurotoxins, and which are not sulphated; the gonyautoxins (GTXs), which are singly sulphated; and the N-sulphocarbamoyl-11-hydrosulphate C-toxins, which are less toxic than the STXs or GTXs. [0005] The toxicity of the PSTs is a result of their binding to voltage-dependent sodium channels, which blocks the influx of sodium ions, and thus blocks neuromuscular transmission. This causes respiratory paralysis, for which no treatment is available. In some outbreaks of paralytic shellfish poisoning up to 40% of the victims have died. The PSTs bind to the same site on the sodium channel as tetrodotoxins, which have a completely different structure (Hall et al., 1990). In some cases, tetrodotoxins can occur together with PSTs, and therefore any assay for detection of PSTs must be able to distinguish them from tetrodotoxins. [0006] The dinoflagellates which are the source of PSTs periodically form algal blooms, known as red tides (Anderson, 1994). Molluscs, fish, and crustaceans, including species of commercial significance or which are raised using aquaculture techniques, may feed on these dinoflagellates and accumulate the toxins. It is not possible to detect by gross examination whether an individual marine animal contains the toxin, and therefore there is a risk that humans will inadvertently consume toxin-containing animals. It is therefore necessary to monitor species which are to be consumed for the presence of PSTs, in order to avoid the risk of poisoning and to prevent social and economic cost. [0007] More than 20 natural analogues of saxitoxin are known, and their toxicity to mammals varies. Some of the naturally-occurring PSTs are listed in Table 1. TABLE 1 Some of the naturally occurring PSTs Common CAS literature Registry Trivial name abbreviations Systematic name number Saxitoxin STX 1H,10H-pyrrolo [1,2-c]purine-10,10-diol-2,6-diamino-4[[(aminocarbonyl)oxy]methyl]-3a,4,8,9- 35523-89-8 terrahydro, [3aS-(3aα, 4α, 10aR*)] α-saxitoxinol — 1H,8H-pyrrolo[1,2-c]purine-4-methanol,2,6-diamino-3a,4,9,10-tetrahydro-10-hydroxy-,α- 75420-34-7 carbamate, [3aS-(3aα, 4α, 10β, 10aR*)] β-saxitoxinol — 1H,8H-pyrrolo[1,2-c]purine-4-methanol,2,6-diamino-3a,4,9,10-tetrahydro-10-hydroxy-,α- 75352-30-6 carbamate, [3aS-(3aα, 4α, 10α, 10aR*)] Neosaxitoxin neoSTX 1H,10H-pyrrolo[1,2-c]purine-10,10-diol, 2-amino-4-[[(aminocarbonyl)oxy]methyl]- 64296-20-4 3a,4,5,6,8,9-hexahydro-5-hydroxy-6-imino, [3aS-(3aα, 4α, 10aR*)] Gonyautoxin I GTX I or 1H,10H-pyrrolo[1,2-c]purine-9,10,10-triol-2-amino-4-[[(aminocarbonyl)oxy]methyl]- 60748-39-2 GTX 1 3a,4,5,6,8,9-hexahydro-5-hydroxy-6-imino-9-(hydrogen sulfate), [3aS-(3aα, 4α, 9β, 10aR*)] Gonyautoxin II GTX II or 1H,10H-pyrrolo[1,2-c]purine-9,10,10-triol-2,6-diamino-4-[[(aminocarbonyl)oxy]methyl]- 60508-89-6 GTX 2 3a,4,8,9-tetrahydro-9-(hydrogen sulfate), [3aS-(3aα, 4α, 9β, 10aR*)] Gonyautoxin III GTX III or 1H,10H-pyrrolo[1,2-c]purine-9,10,10-triol-2,6-diamino-4-[[(aminocarbonyl)oxy]methyl]- 60537-65-7 GTX 3 3a,4,8,9-tetrahydro-9-(hydrogen sulfate), [3aS-(3aα, 4α, 9α, 10aR*)] Gonyautoxin IV GTX IV or 1H,10H-pyrrolo[1,2-c]purine-9,10,10-triol-2-amino-4-[[(aminocarbonyl)oxyl]methyl] 64296-26-0 GTX 4 3a,4,5,6,8,9-hexahydro-5-hydroxy-6-imino-9-(hydrogen sulfate), [3aS-(3aα, 4α, 9α, 10aR*)] Gonyautoxin V GTX V, GTX 5 Carbamic acid, sulfo-, C-[2,6-diamino-3a,4,9,10-tetrahydro-10,10-dihydroxy-1H,8H- 64296-25-9 or B1 pyrrolo[1,2-c]purin-4-yl)methyl]ester, [3aS-3aα, 4α, 10aR*)] Gonyautoxin VI GTX VI, GTX 6 Carbamic acid, sulfo-, C-[(2-amino-3a,4,5,6,9,10-hexahydro-5,10,10-trihydroxy-6-imino-1H, 82810-44-4 or B2 8H-pyrrolo[1,2-c]purine-4-yl)methyl]ester, [3aS-(3aα, 4α, 10aR*)] Gonyautoxin VIII GTX VIII or Carbamic acid, sulfo-, C-[[2,6-diamino-3a,4,9,10-tetrahydro-10,10-dihydroxy-9-(sulfoxy)- 80226-62-6 GTX 8 or C2 1H,8H-pyrrolo[1,2-c]purine-4-yl]methyl]ester, [3aS-(3aα, 4α, 9α, 10aR*)] epi-gonyautoxin VIII epi-GTX VIII Carbamic acid, sulfo-, C-[[2,6-diamino-3a,4,9,10-tetrahydro-10,10-dihydroxy-9-(sulfoxy)- 80173-30-4 or C1 1H,8H-pyrrolo[1,2-c]purine-4-yl]methyl]ester, [3aS-(3aα, 4α, 9β, 10aR*)] [0008] The incidence of algal blooms appears to be increasing world-wide, possibly as a result of increased eutrophication of coastal waters and global warming, and consequently the incidence of outbreaks of paralytic shellfish poisoning or of contamination of shellfish or other organisms with PSTs is also increasing. For example, in 2000 alone, four people in Sabah, Malaysia, were poisoned and shellfisheries were closed for four months. Shellfisheries in Manila Bay, the Philippines, were closed for several months; nine people were poisoned and five admitted to hospital in Washington State, and shellfisheries were closed for several months in the year 2000 in Cape Cod and South Maine, both in the United States; all shellfishing on the west coast of the North Island of New Zealand was stopped in May 2000 as the result of an algal bloom, which was approaching the green-lipped mussel beds, which produce mussels worth NZ$84 million annually ; in Scotland shellfishing was banned in June, 2000; and blooms leading to instances of paralytic shellfish poisoning have occurred in South Africa and China; as the result of contamination detected in July, 2000 in Canada, 3000 aquaculture salmon were destroyed. In particular, in the United States, approximately 150 outbreaks of contamination of shellfish have occurred in the last decade, with closures of shellfisheries of up to twelve months resulting; closures of three years have occurred in some parts of Scotland; in Morocco, in 1994, four people died and 74 were admitted to hospital; almost 1600 people have been poisoned in the Philippines since 1983, whereas virtually no such incidence were observed before 1983; and in one outbreak in India in 1997, seven people died, 500 were admitted to hospital, and the ban on shellfishing resulted in the loss of jobs for 1000 families. [0009] Unfortunately, although the need for a simple, robust and reliable method of detecting contamination of marine organisms to be used for human consumption is evident, methods which are currently available are not satisfactory. Regular testing of shellfish to ensure that toxic product does not enter the market place is required (Van Egmond and Dekker, 1995). Currently, the only officially endorsed method is the mouse lethality bioassay approved by the Association of Official Analytical Chemists (AOAC) official methods of analysis, section 959.08 E,. 1990. This requires intraperitoneal injection of mice with an HCl extract of potentially toxic organisms such as shellfish, and observation of the time from injection to death (Sommer and Meyer, 1937; Hungerford, 1995). The mice must come from a colony of mice which is regularly standardised for its sensitivity to reference toxin samples, and the sample must be diluted so that death occurs between 5 and 7 minutes. The assay is inhumane, expensive, and unpopular, and is at risk of being prohibited as a result of animal welfare regulation, particularly in countries such as the European Union, the Netherlands and Germany. Of even greater concern is that the mouse bioassay assay has a sensitivity of only 180 μg STX/1 (Johnson and Mulberry, 1966). [0010] This lack of sensitivity means that there is a serious risk that levels of PSTs sufficient to cause toxicity in humans may not be detected. For example, children in the Philippines have died as the result of ingestion of shellfish when mouse lethality bioassays indicated that shellfish contained only 40 μg STX/100 g shellfish meat, which equates to around 200 μg when takes into account dilution due to extraction solvent plus shellfish. This level of toxicity is the same as the detection limit for the mouse lethality bioassay. [0011] This problem has led to attempts to develop alternative assays, based on [0012] (a) detecting the presence of intoxicating organisms by biological observation, [0013] (b) in situ detection using methods such as DNA probes, or [0014] (c) detecting the presence of toxins in the marine organism by biochemical, physiological or chemical assay. [0015] One approach utilises blockage of the voltage-gated sodium channel (VGSC), a large transmembrane protein in excitable cells which allows passage of ions through a central pore when it opens in response to alterations in cellular potential difference. (See for example Doucette et al., 1997; Jellett et al., 1992; Vieytes et al., 1993). These-assays are radioligand assays (Weigele and Barchi, 1978), which can be adapted to a microtitre plate format which increases the sample throughput (Doucette et al., 1997). Alternatively cultured cells hyperstimulated so as to increase ion flow through the sodium channel may be used (Jellett et al., 1992; U.S. Pat. No. 5,420,011 and U.S. Pat. No. 5,858,687). [0016] However, these assays are expensive and technically complex, requiring either radioactively-labelled reagents or cell cultures. Moreover they are sensitive to pH fluctuations, because at pH greater than 6.7 PSTs are readily displaced from the ion channel, are similarly sensitive to cation concentration, and, more importantly, are non-specific because they also detect tetrodotoxin. None of these assays is suitable for field use. Chemical assays are complicated by the fact that the individual toxins are tremendously variable in structure, ranging from very polar to lipophilic, and from low to high molecular weight. Furthermore, these chemical methods require the use of standard samples of the known toxins, and any new and biologically active PSTs will not be measurable by these methods. Thus assays based on detection using antibodies or using chemical methods such as high performance liquid chromatography, mass spectrometry, or capillary electrophoresis may not detect the broad range of toxins. [0017] A simple, rapid preliminary clean-up method for crude shellfish extracts, coupled with a bench or desktop lateral flow immuno-chromatographic assay marketed by Jellett Biotek, enables a preliminary result to be obtained within ten minutes; however, confirmatory screening using liquid chromatography-mass spectrometry is required. The preliminary clean-up uses ammonium formate mobile phase on a 5 cm solid-phase column suitable for lipophilic toxins, and this is followed by LCMS on a Tosoh-Haas amide 40 column using a 60-90% gradient of tetranitrile-2 mM ammonium formate, pH3.5. A preliminary report was presented by M. A. Quilliam at the International Marine Biotechnology Conference, Townsville, September 2000. [0018] We have utilised a different approach, which relies on a receptor protein known as saxiphilin, which is completely unrelated to the VGSC in either amino acid sequence or of functional properties, and which specifically binds STX but not tetrodotoxins (Llewellyn and Moczydlowski, 1994). The ability of saxiphilin to bind STX has been used in a low-throughput radioligand binding assay for detection of PSTs in blue-green algae, crustaceans and molluscs (Carmichael et al., 1997; Negri and Llewellyn, 1998). This utilises displacement of 3 H-labelled STX from saxiphilin. We have utilised a crude saxiphilin-containing extract to develop a microtitre plate assay for detection of PSTs (Llewellyn et al., 1998; Llewellyn and Doyle, 2000). While this assay provides high throughput, sensitivity and accuracy, and has the advantage that it does not suffer from interference-by other compounds present in shellfish extracts or from the acidic pH necessary to maintain stability of toxin during extraction from shellfish, it still suffers from the disadvantage that it requires radioactively-labelled material. [0019] The saxiphilin utilised in the assay is a crude preparation prepared by homogenising specimens of the centipede Ethmostigmus rubripes in buffer containing a protease inhibitor cocktail. While this preparation provides good sensitivity, there is still a problem in availability of the reagent, and the fact that it is not a defined, reproducible preparation. Therefore there is still a need in the art for a rapid, robust assay which is suitable for field use, for example on fishing vessels, or at aquaculture facilities, and which detects a wide range of STXs. [0020] It will be clearly understood that, although a number of prior art publications are referred to herein, this reference does not constitute an admission that any of these documents form part of the common general knowledge in the art, in Australia or in any other country. SUMMARY OF THE INVENTION [0021] According to one aspect of the present invention there is provided a method of detecting and/or measuring the amount of paralytic shellfish toxin (PST) present in a sample, comprising the steps of: [0022] 1) providing an isolated and purified invertebrate saxiphilin, or a fragment thereof which contains a saxitoxin binding site; [0023] 2) contacting it with the sample; [0024] 3) measuring binding of PSTs to the invertebrate saxiphilin; and [0025] correlating the amount of binding with either the presence or absence of PSTs in the sample or with the PST concentration in the sample. [0026] The invertebrate saxiphilin, or fragment thereof, may be coupled to a detectable label or immobilised on a solid support. The detectable label may be any suitable label, as would be understood by the person skilled in the art and may be coupled to a solid support in any convenient manner. [0027] In a further aspect of the present invention there is provided method of measuring the amount of paralytic shellfish toxin (PST) present in a sample, comprising the steps of: [0028] (a) pre-treating the filters of a microtitre filtration plate with a polycation; [0029] (b) adding to wells of the plate a known amount of a labelled saxiphilin comprising an isolated and purified invertebrate saxiphilin, or a fragment thereof which contains a saxitoxin binding site labelled with a detectable marker, and a series of dilutions of material suspected to comprise paralytic shellfish toxin; [0030] (c) incubating the plate for a time sufficient to permit binding of any paralytic shellfish toxin present to the labelled saxiphilin; [0031] (d) aspirating the contents of each well through the filter of the well to remove components other than labelled saxiphilin and compounds bound thereto; [0032] (e) rinsing each well and filter to remove residual unbound compounds; and [0033] (f) measuring the amount of labelled saxiphilin retained by the filter, [0034] in which the degree of binding of labelled saxiphilin when compared with a control sample indicates the amount of paralytic shellfish toxin present in the sample. [0035] In a further aspect of the present invention there is provided an isolated and purified invertebrate saxiphilin coupled to a solid support. [0036] In a still further aspect of the present invention there is provided an isolated purified invertebrate saxiphilin labelled with a detectable label. [0037] In a further aspect, the invention provides a method of isolation of an invertebrate saxiphilin, comprising the steps of: [0038] (a) homogenising individuals of a saxiphilin-producing arthropod species in a physiological buffer comprising protease inhibitors; [0039] (b) subjecting the homogenate to low-speed centrifugation to remove cell debris; [0040] (c) subjecting the supernatant from step (b) to high-speed centrifugation; and [0041] (d) precipitating saxiphilin from the supernatant by exposure to ammonium sulphate; [0042] (e) redissolving the precipitate at pH 5.0-6.5 and centrifuging to remove non-saxiphilin molecules; [0043] (f) exposing the supernatant from (e) to a matrix to which saxiphilin binds, such as a glass fibre-polyethylene imine (PEI) support matrix; and [0044] (g) eluting bound material from the matrix under high salt conditions. [0045] Advantageously the saxiphilin is precipitated by exposure to 40-60% ammonium sulphate. Prior to this step, the pH may be temporarily reduced to 5.0 to precipitate some of the non-saxiphilin. [0046] In step (g), the saxiphilin is typically eluted by NaCl or KCl at a concentration from 600 mM to saturation, in buffer at pH5-9. A number of different buffer systems may be used. [0047] Optionally, further purification may be obtained, for example by chromatofocussing on PBE 94 resin quilibrated with 25 mM imidazole-HCl pH 7.4 and eluting with a solution containing 25 mL Polybuffer 74, brought to a final volume of 200 mL and a pH of 4.0 with HCl. [0048] Polybuffer removal and buffer exchange can then be achieved by size exclusion chromatography or desalting on a column, such as PD-10 columns from Amersham Pharmacia Biotech. [0049] The arthropod species may be any species which produces saxiphilin. See for example Llewellyn et al., 1997. Preferably the arthropod is a centipede, such as Ethmostigmus rubripes, an isopod, such as an Oniscus species, a spider, such as Araneus. c.f. Cavaticus, a Xanthid crab, or an insect of the family Clopterygidae. [0050] More preferably the arthropod is a centipede, most preferably Ethmostigmus rubripes. Saxiphilin from this species has been shown to be able to bind PSTs of all the structural sub-class of the PST family with comparable affinity. The arthropod may conveniently be anaesthetised by exposure to hypothermia. Homogenisation can be carried out using any convenient apparatus, such as a Heidolph tissue homogeniser. One suitable homogenisation buffer is 20 mM HEPES-NaOH, pH7.4, containing 0.5 mM EDTA 1 μM leupeptin, 1 μM pepstatin, 0.5 μM aprotonin, and 1 μM phenylmethylsulphonyl fluoride. Suitably 2 ml buffer is used per gram of arthropod material. The low speed centrifugation may conveniently be performed at 8000 g for 10 minutes, followed by high speed centrifugation at 50,000 g for 20 minutes. The supernatant following high-speed centritugation may be frozen in liquid nitrogen and stored at 80° C. prior to further processing. [0051] The PEI support matrix is prepared by conventional methods, for example by incubation of glass fibre with 0.3% PEI in water solution (v/v) for at least 1 hour and removal of the PEI by draining or aspiration under vacuum. [0052] The isolated saxiphilin may be used for detection of PSTs, using the microtitre plate assay which we have previously described (Llewellyn and Doyle 2000; Lewellyn et al., 1998), utilising saxiphilin labelled with a non-radioactive label. The person skilled in the art will be aware of suitable labels, which include fluorescent and chemiluminescent labels, colloidal gold, latex microbeads, liposome-encapsulated dyes and enzymic labels, although these are not favoured as the enhancement of the signal is time dependent due to the need for an enzymatic reaction to take place. The liposome encapsulated dyes may be biotinylated or tagged in some other way to facilitate their capture in an assay. Suitable detection methods using each of these labels are known in the art. [0053] The isolated saxiphilin of the invention is also useful in preparation of affinity materials for purification, concentration or extraction of PSTS, for example in testing water quality of waters suspected to be contaminated by algal blooms. For example, the isolated saxiphilin may be coupled to a suitable solid support, which may then be packed in a column or a cartridge. In one preferred embodiment, the solid support is packed in a cartridge adapted for attachment to a syringe. The person skilled in the art will be aware of suitable coupling methods and supports, for example cyanogen bromide-activated matrices such as agarose; epoxy activated matrices; glutaraldehyde-activated silica; carboxymethylcellulose hydrazide; polyacrylamide hydrazide and oxirane acrylic beads. PSTs can be eluted from the affinity material by treatment with a small volume (eg 1-5 ml) of acid, urea or concentrated salts. [0054] For assays being performed in the laboratory, this preliminary purification may be performed prior to assay of a sample of material suspected to be contaminated with PSTs. [0055] Material suitable for use in the assay or the preliminary concentration method of the invention can be a tissue extract, for example from vertebrates such as fish or a mammalian species who may have ingested PST contaminated material; invertebrates such as molluscs, including shellfish or cephalopods; macroscopic algae such as seaweed; microalgae including cyanobacteria, dinoflagellates and the like; or bacteria. Biological fluids such as blood, urine or saliva of patients suspected to be suffering from PST poisoning, or water samples, such as drinking water supplies suspected of contamination or water from regions manifesting algal blooms, which may contain dissolved toxins released by the bloom organisms, can also be tested. In addition, samples containing synthetic PSTs can be utilised. [0056] PSTs can be extracted from tissue to be tested using any suitable aqueous or alcoholic solvent; preferably the solvent is at acid pH, since saxitoxin is susceptible to degradation under basic conditions. Optionally the extraction may be performed at elevated temperature. A particularly suitable solvent is that utilised in the method endorsed by the Association of Official Analytical Chemists, namely 0.1 N HCl. [0057] There are various specific methodologies for carrying out assays of the invention, and various preferred embodiments of the invention are described below. [0058] In one embodiment the invention provides a method of measuring the amount of a paralytic shellfish toxin present in a sample, comprising the steps of [0059] (a) pre-treating the filters of a microtitre filtration plate with a polycation; [0060] (b) adding to wells of the plate a known amount of invertebrate saxiphilin labelled with a detectable marker, and a series of dilutions of material suspected to comprise paralytic shellfish toxin; [0061] (c) incubating the plate for a time sufficient to permit binding of the paralytic shellfish toxin to the saxiphilin; [0062] (d) aspirating the contents of each well through the filter of the well to remove components other than saxiphilin and compounds bound thereto; [0063] (e) rinsing each well and filter to remove residual unbound compounds; and [0064] (f) measuring the amount of labelled saxiphilin retained by the filter, [0065] in which the degree of binding of labelled saxiphilin when compared with a control sample indicates the amount of paralytic shellfish toxin present in the sample. [0066] Preferably in step (b) the sample comprises a buffer to maintain pH in the range 6.5 to 9, and optionally also comprises a chloride salt, such as sodium chloride or potassium chloride, present at a concentration up to 500 mM. Typically the total volume present in the well is 50 to 350 μl, preferably 100 to 200 μl, more preferably 150 μl. In step (c) the incubation is carried out at 0 to 30° C., preferably at room temperature, for at least 30 minutes; the incubation is preferably for 60 to 120 minutes, more preferably 90 minutes, but can be continued up to about 8 hours. In step (e), the rinse may be performed using any suitable solution, such as a solution buffered at the same pH as for step (b). A single rinse will usually be adequate; however, each well is typically rinsed 2 to 3 times. [0067] In a preferred embodiment, the protocol uses a total volume of 150 μl containing 20 mM MOPS-NaOH (pH 7.4), 200 mM NaCl, and 1 nM labelled STX centipede saxiphilin according to the invention and incubation at room temperature (−25° C.) for 90 min prior to aspiration through the filters. Wells are rinsed three times with 180 μl ice-cold water. The optimum amount of saxiphilin may readily be determined by routine experimentation. [0068] In a further aspect, the invention provides a kit for measuring the amount of paralytic shellfish toxin in a sample, comprising [0069] (a) a microtiter plate; [0070] (b) saxiphilin according to the invention, labelled with a detectable marker; [0071] (c) extraction buffer for extracting material to be tested from a sample of an organism or tissue to be tested; and optionally [0072] (d) a concentrating means for concentrating paralytic shellfish poisons in the extract or removal of contaminants that may interfere with the assay. [0073] Preferably the concentrating means is a column or cartridge comprising a solid support material coupled to purified saxiphilin according to the invention. [0074] According to a still further aspect of the present invention there is provided a device for measuring the amount of paralytic shellfish toxin (PST) present in a sample, comprising: [0075] an immobilised invertebrate saxiphilin, or a fragment thereof which contains a saxitoxin binding site; [0076] means for introducing a sample to said immobilised sample to said immobilised saxiphilin, or fragment thereof; and [0077] means for correlating the amount of binding with either the presence or absence of PSTs or with PST concentration in the sample. [0078] According to a still further aspect of the present invention there is provided a device for measuring the amount of paralytic shellfish toxin (PST) present in a sample, comprising: [0079] an immobilised PST; [0080] means for introducing a sample to said immobilised PST; [0081] means for introducing a predetermined amount of an isolated and purified invertebrate saxiphilin to the sample; [0082] means for measuring binding of the invertebrate saxiphilin introduced to said immobilised PST; and [0083] means for correlating competition for binding between the immobilised PST and any PST contained in the sample with PST concentration in the sample. [0084] Typically an invertebrate saxitoxin is used and this has advantageously been purified as described above. [0085] The device may be a biosensor, and therefore include means for translating the binding event into an electronic signal. [0086] Advantageously, this is by a detection of the change of mass of the protein upon binding. It will therefore be appreciated that, since saxiphilin is a relatively large protein, enhancements in the sensitivity of detection may be achieved through using fragments of the saxiphilin protein in place of immobilised saxiphilin, provided that they contain the saxitoxin binding site. If a fragment is used it will be appreciated that the change in mass upon binding is greater as a proportion of the total weight of the system. In a competitive binding assay in which a PST is immobilised it is preferable to employ full length saxiphilin, as the reverse is true. [0087] According to a still further aspect of the invention there is provided a method for the concentration, purification and/or extraction of paralytic shellfish toxins (PSTs), comprising the steps of: [0088] providing an immobilised invertebrate saxiphilin, or a fragment thereof which contains a saxitoxin binding site; [0089] contacting a sample suspected of containing a PST with said immobilised saxiphilin for a sufficient time for the PST to bind the immobilised saxiphilin; and [0090] optionally, eluting the bound PST from the immobilised saxiphilin. [0091] This method may be used, among other things, to detoxify shellfish and purify water. [0092] There is also provided the use of isolated saxiphilin in the preparation of affinity materials for concentration, purification and/or extraction of paralytic shellfish toxins. [0093] There is also provided an affinity material for concentration, purification and/or extraction of paralytic shellfish toxins, comprising an isolated and purified invertebrate saxiphilin, or fragment thereof which contains a saxitoxin binding site coupled to a solid support. [0094] Advantageously the solid support is selected from the group consisting of azolactone matrices, cyanogen bromide-activated matrices; epoxy activated matrices; glutaraldehyde-activated silica; carboxymethylcellulose hydrazide; polyacrylamide hydrazide and oxirane acrylic beads. [0095] For the purposes of this specification it will be clearly understood that the word “comprising” means “including but not limited to”, and that the word “comprises” has a corresponding meaning. BRIEF DESCRIPTION OF THE FIGURES [0096] [0096]FIG. 1 is a schematic representation of views from above and from the side of a diagnostic test strip for detecting the presence of PSTs. [0097] [0097]FIG. 2 is a schematic representation of an alternative diagnostic test strip; [0098] [0098]FIG. 3 is a schematic representation illustrating the principle of a microtitre plate assay for PSTs; [0099] [0099]FIG. 4 shows schematically the competitive binding in a surface-plasmon resonance (SPR) sensor; [0100] [0100]FIG. 5 is a schematic representation of a saxiphilin-based surface-plasmon resonance (SPR) sensor for the rapid quantification of PSTs; [0101] [0101]FIG. 6 is a graph showing the eluted radioactivity of the binding experiments from Example 3; [0102] [0102]FIG. 7 is a bar graph showing specific binding of radioactivity in pH 5.0 peak in FIG. 6; and [0103] [0103]FIG. 8 is a graph showing the elution profile in the stability testing described in Example 3. DETAILED DESCRIPTION OF THE INVENTION [0104] The invention will now be described in detail by way of reference only to the following non-limiting examples and drawings. EXAMPLE 1 [0105] Purification of Saxiphilin [0106] Crude saxiphilin was obtained by homogenising specimens of the centipede Ethmostigmus rubripes in 10 mM Tris-HCl, 0.2 mM EDTA (pH 7.4) (2×10 sec bursts with a Waring blender at maximum setting; 3 ml buffer:1 g centipede) containing a cocktail of protease inhibitors (5 mM EDTA, 1 μM pepstatin, 1 μM aprotonin, 100 μM phenylmethylsulfonyl fluoride). After centrifuging the homogenate at 24,000 g for 20 min, the pellet was rehomogenised and centrifuged as above. The two supernatants were combined and passed through a 0.2 μm cellulose acetate filter (Nalgene). The saxiphilin was then precipitated from this supernatant by exposure to 40-60% ammonium sulphate, followed by removal of non-saxiphilin molecules from this precipate by redissolving into a buffered solution of Ph 5.0-6.5 and centrifuging to leave a supernatant containing saxiphilin. [0107] This supernatant was then exposed to a glass fibre-polyethylene imine (PEI) support matrix, prepared by incubation of glass fibre with 0.3% PEI in water solution (v/v) for at least 1 hour and removal of the PEI by draining or aspiration under vacuum. Saxiphilin was eluted from the matrix using high salt, with the saxiphilin typically being eluted by NaCl or KCl at a concentration from 600 mM to saturation, at pH 5-9. [0108] The protein has also been subjected to chromatofocussing on PBE 94 resin equilibrated with 25 mM imidazole-HCl pH 7.4 and eluting with a solution containing 25 mL Polybuffer 74, brought to a final volume of 200 mL and a pH of 4.0 with HCl. Polybuffer removal and buffer exchange can then be achieved by size exclusion chromatography or desalting columns, such as PD-10 columns from Amersham Pharmacia Biotech. EXAMPLE 2 [0109] Use of Purified Saxiphilin in Assay [0110] a) Diagnostic Test Strips [0111] One diagnostic kit for qualitative detection of PSTs using the purified saxiphilin of the invention is in the form of a test strip. The kit uses a solid matrix, or “wick”, upon which the reaction occurs. The kit has a band of saxitoxin at one end of this solid matrix, applied using a method known as “printing”. This immobilises the saxitoxin, which then acts as an anchor for modified saxiphilin (described below) as it flows past the “printed” saxitoxin. If the modified saxiphilin is already bound to a PST from a test sample, then it will be unable to bind to “printed” saxitoxin, and will continue to flow, preventing colour development. If the test sample has no PSTs, then the modified saxiphilin will bind to the band of “printed” saxitoxin, forming a coloured spot. To generate a coloured spot upon anchorage of saxiphilin, saxiphilin is conjugated to colloidal gold or coloured latex microbeads. The principle is that the colloidal gold, an intensely coloured reagent, is aggregated into a spot obvious to the human eye when the conjugated saxiphilin binds the STX immobilised on to the membrane. As it flows past the band of printed saxitoxin, it will stop and aggregate, or continue and not form a band visible to the human eye. This is illustrated schematically in FIG. 1. Thus this form of assay provides a qualitative “yes/no” assay for the presence of PSTs in a sample. The test strip provides a positive control. [0112] An alternative approach is to use a liposome encapsulated-dye. Liposomes provide instantaneous enhancement, and have considerable potential for automated assays. [0113] The experimental system is a competitive receptor assay and consists of a wicking reagent containing saxitoxin/biotin-tagged liposomes with entrapped dye and a plastic-backed nitrocellulose strip that has an immobilized saxiphilin competition zone and a liposome avidin capture zone in an ascending sequence (FIG. 2). A mixture of the wicking reagent and a sample containing an unknown quantity of PSTs is allowed to migrate along the strip by capillary action. In the saxiphilin zone, competitive binding with the PSTs receptor occurs. The unbound liposomes, proportional to the amount of saxitoxin in the sample, are carried into the liposome capture zone where they are concentrated. The color intensity of the saxiphilin zone and the avidin zone are estimated either visually or by scanning densitometry. [0114] The amount of immobilized saxiphilin must be as low as possible to increase sensitivity to PSTs, but sufficient to allow visual detection of liposomes. [0115] A typical migration assay requires approximately 100 μL sample solution and should reach the ppb detection level in less than 10 minutes, corresponding to PSTs detection limits in the low ng range. Liposomes are highly stable molecules that can be stored at least one year at +4° C. and several months at room temperature. This assay would be easily used in to field testing, without any special equipment or technical skills required. The kit would include special holders for the individual strips, in which openings are provided for sample application and optical readout. This low cost saxiphilin migration sensor allows easy and rapid screening of environmental samples and constitute an unparalleled and reliable tool for the PSTs risk assessment. [0116] (b) Microtitre Plate Assay [0117] Establishing the assay in a microtitre plate format allows its more sophisticated use, and enables quantitative results to be obtained. One preferred format is a binding inhibition asay. Saxitoxin is coated on a 96-well microtitre plate. Test samples are mixed with labelled saxiphilin and added to the 96 well plate. Toxin-free samples do not prevent the labelled saxiphilin from binding to the saxitoxin-coated surface of the wells of the 96 well plate, forming a coloured region. Toxin-containing samples inhibit colour formation with the degree of inhibition being proportional to the amount of toxin present. The plate is then read in a spectrophotometic plate reader and the amount of toxin quantified. [0118] A further possible technique for quantification of PSTs involves high-performance liquid chromatography coupled to a post-column oxidation system and a fluorescence detector. This procedure is complex and requires expensive PSTs standards. However, the combination of highly specific saxiphilin-based identification and sensitive detection by means of surface plasmon resonance (SPR), overcomes the drawbacks related to chromatographic techniques. [0119] The device requires a PST such as saxitoxin to be coupled to an activated gold surface, which is exposed to a liquid sample during the analysis. The SPR sensor detects changes in the reflection of laser light caused by the change of refractive index at the metal-liquid interface. Thus, when saxitoxin is coupled to the activated gold surface of the sensor, a refractive index alteration is induced by saxiphilin binding (FIG. 4). In the case where PSTs are present in the sample, a competition occurs between the free PSTs and bound saxitoxin, and the resulting signal decrease can be quantified. [0120] This flow-injection receptor assay consists of i) reagent pumping and sample injection systems, ii) a mixing cell where the competitive receptor assay occurs and iii) the SPR sensor including a flow cell and optical devices (FIG. 5). This system can be fully automated, such as in the BIACORE 2000™ available from Biacore AB. EXAMPLE 3 [0121] Affinity Column Preparation [0122] By linking saxiphilin to a solid phase, its ability to bind saxitoxin may be used to separate saxitoxin from liquid samples passed over the saxiphilin linked solid support. Since binding to centipede saxiphilin is pH dependent, the bound toxin can then be eluted. [0123] Making the Saxiphilin Affinity Column [0124] Isolated saxiphilin was used to prepare an affinity column using the Ultralink™ Tm kit manufactured by Pierce Chemical Company. This resin relies upon azolactone coupling chemistry and uses an inert semi-rigid resin with medium to fast flow characteristics. [0125] The method used was as follows: [0126] 1. The ammonium sulphate precipitated saxiphilin was resuspended into the Pierce supplied coupling buffer of BupH citrate-carbonate buffer (pH 9.). [0127] 2. This resuspended saxiphilin was added to 0.15 g of 3M Emphaze Biosupport medium AB 1 (supplied by Pierce) which hydrates the resin and binds available proteins. The resin swelled to 1 ml. [0128] 3. After 1 hour of gentle mixing, the resin and saxiphilin preparation was packed into a mini-column, and the resin was allowed to settle [0129] 4. The column was then washed with phosphate buffered saline (15 mls) [0130] 5. 4 mls of quench buffer (3M ethanolamine pH 9.0) was then added and the resin gently mixed in this buffer for 2.5 hours [0131] 6. The column was then washed with 15 ml phosphate buffered saline [0132] 7. The top of the resin was then sealed with a porous disc insert [0133] 8. Wash the column with 15 ml 1M NaCl [0134] 9. Wash the column with 15 ml 100 mM HEPES-NaOH (pH 7.4) and it is ready for testing for ability to bind saxitoxin [0135] Testing for Column Binding of Saxitoxin [0136] Tritiated saxitoxin (Amersham Pharmacia Biotech) was used to measure the columns ability to bind saxitoxin. [0137] Three 2 μl aliquot of the 3 H-STX (60 nM) was counted in a scintillation counter to measure how much radioactivity was going to be applied to the column. These aliquots contained 2113±42 counts per minute (cpm). [0138] 200 μl of 3 H-STX (=211,300 cpm—see point above) was added to the column and allowed to flow into the resin. The 3 H-STX is prepared by 150-fold dilution of the commercially supplied 3 H-STX (in 0.01 M acteic acid containing 2% ethanol) into 1 mM citrate buffer (pH 5.0). The column was then washed with 5 ml 100 mM HEPES-NaOH (pH 7.4). The flow through was collected. The column was then washed successively with 5 ml of the following with each sample collected separately: [0139] 2nd wash 100 mM HEPES-NaOH (pH 7.4) [0140] 3rd wash 100 mM HEPES-NaOH (pH 7.4) [0141] 100 mM HEPES-NaOH (pH 6.0) [0142] 100 mM HEPES-NaOH (pH 5.0) [0143] 0.001N HCl [0144] 0.005N HCl [0145] 0.01 N HCl [0146] 0.05 N HCl [0147] 0.1 N HCl [0148] 0.5 N HCl [0149] The eluted radioactivity is depicted in FIG. 6. [0150] As can be seen, there are two major peaks of radioactivity. The first elutes in the first fraction and is essentially unbound by the column. The second peak is eluted by 100 mM HEPES-NaOH pH 5.0. Tritiated saxitoxin contains free tritium and so these two peaks were tested for biological activity by measuring their ability to bind to the two known receptors for saxitoxin, namely the sodium channel and saxiphilin. [0151] Measuring Biological Activity of Eluted Peaks form Saxiphilin Column [0152] Conditions in the Assay Used Were: [0153] Sodium channel: 100 mM MOPS-NaOH (pH 7.4), 100 mM choline chloride, 100 μl of fractions 1 and 5 (wash and first pH 7.4 wash, pH 5.0 wash respectively), 10 μl rat brain vesicles containing sodium channels in a final volume of 250 μl. Samples were done in duplicate and a negative control containing an excessive amount of unlabelled tetrodotoxin was also performed to define specific levels of any bound 3 H-STX. [0154] Saxiphilin: 100 mM MOPS-NaOH (pH 7.4), 100 mM sodium chloride, 100 μl of fractions 1 and 5 (wash and first pH 7.4 wash, pH 5.0 wash respectively), 1.5 μl characterised centipede saxiphilin preparation in a final volume of 250 μl. Samples were done in duplicate and a negative control containing an excessive amount of unlabelled saxitoxin was also performed to define specific levels of any bound 3 H-STX. [0155] As can be seen in FIG. 7, only the pH 5.0 eluted peak of radioactivity from the column retained biological activity ie it could bind to the two known saxitoxin receptors. The pH 7.4 peak did not contain any such biological activity (except for a minimal amount of receptor binding activity in the saxiphilin assay) indicating that the radioactivity was tritium unincorporated into saxitoxin (a known property of commercially supplied 3 H-STX). [0156] Stability of Column After Initial Treatment [0157] After the final 0.5N HCl wash, the column was washed with 20 ml 100 mM HEPES-NaOH (pH 7.4) and stored overnight at 4° C. This column was removed and allowed to return to room temperature and the above elution experiment was repeated and the profile shown in FIG. 8 was obtained. [0158] As can be seen, the second peak of activity has shifted to be eluted by the 3rd wash with HEPES-NaOH (pH 7.4) which may indicate degradation of the saxiphilin. These peaks were not tested for biological activity. [0159] Thus it will be appreciated that saxiphilin can be bound to a solid phase chromatography resin such as Pierce's Emphaze Biosupport medium AB 1. On this column saxitoxin is bound by the saxiphilin and separated from other material (eg free tritium), then the saxitoxin can be eluted from the column with pH 5.0. The eluted saxitoxin retains biological activity. Treatment with acid (eg 0.5 N HCl) may degrade the linked saxiphilin. Non-specific retention of the 3 H-STX by the treated resin is not apparent. [0160] It will be apparent to the person skilled in the art that while the invention has been described in some detail for the purposes of clarity and understanding, various modifications and alterations to the embodiments and methods described herein may be made without departing from the scope of the inventive concept disclosed in this specification. [0161] References cited herein are listed on the following pages, and are incorporated herein by this reference. [0162] References [0163] Anderson D. M. (1994) Red Tides. Sci. Am. 271, 62-68. [0164] Carmichael W. W., Evans W. R., Yin Q. Q., Bell P and Moczydlowski E. (1997) Evidence for paralytic shellfish poisons in the freshwater cyanobacterium Lyngbya wollei (Fallow ex Gomont) comb. nov. Appl. Environ. Micro. 63, 3104-3110. [0165] Doucette G. J., Logan M. M., Ramsdell J. S. and Van Dolah F. M. (1997) Development and preliminary validation of a microtiter plate-based receptor binding assay for paralytic shellfish poison toxins. Toxicon 35, 625-636. [0166] Fernandez, M. L. and Cembella, A. D., 1995, Mammalian bioassays. Manual on Harmful Marine Microalgae, edited by G. M. Hallegraeff, D. M. Anderson, and A. D. Cembella (Paris: UNESCO), pp 213-228. [0167] Hall S., Strichartz G., Moczydlowski E., Ravindran A., Reichardt P. B. (1990) The saxitoxins. Sources, Chemistry and Pharmacology. In: Marine Toxins: Origin, Structure and Molecular Pharmacology: 29-63 [American Chemical Society WAshington D.C., USA]. [0168] Hungerford J. M. (1995) AOAC Official method 959.08. Paralytic shellfish poison. Official methods of Analysis, 16 edn (Arlington, Va.: AOAC International) Chapter 35.1.37. [0169] Jellett J. F., Marks L. J. Stewart J. E., Dorey M. L. Watson-Wright W., and Lawrence J. F. (1992) Paralytic shellfish poison (saxitoxin family) bioassays: Automated endpoint determination and standardization of the in vitro tissue culture bioassay, and comparison with the standard mouse bioassay. Toxicon 30, 1143-1156. [0170] Johnson, H. M., and Mulberry, G. (1966) Paralytic shellfish poison: serological assay by passive haemagglutination and bentonite flocculations. Nature 211, 747-748 [0171] Llewellyn L. E., Bell P. M. and Moczydlowski E. G. (1997) Phylogenetic survey of soluble saxitoxin-binding activity in pursuit of the function and molecular evolution of saxiphilin, a relative of tranferrin. Proc. R. Soc. Lond. B. 264, 891-902. [0172] Llewellyn, L. E. and Moczydlowski E. G. (1994) Characterisation of saxitoxin binding to saxiphilin a relative of the transferrin family that displays pH-dependent ligand binding. Biochemistry 33, 12312-12322. [0173] Llewellyn, L. E. and Doyle, J., 2000, The effect of shellfish extracts and other matrices upon the microtitre plate saxiphilin assay for paralytic shellfish poisons. Toxicon 39, 217-224. [0174] Llewellyn, L. E., Doyle J. and Negri, A., 1998, A high throughput, microtitre plate assay for paralytic shellfish poisons using the saxitoxin specific receptor, saxiphilin. Analytical Biochemistry 261, 51-56. [0175] Negri A. and Llewellyn L. E. (1998) Comparative analyses by HPLC and the sodium channel and saxiphilin 3 H-saxitoxin receptor assays fro paralytic shellfish toxins in crustaceans and molluscs from tropical north west Australia. Toxicon, 36, 283-298. [0176] Oshima, Y., 1995, Post-column derivatization HPLC methods for paralytic shellfish poisons. Manual on Harmful Marine Microalgae, edited by G. M. Hallegraeff, D. M. Anderson, and A. D. Cembella (Paris: UNESCO), pp 81-94. [0177] Sommer H and Meyer K. F. (1937) Paralytic shellfish poison. Arch. Pathol 24, 560. [0178] Useleber E., Schneider E. and Terplan G. (1991). Direct enzyme immunoassay in microtitration plate and test strip format for the detection of saxitoxin in shellfish. Lett. Appl Microbiol. 13, 275-277. [0179] Weigele J. B. and Barchi R. L. (1978). Analysis of saxitoxin binding in isolated rate synaptosomse using a rapid filtration assay. FEBS Lett. 91, 310-314. [0180] Van Egmond, H. P., Dekker, W. H., 1995. Worldwide regulations for mycotoxins in 1994. Natural Toxins 3, 332-336.
A method of detecting and/or measuring the amount of a paralytic shellfish toxin (PST) present in a sample, comprising the steps of: 1) providing an isolated and purified saxiphilin, or fragment thereof which contains a saxitoxin binding site; 2) contacting it with the sample; 3) mearsuring binding of PST contained in the sample to said isolated and purified saxiphilin; and correlating the amount of binding with either the presence or absence of PSTs in the sample or with the PST concentration in the sample.
51,855
CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation-in-part of U.S. patent application Ser. No. 14/923,203 filed 26 Oct. 2015 which is a continuation-in-part of U.S. patent application Ser. No. 14/584,656, filed 29 Dec. 2014 (now U.S. Pat. No. 9,168,154) that in turn claims benefit of both U.S. Patent Application No. 61/921,528 and U.S. Patent Application No. 61/980,188, and is related to U.S. patent application Ser. No. 14/965,851 filed 10 Dec. 2015, the contents of these applications in their entireties are hereby expressly incorporated by reference thereto for all purposes. FIELD OF THE INVENTION [0002] The present invention relates generally to orthopedic surgical systems and procedures employing a prosthetic implant for, and more specifically, but not exclusively, to joint replacement therapies such as total hip replacement including controlled installation and positioning of the prosthesis such as during replacement of a pelvic acetabulum with a prosthetic implant. BACKGROUND OF THE INVENTION [0003] The subject matter discussed in the background section should not be assumed to be prior art merely as a result of its mention in the background section. Similarly, a problem mentioned in the background section or associated with the subject matter of the background section should not be assumed to have been previously recognized in the prior art. The subject matter in the background section merely represents different approaches, which in and of themselves may also be inventions. [0004] Total hip replacement refers to a surgical procedure where a hip joint is replaced using a prosthetic implant. There are several different techniques that may be used, but all include a step of inserting an acetabular component into the acetabulum and positioning it correctly in three dimensions (along an X, Y, and Z axis). [0005] In total hip replacement (THR) procedures there are advantages to patient outcome when the procedure is performed by a surgeon specializing in these procedures. Patients of surgeons who do not perform as many procedures can have increased risks of complications, particularly of complications arising from incorrect placement and positioning of the acetabular component. [0006] The incorrect placement and positioning may arise even when the surgeon understood and intended the acetabular component to be inserted and positioned correctly. This is true because in some techniques, the tools for actually installing the acetabular component are crude and provide an imprecise, unpredictable coarse positioning outcome. [0007] Some techniques may employ automated and/or computer-assisted navigation tools, for example, x-ray fluoroscopy or computer guidance systems. A computer assisted surgery technique may help the surgeon in determining the correct orientation and placement of the acetabular component. However, current technology provides that at some point the surgeon is required to employ a hammer/mallet to physically strike a pin or alignment rod. The amount of force applied and the location of the application of the force are variables that would not be controlled by these navigation tools. Thus even when the acetabular component is properly positioned and oriented, when actually impacting the acetabular component into place the actual location and orientation can differ from the intended optimum location and orientation. In some cases the tools used can be used to determine that there is, in fact, some difference in the location and/or orientation. However, once again the surgeon employs an impacting tool (e.g., the hammer/mallet) to strike the pin or alignment rod to attempt an adjustment. However the resulting location and orientation of the acetabular component after the adjustment may not be, in fact, the desired location and/or orientation. The more familiar that the surgeon is with the use and application of these adjustment tools can reduce the risk to a patient from a less preferred location or orientation. In some circumstances, quite large impacting forces are applied to the prosthesis by the mallet striking the rod; these forces make fine tuning difficult at best and there is risk of fracturing and/or shattering the acetabulum during these impacting steps. [0008] Installation and assembly systems for a prosthesis that have employed a guidance system may typically require that the surgeon divert attention from the installation/assembly when accessing information from the navigation system to establish or check the installation/assembly. [0009] For some navigation/guidance systems, each operating room could define a frame of reference with the navigation system calibrated into this frame of reference. Such a use makes it difficult to use the navigation system in a different operating room without first performing calibration procedures. Thus the navigation system imposes an additional cost on the surgeon and the facilities management in implementing these types of solutions. [0010] Different intra-operative evaluation and alignment of a prosthesis, e.g., an acetabular cup during THR, may include use of an A-frame, Fluoroscopy, Computer navigation, and patient specific instrumentation (PSI). Use of devices such as this may allow a surgeon to determine a position/alignment of the prosthesis and provide a map, such as of the pelvis, allowing the surgeon to decide on how to align the prosthesis to the pelvis. [0011] Two processes, considered separate and distinct, are implicated in the installation and positioning of a prosthesis: i) preparation of the installation location, e.g. the acetabulum for the acetabular cup in THR, and ii) insertion of the prosthesis. While many focus on ii) for determining accurate installation, both i) and ii) may be important as errors in alignment and directionality during site preparation, e.g., reaming, could adversely affect the final outcome and which may require more extensive processing in process ii) than may be the case when care is also taken during process i). [0012] Some of the patent applications incorporated above address improvement over the use of a mallet impacting/striking an alignment pin to adjust an orientation of a mispositioned prosthesis. [0013] What is needed is a system and method for improving upon prosthesis installation, such as including a real-time evaluation of tool and/or prosthesis alignment or position. BRIEF SUMMARY OF THE INVENTION [0014] Disclosed is a system and method for improving upon prosthesis installation, such as including a real-time evaluation of tool and/or prosthesis alignment or position. The following summary of the invention is provided to facilitate an understanding of some of technical features related to total hip replacement, and is not intended to be a full description of the present invention. A full appreciation of the various aspects of the invention can be gained by taking the entire specification, claims, drawings, and abstract as a whole. The present invention is applicable to other surgical procedures, including replacement of other joints replaced by a prosthetic implant in addition to replacement of an acetabulum (hip socket) with an acetabular component (e.g., a cup), and other processes in the procedure in addition to installation, including site preparation. [0015] Some of the disclosed concepts involve creation of a system/method/tool/gun that vibrates an attached prosthesis, e.g., an acetabular cup, while an integrated alignment system, e.g., an inertial measurement unit (IMU) and display, measures and reports real-time alignment status. The gun would be held in a surgeon's hands and deployed. It could use a vibratory energy to insert (not impact) and position the cup into desired alignment (using current intra-operation measurement systems, navigation, fluoroscopy, integrated alignment system, and the like). [0016] In one embodiment, a first gun-like device is used for accurate impaction of the acetabular component at the desired location and orientation. [0017] In another embodiment, a second gun-like device is used for fine-tuning of the orientation of the acetabular component, such as one installed by the first gun-like device, by traditional mallet and tamp, or by other methodology. However the second gun-like device may be used independently of the first gun-like device for adjusting an acetabular component installed using an alternate technique. Similarly the second gun-like device may be used independently of the first gun-like device, particularly when the initial installation is sufficiently close to the desired location and orientation. These embodiments are not necessarily limited to fine-tuning as certain embodiments permit complete re-orientation. Some implementations allow for removal of an installed prosthesis. [0018] Another embodiment includes a third gun-like device that combines the functions of the first gun-like device and the second gun-like device. This embodiment enables the surgeon to accurately locate, insert, orient, and otherwise position the acetabular component with the single tool. [0019] Another embodiment includes a fourth device that installs the acetabular component without use of the mallet and the rod, or use of alternatives to strike the acetabular component for impacting it into the acetabulum. This embodiment imparts a vibratory motion to an installation rod coupled to the acetabular component that enables low-force, impactless installation and/or positioning. [0020] A positioning device for an acetabular cup disposed in a bone, the acetabular cup including an outer shell having a sidewall defining an inner cavity and an opening with the sidewall having a periphery around the opening and with the acetabular cup having a desired abduction angle relative to the bone and a desired anteversion angle relative to the bone, including a controller including a trigger and a selector; a support having a proximal end and a distal end opposite of the proximal end, the support further having a longitudinal axis extending from the proximal end to the distal end with the proximal end coupled to the controller, the support further having an adapter coupled to the distal end with the adapter configured to secure the acetabular cup; and a number N, the number N, an integer greater than or equal to 2, of longitudinal actuators coupled to the controller and disposed around the support generally parallel to the longitudinal axis, each the actuator including an associated impact head arranged to strike a portion of the periphery, each impact head providing an impact strike to a different portion of the periphery when the associated actuator is selected and triggered; wherein each the impact strike adjusts one of the angles relative to the bone. [0021] An embodiment of an installation or assembly device may include a vibratory installation system that facilitates installation or assembly of a prosthesis, or portion thereof, using a vibratory Behzadi Medical Device (BMD) including a coupled oscillation engine and pulse transfer assembly. This embodiment may further include an alignment system, e.g., an inertial measurement unit (IMU) and display/indicator system, coupled to the vibratory BMD. Further, the display is preferably coupled to the vibratory BMD. Thus the IMU and the display system would be available on the BMD and directly accessible in real-time, without attention diversion, as the surgeon continuously operates the BMD to install and/or assembly the prosthesis or portion thereof. [0022] Some embodiments include the alignment system provided with other tools, such as a reamer, cutter, or other power device which cuts, abrades, planes, removes, or otherwise removes or shapes tissue at a prosthesis installation site. [0023] An installation device for an acetabular cup disposed in a pelvic bone, the acetabular cup including an outer shell having a sidewall defining an inner cavity and an opening with the sidewall having a periphery around the opening and with the acetabular cup having a desired installation depth relative to the bone, a desired abduction angle relative to the bone, and a desired anteversion angle relative to the bone, including a controller including a trigger; a support having a proximal end and a distal end opposite of said proximal end, said support further having a longitudinal axis extending from said proximal end to said distal end with said proximal end coupled to said controller, said support further having an adapter coupled to said distal end with said adapter configured to secure the acetabular cup; and an oscillator coupled to said controller and to said support, said oscillator configured to control an oscillation frequency and an oscillation magnitude of said support with said oscillation frequency and said oscillation magnitude configured to install the acetabular cup at the installation depth with the desired abduction angle and the desired anteversion angle without use of an impact force applied to the acetabular cup. [0024] An installation system for a prosthesis configured to be implanted into a portion of bone at a desired implantation depth, the prosthesis including an attachment system, including an oscillation engine including a controller coupled to a vibratory machine generating an original series of pulses having a generation pattern, said generation pattern defining a first duty cycle of said original series of pulses; and a pulse transfer assembly having a proximal end coupled to said oscillation engine and a distal end, spaced from said proximal end, coupled to the prosthesis with said pulse transfer assembly including a connector system at said proximal end, said connector system complementary to the attachment system and configured to secure and rigidly hold the prosthesis producing a secured prosthesis with said pulse transfer assembly communicating an installation series of pulses, responsive to said original series of pulses, to said secured prosthesis producing an applied series of pulses responsive to said installation series of pulses; wherein said applied series of pulses are configured to impart a vibratory motion to said secured prosthesis enabling an installation of said secured prosthesis into the portion of bone to within 95% of the desired implantation depth without a manual impact. [0025] A method for installing an acetabular cup into a prepared socket in a pelvic bone, the acetabular cup including an outer shell having a sidewall defining an inner cavity and an opening with the sidewall having a periphery around the opening and with the acetabular cup having a desired installation depth relative to the bone, a desired abduction angle relative to the bone, and a desired anteversion angle relative to the bone, including (a) generating an original series of pulses from an oscillation engine; (b) communicating said original series of pulses to the acetabular cup producing a communicated series of pulses at said acetabular cup; (c) vibrating, responsive to said communicated series of pulses, the acetabular cup to produce a vibrating acetabular cup having a predetermined vibration pattern; and (d) inserting the vibrating acetabular cup into the prepared socket within a first predefined threshold of the installation depth with the desired abduction angle and the desired anteversion angle without use of an impact force applied to the acetabular cup. [0026] This method may further include (e) orienting the vibrating acetabular cup within the prepared socket within a second predetermined threshold of the desired abduction angle and within third predetermined threshold of the desired anteversion angle. [0027] A method for inserting a prosthesis into a prepared location in a bone of a patient at a desired insertion depth wherein non-vibratory insertion forces for inserting the prosthesis to the desired insertion depth are in a first range, the method including (a) vibrating the prosthesis using a tool to produce a vibrating prosthesis having a predetermined vibration pattern; and (b) inserting the vibrating prosthesis into the prepared location to within a first predetermined threshold of the desired insertion depth using vibratory insertion forces in a second range, said second range including a set of values less than a lowest value of the first range. [0028] An apparatus, including a prosthetic tool; and a set of sensors mechanically coupled to the prosthetic tool, the set of sensors including one or more structures selected from the group consisting essentially of one or more accelerometers, one or more gyro meters, and combinations thereof. [0029] An installation device for an acetabular cup disposed in a pelvic bone, the acetabular cup including an outer shell having a sidewall defining an inner cavity and an opening with the sidewall having a periphery around the opening and with the acetabular cup having a desired installation depth relative to the bone, a desired abduction angle relative to the bone, and a desired anteversion angle relative to the bone, including a controller including a trigger; a support having a proximal end and a distal end opposite of the proximal end, the support further having a longitudinal axis extending from the proximal end to the distal end with the proximal end coupled to the controller, the support further having an adapter coupled to the distal end with the adapter configured to secure the acetabular cup; an oscillator coupled to the controller and to the support, the oscillator configured to control a series of vibratory pulses having an oscillation frequency and an oscillation magnitude of the support with the oscillation frequency and the oscillation magnitude configured to install the acetabular cup at the installation depth with the desired abduction angle and the desired anteversion angle responsive to the series of vibratory pulses; and an alignment system mechanically coupled to the support, wherein the alignment system includes a set of sensors and a feedback system configured to provide a direct real-time alignment variation indication during operation. [0030] An installation system for a prosthesis configured to be installed into a portion of bone at a desired installation depth, the prosthesis including an attachment system, including an oscillation engine including a controller coupled to a vibratory machine generating an original series of pulses having a generation pattern, the generation pattern defining a first duty cycle of the original series of pulses; a pulse transfer assembly having a proximal end coupled to the oscillation engine and a distal end, spaced from the proximal end, coupled to the prosthesis with the pulse transfer assembly including a connector system at the proximal end, the connector system complementary to the attachment system and configured to secure and rigidly hold the prosthesis producing a secured prosthesis with the pulse transfer assembly communicating an installation series of pulses, responsive to the original series of pulses, to the secured prosthesis producing an applied series of ultrasonic pulses responsive to the installation series of pulses; and an alignment system mechanically coupled to the support, wherein the alignment system includes a set of sensors and a feedback system configured to provide a direct real-time alignment variation indication during operation; wherein the applied series of ultrasonic pulses are configured to impart a vibratory motion to the secured prosthesis enabling an installation of the secured prosthesis into the portion of bone to within 95% of the desired implantation depth. [0031] A method for installing an acetabular cup into a prepared socket in a pelvic bone, the acetabular cup including an outer shell having a sidewall defining an inner cavity and an opening with the sidewall having a periphery around the opening and with the acetabular cup having a desired installation depth relative to the bone, a desired abduction angle relative to the bone, and a desired anteversion angle relative to the bone, including (a) generating an original series of pulses from an oscillation engine included in a prosthetic tool; (b) communicating the original series of pulses to the acetabular cup producing a communicated series of pulses at the acetabular cup; (c) vibrating, responsive to the communicated series of pulses, the acetabular cup to produce a vibrating acetabular cup having a predetermined vibration pattern; (d) inserting the vibrating acetabular cup into the prepared socket within a first predefined threshold of the installation depth with the desired abduction angle and the desired anteversion angle; and (e) monitoring directly a real-time alignment system coupled mechanically to the prosthetic tool to produce an installed alignment for the acetabular cup at a desired alignment with respect to the pelvic bone. [0032] A method for inserting an implant into a prepared location in a live bone of a patient at a desired insertion depth at a desired relative alignment wherein non-vibratory insertion forces for inserting the prosthesis to the desired insertion depth are in a first range, the method including (a) vibrating the implant using a tool to produce a vibrating implant having a predetermined vibration pattern including an oscillation; (b) inserting the vibrating implant into the prepared location to within a first predetermined threshold of the desired insertion depth using vibratory insertion forces in a second range, the second range including a set of values less than a lowest value of the first range; and (c) aligning the vibrating implant to within a second threshold of the desired relative alignment using a direct view real-time alignment system mechanically coupled to the tool. [0033] Any of the embodiments described herein may be used alone or together with one another in any combination. Inventions encompassed within this specification may also include embodiments that are only partially mentioned or alluded to or are not mentioned or alluded to at all in this brief summary or in the abstract. Although various embodiments of the invention may have been motivated by various deficiencies with the prior art, which may be discussed or alluded to in one or more places in the specification, the embodiments of the invention do not necessarily address any of these deficiencies. In other words, different embodiments of the invention may address different deficiencies that may be discussed in the specification. Some embodiments may only partially address some deficiencies or just one deficiency that may be discussed in the specification, and some embodiments may not address any of these deficiencies. [0034] Special sensors are added to an impact device having a separate device would provide feedback of the orientation of the impact device as measured by the sensors. The surgeon would position the impact device, divert attention from the device to review the orientation and make any desired correction to the orientation, and then bring attention back to the impact device trying to maintain the corrected orientation before striking the impact device. [0035] Other features, benefits, and advantages of the present invention will be apparent upon a review of the present disclosure, including the specification, drawings, and claims. BRIEF DESCRIPTION OF THE DRAWINGS [0036] The accompanying figures, in which like reference numerals refer to identical or functionally-similar elements throughout the separate views and which are incorporated in and form a part of the specification, further illustrate the present invention and, together with the detailed description of the invention, serve to explain the principles of the present invention. [0037] FIG. 1 illustrates a representative installation gun; [0038] FIG. 2 illustrates a right-hand detail of the installation gun of FIG. 1 ; [0039] FIG. 3 illustrates a left-hand detail of the installation gun of FIG. 1 and generally when combined with FIG. 2 produces the illustration of FIG. 1 ; [0040] FIG. 4 illustrates a second representative installation system; [0041] FIG. 5 illustrates a disassembly of the second representative installation system of FIG. 4 ; [0042] FIG. 6 illustrates a first disassembly view of the pulse transfer assembly of the installation system of FIG. 4 ; [0043] FIG. 7 illustrates a second disassembly view of the pulse transfer assembly of the installation system of FIG. 4 ; [0044] FIG. 8 illustrates a third representative installation system; [0045] FIG. 9 illustrates a disassembly view of the third representative installation system of FIG. 8 ; [0046] FIG. 10 illustrates a prosthetic tool; and [0047] FIG. 11 illustrates a representative direct view real-time display for an alignment system used in cooperation with a prosthetic tool. DETAILED DESCRIPTION OF THE INVENTION [0048] Embodiments of the present invention provide a system and method for improving upon prosthesis installation, such as including a real-time evaluation of tool and/or prosthesis alignment or position. The following description is presented to enable one of ordinary skill in the art to make and use the invention and is provided in the context of a patent application and its requirements. [0049] Various modifications to the preferred embodiment and the generic principles and features described herein will be readily apparent to those skilled in the art. Thus, the present invention is not intended to be limited to the embodiment shown but is to be accorded the widest scope consistent with the principles and features described herein. DEFINITIONS [0050] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this general inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein. [0051] The following definitions apply to some of the aspects described with respect to some embodiments of the invention. These definitions may likewise be expanded upon herein. [0052] As used herein, the term “or” includes “and/or” and the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. [0053] As used herein, the singular terms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an object can include multiple objects unless the context clearly dictates otherwise. [0054] Also, as used in the description herein and throughout the claims that follow, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise. It will be understood that when an element is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present. [0055] As used herein, the term “set” refers to a collection of one or more objects. Thus, for example, a set of objects can include a single object or multiple objects. Objects of a set also can be referred to as members of the set. Objects of a set can be the same or different. In some instances, objects of a set can share one or more common properties. [0056] As used herein, the term “adjacent” refers to being near or adjoining. Adjacent objects can be spaced apart from one another or can be in actual or direct contact with one another. In some instances, adjacent objects can be coupled to one another or can be formed integrally with one another. [0057] As used herein, the terms “connect,” “connected,” and “connecting” refer to a direct attachment or link. Connected objects have no or no substantial intermediary object or set of objects, as the context indicates. [0058] As used herein, the terms “couple,” “coupled,” and “coupling” refer to an operational connection or linking. Coupled objects can be directly connected to one another or can be indirectly connected to one another, such as via an intermediary set of objects. [0059] As used herein, the terms “substantially” and “substantial” refer to a considerable degree or extent. When used in conjunction with an event or circumstance, the terms can refer to instances in which the event or circumstance occurs precisely as well as instances in which the event or circumstance occurs to a close approximation, such as accounting for typical tolerance levels or variability of the embodiments described herein. [0060] As used herein, the terms “optional” and “optionally” mean that the subsequently described event or circumstance may or may not occur and that the description includes instances where the event or circumstance occurs and instances in which it does not. [0061] As used herein, the term “bone” means rigid connective tissue that constitute part of a vertebral skeleton, including mineralized osseous tissue, particularly in the context of a living patient undergoing a prosthesis implant into a portion of cortical bone. A living patient, and a surgeon for the patient, both have significant interests in reducing attendant risks of conventional implanting techniques including fracturing/shattering the bone and improper installation and positioning of the prosthesis within the framework of the patient's skeletal system and operation. [0062] As used herein, the term “prosthetic tool” refers to an implement, which may be powered using hydraulics, pneumatics, electricity, magnetics, mechanics, or combination, adapted for operating on, with, or in conjunction with, all or a portion of a prosthesis with regard to its assembly, installation, and/or positioning. [0063] As used herein, the term “size” refers to a characteristic dimension of an object. Thus, for example, a size of an object that is spherical can refer to a diameter of the object. In the case of an object that is non-spherical, a size of the non-spherical object can refer to a diameter of a corresponding spherical object, where the corresponding spherical object exhibits or has a particular set of derivable or measurable properties that are substantially the same as those of the non-spherical object. Thus, for example, a size of a non-spherical object can refer to a diameter of a corresponding spherical object that exhibits light scattering or other properties that are substantially the same as those of the non-spherical object. Alternatively, or in conjunction, a size of a non-spherical object can refer to an average of various orthogonal dimensions of the object. Thus, for example, a size of an object that is a spheroidal can refer to an average of a major axis and a minor axis of the object. When referring to a set of objects as having a particular size, it is contemplated that the objects can have a distribution of sizes around the particular size. Thus, as used herein, a size of a set of objects can refer to a typical size of a distribution of sizes, such as an average size, a median size, or a peak size. [0064] As used herein, mallet or hammer refers to an orthopedic device made of stainless steel or other dense material having a weight generally a carpenter's hammer and a stonemason's lump hammer. [0065] As used herein, an impact force for impacting an acetabular component (e.g., an acetabular cup prosthesis) includes forces from striking an impact rod multiple times with the orthopedic device that are generally similar to the forces that may be used to drive a three inch nail into a piece of lumber using the carpenter's hammer by striking the nail approximately a half-dozen times to completely seat the nail. Without limiting the preceding definition, a representative value in some instances includes a force of approximately 10 lbs./square inch. [0066] As used herein, the term “vibration” or “vibratory” refers to a mechanical displacement oscillations (repetitive positional variation in time) about an equilibrium point that includes one or more axes of motion. The equilibrium point may, in turn, move, such as for impactless implantation in which the equilibrium point is deeper into an installation site, for example, a desired depth into live bone. These vibrations are forced and responsive to a time-varying disturbance from an oscillation engine or the like applied, directly or indirectly, to a structure (e.g., a prosthesis or other implant) to be installed. The disturbance can be a periodic input, a steady-state input, a transient input, and/or a random input. A periodic input may include a harmonic or non-harmonic disturbance. Oscillation about the equilibrium point may be different, or similar, for each degree of freedom available for the vibratory motion. For example, there may be one oscillation profile longitudinally and a second oscillation profile laterally (e.g., perpendicular to the longitudinal axis), the two profiles generally matching, related, derived, or independent. An amount of displacement of an oscillation is generally less than a dimension of the implant, and may be much less, on the order of about a millimeter or less. [0067] As used herein, the term “ultrasonic” refers to a vibration in which at least one oscillation component operates at a frequency greater than about 20 kHz, and more specifically in a range of 20 kHz to 2-3 GHz, and in some instances in a range of about 20 kHz to about 200 kHz [0068] The following description relates to improvements in a wide-range of prostheses installations into live bones of patients of surgeons. The following discussion focuses primarily on total hip replacement (THR) in which an acetabular cup prosthesis is installed into the pelvis of the patient. This cup is complementary to a ball and stem (i.e., a femoral prosthesis) installed into an end of a femur engaging the acetabulum undergoing repair. [0069] As noted in the background, the surgeon prepares the surface of the hipbone which includes attachment of the acetabular prosthesis to the pelvis. Conventionally, this attachment includes a manual implantation in which a mallet is used to strike a tamp that contacts some part of the acetabular prosthesis. Repeatedly striking the tamp drives the acetabular prosthesis into the acetabulum. Irrespective of whether current tools of computer navigation, fluoroscopy, and robotics (and other intra-operative measuring tools) have been used, it is extremely unlikely that the acetabular prosthesis will be in the correct orientation once it has been seated to the proper depth by the series of hammer strikes. After manual implantation in this way, the surgeon then may apply a series of adjusting strikes around a perimeter of the acetabular prosthesis to attempt to adjust to the desired orientation. Currently such post-impaction result is accepted as many surgeons believe that post-impaction adjustment creates an unpredictable and unreliable change which does not therefore warrant any attempts for post-impaction adjustment. [0070] In most cases, any and all surgeons including an inexperienced surgeon may not be able to achieve the desired orientation of the acetabular prosthesis in the pelvis by conventional solutions due to unpredictability of the orientation changes responsive to these adjusting strikes. As noted above, it is most common for any surgeon to avoid post-impaction adjustment as most surgeons understand that they do not have a reliable system or method for improving any particular orientation and could easily introduce more/greater error. The computer navigation systems, fluoroscopy, and other measuring tools are able to provide the surgeon with information about the current orientation of the prosthesis (in real time) during an operation and after the prosthesis has been installed and its deviation from the desired orientation, but the navigation systems (and others) do not protect against torsional forces created by the implanting/positioning strikes. The prosthesis will find its own position in the acetabulum based on the axial and torsional forces created by the blows of the mallet. Even those navigation systems used with robotic systems (e.g., MAKO) that attempt to secure an implant in the desired orientation prior to impaction are not guaranteed to result in the installation of the implant at the desired orientation because the actual implanting forces are applied by a surgeon swinging a mallet to manually strike the tamp. [0071] A Behzadi Medical Device (BMD) is herein described and enabled that eliminates this crude method (i.e., mallet, tamp, and surgeon-applied mechanical implanting force) of the prosthesis (e.g., the acetabular cup). A surgeon using the BMD is able to insert the prosthesis exactly where desired with proper force, finesse, and accuracy. Depending upon implementation details, the installation includes insertion of the prosthesis into patient bone, within a desired threshold of metrics for insertion depth and location) and may also include, when appropriate and/or desired, positioning at a desired orientation with the desired threshold further including metrics for insertion orientation). The use of the BMD reduces risks of fracturing and/or shattering the bone receiving the prosthesis and allows for rapid, efficient, and accurate (atraumatic) installation of the prosthesis. The BMD provides a viable interface for computer navigation assistance (also useable with all intraoperative measuring tools including fluoroscopy) during the installation as a lighter more responsive touch may be used. [0072] The BMD encompasses many different embodiments for installation and/or positioning of a prosthesis and may be adapted for a wide range of prostheses in addition to installation and/or positioning of an acetabular prosthesis during THR. [0073] FIG. 1 illustrates a representative installation gun 100 ; FIG. 2 illustrates a right-hand detail of the installation gun 100 ; and FIG. 3 illustrates a left-hand detail of installation gun of 100 and generally when combined with FIG. 2 produces the illustration of FIG. 1 . Installation gun 100 is represented as operable using pneumatics, though other implementations may use other mechanisms for creating a desired vibratory motion of prosthesis to be installed. [0074] Installation gun 100 is used to control precisely one or both of (i) insertion, and (ii) abduction and anteversion angles of a prosthetic component. Installation gun 100 preferably allows both installation of an acetabular cup into an acetabulum at a desired depth and orientation of the cup for both abduction and anteversion to desired values. The following reference numbers in Table I refer to elements identified in FIG. 1 - FIG. 3 : [0000] TABLE I Device 100 Elements 102 Middle guide housing 104 Klip 106 Kuciste 108 CILINDAR 110 Cjev 112 Poklopac 114 54 mm acetabular cup 116 Body 118 Valve 120 Bottom cap 122 Upper guide housing 124 Handle cam 126 DIN 3771 6 × 1.8-N-NBR 70 128 Main Air Inlet - Input Tube 130 Trigger 132 Trigger pin 134 DIN 3771 6 × 1.8-N-NBR 70 136 MirrorAR15 - Hand Grip 1 138 Crossover Tube 140 9657K103 compression spring 142 Elongate tube 144 Lower guide housing 146 Primary adapter 148 Housing [0075] Installation gun 100 includes a controller with a handle supporting an elongate tube 142 that terminates in adapter 146 that engages cup 114 . Operation of trigger 130 initiates a motion of elongate tube 142 . This motion is referred to herein as an installation force and/or installation motion that is much less than the impact force used in a conventional replacement process. An exterior housing 148 allows the operator to hold and position prosthesis 114 while elongate tube 142 moves within. Some embodiments may include a handle or other grip in addition to or in lieu of housing 148 that allows the operator to hold and operate installation gun 100 without interfering with the mechanism that provides a direct transfer of installation motion to prosthesis 114 . The illustrated embodiment includes prosthesis 114 held securely by adapter 146 allowing a tilting and/or rotation of gun 100 about any axis to be reflected in the position/orientation of the secured prosthesis. [0076] The installation motion includes constant, cyclic, periodic, and/or random motion (amplitude and/or frequency) that allows the operator to install cup 114 into the desired position (depth and orientation) without application of an impact force. There may be continuous movement or oscillations in one or more of six degrees of freedom including translation(s) and/or rotation(s) of adapter 146 about the X, Y, Z axes (e.g., oscillating translation(s) and/or oscillating/continuous rotation(s) which could be different for different axes such as translating back and forth in the direction of the longitudinal axis of the central support while rotating continuously around the longitudinal axis). This installation motion may include continuous or intermittent very high frequency movements and oscillations of small amplitude that allow the operator to easily install the prosthetic component in the desired location, and preferably also to allow the operator to also set the desired angles for abduction and anteversion. [0077] In some implementations, the controller includes a stored program processing system that includes a processing unit that executes instructions retrieved from memory. Those instructions could control the selection of the motion parameters autonomously to achieve desired values for depth, abduction and anteversion entered into by the surgeon or by a computer aided medical computing system such as the computer navigation system. Alternatively those instructions could be used to supplement manual operation to aid or suggest selection of the motion parameters. [0078] For more automated systems, consistent and unvarying motion parameters are not required and it may be that a varying dynamic adjustment of the motion parameters better conform to an adjustment profile of the cup installed into the acetabulum and status of the installation. An adjustment profile is a characterization of the relative ease by which depth, abduction and anteversion angles may be adjusted in positive and negative directions. In some situations these values may not be the same and the installation gun could be enhanced to adjust for these differences. For example, a unit of force applied to pure positive anteversion may adjust anteversion in the positive direction by a first unit of distance while under the same conditions that unit of force applied to pure negative anteversion may adjust anteversion in the negative direction by a second unit of distance different from the first unit. And these differences may vary as a function of the magnitude of the actual angle(s). For example, as the anteversion increases it may be that the same unit of force results in a different responsive change in the actual distance adjusted. The adjustment profile when used helps the operator when selecting the actuators and the impact force(s) to be applied. Using a feedback system of the current real-time depth and orientation enables the adjustment profile to dynamically select/modify the motion parameters appropriately during different phases of the installation. One set of motion parameters may be used when primarily setting the depth of the implant and then another set used when the desired depth is achieved so that fine tuning of the abduction and anteversion angles is accomplished more efficiently, all without use of impact forces in setting the depth and/or angle adjustment(s). [0079] This device better enables computer navigation as the installation/adjustment forces are reduced as compared to the impacting method. This makes the required forces more compatible with computer navigation systems used in medical procedures which do not have the capabilities or control systems in place to actually provide impacting forces for seating the prosthetic component. And without that, the computer is at best relegated to a role of providing after-the-fact assessments of the consequences of the surgeon's manual strikes of the orthopedic mallet. (Also provides information before and during the impaction. It is a problem that the very act of impaction introduces variability and error in positioning and alignment of the prosthesis. [0080] FIG. 4 illustrates a second representative installation system 400 including a pulse transfer assembly 405 and an oscillation engine 410 ; FIG. 5 illustrates a disassembly of second representative installation system 400 ; FIG. 6 illustrates a first disassembly view of pulse transfer assembly 405 ; and FIG. 7 illustrates a second disassembly view of pulse transfer assembly 405 of installation system 400 . [0081] Installation system 400 is designed for installing a prosthesis that, in turn, is configured to be implanted into a portion of bone at a desired implantation depth. The prosthesis includes some type of attachment system (e.g., one or more threaded inserts, mechanical coupler, link, or the like) allowing the prosthesis to be securely and rigidly held by an object such that a translation and/or a rotation of the object about any axis results in a direct corresponding translation and/or rotation of the secured prosthesis. [0082] Oscillation engine 410 includes a controller coupled to a vibratory machine that generates an original series of pulses having a generation pattern. This generation pattern defines a first duty cycle of the original series of pulses including one or more of a first pulse amplitude, a first pulse direction, a first pulse duration, and a first pulse time window. This is not to suggest that the amplitude, direction, duration, or pulse time window for each pulse of the original pulse series are uniform with respect to each other. Pulse direction may include motion having any of six degrees of freedom—translation along one or more of any axis of three orthogonal axes and/or rotation about one or more of these three axes. Oscillation engine 410 includes an electric motor powered by energy from a battery, though other motors and energy sources may be used. [0083] Pulse transfer assembly 405 includes a proximal end 415 coupled to oscillation engine 410 and a distal end 420 , spaced from proximal end 420 , coupled to the prosthesis using a connector system 425 . Pulse transfer assembly 405 receives the original series of pulses from oscillation engine 410 and produces, responsive to the original series of pulses, an installation series of pulses having an installation pattern. Similar to the generation pattern, the installation pattern defines a second duty cycle of the installation series of pulses including a second pulse amplitude, a second pulse direction, a second pulse duration, and a second pulse time window. Again, this is not to suggest that the amplitude, direction, duration, or pulse time window for each pulse of the installation pulse series are uniform with respect to each other. Pulse direction may include motion having any of six degrees of freedom—translation along one or more of any axis of three orthogonal axes and/or rotation about one or more of these three axes. [0084] For some embodiments of pulse transfer assembly 405 , the installation series of pulses will be strongly linked to the original series and there will be a close match, if not identical match, between the two series. Some embodiments may include a more complex pulse transfer assembly 405 that produces an installation series that is more different, or very different, from the original series. [0085] Connector system 425 (e.g., one or more threaded studs complementary to the threaded inserts of the prosthesis, or other complementary mechanical coupling system) is disposed at proximal end 420 . Connector system 425 is configured to secure and rigidly hold the prosthesis. In this way, the attached prosthesis becomes a secured prosthesis when engaged with connector system 425 . [0086] Pulse transfer assembly 405 communicates the installation series of pulses to the secured prosthesis and produces an applied series of pulses that are responsive to the installation series of pulses. Similar to the generation pattern and the installation pattern, the applied pattern defines a third duty cycle of the applied series of pulses including a third pulse amplitude, a third pulse direction, a third pulse duration, and a third pulse time window. Again, this is not to suggest that the amplitude, direction, duration, or pulse time window for each pulse of the applied pulse series are uniform with respect to each other. Pulse direction may include motion having any of six degrees of freedom—translation along one or more of any axis of three orthogonal axes and/or rotation about one or more of these three axes. [0087] For some embodiments of pulse transfer assembly 405 , the applied series of pulses will be strongly linked to the original series and/or the installation series and there will be a close, if not identical, match between the series. Some embodiments may include a more complex pulse transfer assembly 405 that produces an applied series that is more different, or very different, from the original series and/or the installation series. In some embodiments, for example one or more components may be integrated together (for example, integrating oscillation engine 410 with pulse transfer assembly 405 ) so that the first series and the second series, if they exist independently are nearly identical if not identical). [0088] The applied series of pulses are designed to impart a vibratory motion to the secured prosthesis that enable an installation of the secured prosthesis into the portion of bone to within 95% of the desired implantation depth without a manual impact. That is, in operation, the original pulses from oscillation engine 410 propagate through pulse transfer assembly 405 (with implementation-depending varying levels of fidelity) to produce the vibratory motion to the prosthesis secured to connector system 425 . In a first implementation, the vibratory motion allows implanting without manual impacts on the prosthesis and in a second mode an orientation of the implanted secured prosthesis may be adjusted by rotations of installation system 400 while the vibratory motion is active, also without manual impact. In some implementations, the pulse generation may produce different vibratory motions optimized for these different modes. [0089] Installation system 400 includes an optional sensor 430 (e.g., a flex sensor or the like) to provide a measurement (e.g., quantitative and/or qualitative) of the installation pulse pattern communicated by pulse transfer assembly 405 . This measurement may be used as part of a manual or computerized feedback system to aid in installation of a prosthesis. For example, in some implementations, the desired applied pulse pattern of the applied series of pulses (e.g., the vibrational motion of the prosthesis) may be a function of a particular installation pulse pattern, which can be measured and set through sensor 430 . In addition to, or alternatively, other sensors may aid the surgeon or an automated installation system operating installation system 400 , such as a bone density sensor or other mechanism to characterize the bone receiving the prosthesis to establish a desired applied pulse pattern for optimal installation. [0090] The disassembled views of FIG. 6 and FIG. 7 detail a particular implementation of pulse transfer assembly 405 , it being understood that there are many possible ways of creating and communicating an applied pulse pattern responsive to a series of generation pulses from an oscillation engine. The illustrated structure of FIG. 6 and FIG. 7 generate primarily longitudinal/axial pulses in response to primarily longitudinal/axial generation pulses from oscillation engine 410 . [0091] Pulse transfer assembly 405 includes an outer housing 435 containing an upper transfer assembly 640 , a lower transfer assembly 645 and a central assembly 650 . Central assembly 650 includes a double anvil 655 that couples upper transfer assembly 640 to lower transfer assembly 645 . Outer housing 635 and central assembly 650 each include a port allowing sensor 630 to be inserted into central assembly 650 between an end of double anvil 655 and one of the upper/lower transfer assemblies. [0092] Upper transfer assembly 640 and lower transfer assembly 645 each include a support 660 coupled to outer housing 435 by a pair of connectors. A transfer rod 665 is moveably disposed through an axial aperture in each support 660 , with each transfer rod 665 including a head at one end configured to strike an end of double anvil 655 and a coupling structure at a second end. A compression spring 670 is disposed on each transfer rod 665 between support 660 and the head. The coupling structure of upper transfer assembly 640 cooperates with oscillation engine 410 to receive the generated pulse series. The coupling structure of lower transfer assembly 645 includes connector system 425 for securing the prosthesis. Some embodiments may include an adapter, not shown, that adapts connector system 425 to a particular prosthesis, different adapters allowing use of pulse transfer assembly 405 with different prosthesis. [0093] Central assembly 650 includes a support 675 coupled to outer housing 435 by a connector and receives double anvil 655 which moves freely within support 675 . The heads of the upper transfer assembly and the lower transfer assembly are disposed within support 675 and arranged to strike corresponding ends of double anvil 655 during pulse generation. [0094] In operation, oscillation engine 410 generates pulses that are transferred via pulse transfer assembly 405 to the prosthesis secured by connector system 425 . The pulse transfer assembly 405 , via upper transfer assembly 640 , receives the generated pulses using transfer rod 665 . Transfer rod 665 of upper transfer assembly 640 moves within support 660 of upper transfer assembly 640 to communicate pulses to double anvil 655 moving within support 675 . Double anvil 655 , in turn, communicates pulses to transfer rod 665 of lower transfer assembly 645 to produce vibratory motion of a prosthesis secured to connector system 425 . Transfer rods 665 move, in this illustrated embodiment, primarily longitudinally/axially within outer housing 435 (a longitudinal axis defined as extending between proximate end 415 and distal end 420 . In this way, the surgeon may use outer housing 435 as a hand hold when installing and/or positioning the vibrating prosthesis. [0095] The use of discrete transfer portions (e.g., upper, central, and lower transfer assemblies) for pulse transfer assembly 405 allows a form of loose coupling between oscillation engine 410 and a secured prosthesis. In this way pulses from oscillation engine 410 are converted into a vibratory motion of the prosthesis as it is urged into the bone during operation. Some embodiments may provide a stronger coupling by directly securing one component to another, or substituting a single component for a pair of components. [0096] FIG. 8 illustrates a third representative installation system 800 ; and FIG. 9 illustrates a disassembly view of third representative installation system 800 . [0097] The embodiments of FIG. 4 - FIG. 8 have demonstrated insertion of a prosthetic cup into a bone substitute substrate with ease and a greatly reduced force as compared to use of a mallet and tamp, especially as no impaction was required. While the insertion was taking place and vibrational motion was present at the prosthesis, the prosthesis could be positioned with relative ease by torquing on a handle/outer housing to an exact desired alignment/position. The insertion force is variable and ranges between 20 to 800 pounds of force. Importantly the potential for use of significantly smaller forces in application of the prosthesis (in this case the acetabular prosthesis) in bone substrate with the present invention is demonstrated to be achievable. [0098] Similarly to installation system 100 and installation system 400 , installation system 800 is used to control precisely one or both of (i) installation and (ii) abduction and anteversion angles of a prosthetic component. Installation system 800 preferably allows both installation of an acetabular cup into an acetabulum at a desired depth and orientation of the cup for both abduction and anteversion to desired values. The following reference numbers in Table II refer to elements identified in FIG. 8 - FIG. 9 : [0000] TABLE II Device 800 Elements 802 Air Inlet 804 Trigger 806 Needle Valve 808 Valve Body 810 Throttle Cap 812 Piston 814 Cylinder 816 Driver 818 Needle Block 820 Needles 822 Suspension Springs 824 Anvil 826 Nozzle 828 Connector Rod 830 Prosthesis (e.g., acetabular cup) [0099] Installation system 800 includes a controller with a handle supporting an elongate rod that terminates in a connector system that engages prosthesis 830 . Operation of trigger 804 initiates a motion of the elongate rod. This motion is referred to herein as an installation force and/or installation motion that is much less than the impact force used in a conventional replacement process. An exterior housing allows the operator to hold and position prosthesis 830 while the elongate rod moves within. Some embodiments may include a handle or other grip in addition to or in lieu of the housing that allows the surgeon operator to hold and operate installation system 800 without interfering with the mechanism that provides a direct transfer of installation motion. The illustrated embodiment includes prosthesis 830 held securely allowing a tilting and/or rotation of installation system about any axis to be reflected in the position/orientation of the secured prosthesis. [0100] The actuator is pneumatically operated oscillation device that provides the impact and vibration action this device uses to set the socket (it being understand that alternative motive systems may be used in addition to, or alternatively to, a pneumatic system). Alternatives including mechanical and/or electromechanical systems, motors, and/or engines. The actuator includes air inlet port 802 , trigger 804 , needle valve 806 , cylinder 814 , and piston 812 . [0101] Air is introduced through inlet port 802 and as trigger 804 is squeezed needle valve 806 admits air into the cylinder 814 pushing piston 812 to an opposing end of cylinder 814 . At the opposite end piston 812 opens a port allowing the air to be admitted and pushing the piston 812 back to the original position. [0102] This action provides the motive power for operation of the device and functions in this embodiment at up to 70 Hz. The frequency can be adjusted by trigger 804 and an available air pressure at air inlet port 802 . [0103] As piston 812 impacts driver 816 , driver 816 impacts needles 820 of needle block 818 . Needles 820 strike anvil 824 which is directly connected to prosthesis 830 via connecting rod 828 . [0104] Suspension springs 822 provide a flexibility to apply more or less total force. This flexibility allows force to be applied equally around prosthesis 830 or more force to one side of prosthesis 830 in order to locate prosthesis 830 at an optimum/desired orientation. Installation system 800 illustrates a BMD having a more strongly coupled pulse transfer system between an oscillation engine and prosthesis 830 . [0105] The nature and type of coupling of pulse communications between the oscillation engine and the prosthesis may be varied in several different ways. For example, in some implementations, needles 820 of needle block 818 are independently moveable and respond differently to piston 812 motion. In other implementations, the needles may be fused together or otherwise integrated together, while in other implementations needles 820 and needle block 818 may be replaced by an alternative cylinder structure. [0106] As illustrated, while both embodiments provide for a primarily longitudinal implementation, installation system 800 includes a design feature intended to allow the inserting/vibratory force to be “steered” by applying forces to be concentrated on one side or another of the prosthesis. Implementations that produce a randomized vibrational motion, including “lateral” motion components in addition to, or in lieu of, the primarily longitudinal vibrational motion of the disclosed embodiments may be helpful for installation of prosthesis in a wide range of applications including THR surgery. [0107] Installation system 400 and installation system 800 included an oscillation engine producing pulses at approximately 60 Hz. System 400 operated at 60 Hz while system 800 was capable of operating at 48 to 68 Hz. In testing, approximately 4 seconds of operation resulted in a desired insertion and alignment of the prosthesis (meaning about 240 cycles of the oscillation engine). Conventional surgery using a mallet striking a tamp to impact the cup into place is generally complete after 10 blows of the mallet/hammer. EXPERIMENTAL [0108] Both system 400 and system 800 were tested in a bone substitute substrate with a standard Zimmer acetabular cup using standard technique of under reaming a prepared surface by 1 mm and inserting a cup that was one millimeter larger. The substrate was chosen as the best option available to us to study this concept, namely a dense foam material. It was recognized that certain properties of bone would not be represented here (e.g. an ability of the substrate to stretch before failure). [0109] Both versions demonstrated easy insertion and positioning of the prosthetic cup within the chosen substrate. We were able to move the cup in the substrate with relative ease. There was no requirement for a mallet or hammer for application of a large impact. These experiments demonstrated that the prosthetic cups could be inserted in bone substitute substrates with significantly less force and more control than what could be done with blows of a hammer or mallet. We surmise that the same phenomena can be reproduced in human bone. We envision the prosthetic cup being inserted with ease with very little force. [0110] Additionally we believe that simultaneously, while the cup is being inserted, the position of the cup can be adjusted under direct visualization with any intra-operative measurement system (navigation, fluoroscopy, etc.). This invention provides a system that allows insertion of a prosthetic component with NON-traumatic force (insertion) as opposed to traumatic force (impaction). [0111] Experimental Configuration—System 400 [0112] Oscillation engine 410 included a Craftsman G2 Hammerhead nailer used to drive fairly large framing nails into wood in confined spaces by applying a series of small impacts very rapidly in contrast to application of few large impacts. [0113] The bone substitute was 15 pound density urethane foam to represent the pelvic acetabulum. It was shaped with a standard cutting tool commonly used to clean up a patient's damaged acetabulum. A 54 mm cup and a 53 mm cutter were used in testing. [0114] In one test, the cup was inserted using a mallet and tamp, with impaction complete after 7 strikes. Re-orientation of the cup was required by further strikes on a periphery of the cup after impaction to achieve a desired orientation. It was qualitatively determined that the feel and insertion were consistent with impaction into bone. [0115] An embodiment of system 400 was used in lieu of the mallet and tamp method. Several insertions were performed, with the insertions found to be much more gradual; allowing the cup to be guided into position (depth and orientation during insertion). Final corrective positioning is easily achievable using lateral hand pressure to rotate the cup within the substrate while power was applied to the oscillation engine. [0116] Further testing using the sensor included general static load detection done to determine the static (non-impact) load to push the cup into the prepared socket model. This provided a baseline for comparison to the impact load testing. The prosthesis was provided above a prepared socket with a screw mounted to the cup to transmit a force applied from a bench vise. The handle of the vice was turned to apply an even force to compress the cup into the socket until the cup was fully seated. The cup began to move into the socket at about an insertion force of ˜200 pounds and gradually increased as diameter of cup inserted into socket increased to a maximum of 375 pounds which remained constant until the cup was fully seated. [0117] Installation system 400 was next used to install the cup into a similarly prepared socket. Five tests were done, using different frame rates and setup procedures, to determine how to get the most meaningful results. All tests used a 54 mm acetabular Cup. The oscillation engine ran at an indicated 60 impacts/second. The first two tests were done at 2,000 frames/second, which wasn't fast enough to capture all the impact events, but helped with designing the proper setup. Test 3 used the oscillation engine in an already used socket, 4,000 frames per second. Test 4 used the oscillation engine in an unused foam socket at 53 mm, 4,000 frames per second. [0118] Test 3: In already compacted socket, the cup was pulsed using the oscillation engine and the pulse transfer assembly. Recorded strikes between 500 and 800 lbs., with an average recorded pulse duration 0.8 ms. [0119] Test 4: Into an unused 53 mm socket, the cup was pulsed using the oscillation engine and the pulse transfer assembly. Recorded impacts between 250 and 800 lbs., and an average recorded pulse duration 0.8 ms. Insertion completed in 3.37 seconds, 202 impact hits. [0120] Test 5: Into an unused 53 mm socket, the cup was inserted with standard hammer (for reference). Recorded impacts between 500 and 800 lbs., and an average recorded pulse duration 22.0 ms. Insertion completed in 4 seconds using 10 impact hits for a total pressure time of 220 ms. This test was performed rapidly to complete it in 5 seconds for good comparability with tests 3 and 4 used 240 hits in 4 seconds, with a single hit duration of 0.8 ms, for a total pressure time of 192 ms. [0121] In non-rigorous comparison testing without a direct comparison between system 400 and system 800 , generally it appears that the forces used for installation using system 800 were lower than system 400 by a factor of 10. This suggests that there are certain optimizing characteristics for operation of an installation system. There are questions such as to how low these forces can be modulated and still allow easy insertion of the prosthetic cup in this model and in bone. What is the lowest force required for insertion of a prosthetic cup in to this substrate using the disclosed concepts? What is the lowest force required for insertion of a prosthetic cup into hard bone using these concepts? And what is the lowest force required for insertion of a prosthetic cup into soft and osteoporotic bone using these concepts? These are the questions that can be addressed in future phase of implementations of the present invention. [0122] Additionally, it is believed possible to correlate a density and a porosity of bone at various ages (e.g., through a cadaver study) with an appropriate force range and vibratory motion pattern required to insert a cup using the present invention. For example a surgeon will be able to insert sensing equipment in patient bone, or use other evaluative procedures, (preoperative planning or while performing the procedure for example) to assess porosity and density of bone. Once known, the density or other bone characteristic is used to set an appropriate vibratory pattern including a force range on an installation system, and thus use a minimal required force to insert and/or position the prosthesis. [0123] FIG. 10 illustrates a prosthetic tool 1000 . Tool 1000 may be configured to operate on a structure S, such as an acetabular cup for total hip arthroplasty. In other embodiments, tool 1000 may be configured to secure and operate a processing head, for example a reamer, cutter, or other tissue manipulation device. Structure S may include a mounting system, such as a threaded cavity or other mechanical coupling system allowing selective engagement and disengagement or structure S may be integrated with tool 1000 . [0124] Tool 1000 includes a housing 1005 that includes a motor, for example an electric, hydraulic, pneumatic, and/or spring powered assembly, and the like. Some embodiments may not include a motor with housing 1005 including use as a support structure for other components and/or a hand-hold. Housing 1005 includes a proximal end and a distal end with a mount 1010 coupled to the distal end and an alignment system 1015 coupled to the proximal end. Mount 1010 provides a mechanism to join, attach, fix, and/or mount structure S to tool 1000 . When structure S includes a threaded cavity, mount 1010 may include a complementary threaded shaft. There are a wide range of possible embodiments for tool 1000 and for structure S, therefore the mounting/attachment specifics are configured to allow tool 1000 to properly operate and manipulate structure S. [0125] Alignment system 1015 includes an implementation of an inertial measurement system (IMU) for real-time intra-procedure feedback to the surgeon of a current orientation of tool 1000 . One problem for a surgeon is to know exactly the absolute attitude (pointing of tool 1000 in three dimensional space). There are tracking systems that are based on machine-readable markers that do this, but require cameras, calibration, and special procedures to configure them (for a particular 3D space like a single operating room). Once well configured, they work nicely, but need those markers and supporting external equipment which is inconvenient, especially limiting in moving the tool to another 3D space for another procedure. Alignment system 1015 may include an IMU, a variation of systems used in satellites, airplanes, and missiles, and the like. Alignment system 1015 may thus include one or more accelerometers, gyrometers, magnetic sensors, positional sensors, orientation sensors, combinations of these, and other inertial measurement devices. [0126] Alignment system 1015 allows the surgeon using tool 1000 to improve tissue preparation or prosthesis insertion according to real-time steering data. Embodiments may include a distinction in outputting measurements/feedback directly to the surgeon during use. The process is half physical (measurement) and half mathematical (filtering and estimation) in order to fuse information and get a precise pointing. [0127] For example: the surgeon uses the navigation to see correct inclination and anteversion. Once it is achieved, the surgeon may actuate a control 1020 , e.g., a small button, on tool 1000 . The orientation of tool 1000 at the time of actuation of control 1020 would become the orientation target, available to a feedback system 1025 , e.g., a display, coupled to or part of, alignment system 1015 . Now the surgeon does not need to look anywhere other than at feedback system 1025 , or at the site where tissue or the prosthesis is being processed. The surgeon easily references feedback system 1025 as necessary or desirable in real-time which indicates how far a current orientation of tool 1000 is from the desired inclination/anteversion values. Alignment system 1015 may operate as a relative orientation to localized 3D space of the procedure or it may operate as an absolute orientation referenced into a larger 3D space, such as the operating room. [0128] FIG. 11 illustrates a representative direct view real-time feedback system 1025 , e.g., a display, for alignment system 1015 used in cooperation with tool 1000 . In operation, a surgeon locates tool 1000 with a desired orientation alignment and then operates control 1020 . Operation of control 1020 sets the desired alignment indicator element of feedback system 1025 . Subsequent manipulation of tool 1000 is reflected in a current alignment indicator element of feedback system 1025 . As an orientation of tool 1000 changes in 3D space, current alignment indicator element changes. The surgeon can visualize how closely a current alignment of tool 1000 is to the desired orientation by referencing feedback system 1025 at any time to check on any differences between the indicators. When there is a difference, the surgeon easily reorients tool 1000 to the desired orientation by aligning the current alignment indicator element to the desired alignment indicator element. [0129] Feedback system 1025 may include alternative indication systems that include various visual, [0130] Tool 1000 allows a surgeon to have additional options and methods for evaluation, operation, and/or installation of structure S during intra-operative procedures. [0131] For example, with regards to a reaming process, it may be noted that reaming is traditionally performed with little attention to directionality and alignment. Processing in this way may cause the preparation of the acetabulum to be imprecise and lead to a “predetermined path of sinking” that is less than ideal as it can result in an installed acetabular cup in an orientation that is not desired and which could cause compounding problems to correct. Tool 1000 allows for a concept of “directionality for reaming” in which structure S includes a reaming head and tool 1000 is used to maintain a desired orientation during reaming. Tool 1000 allows the surgeon to pay attention to alignment not just during the impaction process but also while reaming or other processing. [0132] Non-tool 1000 methods for assessing alignment include A-frame, computer navigation, anterior approach with fluoroscopy, and patient specific instrumentation. Tool 1000 provides an alternative that is superior for many reasons. [0133] 1. The A-frame is a simple mechanical carpenter's device with known angles and orthogonals, attached to the impaction rod, that allows the surgeon to ascertain 45 degree of abduction and 20 degrees of anti-version, as the surgeon holds the cup in the acetabulum ready for impaction. It is used only during the impaction process. Surgeons who use this technique do not routinely apply the A-frame to the reamer and therefor have no clue of the direction of reaming while performing the operation. [0134] 2. Computer Navigation is a process that allows the surgeon to know the planes of the pelvis, patient's body, the OR table and the acetabular cup in the OR space. It allows the surgeon to have a sense of the direction of the reaming as well as the alignment of the cup. It is a very useful method that provides good intra-operative real time information. However, few surgeons have adopted this technique due to added OR time and its bulky presence in the OR theater. [0135] 3. Anterior Approach with fluoroscopy. The patient is supine and the surgeon has immediate visual information about the position of the reamer and the cup (sometimes computer software may be available that allows exact calculation of the cup's inclination and ante-version angles it is not routinely used). The flow of real time visual information is easily processed in the surgeon's brain and much more usable to many surgeons than navigation. The surgeon has a sense of the direction of reaming and the alignment of the cup during impaction. This is the primary reason fluoroscopy has been adopted. The secondary reason is that the surgeon has an immediate sense of the leg lengths. [0136] 4. PSI or patient specific Instrumentation. This process has been more popular in total knees replacement; however, it has application in total hip replacement as well. Through a CT scan or MRI, a 3D model of the acetabulum is created. This 3D model allows the desired central axis of impaction to be set. A 3D custom guide is made that fits into the acetabulum. Through the computer software the desired angle of ante-version and inclination is predetermined and set on the 3D guide. Once the guide is seated within the patient's acetabulum the desired alignment is set. A double laser system is then used to maintain this alignment throughout the operation, with the reaming and impaction process. [0137] Irrespective of how a surgeon attains and sets a desired alignment, tool 1000 allows the surgeon to maintain the desired alignment without use of bulky equipment in the OR theater. [0138] The IMU technique as described can take the alignment that is set and maintain that vector memorized in the OR space. All measurement equipment and techniques may thereafter be quickly removed from the OR setting (Computer navigation, C-Arm, A-Frame, and the like). All that is used is a small screen or other feedback device attached to tool 1000 (e.g., a reamer, an impactor, a BMD, or the like) that shows the three-dimensional deviation of the axis of the tool from the desired/set axis. [0139] The surgeon can then be fully aware of the directionality and alignment of the reaming during processing. Finishing every reaming in the final desired alignment is expected to improve the placement of the prosthesis by helping “predetermine” the sinking path. Similarly when the surgeon impacts or inserts the cup, an IMU device attached to the impactor/inserter provides immediate real time information as to the three-dimensional position of the cup. The surgeon can watch ONLY the feedback screen and make real-time changes as the prosthesis is impacted or inserted. [0140] The 5th technique of setting the desired alignment is a novel technique that utilizes tool 1000 to assess, choose, and set alignment. An embodiment of this method may revolutionize (unify) the way hip replacement surgery is done. Currently about 20% of surgeons have adopted anterior approach with fluoroscopy. However, many surgeons believe this technique is harder and less intuitive. For example, an embodiment may include a system or method that uses a single X-ray in the lateral position with tool 1000 to set the alignment. The patient can be positioned in the standard lateral decubitus position as is commonly done in posterior approach hip replacement surgery. Once the acetabulum is exposed, the surgeon will hold a “preliminary cup” with IMU monitor attached in the acetabular fossa and get an X-ray. As the X-ray is done, a button is pushed on the IMU to set the position of the cup in the OR space. X-ray software exits that can calculate the exact alignment of the “preliminary cup” in the acetabulum. From here on forward, mathematical calculations can be done in the IMU to determine the position of the cup in the OR space. For example when the IMU knows where 5 degrees of ante-version and 30 degrees of inclination is in the OR space, it can calculate 20 degrees of ante-version and 40 degrees of inclination internally and let you know how to hold the impaction rod to achieve that alignment for the cup. There is no further need for X-ray or C-arm machines (or Navigation units) to remain in the OR. There is no further need to continuously irradiate the patient, the surgeon and the OR staff. At the time the single X-ray is taken the IMU is calibrated in the OR space, and all other points/lines in the OR can be determined by the calculations within the IMU. This technique may allow some of the surgeons who feel uncomfortable with the C-Arm unit and Navigation to utilize a simple X-ray along with the IMU to access the spatial map of the OR. [0141] Incorporated U.S. patent application Ser. No. 14/965,851 includes a tool 1000 , e.g., an installing BMD, that uses a visual line of sight to assure co-axiality for installation forces. Use of an alignment system 1015 in cooperation with the installing BMD may provide improved performance of prosthesis-to-prosthesis and prosthesis to bone/tissue. [0142] BMD is a “must have” device for all medical device companies and surgeons. Without BMD the Implantation problem is not addressed, regardless of the recent advances in technologies in hip replacement surgery (i.e.; Navigation, Fluoroscopy, MAKO/robotics, accelerometers/gyro meters, etc.). Acetabular component (cup) positioning remains the biggest problem in hip replacement surgery. Implantation is the final step where error is introduced into the system and heretofore no attention has been brought to this problem. Current technologies have brought significant awareness to the position of the implants within the pelvis during surgery, prior to impaction. However, these techniques do not assist in the final step of implantation. [0143] BMD allows all real time information technologies to utilize (a tool) to precisely and accurately implant the acetabular component (cup) within the pelvic acetabulum. BMD device coupled with use of navigation technology and fluoroscopy and (other novel measuring devices) is the only device that will allow surgeons from all walks of life, (low volume/high volume) to perform a perfect hip replacement with respect to acetabular component (cup) placement. With the use of BMD, surgeons can feel confident that they are doing a good job with acetabular component positioning, achieving the “perfect cup” every time. Hence the BMD concept eliminates the most common cause of complications in hip replacement surgery which has forever plagued the surgeon, the patients and the society in general. [0144] Some use of ultra sound devices, generally, may be used in connection with some aspects of THR, such as for implant removal (as some components may be installed using a cement that may be softened using ultrasound energy). There may be some suggestion that some ultrasonic devices that employ “ultrasound” energy could be used to insert a prosthesis for final fit, but it is in the context of a femoral component and it is believed that these devices are not presently actually used in the process). Some embodiments of BMD, in contrast, can simply be a vibratory device (non ultrasonic), and may not be ultrasonic and some implementations may include ultrasonic operation, and may be more profound than simply an implantation device as it is most preferably a positioning device for the acetabular component in THR. Further, there is a discussion that ultrasound devices may be used to prepare bones for implanting a prosthesis. BMD does not address preparation of the bone as this is not a primary thrust of this aspect of the present invention. Some implementations of BMD may include a similar or related feature. The forces applied by the vibration will be less than an impact force and preferably enable installation without requiring impact forces applied to the mechanism by which the equilibrium point is moved during installation of the vibrating implant. That mechanism may be hand pressure from the surgeon guiding the vibrating implant into a desired depth and orientation or may include some other mechanical application of less-than-impact force to adjust the equilibrium point. [0145] Some embodiments BMD include devices that concern themselves with proper installation and positioning of the prosthesis (e.g., an acetabular component) at the time of implanting of the prosthesis. Very specifically, it uses some form of vibratory energy coupled with a variety of “real time measurement systems” to POSITION the cup in a perfect alignment with minimal use of force. A prosthesis, such as for example, an acetabular cup, resists insertion. Once inserted, the cup resists changes to the inserted orientation. The BMDs of the present invention produce an insertion vibratory motion of a secured prosthesis that reduces the forces resisting insertion. In some implementations, the BMD may produce a positioning vibratory motion that reduces the forces resisting changes to the orientation. There are some implementations that produce both types of motion, either as a single vibratory profile or alternative profiles. In the present context for purposes of the present invention, the vibratory motion is characterized as “floating” the prosthesis as the prosthesis can become much simpler to insert and/or re-orient while the desired vibratory motion is available to the prosthesis. Some embodiments are described as producing vibrating prosthesis with a predetermined vibration pattern. In some implementations, the predetermined vibration pattern is predictable and largely completely defined in advance. In other implementations, the predetermined vibration pattern includes randomized vibratory motion in one or more motion freedoms of the available degrees of freedom (up to six degrees of freedom). That is, whichever translation or rotational freedom of motion is defined for the vibrating prosthesis, any of them may have an intentional randomness component, varying from large to small. In some cases the randomness component in any particular motion may be large and in some cases predominate the motion. In other cases the randomness component may be relatively small as to be barely detectable. [0146] The system and methods above has been described in general terms as an aid to understanding details of preferred embodiments of the present invention. In the description herein, numerous specific details are provided, such as examples of components and/or methods, to provide a thorough understanding of embodiments of the present invention. Some features and benefits of the present invention are realized in such modes and are not required in every case. One skilled in the relevant art will recognize, however, that an embodiment of the invention can be practiced without one or more of the specific details, or with other apparatus, systems, assemblies, methods, components, materials, parts, and/or the like. In other instances, well-known structures, materials, or operations are not specifically shown or described in detail to avoid obscuring aspects of embodiments of the present invention. [0147] Reference throughout this specification to “one embodiment”, “an embodiment”, or “a specific embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention and not necessarily in all embodiments. Thus, respective appearances of the phrases “in one embodiment”, “in an embodiment”, or “in a specific embodiment” in various places throughout this specification are not necessarily referring to the same embodiment. Furthermore, the particular features, structures, or characteristics of any specific embodiment of the present invention may be combined in any suitable manner with one or more other embodiments. It is to be understood that other variations and modifications of the embodiments of the present invention described and illustrated herein are possible in light of the teachings herein and are to be considered as part of the spirit and scope of the present invention. [0148] It will also be appreciated that one or more of the elements depicted in the drawings/figures can also be implemented in a more separated or integrated manner, or even removed or rendered as inoperable in certain cases, as is useful in accordance with a particular application. [0149] Additionally, any signal arrows in the drawings/Figures should be considered only as exemplary, and not limiting, unless otherwise specifically noted. Combinations of components or steps will also be considered as being noted, where terminology is foreseen as rendering the ability to separate or combine is unclear. [0150] The foregoing description of illustrated embodiments of the present invention, including what is described in the Abstract, is not intended to be exhaustive or to limit the invention to the precise forms disclosed herein. While specific embodiments of, and examples for, the invention are described herein for illustrative purposes only, various equivalent modifications are possible within the spirit and scope of the present invention, as those skilled in the relevant art will recognize and appreciate. As indicated, these modifications may be made to the present invention in light of the foregoing description of illustrated embodiments of the present invention and are to be included within the spirit and scope of the present invention. [0151] Thus, while the present invention has been described herein with reference to particular embodiments thereof, a latitude of modification, various changes and substitutions are intended in the foregoing disclosures, and it will be appreciated that in some instances some features of embodiments of the invention will be employed without a corresponding use of other features without departing from the scope and spirit of the invention as set forth. Therefore, many modifications may be made to adapt a particular situation or material to the essential scope and spirit of the present invention. It is intended that the invention not be limited to the particular terms used in following claims and/or to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include any and all embodiments and equivalents falling within the scope of the appended claims. Thus, the scope of the invention is to be determined solely by the appended claims.
A system and method for allowing any surgeon, including those surgeons who perform a fewer number of a replacement procedure as compared to a more experienced surgeon who performs a greater number of procedures, to provide an improved likelihood of a favorable outcome approaching, if not exceeding, a likelihood of a favorable outcome as performed by a very experienced surgeon with the replacement procedure.
96,451
[0001] The present invention is a process for preparation of carboxylated carbohydrates having available primary hydroxyl groups. It is particularly applicable for preparation of a heat and light stable fibrous carboxylated cellulose suitable for papermaking and related applications. The cellulose product of the invention is one in which fiber strength and degree of polymerization are not significantly sacrificed. The process is particularly environmentally advantageous since no chlorine or hypochlorite compounds are required. BACKGROUND OF THE INVENTION [0002] Carbohydrates are polyhydroxy aldehyde or ketone compounds or substances that yield these compounds on hydrolysis. They frequently occur in nature as long chain polymers of simple sugars. As the term is used in the present invention it is intended to be inclusive of any monomeric, oligomeric, and polymeric carbohydrate compound which has a primary hydroxyl group available for reaction. [0003] Cellulose is a carbohydrate consisting of a long chain of glucose units, all β-linked through the 1′-4 positions. Native plant cellulose molecules may have upwards of 2200 anhydroglucose units. The number of units is normally referred to as degree of polymerization or simply D.P. Some loss of D.P. inevitably occurs during purification. A D.P. approaching 2000 is usually found only in purified cotton linters. Wood derived celluloses rarely exceed a D.P. of about 1700. The structure of cellulose can be represented as follows: [0004] Chemical derivatives of cellulose have been commercially important for almost a century and a half Nitrocellulose plasticized with camphor was the first synthetic plastic and has been in use since 1868. A number of cellulose ether and ester derivatives are presently commercially available and find wide use in many fields of commerce. Virtually all cellulose derivatives take advantage of the reactivity of the three available hydroxyl groups. Substitution at these groups can vary from very low; e.g. about 0.01 to a maximum 3.0. Among important cellulose derivatives are cellulose acetate, used in fibers and transparent films; nitrocellulose, widely used in lacquers and gun powder; ethyl cellulose, widely used in impact resistant tool handles; methyl cellulose, hydroxyethyl, hydroxypropyl, and sodium carboxymethyl cellulose, water soluble ethers widely used in detergents, as thickeners in foodstuffs, and in papermaking. [0005] Cellulose itself has been modified for various purposes. Cellulose fibers are naturally anionic in nature as are many papermaking additives. A cationic cellulose is described in Harding et al. U.S. Pat. No. 4,505,775. This has greater affinity for anionic papermaking additives such as fillers and pigments and is particularly receptive to acid and anionic dyes. Jewell et al., in U.S. Pat. No. 5,667,637, teach a low degree of substitution (D.S.) carboxyethyl cellulose which, along with a cationic resin, improves the wet to dry tensile and burst ratios when used as a papermaking additive. Westland, in U.S. Pat. No. 5,755,828 describes a method for increasing the strength of articles made from cross linked cellulose fibers having free carboxylic acid groups obtained by covalently coupling a polycarboxylic acid to the fibers. [0006] For some purposes cellulose has been oxidized to make it more anionic; e.g., to improve compatibility with cationic papermaking additives and dyes. Various oxidation treatments have been used. U.S. Pat. No. 3,575,177 to Briskin et al. describes a cellulose oxidized with nitrogen dioxide useful as a tobacco substitute. The oxidized material may then be treated with a borohydride to reduce functional groups, such as aldehydes, causing off flavors. After this reduction the product may be further treated with an oxidizing agent such as hydrogen peroxide for further flavor improvement. Other oxidation treatments use nitrogen dioxide and periodate oxidation coupled with resin treatment of cotton fabrics for improvement in crease recovery as suggested by R. T. Shet and A. M. Yabani, Textile Research Journal November 1981: 740-744. Earlier work by K. V. Datye and G. M. Nabar, Textile Research Journal , July 1963: 500-510, describes oxidation by metaperiodates and dichromic acid followed by treatment with chlorous acid for 72 hours or 0.05 M sodium borohydride for 24 hours. Copper number was greatly reduced by borohydride treatment and less so by chlorous acid. Carboxyl content was slightly reduced by borohydride and significantly increased by chlorous acid. The products were subsequently reacted with formaldehyde. P. Luner et al., Tappi 50(3): 117-120 (1967) oxidized southern pine kraft spring wood and summer wood fibers with potassium dichromate in oxalic acid. Handsheets made with the fibers showed improved wet strength believed due to aldehyde groups. P. Luner et al., in Tappi 50(5): 227-230 (1967) expanded this earlier work and further oxidized some of the pulps with chlorite or reduced them with sodium borohydride. Handsheets from the pulps treated with the reducing agent showed improved sheet properties over those not so treated. R. A. Young, Wood and Fiber , 10(2): 112-119 (1978) describes oxidation primarily by dichromate in oxalic acid to introduce aldehyde groups in sulfite pulps for wet strength improvement in papers. [0007] Brasey et al, in U.S. Pat. No. 4,100,341, describe oxidation of cellulose with nitric acid. They note that the reaction was specific at the C6 position and that secondary oxidation at the C2 and C3 positions was not detected. They further note that the product was “ . . . stable without the need for subsequent reduction steps or the introduction of further reactants [e.g., aldehyde groups] from which the oxidized cellulose has to be purged”. [0008] V. A. Shenai and A. S. Narkhede, Textile Dyer and Printer May 20, 1987: 17-22 describe the accelerated reaction of hypochlorite oxidation of cotton yarns in the presence of physically deposited cobalt sulfide. The authors note that partial oxidation has been studied for the past hundred years in conjunction with efforts to prevent degradation during bleaching. They also discuss in some detail the use of 0.1 M sodium borohydride as a reducing agent following oxidation. The treatment was described as a useful method of characterizing the types of reducing groups as well as acidic groups formed during oxidation. The borohydride treatment noticeably reduced copper number of the oxidized cellulose. Copper number gives an estimate of the reducing groups such as aldehydes present on the cellulose. Borohydride treatment also reduced alkali solubility of the oxidized product but this may have been related to an approximate 40% reduction in carboxyl content of the samples. [0009] R. Andersson et al. in Carbohydrate Research 206: 340-346 (1990) teach oxidation of cellulose with sodium nitrite in orthophosphoric acid and describe nuclear magnetic resonance elucidation of the reaction products. [0010] An article by P. L. Anelli et al. in Journal of Organic Chemistry 54: 2970-2972 (1989) appears to be one of the earlier papers describing oxidation of hydroxyl compounds by oxammonium salts. They employed a system of 2,2,6,6-tetramethyl-piperidinyloxy free radical (TEMPO) with sodium hypochlorite and sodium bromide in a two phase system to oxidize 1,4-butanediol and 1,5-pentanediol. [0011] R. V. Casciani et al, in French Patent 2,674,528 (1992) describe the use of sterically hindered N-oxides for oxidation of polymeric substances, among them alkyl polyglucosides having primary hydroxyl groups. A preferred oxidant was TEMPO although many related nitroxides were suggested. Calcium hypochlorite was present as a secondary oxidant. [0012] N. J. Davis and S. L. Flitsch, Tetrahedron Letters 34(7): 1181-1184 (1993) describe the use and reaction mechanism of (TEMPO) with sodium hypochlorite to achieve selective oxidation of primary hydroxyl groups of monosaccharides. Following the Davis et al. paper this route to carboxylation then began to be very actively explored, particularly in the Netherlands and later in the United States. A. E. J. de Nooy et al., in a short paper in Receuil des Travaux Chimiques des Pays - Bas 113: 165-166 (1994), report similar results using TEMPO and hypobromite for oxidation of primary alcohol groups in potato starch and inulin. The following year, these same authors in Carbohydrate Research 269: 89-98 (1995) report highly selective oxidation of primary alcohol groups in water soluble glucans using TEMPO and a hypochlorite/ bromide oxidant. [0013] European Patent Application 574,666 to Kaufhold et al. describes a group of nitroxyl compounds based on TEMPO substituted at the 4-position. These are useful as oxidation catalysts using a two phase system. Formation of carboxylated cellulose did not appear to be contemplated. [0014] PCT published patent application WO 95/07303 (Besemer et al.) describes a method of oxidizing water soluble carbohydrates having a primary alcohol group, using TEMPO, or a related di-tertiary-alkyl nitroxide, with sodium hypochlorite and sodium bromide. Cellulose is mentioned in passing in the background although the examples are principally limited to starches. The method is said to selectively oxidize the primary alcohol at C-6 to carboxyl. None of the products studied were fibrous in nature. [0015] A year following the above noted Besemer PCT publication, the same authors, in Cellulose Derivatives , T. J. Heinze and W. G. Glasser, eds., Ch. 5, pp 73-82 (1996), describe methods for selective oxidation of cellulose to 2,3-dicarboxy cellulose and 6-carboxy cellulose using various oxidants. Among the oxidants used were a periodate/chlorite/hydrogen peroxide system, oxidation in phosphoric acid with sodium nitrate/nitrite, and with TEMPO and a hypochlorite/bromide primary oxidant. Results with the TEMPO system were poorly reproduced and equivocal. The statement that “ . . . some of the material remains undissolved” was puzzling. In the case of TEMPO oxidation of cellulose, little or none would have been expected to go into water solution unless the cellulose was either badly degraded and/or the carboxyl substitution was very high. The homogeneous solution of cellulose in phosphoric acid used for the sodium nitrate/sodium nitrite oxidation was later treated with sodium borohydride to remove any carbonyl function present. [0016] De Nooy et al. have published a very extensive review, both of the literature and the chemistry of nitroxyls as oxidizers of primary and secondary alcohols, in Synthesis: Journal of Synthetic Organic Chemistry (10): 1153-1174 (1996). [0017] Heeres et al., in PCT application WO 96/38484, discuss oxidation of carbohydrate ethers useful as sequestering agents. They use the TEMPO oxidation system described by the authors just noted above to produce relatively highly substituted products, including cellulose. [0018] P.-S. Chang and J. F. Robyt, Journal of Carbohydrate Chemistry 15(7): 819-830 (1996), describe oxidation of ten polysaccharides including α-cellulose at 0° C. and 25° C. using TEMPO with sodium hypochlorite and sodium bromide. Ethanol addition was used to quench the oxidation reaction. The resulting oxidized α-cellulose had a water solubility of 9.4%. The authors did not further describe the nature of the α-cellulose. It is presumed to have been a so-called dissolving pulp or cotton linter cellulose. [0019] Heeres et al., in WO 96/36621, describe a method of recovering TEMPO and its related compounds following their use as an oxidation catalyst. An example is given of the oxidation of starch followed by TEMPO recovery using azeotropic distillation. [0020] D. Barzyk et al., in Journal of pulp and paper Science 23(2): J59-J61 (1997) and in Transactions of the 11 th Fundamental Research Symposium , Vol. 2, 893-907 (1997), note that carboxyl groups on cellulose fibers increase swelling and impact flexibility, bonded area and strength. They designed experiments to increase surface carboxylation of fibers. However, they ruled out oxidation to avoid fiber degradation and chose to form carboxymethyl cellulose in an isopropanol/methanol system. [0021] Isogai, A. and Y. Kato, in Cellulose 5: 153-164 (1998) describe treatment of several native, mercerized, and regenerated celluloses with TEMPO to obtain water soluble and insoluble polyglucuronic acids. They note that the water soluble products had almost 100% carboxyl substitution at the C-6 site. They further note that oxidation proceeds heterogeneously at the more accessible regions on solid cellulose. [0022] Isogai, in Cellulose Communications 5(3): 136-141 (1998) describes preparation of water soluble oxidized cellulose products using mercerized or regenerated celluloses as starting materials in a TEMPO oxidation system. Using native celluloses or bleached wood pulp he was unable to obtain a water soluble material since he achieved only low amounts of conversion. He further notes the beneficial properties of the latter materials as papermaking additives. [0023] Kitaoka et al., in a preprint of a short 1998 paper for Sen'i Gakukai (Society of Studies of Fiber) speak of their work in the surface modification of fibers using a TEMPO mediated oxidation system. They were concerned with the receptivity of alumbased sizing compounds. [0024] PCT application WO 99/23117 (Viikari et al.) teaches oxidation using TEMPO in combination with the enzyme laccase or other enzymes along with air or oxygen as the effective oxidizing agents of cellulose fibers, including kraft pine pulps. [0025] Kitaoka, T., A., A. Isogai, and F. Onabe, in Nordic Pulp and Paper Research Journal , 14(4): 279-284 (1999), describe the treatment of bleached hardwood kraft pulp using TEMPO oxidation. Increasing amounts of carboxyl content gave some improvement in dry tensile index, Young's modulus and brightness, with decreases in elongation at breaking point and opacity. Other strength properties were unaffected. Retention of PAE-type wet strength resins was somewhat increased. The products described did not have any stabilization treatment after the TEMPO oxidation. [0026] Van der Lugt et al., in WO 99/57158, describe the use of peracids in the presence of TEMPO or another di-tertiary alkyl nitroxyl for oxidation of primary alcohols in carbohydrates. They claim their process to be useful for producing uronic acids and for introducing aldehyde groups which are suitable for crosslinking and derivitization. Among their examples are a series of oxidations of starch at pH ranges from 5-10 using a system including TEMPO, sodium bromide, EDTA, and peracetic acid. Carboxyl substitution was relatively high in all cases, ranging from 26-91% depending on reaction pH. [0027] Besemer et al. in PCT published application WO 00/50388 teach oxidation of various carbohydrate materials in which the primary hydroxyls are converted to aldehyde groups. The system uses TEMPO or related nitroxyl compounds in the presence of a transition metal using oxygen or hydrogen peroxide. [0028] Jaschinski et al. In PCT published application WO 00/50462 teach oxidation of TEMPO oxidized bleached wood pulps to introduce carboxyl and aldehyde groups at the C6 position. The pulp is preferably refined before oxidation. One process variation uses low pH reaction conditions without a halogen compound present. The TEMPO is regenerated by ozone or another oxidizer, preferably in a separate step. In particular, the outer surface of the fibers are said to be modified. The products were found to be useful for papermaking applications. [0029] Jetten et al. in related PCT applications WO 00/50463 and WO 00/50621 teach TEMPO oxidation of cellulose along with an enzyme or complexes of a transition metal. A preferred complexing agent is a polyamine with at least three amino groups separated by two or more carbon atoms. Manganese, iron, cobalt, and copper are preferred transition metals. Although aldehyde substitution at C6 seems to be preferred, the primary products can be further oxidized to carboxyl groups by oxidizers such as chlorites or hydrogen peroxide. [0030] TEMPO catalyzed oxidation of primary alcohols of various organic compounds is reported in U.S. Pat. Nos. 6,031,101 to Devine et al. and 6,127,573 to Li et al. The oxidation system is a buffered two phase system employing TEMPO, sodium chlorite, and sodium hypochlorite. The above investigators are joined by others in a corresponding paper to Zhao et al. Journal of Organic Chemistry 64: 2564-2566 (1999). Similarly, Einhorn et al., Journal of Organic Chemistry 61: 7452-7454 (1996) describe TEMPO used with N-chlorosuccinimide in a two phase system for oxidation of primary alcohols to aldehydes. [0031] I. M. Ganiev et al in Journal of Physical Organic Chemistry 14: 38-42 (2001) describe a complex of chlorine dioxide with TEMPO and its conversion into oxammonium salt. Specific applications of the synthesis product were not noted. [0032] Isogai, in Japanese Kokai 2001-4959A, describes treating cellulose fiber using a TEMPO/hypochlorite oxidation system to achieve low levels of surface carboxyl substitution. The treated fiber has good additive retention properties without loss of strength when used in papermaking applications. [0033] Published European Patent Applications 1,077,221; 1,077,285; and 1,077,286 to Cimecloglu et al. respectively describe a polysaccharide paper strength additive, a paper product, and a modified cellulose pulp in which aldehyde substitution has been introduced using a TEMPO/hypochlorite system. [0034] Published PCT application WO 01/29309 to Jewell et al. describes a cellulose fiber carboxylated using TEMPO or its related compounds which is stabilized against color or D.P. degradation by the use of a reducing or additional oxidizing step to eliminate aldehyde or ketone substitution introduced during the primary oxidation. [0035] None of the previous workers have described a stable fibrous carboxylated cellulose or related carbohydrate material that can be made and used in conventional papermill equipment, using environmentally friendly chemicals, with no requirement for hypochlorites. SUMMARY OF THE INVENTION [0036] The present invention is directed to a method for preparation of a carboxylated carbohydrate product using a catalytic amount of a hindered cyclic oxammonium salt as the effective primary oxidant. This may be generated in situ by the use of a corresponding amine, hydroxylamine, or nitroxide. The catalyst is not consumed and may be recycled for reuse. The method does not require an alkali metal or alkaline earth hypohalite compound as a secondary oxidant to regenerate the oxammonium salt. Instead, chlorine dioxide has proved to be very satisfactory for this function. If maximum stability of the product is desired, the initially oxidized product may be treated, preferably with a tertiary oxidant or, alternatively, a reducing agent, to convert any unstable substituent groups into carboxyl or hydroxyl groups. [0037] In the discussion and claims that follow, the terms nitroxide, oxammonium salt, amine, or hydroxylamine of a corresponding hindered heterocyclic amine compound should be considered as full equivalents. The oxammonium salt is the catalytically active form but this is an intermediate compound that is formed from a nitroxide, continuously used to become a hydroxylamine, and then regenerated, presumably back to the nitroxide. The secondary oxidant will convert the amine form to the free radical nitroxide compound. Unless otherwise specified, the term “nitroxide” will normally be used hereafter in accordance with the most common usage in the related literature. [0038] The method is broadly applicable to many carbohydrate compounds having available primary hydroxyl groups, of which only one is cellulose. The terms “cellulose” and “carbohydrate” should thus be considered equivalents when used hereafter. [0039] The method is suitable for carboxylation of many carbohydrate products such as simple sugars, relatively low molecular weight oligomers of sugars, starches, chitin, chitosan and many others that have an accessible primary hydroxyl group. Cellulose is preferred carbohydrate material and a chemically purified fibrous cellulose market pulp is a particularly preferred raw material for the process. This may be, but is not limited to, bleached or unbleached sulfite, kraft, or prehydrolyzed kraft hardwood or softwood pulps or mixtures of hardwood and softwood pulps. While included within the broad scope of the invention, so-called high alpha cellulose or chemical pulps; i.e., those with an α-cellulose content greater than about 92%, are not generally preferred as raw materials. [0040] The suitability of lower cost market pulps is a significant advantage of the process. Market pulps are used for many products such as fine papers, diaper fluff, paper towels and tissues, etc. These pulps generally have about 86-88% α-cellulose and 12-14% hemicellulose whereas the high α-cellulose chemical or dissolving pulps have about 92-98% α-cellulose. By stable is meant minimum D.P. loss in alkaline environments, and very low self cross linking and color reversion. The method of the invention is particularly advantageous for treating secondary (or recycled) fibers. Bond strength of the sheeted carboxylated fibers is significantly improved over untreated recycled fiber. [0041] The “cellulose” used with the present invention is preferably a wood based cellulose market pulp below 90% α-cellulose, generally having about 86-88% α-cellulose and a hemicellulose content of about 12%. [0042] The process of the invention will lead to a product having an increase in carboxyl substitution over the starting material of at least about 2 meq/100 g, preferably at least about 5 meq/100 g. Carboxylation occurs predominantly at the hydroxyl group on C-6 of the anhydroglucose units to yield uronic acids. [0043] The cellulose fiber in an aqueous slurry or suspension is first oxidized by addition of a primary oxidizer comprising a cyclic oxammonium salt. This may conveniently be formed in situ from a corresponding amine, hydroxylamine or nitroxyl compound which lacks any a-hydrogen substitution on either of the carbon atoms adjacent the nitroxyl nitrogen atom. Substitution on these carbon atoms is preferably a one or two carbon alkyl group. For sake of convenience in description it will be assumed, unless otherwise noted, that a nitroxide is used as the primary oxidant and that term should be understood to include all of the percursors of the corresponding nitroxide or its oxammonium salt. [0044] Nitroxides having both five and six membered rings have been found to be satisfactory. Both five and six membered rings may have either a methylene group or a heterocyclic atom selected atom nitrogen, sulfur or oxygen at the four position in the ring, and both rings may have one or two substituent groups at this location. [0045] A large group of nitroxide compounds have been found to be suitable. 2,2,6,6-tetramethylpiperidinyl-1-oxy free radical (TEMPO) is among the exemplary nitroxides found useful. Another suitable product linked in a mirror image relationship to TEMPO is 2,2,2′2′,6,6,6′,6′-octamethyl-4,4′-bipiperidinyl-1,1′-dioxy di-free radical (BI-TEMPO). Similarly, 2,2,6,6-tetramethyl-4-hydroxypiperidinyl-1-oxy free radical; 2,2,6,6-tetramethyl-4-methoxypiperidinyl-1-oxy free radical; and 2,2,6,6-tetramethyl-4-benzyloxypiperidinyl-1-oxy free radical; 2,2,6,6-tetramethyl-4-aminopiperidinyl-1-oxy free radical; 2,2,6,6-tetramethyl-4-acetylaminopiperidinyl-1-oxy free radical; 2,2,6,6-tetramethyl-4-piperidone-1-oxy free radical and ketals of this compound are examples of compounds with substitution at the 4 position of TEMPO that have been found to be very satisfactory oxidants. Among the nitroxides with a second hetero atom in the ring at the four position (relative to the nitrogen atom), 3,3,5,5-tetramethylmorpholine-1-oxy free radical (TEMMO) is useful. [0046] The nitroxides are not limited to those with saturated rings. One compound anticipated to be a very effective oxidant is 3,4-dehydro-2,2,6,6-tetramethyl-piperidinyl-1-oxy free radical. [0047] Six membered ring compounds with double substitution at the four position have been especially useful because of their relative ease of synthesis and lower cost. Exemplary among these are the 1,2-ethanediol, 1,3-propanediol, 2,2-dimethyl-1-3-propanediol (1,3-neopentyldiol) and glyceryl cyclic ketals of 2,2,6,6-tetramethyl-4-piperidone-1-oxy free radical. [0048] Among the five membered ring products, 2,2,5,5-tetramethyl-pyrrolidinyl-1-oxy free radical is anticipated to be very effective. [0049] The above named compounds should only be considered as exemplary among the many representatives of the nitroxides suitable for use with the invention and those named are not intended to be limiting in any way. [0050] During the oxidation reaction the nitroxide is consumed and converted to an oxammonium salt then to a hydroxylamine. Evidence indicates that the nitroxide is continuously regenerated by the presence of a secondary oxidant. Chlorine dioxide, or a latent source of chlorine dioxide, is a preferred secondary oxidant. Since the nitroxide is not irreversibly consumed in the oxidation reaction only a catalytic amount of it is required. During the course of the reaction it is the secondary oxidant which will be depleted. [0051] The amount of nitroxide required is in the range of about 0.005% to 1.0% by weight based on carbohydrate present, preferably about 0.02-0.25%. The nitroxide is known to preferentially oxidize the primary hydroxyl which is located on C-6 of the anhydroglucose moiety in the case of cellulose or starches. It can be assumed that a similar oxidation will occur at primary alcohol groups on hemicellulose or other carbohydrates having primary alcohol groups. [0052] The chlorine dioxide secondary oxidant is present in an amount of 0.2-35% by weight of the carbohydrate being oxidized, preferably about 0.5-10% by weight. [0053] As was noted earlier, it is considered to be within the scope of the invention to form nitroxides or their oxammonium salts in situ by oxidation of the corresponding amines or hydroxylamines of any of the nitroxide free radical products. While the free radical form of the selected nitroxide may be used, it is often preferable to begin with the corresponding amine. Among the many possible amino compounds useful as starting materials can be mentioned 2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidone (triacetone amine) and its 1,2-ethanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol and glyceryl cyclic ketals. [0054] When cellulose is the carbohydrate being treated, the usual procedure is to slurry the cellulose fiber in water with a small amount of sodium bicarbonate or another buffering material for pH control. The pH of the present process is not highly critical and may be within the range of about 4-12, preferably about 6-8. The nitroxide may be added in aqueous solution and chlorine dioxide added separately or premixed with the nitroxide. If the corresponding amine is used, they are preferably first reacted inaqueous solution with chlorine dioxide at somewhat chlorine dioxide is added to the cellulose slurry and the catalytic solution is then added and allowed to react, preferably at elevated temperature for about 30 seconds to 10 hours at temperatures from about 5°-110° C., preferably about 20°-95° C. [0055] To achieve maximum stability and D.P. retention the oxidized product may be treated with a stabilizing agent to convert any substituent groups, such as aldehydes or ketones, to hydroxyl or carboxyl groups. The stabilizing agent may either be another oxidizing agent or a reducing agent. Unstabilized oxidized cellulose pulps have objectionable color reversion and may self crosslink upon drying, thereby reducing their ability to redisperse and form strong bonds when used in sheeted products. If sufficient unreacted ClO 2 remains after the initial oxidation, it is only necessary to acidify the initial reaction mixture without even draining or washing the product. Otherwise one of the following oxidation treatments may be used [0056] Alkali metal chlorites are one class of oxidizing agents used as stabilizers, sodium chlorite being preferred because of the cost factor. Other compounds that may serve equally well as oxidizers are permanganates, chromic acid, bromine, silver oxide, and peracids. A combination of chlorine dioxide and hydrogen peroxide is also a suitable oxidizer when used at the pH range designated for sodium chlorite. Oxidation using sodium chlorite may be carried out at a pH in the range of about 0-5, preferably 2-4, at temperatures between about 10°-110° C., preferably about 20°-95° C., for times from about 0.5 minutes to 50 hours, preferably about 10 minutes to 2 hours. One factor that favors oxidants as opposed to reducing agents is that aldehyde groups on the oxidized carbohydrate are converted to additional carboxyl groups, thus resulting in a more highly carboxylated product. These stabilizing oxidizers are referred to as “tertiary oxidizers” to distinguish them from the nitroxide/chlorine dioxide primary/secondary oxidizers. The tertiary oxidizer is used in a molar ratio of about 1.0-15 times the presumed aldehyde content of the oxidized carbohydrate, preferably about 5-10 times. In a more convenient way of measuring the needed tertiary oxidizer, the preferred sodium chlorite usage should fall within about 0.01-20% based on carbohydrate, preferably about 1-9% by weight based on carbohydrate, the chlorite being calculated on a 100% active material basis. [0057] When stabilizing with a ClO 2 and H 2 O 2 mixture, the concentration of ClO 2 present should be in a range of about 0.01-20% by weight of carbohydrate, preferably about 0.3-1.0%, and concentration of H 2 O 2 should fall within the range of about 0.01-10% by weight of carbohydrate, preferably 0.05-1.0%. Time will generally fall within the range of 0.5 minutes to 50 hours, preferably about 10 minutes to 2 hours and temperature within the range of about 10°-100° C., preferably about 30°-95° C. The pH of the system is preferably about 3 but may be in the range of 0-5. [0058] A preferred reducing agent is an alkali metal borohydride. Sodium borohydride (NaBH 4 ) is preferred from the standpoint of cost and availability. However, other borohydrides such as LiBH 4 , or alkali metal cyanoborohydrides such as NaBH 3 CN are also suitable. NaBH4 may be mixed with LiCl to form a very useful reducing agent. When NaBH 4 is used for reduction, it should be present in an amount between about 0.1 and 10.0 g/L. A more preferred amount would be about 0.25-5 g/L and a most preferred amount from about 0.5-2.0 g/L. Based on carbohydrate the amount of reducing agent should be in the range of about 0.1% to 4% by weight, preferably about 1-3%. Reduction may be carried out at room or higher temperature for a time between 10 minutes and 10 hours, preferably about 30 minutes to 2 hours. [0059] After stabilization is completed, the carbohydrate is washed and may be dried if desired. Alternatively, the carboxyl substituents may be converted to other cationic forms beside hydrogen or sodium; e.g., calcium, magnesium, or ammonium. [0060] One particular advantage of the process is that all reactions are carried out in an aqueous medium. A further advantage when the process is used with cellulose fiber is that the carboxylation is primarily located on the fiber surface. This conveys highly advantageous properties for papermaking. The product of the invention will have at least about 20% of the total carboxyl content on the fiber surface. Untreated fiber will typically have no more than a few milliequivalents of total carboxyl substitution and, of this, no more than about 10% will be located on the fiber surface. [0061] Carboxylated cellulose made using the process of the invention is highly advantageous as a papermaking furnish, either by itself or in conjunction with conventional fiber. It may be used in amounts from 0.5-100% of the papermaking furnish. The carboxylated fiber is especially useful in admixture with recycled fiber to add strength. The method can be used to improve properties of either virgin or recycled fiber. The increased number of anionic sites on the fiber should serve to ionically hold significantly larger amounts of cationic papermaking additives than untreated fiber. These additives may be wet strength resins, sizing chemical emulsions, filler and pigment retention aids, charged filler particles, dyes and the like. Carboxylated pulps do not hornify (or irreversibly collapse) as much on drying and are a superior material when recycled. They swell more on rewetting, take less energy to refine, and give higher sheet strength. [0062] It is a primary object of the invention to provide a convenient method whereby carboxyl substitution may be introduced into carbohydrate materials having primary hydroxyl groups. [0063] It is an important object of the invention to provide a method of making a cellulose fiber having enhanced carboxyl content using an aqueous reaction medium. [0064] It is also an object to provide a method for making a carboxylated cellulose fiber that does not employ chlorine or hypohalite compounds. [0065] It is another object to provide a process for making a carboxylated cellulose fiber that can be carried out in equipment and with many chemicals commonly found in pulp or paper mills. [0066] It is a further object to provide a cellulose fiber having an enhanced carboxyl content at the fiber surface. [0067] It is yet an object to provide a carboxylated cellulose fiber that is stable against D.P. loss in alkaline environments. [0068] It is an object to provide a stable cellulose fiber of enhanced carboxyl content with a D.P. of at least 850 measured as a sodium salt or 700 when measured in the free acid form. [0069] It is still an object to provide a cellulose fiber having a high ionic attraction to cationic papermaking additives. [0070] It is an additional object to provide cellulose pulp and paper products containing the carboxyl enhanced fiber. [0071] These and many other objects will become readily apparent upon reading the following detailed description taken in conjunction with the drawings DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0072] Abundant laboratory data indicates that a nitroxide catalyzed cellulose oxidation predominantly occurs at the primary hydroxyl group on C-6 of the anhydro-glucose moeity. In contrast to some of the other routes to oxidized cellulose, only very minor reaction has been observed to occur at the secondary hydroxyl groups at the C-2 and C-3 locations. Using TEMPO as an example, the mechanism to formation of a carboxyl group at the C-6 location proceeds through an intermediate aldehyde stage. [0073] The TEMPO is not irreversibly consumed in the reaction but is continuously regenerated. It is converted by the secondary oxidant into the oxammonium (or nitrosonium) ion which is the actual oxidant. During oxidation the oxammonium ion is reduced to the hydroxylamine from which TEMPO is again formed. Thus, it is the secondary oxidant which is actually consumed. TEMPO may be reclaimed or recycled from the aqueous system. The reaction is postulated to be as follows: [0074] As was noted earlier, formation of the oxammonium salt in situ by oxidation of the hydroxylamine or the amine is considered to be within the scope of the invention. [0075] The resulting oxidized cellulose product will have a mixture of carboxyl and aldehyde substitution. Aldehyde substituents on cellulose are known to cause degeneration over time and under certain environmental conditions. In addition, minor quantities of ketone carbonyls may be formed at the C-2 and C-3 positions of the anhydroglucose units and these will also lead to degradation. Marked D.P., fiber strength loss, crosslinking, and yellowing are among the problems encountered. For these reasons, we have found it very desirable to oxidize aldehyde substituents to carboxyl groups, or to reduce aldehyde and ketone groups to hydroxyl groups, to ensure stability of the product. wherein R 1 -R 4 are one to four carbon alkyl groups but R 1 with R 2 and R 3 with R 4 may together be included in a five or six carbon alicyclic ring structure; X is methylene, oxygen, sulfur, or alkylamino; and R 9 and R 10 are one to five carbon alkyl groups and may together be included in a five or six member ring structure, which, in turn may have one to four lower alkyl or hydroxy alkyl substitutients. Examples include the 1,2-ethanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and glyceryl cyclic ketals of 2,2,6,6-tetramethyl-4-piperidone-1-oxy free radical. These compounds are especially preferred primary oxidants because of their effectiveness, lower cost, ease of synthesis, and suitable water solubility. in which R 1 -R 4 are one to four carbon alkyl groups but R 1 with R 2 and R 3 with R 4 may together be included in a five or six carbon alicyclic ring structure; and X may be methylene, sulfur, oxygen, —NH, or NR 11 , in which R 11 is a lower alkyl. An example of these five member ring compounds is 2,2,5,5-tetramethylpyrrolidinyl-1-oxy free radical. [0078] Where the term “lower alkyl” is used it should be understood to mean an aliphatic straight or branched chain alkyl moiety having from one to four carbon atoms. [0079] In the following examples, unless otherwise specified, the cellulose used was a bleached, never dried northern softwood kraft wet lap market pulp produced in an Alberta mill. EXAMPLE 1 Use of the Plyceryl Ketal of Triacetone Amine to Form the Primary Oxidizing Agent [0080] The glyceryl ketal of triacetone amine (gk-TAA) is 7,7,9,9-tetramethyl-1,4-dioxa-8-azaspiro[4.5]decane-2-methanol. This is a commercially available chemical. However, it may be synthesized by reaction of 2,2,6,6-tetramethyl-4-piperidone with glycerine under strongly acidic conditions. [0081] Part 1: 10.3 mg of gk-TAA was reacted with 2 g of a 6.7 g/L solution of ClO 2 at 60° for about 2 minutes. To this was then added an additional 2 g of the ClO 2 solution and the reaction continued for an additional 2 minutes at 60° C. The reaction mixture was added to 30 mL of the ClO 2 solution and 60 mL water. This solution was placed in a sealable polyethylene bag and to it was then added a 45 g wet sample (10 g O.D. basis) of cellulose combined with 1 g NaHCO 3 . The pH at this time was 7.3. The bag with its contents was placed in a 60-70° C. water bath for 31 minutes. The oxidized pulp was drained leaving a wet mass of 34 g. The 98 g of liquor recovered was retained in order to recycle the catalyst. A small portion of the oxidized pulp was retained for analysis. The remainder was stabilized by adjusting the pH to about 3 with 1 M H 2 SO 4 solution and adding 30 mL of the 6.7 g/l ClO 2 solution, 3 mL of 3% H 2 O 2 , and 40 mL water. The stabilization reaction was continued for about 1 hour at 60°-70° C. The pulp was washed and converted to the sodium form by treating it in a solution of Na 2 CO 3 at about pH 8-9. [0082] Part 2: The recovered liquor from the oxidation step above was combined with 41 g (10 g O.D.) of the never dried cellulose pulp, 30 mL of the 6.7 g/L ClO 2 solution and 1 g NaHCO 3 . These were placed in a sealed polyethylene bag as before and reacted in a 60-70° C. water bath for 40 minutes. The oxidized pulp was drained and stabilized as above. [0083] Carboxyl contents of the materials made above were determined to be as follows: Sample Carboxyl, meq/100 g Part 1, unstabilized 7.7 Part 1, stabilized 11.7 Part 2, Unstabilized 7.0 Part 2, Stabilized 12.3 [0084] These results indicate both the efficiency of gk-TAA as a primary oxidation catalyst but also show that it may be recycled without loss of efficiency. EXAMPLE 2 Investigation of Effect of Primary Catalyst Loading [0085] A catalyst solution was made by adding 20.0 mg gk-TAA to ˜2.0 g of a solution of 6.7 g/L ClO 2 at 70° C. for 1-2 minutes. The gk-TAA appeared to be totally dissolved. Cellulose was oxidized as above using 41 g (10 g O.D.) of the never dried pulp, 0.5 g NaHCO 3 , 75 mL water, and 14 mL of the 6.7 g/L ClO 2 solution. To this was added either 0.11 g, 0.26 g, 0.50 g, or 0.75 g of the catalyst solution. These catalyst additions correspond to 0.011%, 0.026%, 0.050%, and 0.075% by weight based on dry cellulose. After 30 minutes reaction time at 70° C. the samples with the two highest catalyst usages were white in appearance, the next lower usage sample had a faint off-white color and the lowest catalyst usage sample was a light yellow. After 2 hours the samples were removed from the water bath and drained. The unwashed oxidized material was stabilized by treatment with 30 mL of the 6.7 g/l ClO 2 solution and 3 g 3% H 2 O 2 . The pH was adjusted to ˜1 by 1 M H 2 SO 4 . Treatment was continued for about 30 minutes at 60° C. The samples were then filtered off and washed with deionized water. Carboxyl analyses indicated the following levels of substitution: Sample No. Catalyst, wt % Carboxyl, meq/100 g 1 0.011 5.5 2 0.026 8.6 3 0.050 8.7 4 0.075 9.4 [0086] It is evident from the substitution data that carboxylation level is not a linear function of catalyst usage. Little gain was seen using more than 0.026% of the gk-TAA catalyst. EXAMPLE 3 Use of 1,3-Propanediol Ketal of Triacetone Amine to Form the Primary Oxidizing Agent [0087] A catalyst solution was formed by reacting 10.5 mg of the 1,3-propanediol acetal of triacetone amine and 1.5 mL of a 5.7 g/L solution of ClO 2 in a sealed tube for about 1 minute. The resulting dark material readily dissolved in the liquid. Water (75 mL), 0.5 g NaHCO 3 , 15 mL of the 5.7 g/L ClO 2 solution, and the activated catalyst solution, along with a few mL of rinse water were combined in that order. This was combined with 41 g of the wet (10 g O.D.) cellulose and mixed in a sealed polyethylene bag. The mixture was placed in a 70° C. water bath and allowed to react for 33 minutes. The slurry was acidified with 1 M H 2 SO 4 to pH ˜3. Then 5.0 mL of the 5.7 g/L ClO 2 solution and 1.5 mL of 3% H 2 O 2 were mixed in. The sealed bag was again placed in the 70° C. hot water bath for about 1 hour. The resulting stabilized carboxylated cellulose was washed and dried as before. Carboxyl content was measured as 8.3 meq/100 g. EXAMPLE 4 Use of TEMPO as a Primary Oxidizing Agent with a ClO 2 Secondary Oxidant [0088] A 10.6 g dried sample (10.0 g O.D.) of the northern softwood pulp was slurried in 200 g water with 3 g NaHCO 3 . Then 0.1 g TEMPO and ˜2 mL of a 6 g/L ClO 2 solution were combined and gently heated to form an oxidation catalyst. An additional 68 mL of the 6 g/L ClO 2 solution was stirred into the pulp slurry, then the catalyst mixture. The slurry was contained in a sealed polyethylene bag and immersed in a 70° C. water bath for 30 minutes. The reacted cellulose was then washed and stabilized by combining 0.7 g 30% H 2 O 2 , 0.7 g NaClO 2 , wet pulp, and water to make 100 g total. The pH was reduced to below 3 by adding about 1.5 g of 1 M H 2 SO 4 and the mixture was heated and allowed to react for about 1 hour at 70° C. Analyses showed that the unstabilized material had a carboxyl content of 8.7 meq/100 g while the stabilized sample had 17 meq/100 g carboxyl. EXAMPLE 5 Use of 2,2,6,6-Tetramethylpiperidine to Form Primary Oxidation Catalyst [0089] Rather than use the nitroxide form of TEMPO as a starting catalyst material, the corresponding amine was employed to generate a catalyst. A water solution containing 7.1 g/L ClO 2 was prepared. About 5 mL of this was reacted with about 80 mg 2,2,6,6-tetramethylpiperidine to form the oxammonium salt. Then 85-90 mL of the ClO 2 solution was combined with 41 g (10.0 g O.D.) of the never dried pulp, 3 g of NaHCO 3 , and 0.08 g of 3.3% H 2 O 2 . The catalyst solution was added and the whole, contained in a sealed polyethylene bag, was immersed in a 70° C. water bath for 40 minutes. The pH was then adjusted below 3 with 1 M H 2 SO 4 . Then 3 g of 3.3% H 2 O 2 and 30 mL of the ClO 2 solution were mixed in and again placed in the 70° C. water bath for 1 hour for stabilization. The stabilized carboxylated cellulose was washed and dried as before. Carboxyl content was 22 meq/100 g. EXAMPLE 6 Use of 4-oxo-TEMPO-1,3-propanediol Ketal to Form the Primary Oxidizing Agent [0090] A catalyst mixture was formed by mixing 0.10 g of 2,2,6,6-tetramethyl-4-piperidonel-3-propanediol ketal was reacted with about 3 mL of a 6.8 g/L ClO 2 solution to form the corresponding catalytic oxammonium compound. Then 41 g (10 g O.D.) of never dried bleached northern softwood kraft pulp was added to 87 mL of the ClO 2 solution along with 3 g NaHCO 3 followed by the rapid addition of the catalyst solution. The mixture at pH 7.5 was placed in a sealed polyethylene bag and submerged in a 70° C. hot water bath for about 30 minutes. The pH of the reaction mixture was reduced below 3 with 1 M H 2 SO 4 . At this time about 6 g of 3.2% H 2 O 2 and 30 mL of the 6.8 g/L ClO 2 solution were added. The polyethylene bag was again sealed and placed in the 70° C. water bath for 1 hour. The stabilized pulp was then washed and dried as before. Upon analysis the carboxyl content was 23 meq/100 g. EXAMPLE 7 Effect of Oxidation pH on Carboxyl Content [0091] The catalyst mixture of Example 6 was again made up, this time using a fresh 7.1 g/L solution of ClO 2 . Instead of the NaHCO 3 buffer used earlier, which gave a pH of about 7.5, the buffering system used was a mixture of Na 2 HPO 4 and citric acid as shown in the table that follows. With the exception of the buffers, the procedure used was generally similar to that of Example 6 with the following exceptions. Only 30 mL of the 7.1 g/L ClO 2 solution was used and the initial reaction time was extended to 2¾ hours. Stabilization was under similar conditions except that only 25 mL of the ClO 2 solution was used, the temperature was 60° C., and the bags with the samples were removed from the water bath after 1 hour but allowed to remain at room temperature over the weekend. Reaction conditions and carboxyl content were as follows. Sample 0.2 M Na 2 HPO 4 , 0.1 M citric Catalyst, Carboxyl No. pH mL acid, mL mg meq/100 g 1 7.0 43.6 6.5 10.2 16 2 6.6 36.4 13.6 10.5 17 3 6.2 33.1 16.9 10.1 14 4 5.8 30.3 19.7 10.3 13 [0092] It is evident that the pH of the carboxylation reaction with ClO 2 is not extremely critical. Contrary to the traditional use of sodium hypochlorite as the secondary oxidant, which requires a pH of about 9-10.5 for best efficiency, the reaction using ClO 2 will proceed on the acidic side with little or no reduction in carboxyl substitution. EXAMPLE 8 Effect of Stabilization on Brightness Reversion of Oxidized Pulps [0093] A catalyst mixture was made by reacting 0. 11 g of 2,2,6,6-tetramethylpiperidine with about 25 mL of 6.9 g/L ClO 2 solution at 70° C. for a few minutes. Then the activated catalyst, 10 g NaHCO 3 , 410 g (100 g O.D.) of never dried northern bleached kraft softwood pulp, and 575 mL of the 6.9 g/L % ClO 2 solution were intimately mixed. The pH of the mixture was in the 8.0-8.5 range. The sealed container was placed in a 70° C. hot water bath. Gases given off during the reaction were vented as necessary. After 38 minutes the product was divided into two portions. A first portion was washed and treated with a solution of about 2 g/L Na 2 CO 3 for about 5 minutes at a pH between 9-10. The unstabilized product was then washed with deionized water but left undried. The second portion was stabilized by removing about 200 mL of the remaining reaction liquor which was replaced by an equal amount of a solution of 5.0 g 80% NaClO 2 , 5.0 g of 3% H 2 O 2 , and 12.8 g of 1 M H 2 SO 4 . This was again reacted for 45 minutes at 70° C. The product was drained and washed, treated with basic water at pH ˜10, and again washed. [0094] Analyses of the original and two treated samples gave the following results: Sample D.P. Carboxyl, meq/100 g Untreated 1650 ± 100  4.0 ± 0.5 Unstabilized 650* 13.7 ± 0.5 Stabilized 1390 ± 60  21.6 ± 0.1 *D.P. results of unstabilized materials are unreliable due to degradation in the alkaline cuene solvent. [0095] Handsheets were then made of the above three samples for study of color reversion after accelerated aging. These were dried overnight at room temperature and 50% R.H. Brightness was measured before and after samples were heated in an oven at 105° C. for 1 hour. Heated samples were reconditioned for at least 30 minutes at 50% R.H. Results are as follows: Brightnes Initial ISO Oven-aged ISO Reversion, Sample pH Brightness, % Brightness, % % Control 5 89.84 ± 0.13 88.37 ± 0.12 1.48 Control* 5 90.13 ± 0.07 88.61 ± 0.13 1.52 Unstabilized Unadjusted 91.43 ± 0.16 78.85 ± 0.28 12.59 Unstabilized 5 91.93 ± 0.08 87.38 ± 4.55 Stabilized Unadjusted 92.68 ± 0.09 90.74 ± 0.12 1.94 Stabilized 5 92.89 ± 0.14 91.31 ± 0.12 1.57 *Base washed before testing [0096] The superior brightness retention of the stabilized samples is immediately evident from the above test results. EXAMPLE 9 Stabilization Retaining Primary Oxidation Liquor [0097] A catalytic composition was formed by reacting 12 mg of TEMPO and about 2 mL of 7 g/L ClO 2 solution at 70° C. for about 1 minute. The activated catalyst was added to a slurry of 41 g (10 g O.D.) of northern mixed conifer bleached kraft pulp and 2 g Na 2 CO 3 in about 88 mL of the 7 g/L ClO 2 solution. The mixture was contained in a sealed polyethylene bag and placed in a 70° C. water bath for 30 minutes. The mixture was occasionally mixed and vented as needed. After the initial oxidation the sample was divided into two equal portions of about 66 g each. [0098] One portion was stabilized by acidification to a pH below 3 with 1 M H 2 SO 4 and again placed in the hot water bath at 70° C. for 1 hour. No ClO 2 or H 2 O 2 was added. The fiber was then recovered, thoroughly washed, treated with a Na 2 CO 3 solution at a pH ˜10, and again washed and dried. [0099] The second portion was stabilized by treatment with 2.3 g of 3% H 2 O 2 and then with 1 M H 2 SO 4 to adjust pH below 3. This too was retained in the hot water bath at 70° C. for 1 hour. The stabilized cellulose was then treated as above. Carboxyl content was measured for both samples. Stabilization Carboxyl Content Treatment D.P. meq/100 g Neither H 2 O 2 or ClO 2 1050 21 H 2 O 2 but no ClO 2 1100 28 [0100] It is clearly evident that under the initial oxidation conditions employed, no additional oxidants are needed for stabilization and that pH adjustment by acidification is sufficient. EXAMPLE 10 Oxidation of Starch Using ClO 2 and the Glyceryl Ketal of Triacetoneamine [0101] A 10.7 mg portion of the glyceryl ketal of triacetoneamine was reacted with about 2 mL of 5.2 g/L ClO 2 at 70° C. Then a solution of 61 g of 16.4% (10.0 g O.D.) FilmFlex® 50 starch, which had been solubilized by heating the starch in water, 3 g of NaHCO 3 , and about 98 mL of the 5.2 g/L ClO 2 was prepared. FilmFlex is a registered trademark of Cargill Corp. for a hydroxyethyl corn starch product. The activated catalyst was added. System pH was about 7.5. After about 5 minutes a first small (about 10 g) portion was removed (Sample A). The remainder was placed in a sealed polyethylene bag and then in a 70° C. water bath for 23 minutes. A second portion of about 71 g was then removed from the bag (Sample B). Then 30 mL of the ClO 2 solution and 9 mL of 3% H 2 O 2 was added to the remainder of the material in the bag after the pH had been reduced to about 3 with 1M H 2 SO 4 . The bag was again placed in the 70° C. water bath for 40 minutes (Sample C). The starch remained in solution for all treatments. [0102] An 18 g control sample of the 16.4% FilmFlex® 50 starch was diluted to 50 mL with deionized water. The pH was then adjusted to about 2 with 1 M H 2 SO 4 (Sample D). [0103] Samples A (about 0.4 g) and B (about 3 g) which had been dried at 105° C. for about 1 hour were dissolved separately in about 10 mL water. The pH was reduced to about 1 with 1 M H 2 SO 4 . Then 25 mL acetone was stirred into each of the samples and later decanted off Following this 125 mL absolute ethanol divided into four separate aliquots was used to treat the samples so that the product was no longer gummy and was loose and granular in appearance. After each ethanol wash the supernatant liquid was decanted off The slightly yellow granular washed products were dried at 105° C. for about 1 hour and sent for analysis. [0104] To isolate the treated Sample C starch, 150 mL of acetone was stirred slowly into the solution. After the resulting precipitate had settled, the supernatant liquid was decanted off Then 150 mL ethanol in four separate portions was added to the gummy precipitate to extract remaining water and chemicals and each time the supernatant was decanted off. The white granular product was oven dried at about 105° C. for 1 hour and a sample submitted for carboxyl analysis. [0105] Sample D was treated in a similar manner except the initial treatment was with 100 mL ethanol rather than acetone. Again the washed material was oven dried at 105° C. for about 1 hr. [0106] Upon analysis, Samples A and D did not have a significant carboxyl content. However, sample B had a carboxyl content of about 29 meq/100 g and sample C about 30 meq/100 g. [0107] It will be evident to those skilled in the art that many reaction conditions, many carbohydrate compounds, and many hindered nitroxide compounds that have not been exemplified will be satisfactory for use with ClO 2 as a secondary oxidant. Thus, it is the intent of the inventors that these variations be included within the scope of the invention if encompassed within the following claims.
A method of making a carboxylated carbohydrate is disclosed, cellulose being a preferred carbohydrate material. Carboxylated cellulose fibers can be produced whose fiber strength and degree of polymerization is not significantly sacrificed. The method involves the use of a catalytic amount of a hindered cyclic oxammonium compounds as a primary oxidant and chlorine dioxide as a secondary oxidant in an aqueous environment. The oxammonium compounds may be formed in situ from their corresponding amine, hydroxylamine, or nitroxyl compounds. The oxidized cellulose may be stabilized against D.P. loss and color reversion by further treatment with an oxidant such as sodium chlorite or a chlorine dioxide/hydrogen peroxide mixture. Alternatively it may be treated with a reducing agent such as sodium borohydride. In the case of cellulose the method results in a high percentage of carboxyl groups located at the fiber surface. The product is especially useful as a papermaking fiber where it contributes strength and has a higher attraction for cationic additives. The product is also useful as an additive to recycled fiber to increase strength. The method can be used to improve properties of either virgin or recycled fiber. It does not require high α-cellulose fiber but is suitable for regular market pulps.
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SUMMARY OF THE INVENTION This invention is concerned with novel compounds of structural formula: ##STR1## and pharmaceutically acceptable salts thereof, wherein R 1 , R 2 , R 3 , n and Y are as defined below, which have β-adrenergic blocking activity with some cardioselectivity and hence useful as antihypertensive, antianginal, antiarrhythmic and cardioprotective agents, and in the treatment of elevated intraocular pressure such as glaucoma. The invention is also concerned with processes for the preparation of the novel compounds; pharmaceutical formulations comprising one or more of the novel compounds as active ingredient; and a method of treating hypertension, arrhythmia, post myocardial infarction, angina and elevated intraocular pressure such as glaucoma by administration of a novel compound or pharmaceutical formulation thereof. BACKGROUND OF THE INVENTION A class of pharmaceutical agents known as β-adrenergic blocking agents, are available which affect cardiac, vascular and pulmonary functions and are mild antihypertensives. Specifically, these agents have the capability of reducing heart rate, without counteracting vasodepression or suppressing bronchodilation. β-adrenergic blocking agents, their chemical structure and activity, are disclosed in "Clinical Pharmacology and Therapeutics" 10, 292-306 (1969). Various β-adrenergic blocking agents are also described in the following U.S. Pat. Nos. 3,048,387; 3,337,628; 3,655,663; 3,794,650; 3,832,470; 3,836,666; 3,850,945; 3,850,946; 3,850,947; 3,852,291; 3,928,412; 4,134,983; 4,199,580; British Pat. No. 1,194,548; EP 42,592; and South African 74/1070. Now, with the present invention there are provided novel β-blocking agents; processes for their synthesis, pharmaceutical formulations comprising one or more of the novel compounds; and methods of treatment with the novel compounds or pharmaceutical compositons thereof wherein an antihypertensive, antianginal, antiarrhythmic, cardioprotective, or antiglaucoma agent is indicated. DETAILED DESCRIPTION OF THE INVENTION The novel compounds of this invention are represented by the formula I: ##STR2## or a pharmaceutically acceptable salt thereof, wherein: Y is (1) ##STR3## wherein m is 1 or 2, ##STR4## n is 1 to 8 R 1 is (1) hydrogen, (2) hydroxy, or (3) hydroxymethyl; R 2 and R 3 are independently: (1) hydrogen, (2) halo such as chloro, bromo or fluoro, (3) hydroxy, (4) amino, (5) di(C 1-5 alkyl)amino, (6) mono(C 1-5 alkyl)amino, (7) nitro, (8) cyano, (9) C 1-6 alkyl, (10) C 3-8 cycloalkyl, (11) C 2-5 alkenyl, (12) C 1-4 alkoxy, (13) C 1-4 alkylthio, (14) C 2-5 alkenyloxy, (15) C 1-5 alkanoyl, such as formyl, pentanoyl or the like; R 4 and R 5 are independently: (1) hydrogen, (2) C 1-6 alkyl, either unsubstituted or substituted with: (a) hydroxy, (b) C 1-4 alkoxy, or (c) phenyl; ##STR5## wherein X is 0, 1 or 2; R 4 and R 5 are joined together to form a 5 or 6 membered ring with the nitrogen to which they are attached, the 6-membered ring optionally including another heteroatom selected from O, S and C 1-3 alkyl-N, such as morpholino, N-methylpiperazino, pyrrolidino, or piperidino; R 6 is (1) --CN, (2) ##STR6## and R 7 is (1) C 1-6 alkyl, (2) C 1-4 alkoxy, or (3) halo, such as chloro, bromo or fluoro, In a preferred embodiment of the compound of this invention R 1 is hydrogen; R 2 and R 3 are selected from hydrogen, halo, cyano, nitro and C 1-5 alkanoyl; n is 2, and Y is: ##STR7## In an even more preferred embodiment, R 1 and R 2 are hydrogen, R 3 is cyano, n is 2 and Y is as defined in the preferred embodiment. The novel compounds of this invention include all the optical isomer forms as pure enantiomers or as mixtures containing the optical isomers such as racemic mixtures and compounds. The compounds of the present invention also include the non-toxic pharmaceutically acceptable acid addition and quaternary ammonium salts. The acid addition salts are prepared by treating the compounds with an appropriate amount of a suitable organic or inorganic acid. Examples of useful organic acids are carboxylic acids such as maleic acid, tartaric acid, acetic acid, pamoic acid, oxalic acid, propionic acid, salicyclic acid, succinic acid, citric acid, malic acid, isethionic acid, and the like. Useful inorganic acids are hydrohalo acids such as hydrochloric, hydrobromic, hydriodic, sulfuric, phosphoric acid, or the like. Compounds of the present invention may be prepared by any convenient method, however, the preferred methods utilized will depend upon the R 1 , R 2 , R 3 , R 4 , R 5 and Y groups and n. In the methods described below, the R 1 -R 5 and Y groups and n are as defined above unless otherwise indicated. Also, unless otherwise indicated, the starting materials employed are known in the literature, are commercially available, or can be prepared by methods known to those skilled in the art. ##STR8## For Method A, an epoxide I is reacted with a diamine of the type II in a suitable solvent such as methanol, ethanol, isopropanol, methylene chloride, THF or the like, at 0° C. to the reflux temperature of the solvent for about 1-48 hours, preferably in isopropanol at 45° C. for 18 hours, to yield III. Compound III can then be reacted with L-Y wherein L is a leaving group such as ethoxy, chloro, bromo, methylthio, or the like, and Y is as defined below, to yield IV. Examples of Y are: ##STR9## In Method B, the order in which the leaving groups are displaced is reversed. For example, amine III is reacted first with L-Q-L as defined above, and then in a last step with amine VI to yield IVa. The conditions utilized are the same as described in Method A. ##STR10## For Method C, epoxide I is reacted with a diamine of the type VII to yield IV by the conditions described in Method A. The β-adrenergic blocking properties of the novel compounds of this invention indicates that they are useful in the treatment of conditions such as hypertension, angina pectoris or certain arrhythmias which are known to be amenable to treatment with β-adrenergic blocking agents. For use as β-adrenergic blocking agents, the present compounds can be administered orally, transdermally, or parenterally; i.e., intravenously, interperitoneally, etc. and in any suitable dosage form. The compounds may be offered in a form (a) for oral administration; e.g., as tablets, in combination with other compounding ingredients customarily used such as talc, vegetable oils, polyols, benzyl alcohols, gums, gelatin, starches and other carriers; as liquids dissolved or dispersed or emulsified in a suitable liquid carrier; in capsules encapsulated in a suitable encapsulating material; or (b) for parenteral administration dissolved or dispersed in a suitable liquid carrier such as solution or as an emulsion, or (c) as an aerosol or patch for transdermal administration. The ratio of active compound to compounding ingredients; i.e., carrier, diluent, etc., will vary as the dosage form requires. Generally, doses of the present compounds of from about 0.01 to about 50 mg/kg and preferably from about 0.1 to about 20 mg/kg of body weight per day may be used. Dosage may be single or multiple depending on the daily total required and the unit dosage. EXAMPLE 1 3-Methylamino-4[[2-[3-(2-cyanophenoxy)-2-hydroxypropylamino]ethyl]amino]-1,2,5-thiadiazole-1-oxide hemihydrate, (4) ##STR11## To 1 (1.76 g, 7.5 mmole) in 2-propanol (10 ml) the diethoxythiadiazole oxide, 2, in 2-propanol (20 ml) was added. The mixture was stirred at room temperature for 1 hour then CH 3 NH 2 was bubbled through the solution for 1 hour. The solvent was removed in vacuo and the residue was purified on silica gel 60 by eluting with CHCl 3 -CH 3 OH-H 2 O (70-30-3 v:v:v) to yield 1.82 g (63.9%) of product 4. Analysis satisfactory for C 15 H 20 N 6 O 3 S.1/2H 2 O EXAMPLE 2 3-Amino-4-[[2-[3-(2-cyanophenoxy)-2-hydroxypropylamino]ethyl]amino]-1,2,5-thiadiazole-1-oxide (0.25 CHCl 3 Following the same procedure as in Example 1, the title compound was obtained by using ammonia instead of methylamine (64% yield). Analysis satisfactory for C 14 H 18 N 6 O 3 S.1/4CHCl 3 . EXAMPLE 3 N-Cyano-N'-[2-[3-(2-cyanophenoxy)-2-hydroxypropylamino]ethyl]-N"-methylguanidine, (8) ##STR12## Step A: Preparation of N-(2-Aminoethyl)-N'-cyano-N"-methylguanidine Methylamine (1.58 g, 50.9 mmole) was condensed into 20 ml of 2-propanol. To this solution, (CH 3 S) 2 C=NCN (7.44 g, 50.9 mmole) in 2-propanol (40 ml) was added (slight exotherm). The mixture was stirred for 15 minutes and then added dropwise over 15 minutes to 68.2 ml (1.02M) of ethylenediamine while stirring vigorously. After 31/2 hours the solvent and the excess ethylenediamine were removed in vacuo. The residue was evaporated to dryness in vacuo twice with 100 ml of 2-propanol then washed with ether (4×50 ml) and dried in vacuo to yield 7.0 g (97.4%) of 9. Employing the procedure substantially as described in Example 3, Step A, but substituting dimethylamine for monomethylamine used therein, there is produced N-(2-aminoethyl)-N'-cyano-N"-dimethylguanidine. Step B: Preparation of N-Cyano-N'-[2-[3-(2-cyanophenoxy)-2-hydroxypropylamino]ethyl]-N"-methylguanidine, (8) The amine 6 (2.12 g, 15 mmole) in 2-propanol (30 ml) was heated to 40° C. and then the epoxide 7 (2.63 g, 15 mmole) in a mixture of 2-propanol (20 ml) and toluene (10 ml) was added dropwise to this solution. The reaction mixture was stirred at 40° C. for 6 hours. The solvent was removed in vacuo and the product was purified on a silica gel column using CHCl 3 -CH 3 OH-H 2 O (70-30-3 v:v:v) as the eluent to yield 2.75 g (58%) of product 8; m.p. 128°-130° C. Analysis satisfactory for C 15 H 20 N 6 O 2 .1/4H 2 O. EXAMPLE 4 N-Cyano-N'-[2-[3-(2-cyanophenoxy)-2-hydroxypropylamino]ethyl-N",N"-dimethylguanidine Following the same procedure as in Example 3, Step B, the title compound was obtained in 4.5% yield by using N-(2-aminoethyl)-N'-cyano-N"-dimethylguanidine in place of N-(2-aminoethyl)-N'-cyano-N"-methylguanidine. EXAMPLE 5 [[2-[[3-(2-Cyanophenoxy)-2-hydroxypropyl]amino]ethyl]-amino](methylamino)methylene urea, (10) ##STR13## Step A: Preparation of N'-carbamoyl-S,N"-dimethylisothiourea, (9) (CH 3 NH) (CH 3 S)C=NCN, 5, (3.23 g, 25 mmole) was dissolved in a mixture of H 2 O (50 ml) and concentrated HCl (100 ml) and stirred overnight at room temperature. Another 50 ml concentrated HCl was added to the suspension and the mixture was stirred at room temperature for an additional 2 days. The aqueous solution was extracted with CHCl 3 (2×100 ml) and evaporated to dryness in vacuo to yield 4.4 g (95.6%) of 9. Step B: Preparation of [[2-[[3-(2-cyanophenoxy-2-hydroxypropyl]amino]ethyl]amino](methylamino)-methylene urea dihydrochloride, (10) Compounds 1 (2.35 g, 10 mmole) and 9 (1.83 g, 10 mmole) were dissolved in 2-propanol (25 ml) and stirred overnight at room temperature. The solvent was removed in vacuo and the product purified on a silica gel 60 column using CH 2 Cl 2 -CH 3 OH-H 2 O (80-20-2 v:v:v) as the eluent to yield 0.9 g (24.3%) of product 10; m.p. 170° C. (dec.). Analysis satisfactory for C 15 H 22 N 6 O 3 .2HCl.11/2H 2 O. EXAMPLE 6 N-[Cyanoimino-[[2-[[3-(2-cyanophenoxy)-2-hydroxypropyl]amino]ethyl]amino]]methylmorpholine, (11) ##STR14## (CH 3 S) 2 C=NCN (2.19 g, 15 mmole) and morpholine (1.30 g, 15 mmole) were dissolved in 2-propanol (15 ml) and stirred at room temperature for 1 hour. The reaction mixture was diluted with 2-propanol (15 ml), heated to 45° C. and then 1 (3.53 g, 15 mmole) in 2-propanol (15 ml) was added. The reaction mixture was stirred overnight at 45° C., the solvent was removed in vacuo and the product purified on silica gel 60 using CH 2 Cl 2 -CH 3 OH-H 2 O (80-20-2 v:v:v) as the eluent. Crystallization from CH 3 CN yielded 3.05 g of impure product which was rechromatographed on silica gel 60 using CHCl 3 -CH 3 OH-H 2 O (90-10-1 v:v:v) as the eluent. Crystallization from CH 3 CN-ether yielded 1.6 g (28.7%) of product 11. Analysis satisfactory for C 18 H 24 N 6 O 3 . EXAMPLE 7 N-Cyano-N'-[2-[3-(2-cyanophenoxy)-2-hydroxypropylamino]ethyl]-N"-phenylguanidine Following the same procedure as in Example 6, the title compound was obtained by using aniline in place of morpholine. The title compound was purified by chromatography on silica gel 60 by elution with CHCl 3 -CH 3 OH-H 2 O (80-20-2 v:v:v); m.p. 146°-147° C. Analysis satisfactory for C 20 H 22 N 6 O 2 . EXAMPLE 8 N-2-[(3-(2-Cyanophenoxy)-2-hydroxypropyl)amino]-ethyl-N'-phenylthiourea ##STR15## Step A: Preparation of N-(2-Aminoethyl)-N'-phenylthiourea, (12) Compound 12 was prepared in 24% yield according to the procedure of O. Stoutland et al. [J. Org. Chem., (1959), 24 818] m.p., 131°-132°: (lit., 136°-137° C.). Step B: Preparation of N-2-[(3-(2-cyanophenoxy)-2-hydroxypropyl)amino]ethyl-N'-phenylthiourea hydrate, (13) A solution was prepared of 1.75 g (0.01 mole) of 2,3-epoxy-1-(2-cyanophenoxy)propane, 7, in 50 ml of isopropyl alcohol, assisted by gentle warming and sonication. To this was next added 2.95 g (0.01 mole) of 12 all at once. The solution was refluxed for one hour then stirred overnight at room temperature. The solution was concentrated in vacuo to 5.6 of gum, which was chromatographed over 150 g of silica gel using 10% CH 3 OH/CHCl 3 (saturated with NH 3 ) and taking 10 ml fractions. Fractions 12-41 gave 1.8 g of a foam which was found to be nonhomogeneous. This material was rechromatographed over 200 g of silica gel using the same solvent system as before and taking 10 ml cuts. Fractions 12-30 gave 400 mg (12%) of yellow sticky 13, m.p. 41°-47° C. R f =0.64 (silica gel GF, 10% CH.sub. 3 OH/CHCl 3 (NH 3 )). Mass spectrum, m/e 370 (M+); liquid chromatography showed 98% pure. Analysis satisfactory for C 19 H 22 N 4 O 2 S.1.6H 2 O. EXAMPLE 9 N-2-[(3-(2-Cyanophenoxy)-2-hydroxypropyl)amino]ethyl-N'-(3,5-dimethoxyphenyl)thiourea 0.6 hydrate, (15) ##STR16## Step A: Preparation of N-(2-Aminoethyl)-N'(3,5-dimethoxyphenyl)thiourea, (14) A slurry of 9.75 g (0.05 mole) of 3,5-dimethoxyphenyl isothiocyanate in 27 ml of ether was added dropwise to a stirred solution of 3.0 g (0.05 mole) of ethylenediamine at room temperature. A five-degree rise in temperature was noted at the start of the one hour addition period. A solid appeared during the addition, and stirring was continued for 2.5 hours. The batch was allowed to stand overnight, and 100 ml of H 2 O was added. The solid was removed by filtration and the filtrate acidified with 4.5 ml of concentrated HCl and evaporated to dryness on the steam bath. The residue was sonicated with 100 ml of water and warmed to 50° C. for 10 minutes. This was filtered and basified to pH 10 with 10% NaOH. This gave 2.6 g of 14, m.p. 125°-126° C. Analysis satisfactory for C 11 H 17 N 3 O 2 S. Step B: Preparation of N-2-[(3-(2-cyanophenoxy)-2-hydroxypropyl)amino]ethyl-N'-(3,5-dimethoxyphenyl)thiourea, (15) A solution of 1.28 g (7.3 mmoles) of 2,3-epoxy-1-(2-cyanophenoxy)propane, 7, in 30 ml of isopropyl alcohol (warmed and sonicated) was treated with 1.86 g (7.3 mmoles) of 14 all at once. This was heated under reflux for 2 hours and stirred overnight at room temperature. After this, a small amount of solid (860 mg) was removed and the solution was concentrated to 2.3 g of semi-solid gum. This was chromatographed over 150 g of silica gel 60 using 10% (v/v) CH 3 OH/CHCl 3 saturated with NH 3 . Three fractions of 150 ml each were taken after an 800-ml forerun. The third fraction provided 1.31 g of a white foam. This was chromatographed again, taking 10-ml fractions. Cuts 17, 18 and 19 provided 80 mg (2.5%) of 15, m.p., 45°-55° C. Mass spectrum, m/e 430 (M+), base peak, m/e 195. Liquid chromatography showed 93.6% purity. Analysis satisfactory for C 21 H 26 N 4 O 4 S.0.6H 2 O. EXAMPLE 10 3-Amino-5-(2-{3-[(2-cyanophenoxy)-2-hydroxypropyl]-amino}ethylamino)-1,2,4-triazine ##STR17## Step A: Preparation of 3-Amino-5-(2-amino-1-ethylamino)-1,2,4-triazine, (16) To a slurry of 3-amino-5-ethoxy-1,2,4-triazine (1.40 g, 0.0100 mol) in xylene (5 ml) was added ethylenediamine (1.00 ml, 0.0150 mol). The mixture was stirred at 120° C. for 3.5 hours, cooled, and concentrated to dryness in vacuo. The residue was stirred under ether, filtered off, and dried to give the title product, 16, (1.47 g, 95%, m.p. 186°-191° C.). TLC (20% methanol/chloroform/ammonia, silica): R f =0.14. Step B: Preparation of 3-Amino-5-(2-{3-[(2-cyanophenoxy)-2-hydroxypropyl]amino}ethylamino)-1,2,4-triazine, (17) To a solution of 3-(2-cyanophenoxy)propylene oxide (1.40 g, 0.0080 mol) in isopropanol (40 ml) was added a suspension of 3-amino-5-(2-amino-1-ethylamino)-1,2,4-triazine (1.23 g, 0.0080 mol) in isopropanol (30 ml). The resulting solution was heated at 40° C. for 18 hours. The warm mixture was then filtered and the insoluble material was washed with isopropanol (20 ml). The combined filtrate was concentrated in vacuo to leave 2.40 g of solid which was chromatographed on a column of silica gel 60 and eluted gradiently with 0-20% (v/v) methanol/chloroform followed by 20-50% methanol/chloroform saturated with ammonia. From the fraction eluted with 20% methanol/chloroform saturated with ammonia there was obtained the crude product 17 (0.47 g, 18%). The crude product was recrystallized from chloroform/ether to give the purified product, 17, (0.22 g, 8%, m.p. 115°-120° C.). Analysis satisfactory for C 15 H 19 N 7 O 2 : TLC (20% methanol/chloroform, silica): R f =0.23. EXAMPLE 11 2-[2-[[3-(2-Cyanophenoxy)-2-hydroxypropyl]amino]ethylaminopyrimidine, (18) ##STR18## The amine 1 (1.52 g, 6.46 mmole) and 2-chloropyrimidine (740 mg, 6.46 mmole) were heated at 60° C. in 2-propanol (5 ml) for 41/2 hours and then stirred at room temperature overnight. The mixture was heated at 60° C. for an additional 81/2 hours. The solvent was removed in vacuo and the product was purified by chromatography on silica gel 60 using CH 2 Cl 2 -CH 3 OH-H 2 O (70-30-3 v:v:v) as the eluent to yield 870 mg (43%) of 18, m.p. 126°-128° C. Analysis satisfactory for C 16 H 19 N 5 O 2 .1.5H 2 O. Following the procedures of the foregoing examples employing appropriate starting materials, there are produced the following compounds. __________________________________________________________________________ ##STR19##R.sup.1 R.sup.2 R.sup.3 n Y__________________________________________________________________________H H F 1 ##STR20##HO H H 2 ##STR21##HOCH.sub.2 H H 3 ##STR22##H HO H 4 ##STR23##H H H.sub.2 N 5 ##STR24##H (CH.sub.3).sub.2 N H 6 ##STR25##H CH.sub.3 CH.sub.3 NH 7 ##STR26##H O.sub.2 N C.sub.2 H.sub.5 8 ##STR27##H CH.sub.3 O CH.sub.3 1 ##STR28##H H C.sub.2 H.sub.5 2 ##STR29##H n-C.sub.3 H.sub.7 H 2 ##STR30##H H n-C.sub.6 H.sub.13 2 ##STR31##H c-C.sub.3 H.sub.5 CH.sub.3 2 ##STR32##H H c-C.sub.6 H.sub.11 2 ##STR33##H CH.sub.3CHCH H 2 ##STR34##H H CH.sub.3 O 2 ##STR35##H (CH.sub.3).sub.2 CHO H 1 ##STR36##H H C.sub.2 H.sub.5 S 2 ##STR37##H CH.sub.3 CHCHO H 3 ##STR38##H H ##STR39## 4 ##STR40## ##STR41## H 5 ##STR42##__________________________________________________________________________ ______________________________________INGREDIENT AMOUNT (Mg.)______________________________________TABLET FORMULATION I3-Methylamino-4[[2-[3-(2-cyano- 40.0phenoxy)-2-hydroxypropylamino]-ethyl]amino]-1,2,5-thiadiazole-1-oxidecalcium phosphate 120.0CAPSULE FORMULATION[[2-[[3-(2-Cyanophenoxy)-2-hydroxy- 250propyl]amino]ethyl]amino](methyl-amino)methylene urealactose, U.S.P. 93talc 7INJECTABLE SOLUTIONN--[Cyanoimino-[[2-[[3-(2-cyano- 5phenoxy)-2-hydroxypropyl]amino]-ethyl]amino]]methylmorpholinesodium chloride 9distilled water, q.s. 1.0 ml.LIQUID SUSPENSIONN--2-[(3-(2-Cyanophenoxy)-2-hydroxy- 5.0propyl)amino]ethyl -N'--phenylthio-urea 1.6 hydrateVeegum H.V. 3.0methyl paraben 1.0kaolin 10.0glycerin 250.0water, q.s. 1 liter______________________________________
1-Aryloxy-3-(substituted aminoalkylamino)-2-propanols and pharmaceutically acceptable salts thereof have β-adrenergic blocking activity with some cardioselectivity and hence are useful as antihypertensive, antianginal, antiarrhythmic and cardioprotective agents and in the treatment of elevated intraocular pressure such as glaucoma.
21,920
CROSS-REFERENCE TO RELATED PATENT APPLICATION The present application claims priority under 35 USC section 119(e) to U.S. Provisional application Ser. No. 60/384,478, filed May 31, 2002, which is incorporated by reference herein as if fully set forth. BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to a process for preparing polycyclic xanthine phosphodiesterase V (“PDE V”) inhibitors. The invention further relates to compounds useful for preparing PDE V inhibitors. 2. Background Processes for preparing PDE V inhibitor compounds can be found in U.S. Pat. Nos. 6,207,829, 6,066,735, 5,955,611, 5,939,419, 5,393,755, 5,409,934, 5,470,579, 5,250,534, WO 02/24698, WO 99/24433, WO 93/23401, WO 92/05176, WO 92/05175, EP 740,668 and EP 702,555. One type of PDE V inhibitor compound contains a xanthine functionality in its structure. Xanthines can be prepared as described by Peter K. Bridson and Xiaodong Wang in 1-Substituted Xanthines, Synthesis, 855 (July, 1995), which is incorporated herein by reference in its entirety. WO 02/24698, which is incorporated herein by reference in its entirety, teaches a class of xanthine PDE V inhibitor compounds useful for the treatment of impotence. A general process disclosed therein for preparing xanthine PDE V inhibitor compounds having the formula (I) follows: (i) reacting a compound having the formula (III) with an alkyl halide in the presence of a base (introduction of R II or a protected form of R II ); (ii) (a) debenzylating and then (b) alkylating the compound resulting from step (i) with an alkyl halide, XCH 2 R III ; (iii) (a) deprotonating and then (b) halogenating the compound resulting from step (ii); (iv) reacting the compound resulting from step (iii) with an amine having the formula R IV NH 2 ; and (v) removing a protecting portion of R II , if present, on the compound resulting from step (iv) to form the compound having the formula (I). R I , R II , R III and R IV correspond to R 1 , R 2 , R 3 and R 4 , respectively, in WO 02/24698, and are defined therein. WO 02/24698 (pages 44 and 68–73) also teaches a synthesis for the following xanthine compound (identified therein as Compound 13 or Compound 114 of Table II): 1-ethyl-3,7-dihydro-8-[(1R,2R)-(hydroxycyclopentyl)amino]-3-(2-hydroxyethyl)-7-[(3-bromo-4-methoxyphenyl)methyl]-1H-purine-2,6-dione: It would be beneficial to provide an improved process for preparing polycyclic xanthine PDE V inhibitor compounds. It would further be beneficial if the process provided high yields without the need for chromatographic purification. It would still further be beneficial if the process provided compounds of high thermodynamic stability. It would be still further beneficial to provide intermediate compounds that can be used in the improved process. The invention seeks to provide these and other benefits, which will become apparent as the description progresses. SUMMARY OF THE INVENTION One aspect of the invention is a method for preparing a Compound 13, comprising: (a) reacting glycine ethyl ester or a salt thereof with  wherein Et is CH 3 CH 2 —, (b) reducing to form a Compound 1: (c) reacting cyanamide with an excess of triethylorthoformate to form a Compound 2: (d) reacting the Compound 2 with the Compound 1 to form a Compound 3: (e) reacting the Compound 3 with a base to form a Compound 4: (f) reacting the Compound 4 with R 2 NHCO 2 R 1 in the presence of a metallic base to form a Compound Salt 5K:  wherein M + is a metal ion, (g) optionally, reacting the Compound Salt 5K with an acid to form a Compound 5: (h) reacting the Compound Salt 5K or the Compound 5 with BrCH 2 L in the presence of a phase transfer catalyst to form a Compound 6: wherein L is R 3 or a protected form of R 3 comprising R 3 with a protective substituent selected from the group consisting of acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 and —SC(O)R 5 group, wherein R 5 is H or C 1-12 alkyl; (i) dihalogenating the Compound 6 to form a Compound 7: (j) reacting the Compound 7 with R 4 NH 2 , and adding a base thereto, to form a Compound 9: (k) (i) when L is R 3 , the Compound 9 is a Compound 13, and (ii) when L is a protected form of R 3 , reacting the Compound 9 with a base to form the Compound 13: wherein, R 1 , R 2 and R 3 are each independently selected from the group consisting of: H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, allyl, —OR 5 , —C(O)OR 5 , —C(O)R 5 , —C(O)N(R 5 ) 2 , —NHC(O)R 5 and —NHC(O)OR 5 , wherein each R 5 is independently H or alkyl; provided that R 2 and R 3 are not both —H; R 4 is an alkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl group; wherein R 1 , R 2 , R 3 and R 4 are optionally substituted with one or more moieties independently selected from the group consisting of: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl, heterocycloalkyl, halo, thio, nitro, oximino, acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 or —SC(O)R 5 , —OR 50 , —NR 50 OR 51 , —C(O)OR 50 , —C(O)R 50 , —SO 0-2 R 50 , —SO 2 NR 50 R 51 , —NR 52 SO 2 R 50 , ═C(R 50 R 51 ), ═NOR 50 , ═NCN, ═C(halo) 2 , ═S, ═O, —C(O)N(R 50 R 51 ), —OC(O)R 50 , —OC(O)N(R 50 R 51 ), —N(R 52 )C(O)(R 50 ), —N(R 52 )C(O)OR 50 and —N(R 52 )C(O)N(R 50 OR 51 ), wherein each R 5 is independently H or alkyl and R 50 , R 51 and R 52 are each independently selected from the group consisting of: H, alkyl, cycloalkyl, heterocycloalkyl, heteroaryl and aryl, and when chemically feasible, R 50 and R 51 can be joined together to form a carbocyclic or heterocyclic ring; Et is CH 3 CH 2 —; Hal is a halogen group; and L is a protected form of R 3 comprising R 3 with a protective substituent selected from the group consisting of acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 and —SC(O)R 5 group, wherein R 5 is H or C 1-12 alkyl. A further understanding of the invention will be had from the following detailed description of the invention. DETAILED DESCRIPTION Definitions and Usage of Terms The following definitions and terms are used herein or are otherwise known to a skilled artisan. Except where stated otherwise, the definitions apply throughout the specification and claims. Chemical names, common names and chemical structures may be used interchangeably to describe the same structure. These definitions apply regardless of whether a term is used by itself or in combination with other terms, unless otherwise indicated. Hence, the definition of “alkyl” applies to “alkyl” as well as the “alkyl” portions of “hydroxyalkyl,” “haloalkyl,” “alkoxy,” etc. Unless otherwise known, stated or shown to be to the contrary, the point of attachment for a multiple term substituent (two or more terms that are combined to identify a single moiety) to a subject structure is through the last named term of the multiple term substituent. For example, a cycloalkylalkyl substituent attaches to a targeted structure through the latter “alkyl” portion of the substituent (e.g., structure-alkyl-cycloalkyl). The identity of each variable appearing more than once in a formula may be independently selected from the definition for that variable, unless otherwise indicated. Unless stated, shown or otherwise known to be the contrary, all atoms illustrated in chemical formulas for covalent compounds possess normal valencies. Thus, hydrogen atoms, double bonds, triple bonds and ring structures need not be expressly depicted in a general chemical formula. Double bonds, where appropriate, may be represented by the presence of parentheses around an atom in a chemical formula. For example, a carbonyl functionality, —CO—, may also be represented in a chemical formula by —C(O)— or —C(═O)—. Similarly, a double bond between a sulfur atom and an oxygen atom may be represented in a chemical formula by —SO—, —S(O)— or —S(═O)—. One skilled in the art will be able to determine the presence or absence of double (and triple bonds) in a covalently-bonded molecule. For instance, it is readily recognized that a carboxyl functionality may be represented by —COOH, —C(O)OH, —C(═O)OH or —CO 2 H. The term “substituted,” as used herein, means the replacement of one or more atoms or radicals, usually hydrogen atoms, in a given structure with an atom or radical selected from a specified group. In the situations where more than one atom or radical may be replaced with a substituent selected from the same specified group, the substituents may be, unless otherwise specified, either the same or different at every position. Radicals of specified groups, such as alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups, independently of or together with one another, may be substituents on any of the specified groups, unless otherwise indicated. The term “optionally substituted” means, alternatively, not substituted or substituted with the specified groups, radicals or moieties. It should be noted that any atom with unsatisfied valences in the text, schemes, examples and tables herein is assumed to have the hydrogen atom(s) to satisfy the valences. The term “chemically-feasible” is usually applied to a ring structure present in a compound and means that the ring structure (e.g., the 4- to 7-membered ring, optionally substituted by . . . ) would be expected to be stable by a skilled artisan. The term “heteroatom,” as used herein, means a nitrogen, sulfur or oxygen atom. Multiple heteroatoms in the same group may be the same or different. As used herein, the term “alkyl” means an aliphatic hydrocarbon group that can be straight or branched and comprises 1 to about 24 carbon atoms in the chain. Preferred alkyl groups comprise 1 to about 15 carbon atoms in the chain. More preferred alkyl groups comprise 1 to about 6 carbon atoms in the chain. “Branched” means that one or more lower alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkyl chain. The alkyl can be substituted by one or more substituents independently selected from the group consisting of halo, aryl, cycloalkyl, cyano, hydroxy, alkoxy, alkylthio, amino, —NH(alkyl), —NH(cycloalkyl), —N(alkyl) 2 (which alkyls can be the same or different), carboxy and —C(O)O-alkyl. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, heptyl, nonyl, decyl, fluoromethyl, trifluoromethyl and cyclopropylmethyl. “Alkenyl” means an aliphatic hydrocarbon group (straight or branched carbon chain) comprising one or more double bonds in the chain and which can be conjugated or unconjugated. Useful alkenyl groups can comprise 2 to about 15 carbon atoms in the chain, preferably 2 to about 12 carbon atoms in the chain, and more preferably 2 to about 6 carbon atoms in the chain. The alkenyl group can be substituted by one or more substituents independently selected from the group consisting of halo, alkyl, aryl, cycloalkyl, cyano and alkoxy. Non-limiting examples of suitable alkenyl groups include ethenyl, propenyl, n-butenyl, 3-methylbut-enyl and n-pentenyl. Where an alkyl or alkenyl chain joins two other variables and is therefore bivalent, the terms alkylene and alkenylene, respectively, are used. “Alkoxy” means an alkyl-O— group in which the alkyl group is as previously described. Useful alkoxy groups can comprise 1 to about 12 carbon atoms, preferably 1 to about 6 carbon atoms. Non-limiting examples of suitable alkoxy groups include methoxy, ethoxy and isopropoxy. The alkyl group of the alkoxy is linked to an adjacent moiety through the ether oxygen. The term “cycloalkyl” as used herein, means an unsubstituted or substituted, saturated, stable, non-aromatic, chemically-feasible carbocyclic ring having preferably from three to fifteen carbon atoms, more preferably, from three to eight carbon atoms. The cycloalkyl carbon ring radical is saturated and may be fused, for example, benzofused, with one to two cycloalkyl, aromatic, heterocyclic or heteroaromatic rings. The cycloalkyl may be attached at any endocyclic carbon atom that results in a stable structure. Preferred carbocyclic rings have from five to six carbons. Examples of cycloalkyl radicals include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or the like. The term “hydrocarbon,” as used herein, means a compound, radical or chain consisting of only carbon and hydrogen atoms, including aliphatic, aromatic, normal, saturated and unsaturated hydrocarbons. The term “alkenyl,” as used herein, means an unsubstituted or substituted, unsaturated, straight or branched, hydrocarbon chain having at least one double bond present and, preferably, from two to fifteen carbon atoms, more preferably, from two to twelve carbon atoms. The term “cycloalkenyl,” as used herein, means an unsubstituted or substituted, unsaturated carbocyclic ring having at least one double bond present and, preferably, from three to fifteen carbon atoms, more preferably, from five to eight carbon atoms. A cycloalkenyl goup is an unsaturated carbocyclic group. Examples of cycloalkenyl groups include cyclopentenyl and cyclohexenyl. “Alkynyl” means an aliphatic hydrocarbon group comprising at least one carbon-carbon triple bond and which may be straight or branched and comprising about 2 to about 15 carbon atoms in the chain. Preferred alkynyl groups have about 2 to about 10 carbon atoms in the chain; and more preferably about 2 to about 6 carbon atoms in the chain. Branched means that one or more lower alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkynyl chain. Non-limiting examples of suitable alkynyl groups include ethynyl, propynyl, 2-butynyl, 3-methylbutynyl, n-pentynyl, and decynyl. The alkynyl group may be substituted by one or more substituents which may be the same or different, each substituent being independently selected from the group consisting of alkyl, aryl and cycloalkyl. The term “aryl,” as used herein, means a substituted or unsubstituted, aromatic, mono- or bicyclic, chemically-feasible carbocyclic ring system having from one to two aromatic rings. The aryl moiety will generally have from 6 to 14 carbon atoms with all available substitutable carbon atoms of the aryl moiety being intended as possible points of attachment. Representative examples include phenyl, tolyl, xylyl, cumenyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, or the like. If desired, the carbocyclic moiety can be substituted with from one to five, preferably, one to three, moieties, such as mono- through pentahalo, alkyl, trifluoromethyl, phenyl, hydroxy, alkoxy, phenoxy, amino, monoalkylamino, dialkylamino, or the like. “Heteroaryl” means a monocyclic or multicyclic aromatic ring system of about 5 to about 14 ring atoms, preferably about 5 to about 10 ring atoms, in which one or more of the atoms in the ring system is/are atoms other than carbon, for example nitrogen, oxygen or sulfur. Mono- and polycyclic (e.g., bicyclic) heteroaryl groups can be unsubstituted or substituted with a plurality of substituents, preferably, one to five substituents, more preferably, one, two or three substituents (e.g., mono- through pentahalo, alkyl, trifluoromethyl, phenyl, hydroxy, alkoxy, phenoxy, amino, monoalkylamino, dialkylamino, or the like). Typically, a heteroaryl group represents a chemically-feasible cyclic group of five or six atoms, or a chemically-feasible bicyclic group of nine or ten atoms, at least one of which is carbon, and having at least one oxygen, sulfur or nitrogen atom interrupting a carbocyclic ring having a sufficient number of pi (π) electrons to provide aromatic character. Representative heteroaryl (heteroaromatic) groups are pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, furanyl, benzofuranyl, thienyl, benzothienyl, thiazolyl, thiadiazolyl, imidazolyl, pyrazolyl, triazolyl, isothiazolyl, benzothiazolyl, benzoxazolyl, oxazolyl, pyrrolyl, isoxazolyl, 1,3,5-triazinyl and indolyl groups. The term “heterocycloalkyl,” as used herein, means an unsubstituted or substituted, saturated, chemically-feasible cyclic ring system having from three to fifteen members, preferably, from three to eight members, and comprising carbon atoms and at least one heteroatom as part of the ring. The term “heterocyclic ring” or “heterocycle,” as used herein, means an unsubstituted or substituted, saturated, unsaturated or aromatic, chemically-feasible ring, comprised of carbon atoms and one or more heteroatoms in the ring. Heterocyclic rings may be monocyclic or polycyclic. Monocyclic rings preferably contain from three to eight atoms in the ring structure, more preferably, five to seven atoms. Polycyclic ring systems consisting of two rings preferably contain from six to sixteen atoms, most preferably, ten to twelve atoms. Polycyclic ring systems consisting of three rings contain preferably from thirteen to seventeen atoms, more preferably, fourteen or fifteen atoms. Each heterocyclic ring has at least one heteroatom. Unless otherwise stated, the heteroatoms may each be independently selected from the group consisting of nitrogen, sulfur and oxygen atoms. The term “carbocyclic ring” or “carbocycle,” as used herein, means an unsubstituted or substituted, saturated, unsaturated or aromatic (e.g., aryl), chemically-feasible hydrocarbon ring, unless otherwise specifically identified. Carbocycles may be monocyclic or polycyclic. Monocyclic rings, preferably, contain from three to eight atoms, more preferably, five to seven atoms. Polycyclic rings having two rings, preferably, contain from six to sixteen atoms, more preferably, ten to twelve atoms, and those having three rings, preferably, contain from thirteen to seventeen atoms, more preferably, fourteen or fifteen atoms. The term “hydroxyalkyl,” as used herein, means a substituted hydrocarbon chain preferably an alkyl group, having at least one hydroxy substituent (-alkyl-OH). Additional substituents to the alkyl group may also be present. Representative hydroxyalkyl groups include hydroxymethyl, hydroxyethyl and hydroxypropyl groups. The terms “Hal,” “halo,” “halogen” and “halide,” as used herein, mean a chloro, bromo, fluoro or iodo atom radical. Chlorides, bromides and fluorides are preferred halides. The term “thio,” as used herein, means an organic acid radical in which divalent sulfur has replaced some or all of the oxygen atoms of the carboxyl group. Examples include —R 53 C(O)SH, —R 53 C(S)OH and —R 53 C(S)SH, wherein R 53 is a hydrocarbon radical. The term “nitro,” as used herein, means the —N(O) 2 radical. The term “allyl,” as used herein, means the —C 3 H 5 radical. The term “phase transfer catalyst,” as used herein, means a material that catalyzes a reaction between a moiety that is soluble in a first phase, e.g., an alcohol phase, and another moiety that is soluble in a second phase, e.g., an aqueous phase. The following abbreviations are used in this application: EtOH is ethanol; Me is methyl; Et is ethyl; Bu is butyl; n-Bu is normal-butyl, t-Bu is tert-butyl, OAc is acetate; KOt-Bu is potassium tert-butoxide; NBS is N-bromo succinimide; NMP is 1-methyl-2-pyrrolidinone; DMA is N,N-dimethylacetamide; n-BU 4 NBr is tetrabutylammonium bromide; n-Bu 4 NOH is tetrabutylammonium hydroxide, n-Bu 4 NH 2 SO 4 is tetrabutylammonium hydrogen sulfate, and equiv. is equivalents. In certain of the chemical structures depicted herein, certain compounds are racemic, i.e., a mixture of dextro- and levorotatory optically active isomers in equal amounts, the resulting mixture having no rotary power. General Synthesis One aspect of the invention comprises a general synthesis of xanthines based on a one-pot, five-step sequence from cyanamide and N-aryl glycine ester. Compound 1 can be prepared from glycine ethyl ester or a salt thereof (e.g., hydrochloric or sulfuric acid salt) and an aromatic aldehyde. As shown in Scheme I below, Compound 1 is prepared from glycine ethyl ester hydrochloride and an aromatic aldehyde. Compound 2 is prepared by reacting cyanamide with an excess of triethylorthoformate. Compound 3 is prepared by reacting Compound 2 with Compound 1. Compound 3 is converted into Compound 4 by reacting it with a base (e.g., potassium tert-butoxide). Compound 4 is reacted with a N—R 2 -substituted carbamate (e.g., urethane) in the presence of a base to obtain Compound Salt 5K. Based on the N—R 2 -substituent of the carbamate used, a desired N-1-R 2 -substituted xanthine Compound Salt 5K is obtained. Compound Salt 5K is then N-3-L-substituted with an L-halide using a phase transfer catalyst to provide a tri-substituted (R 1 , R 2 and L) xanthine Compound 6. Alternatively, Compound Salt 5K can be neutralized to Compound 5, which can then be selectively N-L-substituted to provide Compound 6. A selective dihalogenation of Compound 6 leads to a dihalo Compound 7, which is then coupled with an R 4 -substituted amine, followed by an addition of a base (e.g., sodium bicarbonate), to provide a tetrasubstituted (R 1 , R 2 , R 3 and R 4 ) xanthine Compound 13 when L is the same as R 3 . If L is a protected form of R 3 , intermediate Compound 9 is deprotected with a base (e.g., tetrabutylammonium hydroxide) to provide the tetrasubstituted (R 1 , R 2 , R 3 and R 4 ) xanthine Compound 13. Scheme I depicts this process: wherein, R 1 , R 2 and R 3 are each independently selected from the group consisting of: H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, allyl, —OR 5 , —C(O)OR 5 , —C(O)R 5 , —C(O)N(R 5 ) 2 , —NHC(O)R 5 and —NHC(O)OR 5 , wherein each R 5 is independently H or alkyl; provided that R 2 and R 3 are not both —H; R 4 is an alkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl group; wherein R 1 , R 2 , R 3 and R 4 are optionally substituted with moieties independently selected from the group consisting of: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl, heterocycloalkyl, halo, thio, nitro, oximino, acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 or —SC(O)R 5 , —OR 50 , —NR 50 R 51 , —C(O)OR 50 , —C(O)R 50 , —SO 0-2 R 50 , —SO 2 NR 50 R 51 , —NR 52 SO 2 R 50 , ═C(R 50 R 51 ), ═NOR 50 , ═NCN, ═C(halo) 2 , ═S, ═O, —C(O)N(R 50 R 51 ), —OC(O)R 50 , —OC(O)N(R 50 R 51 ), —N(R 52 )C(O)(R 50 ), —N(R 52 )C(O)OR 50 and —N(R 52 )C(O)N(R 50 R 51 ), wherein each R 5 is independently H or alkyl and R 50 , R 51 and R 52 are each independently selected from the group consisting of: H, alkyl, cycloalkyl, heterocycloalkyl, heteroaryl and aryl; Hal is a halogen group; L is R 3 or a protected form of R 3 comprising R 3 with a protective substituent selected from the group consisting of acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 and —SC(O)R 5 group, wherein R 5 is H or alkyl; and M + is a metal ion. While some compounds are shown in Scheme I as non-isolated intermediates, it is understood that they can be isolated using routine chemistry techniques. Preferred embodiments of the invention utilize compounds with the following R 1 , R 2 , R 3 and R 4 radicals: R 1 is preferably alkyl, aryl, heteroaryl, —OR 5 , —C(O)OR 5 , —C(O)R 5 or —C(O)N(R 5 ) 2 , wherein R 5 is H or alkyl. Each R 1 group is optionally substituted as defined above. More preferably, R 1 is —OR 5 , wherein R 5 is H or alkyl. Even more preferably, R 1 is alkoxy, such as methoxy. R 2 is preferably C 1-12 alkyl, C 3-8 cycloalkyl, aryl or heteroaryl. Each R 2 group is optionally substituted as defined above. More preferably, R 2 is C 1-6 alkyl, optionally substituted as defined above. Even more preferably, R 2 is ethyl. R 3 is preferably C 1-12 alkyl, C 3-8 cycloalkyl, aryl, heteroaryl, allyl, —NHC(O)R 5 or —NHC(O)OR 5 , wherein R 5 is H or C 1-12 alkyl. Each R 3 group is optionally substituted as defined above. More preferably, R 3 is C 1-6 alkyl, optionally substituted with one of the groups defined above. Even more preferably, R 3 is C 1-6 alkyl, substituted with —OR 50 , wherein R 50 is H, such as hydroxymethyl. R 4 is preferably C 1-12 alkyl, C 3-8 cycloalkyl, C 5-8 cycloalkenyl, heterocycloalkyl, aryl or heteroaryl. Each R 4 group is optionally substituted as defined above. More preferably, R 4 is C 3-8 cycloalkyl, optionally substituted as defined above. Even more preferably, R 4 is C 4-7 cycloalkyl, substituted with —OR 50 , wherein R 50 is defined as above. For example, R 4 can be 2-hydroxy cyclopentyl. In some embodiments of the invention, L is the same as R 3 . In other embodiments of the invention, L is a protected form of R 3 , in which case the protective substituent on R 3 is preferably an acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 or —SC(O)R 5 group, wherein R 5 is H or C 1-12 alkyl. Hal is preferably chlorine, bromine and fluorine. More preferably, Hal is chlorine or bromine. Even more preferably, Hal is bromine. M + is, preferably, an alkali metal or alkaline earth metal ion. More preferably, M + is a potassium or sodium ion. Compound 1 can be prepared by reacting about equimolar amounts of p-anisaldehyde and glycine ethyl ester hydrochloride (or its free form) in the presence of a base (e.g., potassium carbonate, sodium carbonate, sodium bicarbonate, potassium butoxide, or the like) and in an alcoholic solvent (e.g., ethanol, isopropanol, or the like). Preferably, up to about 2 moles (e.g., about 1.3–1.5 moles) of glycine ethyl ester hydrochloride and up to about 2 moles (e.g., about 1 mole) of inorganic salt can each be used per mole of p-anisaldehyde. The reaction proceeds through an intermediate imine (not shown), which is reduced with a reducing agent (e.g., NaBH 4 , catalytic hydrogenation, H 2 /Pd/C, or the like), preferably, a borohydride reducing agent. The reaction can be run at room temperature. Preferably, the reaction is run at about 20–45° C., more preferably, about 30–40° C. At the end of the reaction, Compound 1 is isolated in a solution form in an organic solvent (e.g., toluene), and used as such for the next step. Compound 2 is N-cyanomethanimidic acid ethyl ester, and is prepared by reacting cyanamide with an excess of triethylorthoformate. Preferably, from about 1.2 to about 1.5 moles of triethylorthoformate (e.g., 1.33 moles) are reacted with about 1 mole of cyanamide. Preferably, the reaction mixture is gradually heated up to about 85–95° C. for about 2 hours. Compound 2 is not isolated, and is used in-situ for the next step. The structure of Compound 3 is novel. An equimolar reaction mixture of Compound 2 (obtained in-situ above) is added to a solution of Compound 1 in an anhydrous, ethereal organic solvent (e.g., tetrahydrofuran (“THF”), diethyl ether, monoethyl ether, monoglyme, diglyme, ethylene glycol, or the like), and heated to about 65–70° C. for about 1 hour. About 1.1 to about 1.3 moles (e.g., 1.2 moles) of Compound 2 is used per mole of Compound 1. At the end of the reaction, the product is not isolated, and is used in-situ for the next step. The structure of Compound 4 is novel. Compound 4 is prepared by reacting Compound 3 (obtained in-situ above) with a base (e.g., potassium tert-butoxide, potassium pentoxide, potassium tert-amylate, sodium ethoxide, sodium tert-butoxide, or the like) in an alcoholic solvent (e.g., anhydrous EtOH). A catalytic amount of base is preferably used, generally, about 5–20 mol % per mol of Compound 3 in the alcoholic solvent. More preferably, about 15 mol % of base is used. Preferably, the reaction mixture is heated to about 75–85° C. for about 1 hour. At the end of reaction, the product is not isolated, and is used in-situ for the next step. The structure of Compound Salt 5K is novel. Compound 4 can be converted to Compound Salt 5K by reacting it in-situ with from about 1 to about 3 moles (e.g., 1.5 moles) of a N—R 2 -substituted carbamate, R 2 NHCO 2 R 1 (e.g., the urethane EtNHCO 2 Et), and from about 1 to about 3 moles (e.g., 2.1 moles) of a base (e.g., potassium tert-butoxide, potassium pentoxide, potassium tert-amylate, sodium ethoxide, sodium tert-butoxide, or the like), in an ethereal organic solvent (e.g., THF, diethyl ether, monoethyl ether, monoglyme, diglyme, ethylene glycol, or the like) or a sulfolane, at 80–130° C. (preferably 115–125° C.), wherein R 1 and R 2 are each independently defined as above. The base provides a metal ion (M + ) to Compound Salt 5K. Potassium tert-butoxide provides a potassium ion (K + ), while sodium tert-butoxide provides a sodium ion (Na + ) to Compound Salt 5K. The inventive methodology provides an efficient synthesis for directly converting (in one step) Compound 4 to Compound Salt 5K in solution without the use of any toxic chemicals or harsh thermal conditions. The potassium Compound Salt 5K is isolated by filtration, but not dried. Compound Salt 5K is selectively N-3 alkylated in-situ to Compound 6 with BrCH 2 -L (e.g., 2-bromoethyl acetate in an anhydrous, organic solvent (e.g., THF, methyl tert-butyl ether, or the like) in the presence of a phase transfer catalyst (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, or the like), wherein L is defined as above. The reaction takes place rapidly (e.g., about 1 hour at about 65–70° C.), and no base is required. This is in contrast to known N-alkylation reactions, many of which use dimethylformamide (“DMF”) and potassium carbonate or an organic base (e.g., triethylamine, diisopropylethylamine, etc.) to achieve the N-alkylation, and which generally take from several hours to days to complete. Alternatively, the potassium Compound Salt 5K can be neutralized with an acid (e.g., aqueous acetic acid, dilute hydrochloric acid, dilute sulfuric acid, or the like) to provide Compound 5. Under this alternative process, Compound 5 can be selectively N-3 alkylated by treatment with an inorganic base (e.g., potassium carbonate, sodium carbonate, sodium bicarbonate, potassium butoxide, or the like) in a polar solvent (e.g., acetonitrile and its higher homologs, DMF, N,N-dimethylacetamide (“DMA”), 1-methyl-2-pyrrolidinone (“NMP”), or the like) in the presence of a phase transfer catalyst (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, or the like) and an alkylating agent (e.g., BrCH 2 -L, where L is defined as above) to provide Compound 6. The structure of Compound 6 is novel. The conversion from Compound 1 to Compound 6 is a 5-step process that can be carried out in one pot or container. The overall yield for Compound 6 is generally about 45–55%. The structure of Compound 7 is novel. Compound 6 is regioselectively dihalogenated (e.g., dibrominated or dichlorinated) to Compound 7 under mild conditions with about 2–3 moles (preferably, about 2.7–2.8 moles) of a dihalogenating agent (e.g., a dibrominating agent, such as N-bromo succinimide (“NBS”), dibromo-1,3-dimethyl hydantoin or N-bromo acetamide). The use of a strong acid (e.g., triflic or sulfuric acid) as a catalyst in an amount of about 1–10 mol %, preferably, about 3 mol %, allows the reaction to proceed at room temperature. Alternatively, tetrabutylammonium hydrogensulfate can be used as the catalyst, but it would require an application of heat (e.g., about 80° C.) to drive the reaction to completion. It is preferred that the reaction is run in a dry polar solvent, such as acetonitrile, DMF, NMP, DMA, or a mixture thereof. Under these conditions, the amounts of mono- and tri-bromo side products are minimized. Compound 7 is coupled with Compound 8 (an R 4 NH 2 amine) to form Compound 13 via Compound 9, a novel intermediate. Typical coupling reaction conditions for this step generally require the use of a polar, aprotic solvent (e.g., NMP, DMA, or the like), an inorganic base (e.g., potassium carbonate, sodium carbonate, sodium bicarbonate, or the like), and an excess of Compound 8, preferably, up to about 3 moles of Compound 8 per mole of Compound 7. A preferred mild, inorganic base is sodium bicarbonate. The application of heat will drive the reaction to completion faster. For example, at about 130–140° C., the reaction time can be shortened in half, from about 24 hours to about 12 hours. L is R 3 or a protected form of R 3 (i.e., where a moiety is attached to R 3 for protecting it from reacting with other ingredients). When L is the same as R 3 , Compound 9 is the same as Compound 13, so the addition of an inorganic base to the intermediate Compound 9 (step (k) (ii) of the summary of the invention) is not necessary. On the other hand, when L is a protected form of R 3 , deprotection can be accomplished in the same pot, without isolating Compound 9, by using a catalytic amount of an inorganic base (e.g., potassium carbonate, tetrabutylammonium hydroxide, or the like). Protected forms of R 3 include R 3 moieties substituted with protective groups such as acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 or —SC(O)R 5 groups, wherein R 5 is H or C 1-12 alkyl. When the protecting substituent is an acetate group, deprotection is preferably carried out with tetrabutylammonium hydroxide because it results in a faster and cleaner reaction, and product isolation is facile. In another embodiment of the invention, a pivaloyl protecting group can be used in place of the acetate protecting group, and the application of similar chemistry will lead from Compound 5K (or Compound 5) to Compound 13. The deprotection and work-up conditions are adjusted so as to minimize formation of isomeric impurities. For instance, care should be taken to monitor the basicity of the reaction during deprotection because when the deprotection steps are carried out under very strong basic conditions, diastereomers may form. Specific Synthesis The general synthesis of Scheme I can be applied to prepare specific xanthines. For example, if R 1 is —OCH 3 , R 2 is —CH 2 CH 3 , L is —CH 2 CO 2 CH 3 , R 3 is —CH 2 OH, and R 4 is then the product obtained from Scheme I (Compound 13) can be called 1-ethyl-3,7-dihydro-8-[(1R,2R)-(hydroxycyclopentyl)amino]-3-(2-hydroxyethyl)-7-[(3-bromo-4-methoxyphenyl)methyl]-1H-purine-2,6-dione (Compound 13A), a PDE V inhibitor useful for the treatment of erectile dysfunction. An illustration of this synthesis is shown in the following Scheme II, which allows for an efficient, commercial scale preparation of Compound 13A, without the need for chromatographic purification of intermediates: The experimental conditions disclosed herein are preferred conditions, and one of ordinary skill in the art can modify them as necessary to achieve the same products. EXAMPLES Compound 1A: glycine-N-[(4-methoxyphenyl)methyl] ethyl ester To a mixture of glycine ethyl ester hydrochloride (about 1.4 equiv) and potassium carbonate (about 1.0 equiv) was added anhydrous ethanol. The mixture was stirred at about 40–45° C. for about 3 hours. Then, p-anisaldehyde (about 1.0 equiv.) was added, and the reaction mixture was stirred for a minimum of about 3 hours to provide an imine (not shown). Upon reaction completion (about ≦5.0% p-anisaldehyde remaining by GC analysis), the reaction mixture was cooled to about 0–10° C. Then, an aqueous solution of sodium borohydride (about 0.50 equiv) was added to the reaction mixture at a temperature of between about 0° C. and about 20° C., and stirred for about 1 hour to provide Compound 1A. Upon completion of the reduction reaction, the reaction mixture was quenched with the slow addition of an aqueous solution of aqueous glacial acetic acid. After quenching, the reaction mixture was warmed to room temperature and filtered to remove solids. The filtrate was then concentrated under vacuum, followed by the addition of toluene and water to facilitate layer separation. Aqueous potassium carbonate solution was added to adjust the pH of the mixture to about 8–9. The organic layer was separated and the aqueous layer was extracted with toluene. The combined toluene extracts were concentrated to provide the product in about a 80–85% yield (based on GC and HPLC in solution assay). 1 H NMR 400 MHz (CDCl 3 ): δ 7.23 (d, J=8.5 Hz, 2H), 6.85 (d, J=8.5 Hz, 2H), 4.17 (q, J=7.1 Hz, 2H), 3.78 (s, 3H), 3.73 (s, 2H), 3.38 (s, 2H), 1.88 (s, br, 1H), 1.26 (t, J=7.1 Hz, 3H); 13 C NMR 100 MHz (CDCl 3 ): δ 172.8, 159.2, 132.0, 129.9, 114.2, 61.1, 55.6, 53.1, 50.4, 14.6. Compound 2: N-cyanomethanimidic acid ethyl ester To cyanamide (about 1.2 mole) was added triethylorthoformate (about 1.33 mole), and the reaction mixture was heated to about 85–95° C. for approximately 2 hours to form Compound 2. Estimated in-solution yield was about 95–100%. The product was optionally purified by vacuum distillation. 1 H NMR 400 MHz (CDCl 3 ): δ 8.38 (s, 1H), 4.28 (t, J=6.7 Hz, 2H), 1.29 (t, J=6.8 Hz, 3H); 13 CNMR 100 MHz (CDCl 3 ): δ 171.5, 113.4, 65.5, 13.1. Compound 3A: cis- and trans-glycine N-[(cyanoimino)methyl]-N-[(4-methoxyphenyl)methyl] ethyl ester A solution of Compound 1A (about 1.0 mole) in toluene was concentrated under vacuum to distill off toluene. Anhydrous tetrahydrofuran (“THF”) was added to the concentrate, then Compound 2 (about 1.2 moles, obtained above) was added to that, and the solution was heated at reflux for about 1 hour. At this stage, the formation of Compound 3A was complete. Estimated in-solution yield was about 95% (about 2:1 mixture of cis and trans isomers). Compound 4A: 1H-imidazole-5-carboxylic acid, 4-amino-1-[(4-methoxyphenyl)methyl] ethyl ester Compound 3A (obtained above) was concentrated by distilling off THF. Then, anhydrous ethanol was added to afford a reaction mixture solution. Separately, potassium t-butoxide (about 0.15 mole) was dissolved in anhydrous ethanol to afford a solution. The potassium t-butoxide solution was added to the reaction mixture solution and heated to about 75–85° C. for about 1 hour. The overall in-solution yield of Compound 4A was about 85–90%. 1 H NMR 400 MHz (CDCl 3 ): δ 7.16 (s, 1H), 7.08 (d, J=8.6 Hz, 2H), 6.82 (d, J=8.7 Hz, 2H), 5.23 (s, 2H), 4.93 (s, br, 2H), 4.23 (q, J=7.1, 2H), 3.76 (s, 3H), 1.26 (t, J=7.1 Hz, 3H); 13 C NMR 400 MHz (CDCl 3 ): δ 160.9, 159.2, 139.0, 128.6, 128.5, 114.0, 101.8, 59.5, 55.2, 50.1, 14.4. Compound 5AK: 1-ethyl-3,7-dihydro-7-[(4-methoxyphenyl)methyl]-1H-Purine-2,6-dione potassium salt The reaction mixture containing Compound 4A in ethanol (obtained above) was added to diglyme and distilled under vacuum to remove the ethanol. After being cooled to room temperature, N-ethylurethane (about 1.2 equiv.) was added and the reaction mixture was heated to about 110–120° C. A solution of potassium t-butoxide (2.2 equiv.) in diglyme was added to the hot solution. The reaction mixture was cooled to room temperature. THF was added to precipitate additional product, which was filtered and washed to provide Compound Salt 5AK in 55–65% overall yield. The wet cake can be used as such for conversion to Compound 6A. 1 H NMR (DMSO-d 6 , 400 MHz): δ 7.73 (s, 1H) 7.31 (d, J=8.6 Hz, 2H) 6.86 (d, J=8.6 Hz, 2H) 5.24 (s, 1H) 3.88 (q, J=6.8 Hz, 2H) 3.71 (s, 3H) 1.07 (t, J=6.8 Hz, 3H); 13 C NMR (DMSO-d 6 , 100 MHz): δ 161.1, 159.0, 158.4, 157.2, 141.4, 131.0, 129.5, 114.1, 105.6, 55.4, 48.2, 34.4, 14.3. Optional Neutralization of Compound Salt 5AK to Compound 5A: Compound 5A: 1-ethyl-3,7-dihydro-7-[(4-methoxyphenyl)methyl]-1H-Purine-2,6-dione The wet cake filtered solid of Compound Salt 5AK (obtained above) was suspended in water and then acidified to a pH of about 5 using glacial acetic acid. The resulting slurry was filtered to obtain the neutralized product, which was then washed with water and dried. The overall isolated yield of neutralized Compound 5A from Compound 1A was about 45–55%. Spectroscopic data for neutralized Compound 5A was identical to that of Compound Salt 5AK. Compound 6A: 3-[2-(acetyloxy)ethyl]-1-ethyl-3.7-dihydro-7-[(4-methoxyphenyl)methyl]-1H-purine-2,6-dione To the wet cake filtered solid of Compound Salt 5AK (obtained above) were added tetrabutylammonium bromide (about 0.05 mole) and 2-bromoethyl acetate (about 1.2 moles) in THF. After being heated to reflux for about 2 hours, part of the THF was distilled off, and isopropyl alcohol was added to the reaction mixture. The reaction mixture was then concentrated under reduced pressure and cooled to around room temperature. Water was added to precipitate the product. After being cooled to about 0–5° C. for about a few hours, the product was isolated by filtration. The wet cake was washed with aqueous isopropyl alcohol (about 30% in water), and dried under vacuum to afford Compound 6A as a pale yellow solid in about a 45–55% overall yield (based on Compound 1A). The crude product may be purified further by decolorizing with Darco in methanol, followed by filtration and concentration to afford crystalline Compound 6A. 1 H NMR (CDCl 3 , 400 MHz): δ 7.54 (s, 1H) 7.32 (d, J=8.6 Hz, 2H) 6.90 (d, J=8.6 Hz, 2H) 5.43 (s, 2H) 4.41 (m, 2H) 4.38 (m, 2H) 4.10 (q, J=7.2 Hz, 2H) 3.79 (s, 3H) 1.96 (s, 3H); 1.25 (t, J=7.2, 3H) 13 C NMR (CDCl 3 , 100 MHz): δ 171.1 160.2, 155.3, 151.4, 148.9, 140.9, 130.1, 127.7, 114.8, 107.5, 61.7, 55.6, 50.2, 42.4, 36.9, 21.2, 13.6. After Optional Neutralization of Compound Salt 5AK to Compound 5A: Compound 6A: 3-[2-(acetyloxy)ethyl]-1-ethyl-3,7-dihydro-7-[(4-methoxyphenyl)methyl]-1H-purine-2,6-dione Acetonitrile was added to a mixture of Compound 5A (about 1.0 mole), anhydrous potassium carbonate (about 1.5 moles) and tetrabutylammonium hydrogen sulfate (about 0.05 mole). 2-bromoethyl acetate (about 1.5 moles) was added in three separate portions (0.72 mole in the beginning, another 0.45 mole after about 2 hours of reaction, and then the remaining 0.33 mole after about another 1 hour of reaction) during the course of the reaction at about 80–85° C. The total reaction time was about 7 hours. The reaction mixture was cooled to about room temperature and filtered. The filtrate was concentrated. Aqueous isopropanol was added to crystallize the product. The product was filtered, washed with aqueous isopropanol, and dried to provide Compound 6A in about a 75–80% yield. Compound 7A: 8-bromo-1-ethyl-3-[2-(acetyloxy)ethyl]-3,7-dihydro-7-[(3-bromo-4-methoxyphenyl)methyl]-1H-Purine-2,6-dione Compound 6A (about 1 mole) and NBS (about 2.8 moles) were dissolved in dry acetonitrile and agitated at about 15–20° C. To this reaction mixture, a solution of sulfuric acid (about 0.03 mol) in acetonitrile was added, while maintaining the reaction temperature below about 25° C. The reaction mixture was agitated at about 20–25° C. for about 12–15 hours until complete consumption of the starting material was indicated. The reaction mixture was cooled to about 0–5° C. and a cold (about 5–10 ° C.) aqueous solution of sodium sulfite was added, keeping the temperature below about 10° C. The reaction was agitated for about 2 hours at about 0–10° C., and then filtered. The isolated cake was washed with water, followed by methanol, then dried under a vacuum to obtain Compound 7A in about an 85% yield. 1 H NMR (CDCl 3 , 400 MHz): □ 7.60 (d, J=2.0 Hz, 1H), 7.35 (dd, J=8.4 Hz, 2.0 Hz, 1H), 6.83 (d, J=8.4 Hz, 1H), 5.43 (s, 2H), 4.35 (m, 4H), 4.05 (q, J=7.0 Hz, 2H), 3.85 (s, 3H), 1.96 (s, 3H), 1.23 (t, J=7.0 Hz, 3H); 13 C NMR (CDCl 3 , 100 MHz): □ 171.0, 156.2, 154.2, 150.8, 148.2, 138.3, 128.9, 128.7, 127.5, 112.1, 112.0, 109.1, 61.5, 56.5, 49.3, 42.5, 37.0, 21.0, 13.3. MS (ES) m/e 545.2 (M+H) + . Compound 13A: 1-ethyl-3,7-dihydro-8-[(1R,2R)-(hydroxycyclopentyl)amino]-3-(2-hydroxyethyl)-7-[(3-bromo-4-methoxyphenyl)methyl]-1H-purine-2,6-dione Compound 7A (about 1 mole) was combined with (R,R)-2-amino-1-cyclopentanol hydrochloride (Compound 8A, about 1.2 moles) and sodium bicarbonate (about 3 moles). To this reaction mixture was added N,N-dimethylacetamide (“DMA”), and the reaction mixture was agitated at about 135–140° C. for about 15–17 hours until complete consumption of the starting material was indicated. Compound 9A is an intermediate that is formed, but not isolated, from the reaction mixture. The reaction mixture was then cooled to about 45–50° C., and tetrabutylammonium hydroxide (about 0.05 moles of about a 40% solution in water) was charged therein, followed by methanol. The reaction mixture was refluxed at about 80–85° C. for about 8–9 hours until complete deprotection of the acetate group was indicated. The reaction mixture was cooled to about 40–45° C. and concentrated under vacuum. The pH of the reaction mixture was adjusted to about 5–6 with dilute acetic acid, and the reaction mixture was heated to about 55–65° C., and seeded with a small amount of Compound 13A. The reaction mixture was then cooled to about 30–35° C. over a period of about 2 hours, and water was added over a period of about 1 hour. The reaction mixture was further cooled to about 0–5° C. over a period of about 1 hour, and agitated at that temperature for about 4 hours. The Compound 13A product was isolated by filtration, washed with water and dried to provide about an 85–90% yield. 1 H NMR (CDCl 3 , 400 MHz): □ 7.47 (d, J=2.1 Hz, 1H), 7.18 (dd, J=8.4 Hz, 2.0 Hz, 1H), 6.87 (d, J=8.4 Hz, 1H), 5.23 (s, 2H), 5.01 (s, 1H), 4.22 (m, 2H), 4.15 (m 1H), 4.05 (q, J=7.0 Hz, 2H), 3.93 (m, 3H), 3.88 (s, 3H), 3.77 (m,1H), 2.95 (m, 1H), 2.15 (m, 1H), 2.05 (m, 1H), 1.60–1.80 (m, 4H), 1.35 (m, 1H), 1.23 (t, J=7.0 Hz, 3H); 13 C NMR (CDCl 3 , 100 MHz): □ 156.2, 154.0, 153.5, 151.8, 148.3, 132.6, 129.1, 127.9, 112.5, 103.2, 79.5, 77.8, 63.2, 61.3, 56.7, 46.5, 45.9, 36.8, 32.9, 31.5, 21.4, 13.8. MS (ES) m/e 523.4 (M+H) + . Micronization Materials prepared by the above-described processes without further processing can exhibit particle sizes that are greater than optimal for purposes of bioabsorption, and thus, bioavailability. In certain preferred embodiments of the invention, the compounds disclosed herein are subject to a micronization process to generate particle size distributions more favorable for bioabsorption. Form 2 of Compound 13 (disclosed in the co-pending patent application “Xanthine Phosphodiesterase V Inhibitor Polymorphs,” incorporated by reference thereto) was micronized on a fluid energy mill (Jet Pulverizer Micron Master, model 08-620). A feeder (K-Tron Twin Screw Feeder) was used to feed material to the mill at a rate of about 80 grams/min. A mill jet pressure of 110 psig was used. The resulting material was then heated to convert amorphous material generated during micronization to crystalline material. The setpoint on the dryer (Stokes Tray Dryer, model 438H) was set to 95° C. The batch was heated at a temperature between 90 and 100° C. for 8 hours. Differential Scanning Calorimetry (“DSC”) analysis indicated no amorphous material was present. The particle size distribution of the resulting material was characterized, using a Sympatec particle size analyzer, as having a volume mean diameter of 8.51 μm and a median particle diameter of 5.92 μm. Cryogenic micronization processes may result in even more favorable particle size distributions. The above description is not intended to detail all modifications and variations of the invention. It will be appreciated by those skilled in the art that changes can be made to the embodiments described above without departing from the inventive concept. It is understood, therefore, that the invention is not limited to the particular embodiments described above, but is intended to cover modifications that are within the spirit and scope of the invention, as defined by the language of the following claims.
A process for preparing xanthine phosphodiesterase V inhibitors, and compounds utilized in said process. The process includes a five-step methodology for efficient synthesis of Compound 5 without intermediate purifications or separations, a dihalogenation step to synthesize Compound 7, and a coupling reaction to produce Compound 9
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CROSS-REFERENCE TO RELATED APPLICATION The present application claims benefit of and priority to U.S. Provisional Patent Application Ser. No. 61/233,928 filed Aug. 14, 2009 and entitled “Metadata Tagging of Moving and Still Image Content”, the contents of which are incorporated herein by reference for all purposes. FIELD OF THE INVENTION The present invention relates to the tagging of moving and still image content with metadata, and more particularly to an improved method and system for the metadata input and to the provision of tagged content. BACKGROUND TO THE INVENTION The creative industries worldwide are facing a time-bomb that threatens their future profitability. It is data, and more specifically the thousands of terabytes of moving image content being created every day. At the same time they are unable to access and realise the value of the hundreds of thousands of hours of archive content they have already created. This failure to “sweat” their most valuable asset, their content, is the biggest barrier to the success and long term value of all video based creative companies, from broadcasters, to government agencies, independent television production companies, to advertising agencies and beyond. They are already unable to cope with the current volume of data, but with the move to filming on Digital Film cameras, which no longer capture to film or tape, the problem is set to explode. As a temporary expedient the industry has resorted to stopgap measures, whereby millions of pounds worth of footage is being stored on consumer grade portable hard drives in insecure locations, with no backup. Thus, a library of tapes that can be stored securely for up to 30 years and be catalogued, is being replaced by drives that have an average life span of 5 years, on which the data is degrading every single day, with thousands of video files that cannot be searched. A piece of footage is considered valueless if it cannot be found within two hours. As a result, creative companies are losing millions of pounds worth of assets every single year. If unchecked, hundreds of thousands of hours of content will be lost. This will not only affect straight initial revenue, companies also by definition will not be able to reuse it in future productions, be unable to deliver it to the fast growing (£4.37 billion by 2012) online video market, and miss the opportunity to market raw footage to other content creators. Their archives of existing content are also sitting, unexploited, in costly storage facilities. In the UK the BBC has 5.5 miles of shelves of un-digitized archive content. IMG media has 300,000 tapes stored at a cost of £2 per tape per year. All such companies are missing out on valuable revenue, with the UK archive market alone valued at £1.5 billion by 2014. These companies are faced with a huge infrastructure and staffing investment in order to rectify this. They simply cannot afford to do it, but nor can they afford not to. The obvious solution is outsourcing and yet, until now, no commercial company has presented a viable alternative. Video content cannot be found because it cannot be searched. It has no associated words. The key is to add associated words to footage in the form of keywords, known as “metadata”. Once “tagged” with such metadata, the tagged content can be searched by a search engine, either an internal engine or else an external engine, such as Google or Yahoo. Currently, companies are attempting to automate metadata addition to finished video content, by using technologies such as speech to text, which is only 40% accurate, and face recognition. However, neither technique gives the user the actual content of a scene, which is crucial for making it searchable on multiple criteria, and hence valuable to an end user. Moreover, these methods are not reliable and, since they are only currently used on finished content, do not help content producers search their raw footage in order to create quicker, more profitable programming. In addition there is often no money available to create accurate or adequate metadata, as a programme's budget has already been spent. The only way of adding rich metadata is to get human beings to do it. However, even then, adding metadata with multiple layers by typing it in manually is far too slow a process. For example, content may be tagged with multiple layers relating to Character, Location, Object, Story, Context, and Emotion. Studies on the manual addition of such rich metadata show it taking between 4-8 hours per hour of content. Within the production community, basic metadata is being added to raw content by teams of untrained assistants who hate doing the job, and hence do it poorly and slowly. “Logging” as this process is called is frequently still done on paper. However, the logging tools currently in existence do not provide enough fields for rich metadata to be added. As it has to be typed in, the process is too slow. Moreover, because these are bespoke systems, once the footage leaves the system it instantly loses the associated metadata, rendering it less valuable. Some metatagging software has been created to facilitate the tagging process, a good example being “Frameline” (see http://www.frameline.tv). However, as it is still involves manual entry by keyboard, it is too slow, and again, it is bespoke. Since the only viable current solution to adding metadata involves humans and manually typed input, the process is too slow and makes the proposition of adding metadata quickly to large quantities of footage financially unviable. The use of manual typed input is one of the key limiting factors. Even with an automatic spell-check facility, it is slow and inaccurate. It also means that an operator has to concentrate on the keyboard as well as the screen, regardless as to whether they are a touch typist. In conjunction with this, in order to move between different metadata layers in each clip, the operator typically has to move a computer mouse to select to different entry boxes. Whilst doing this, the operator is no longer able to type, which means they that the footage being watched must temporarily be paused, thereby slowing the process yet further. In addition to the issues discussed above, there are a number of other problems which arise when using humans for manual logging. Although straightforward in principle, the repetitive adding of metadata to large quantities of content results in lack of concentration and boredom. As a consequence, greater than a few minutes spent concentrating on a single clip can lead to a rapid decrease in the quality of tagging. Further to this, a major problem is what might be termed “brainfreeze”, where an operator simply runs out of things to say and is left unable to add metadata to content quickly enough. This again, means the footage having to be paused, or most likely rewound, demoralising the operator and resulting in further decreases in quality. As will be appreciated, there is a clear need for an improved method of processing and metatagging image content such as video content, which would in turn facilitate the provision of such metatagged content and alleviate many of the problems outlined above. SUMMARY OF THE INVENTION According to a first aspect of the present invention, a computer implemented method of tagging image content comprises the steps of: receiving image data comprising digital image content; displaying the digital image content visually; receiving an indication of a selected one of a plurality of characteristics associated with the image content currently being displayed; identifying a respective metadata tagline corresponding to the selected characteristic; receiving an audio data stream comprising audio content, the audio content comprising spoken keywords describing one or more characteristics associated with the image content being displayed, respective keywords being spoken by a human tagger in response to the image content currently being displayed; identifying the keywords received in the audio content and generating metadata therefrom; and, associating the metadata with the image content as metadata tags synchronously with the occurrence of the respective keywords in the audio data stream, wherein the steps of generating and associating the metadata with the image content are performed in dependence on the respective metadata tagline, and wherein the indication of the selected one of the plurality of characteristics is received from a control pad having a plurality of keys or buttons, each of the keys or buttons being assigned to a different one of the plurality of characteristics. The method is typically implemented on a computer with processor, memory, visual display unit, keyboard and mouse. However, the invention removes the need for a keyboard for manual data entry of the keywords for the metadata tagging process, instead using voice input, and likewise removes the need for keyboard and/or mouse for selecting the metadata taglines, instead using a separate control pad. The combination of receiving audio data input and navigation signals from a control pad provides a powerful alternative technique for metadata tagging of image content by a human tagger, which for the first time facilitates rich metadata tagging at a speed and accuracy to make the process viable for many applications. A conventional keyboard and mouse may still be used for ancillary navigation and data entry. Preferably, the tagline is displayed visually together with the respective keywords describing the selected characteristic associated with the image content currently being displayed. The selected characteristics could relate to a wide range of different aspects of the image content and for which multiple layers of metadata can be associated with the content to provide for very rich tagging. Such characteristics may comprise one or more of: Character, Location, Story, Object, Background, Emotion, and Action. In this way, rich metadata may be added to content up to four times faster and significantly more cost effectively than is currently possible. In some embodiments, the received image data comprises digital image content having a second image resolution and the method further comprises the steps of: storing the metadata in a central database; and, associating the metadata with a stored file comprising the image content having a first image resolution which is greater than the second image resolution. This allows a lower resolution version of the image content to be transmitted to the local or remote tagging station and to be more readily manipulated by the human tagger during the tagging process, whilst ensuring that the resulting rich metadata tags are associated Typically, the keywords are extracted from the audio data using a digital speech recognition technique. The audio content may be filtered to remove extraneous noise and/or predetermined words. Although the metadata is associated with the image content near synchronously with the occurrence of the respective keywords in the audio data stream, account may be taken of the length of the respective keywords. Furthermore, allowance may be made for the latency of the human tagger speaking the keywords. In this way, the association of the metadata can take account of various factors affecting the precise synchronisation of the original spoken keywords with the corresponding image content. In preferred applications, the digital image content is digital video content, either with or without sound. More preferably, the image content is unfinalised “raw” content that can be further manipulated following its tagging with metadata. Thus, unlike known techniques, the present invention allows the addition metadata to raw content at the most cost effective stage, namely the moment it is created. Of course, the invention may equally be applied to still images or a series thereof, as well as finalised video content. The tagging activity can be performed in a collaborative manner, with several human taggers working on the tagging of related content, including different sections of the same image content. As such, data derived from the input of one tagger can automatically and advantageously be displayed to another tagger. The data can take many forms, including information directly related to the content being tagged and also motivational information. For example, in order to keep a given human tagger informed of the activity of other taggers, and to provide a useful accessible “dictionary” of keywords, the method may further comprise the step of displaying tags generated from the spoken input of other human taggers working on the tagging of related image content. In addition, or alternatively, in order to provide incentive and promote competition between taggers, performance data associated with the performance of a given human tagger may be stored and displayed, as may the performance data for other human taggers working on the tagging of related image content. It should be noted that the collaborative aspect of the present invention is capable of utility with any suitable computer-implemented method of tagging, not just the audio-input/control pad method according to the first aspect According to a second aspect of the present invention, there is provided a computer implemented method of tagging and managing image content, the method comprising the steps of: receiving and storing image data comprising digital image content; displaying stored digital image content visually to a plurality of human taggers; receiving an indication of a selected one of a plurality of characteristics associated with the image content currently being displayed to each human tagger; identifying a respective metadata tagline corresponding to the selected characteristic; receiving keywords entered by each human tagger and generating metadata therefrom, said keywords describing one or more characteristics associated with the image content being displayed to each tagger; and, associating the metadata with the image content as metadata tags in dependence on the respective metadata taglines, wherein the method further comprises the step of displaying visually to at least one human tagger information derived from at least one other human tagger. The method will typically be implemented on a plurality of computers, each with processor, memory, visual display unit, keyboard and mouse, and in communication with a central computer system. In some preferred embodiments of the present invention, the method further comprises the steps of: receiving data identifying the physical location where received image content was first generated and also the time at which the received image content was generated; associating the identifying data synchronously with the relevant image content; determining, in dependence on the received identifying data, information about the physical location where the received image content was first generated; and, displaying the information about the physical location synchronously with displaying the image content. This allows additional useful identifying information to be provided with the raw (or finalised) content, thereby enhancing its value still further. The identifying data will typically comprise GPS data identifying the physical location and allowing geotagging of the image content. The information displayed may provide useful prompts to the human taggers and the audio content received in the audio data stream may comprise keywords spoken in response to the physical location information currently being displayed. Alternatively, the human tagger may speak a primary descriptive keyword in response to the image currently being viewed and the remaining descriptors for the metatagging may be generated automatically from a database of information about the physical location associated with the geotagged image. In this way, the client may interface with the invention through an application running on a mobile device and may transmit the time-stamped location data independently of supplying the actual image content or footage being shot at the location. The location data can then be associated with the relevant uploaded image content in a time synchronous manner, thereby providing useful information per se or else a source for rich descriptive metatagging to be generated from the input of a human tagger. Although the geotagging concept has been described in the context of the metadata tagging of image content according to the first or second aspect of the invention, it should be noted that it is capable of independent utility and can be used with a variety of metadata tagging techniques. According to a third aspect of the present invention, there is provided a computer implemented method of tagging image content comprising the steps of: receiving image data comprising digital image content; displaying digital image content visually to a human tagger; receiving data identifying the physical location where received image content was first generated and also the time at which the received image content was generated; associating the identifying data synchronously with the relevant image content; determining, in dependence on the received identifying data, information about the physical location where the received image content was first generated; displaying said information about the physical location visually to said human tagger synchronously with displaying the image content; receiving an indication of a selected one of a plurality of characteristics associated with the image content currently being displayed to the human tagger; identifying a respective metadata tagline corresponding to the selected characteristic; receiving keywords entered by the human tagger and generating metadata therefrom, said keywords describing one or more characteristics associated with the image content being displayed to the tagger; and, associating the metadata with the image content as metadata tags in dependence on the respective metadata taglines. The method will typically be implemented on a computer with processor, memory, visual display unit, keyboard and mouse, which is in communication with a central computer system. Furthermore, the concept is capable of even more independent utility and, as such, the basic geotagging method described above could be used to add geotags to image content after it has been generated (post-shoot) independently of whether any rich metadata tagging is subsequently performed. According to a fourth aspect of the present invention, there is provided a computer program product for causing a computer or computers to execute the method steps of the above aspects of the present invention. Again, the geotagging method steps could be performed independently and a computer program product for causing a computer to execute these method steps is contemplated. In reality this program product would typically be a mobile application for running on a mobile device such as a mobile telephone or PDA. According to a fifth aspect of the present invention, apparatus for tagging image content comprises: display means for receiving image data comprising digital image content and for displaying the image content visually; means to receive audio content and to generate an audio data steam therefrom, wherein the means comprises a microphone and wherein the audio content comprises spoken keywords describing one or more characteristics associated with the image content being displayed, respective keywords being spoken by a human tagger in response to the image content currently being displayed; processing means adapted to process the audio data steam and identify the keywords therein, the processing means being further adapted to generate metadata from the keywords and to associate the metadata with the image content as metadata tags synchronously with the occurrence of the respective keywords in the audio data stream; and, means to select each of a plurality of characteristics associated with the image content being displayed and to generate a signal representative thereof, wherein the processing means is adapted to identify a respective metadata tagline corresponding to each representative signal and to generate and associate the metadata with the image content in dependence on the respective metadata taglines, wherein the selection means comprises a control pad having a plurality of keys or buttons, each of the plurality being assigned to a different characteristic. The apparatus will generally comprise a computer with processor, memory, visual display unit, keyboard and mouse. However, the use of an audio input means allows the keywords from which metadata is to be generated to be spoken by a human tagger whilst simultaneously viewing the image content to be tagged. Moreover, for the selection and entry of each tagline, the usual combination of mouse and keyboard is replaced with a single control method nearly all people know, namely a control pad, such as a games console joy pad. Each of the keys or buttons of the control pad are assigned to a different characteristic. By assigning the different metadata layers to buttons on the pad, the operator will be able to jump between layers instantly, speeding up the process. This allows for the easy “layering” of metadata and the attendant advantages in terms of the richness of the metadata tagging. The control pad may also comprise means to navigate an onscreen menu displayed on the display means. Preferably, the control pad comprises means to control the speed of playback of the image content being displayed. In this way, the operator is also able to pause, fast-forward, rewind, jump scenes and generally interact with the content via the shoulder buttons and d-pad on the games controller. This further immerses them in the content, promoting enjoyment, and hence more accurate tagging. The navigation and control means of the control pad can take any suitable form, such as d-pad, roller ball, and joystick, which facilitate easy use by the operator alongside the keys or buttons used to select characteristic/tagline. Of course, a conventional keyboard and mouse may be used for the usual data entry and navigation functions to supplement those of the microphone and control pad. For example, whilst the primary data entry is performed using the microphone and control pad, subsequent correction or amendment of the metadata keywords may be performed using the keyboard, and if required, the mouse. It is preferred that the audio content receiving means comprises a directional microphone. This type of microphone is well suited to capturing words spoken by a human operator and may be part of a headset. The combination of a headset (with directional microphone) and games controller connected to a computer performing the necessary processing provides an optimum and coordinated method for fast and detailed data entry by a human operator, which is then converted into a rich, layered meta-tagging of image content. Thus, operators will “talk” in the metadata via a headset microphone. They will simply “say what they see”. This has multiple benefits. It takes them away from the keyboard and makes it feel like they are interacting with the content. It is by far the fastest way to describe what is happening on screen. Noise words (the, err, a, swear words etc) can be filtered by the software. According to a sixth aspect of the present invention, an image content management system comprises: a plurality of image content tagging apparatus according to the fifth aspect of the present invention; a central processing system in communication with each of the plurality of image content tagging apparatus, the central processing system comprising a server for serving image content to the plurality of image content tagging apparatus and to one or more clients; and, a data store for storing image data and associated metadata, the data store being in communication with the central processing system. In this way a centralised system is provided for storing and managing image content and the associated metadata and for sharing information. Moreover, the centralised system allows for a more collaborative approach to tagging. This collaborative approach need not be limited to image content tagging apparatus according the fifth aspect of the invention, but with a wider range of image content tagging apparatus. According to a seventh aspect of the present invention, an image content tagging and management system comprises: a plurality of image content tagging apparatus; a central processing system in communication with each of the plurality of image content tagging apparatus, the central processing system comprising a server for serving image content to the plurality of image content tagging apparatus and to one or more clients; and, a data store for storing image data and associated metadata, the data store being in communication with the central processing system, wherein each of the plurality of image content tagging apparatus comprises: display means for receiving image data comprising digital image content and for displaying the image content visually to a human tagger; means for the human tagger to enter keywords describing one or more characteristics associated with the image content being displayed; means for the human tagger to select each of a plurality of characteristics associated with the image content being displayed and to generate a signal representative thereof; and, processing means adapted to generate metadata from the keywords, to identify a respective metadata tagline corresponding to each signal representative of a characteristic, and to generate and associate the metadata with the image content as metadata tags in dependence on the respective metadata taglines, and wherein the system is adapted to display visually on the display means of one image content tagging apparatus information derived from entries by a human tagger using another of the plurality of image content tagging apparatus. The system will typically comprise a plurality of computers, each with processor, memory, visual display unit, keyboard and mouse, and in communication with a central computer system with central data storage. Preferably, in the content management system, the image data comprising digital image content having a first image resolution is stored in the data store and image data comprising the digital image content having a second image resolution lower than the first is served to the image content tagging apparatus. In a similar manner, the tagged image data comprising digital image content having a first image resolution and associated metadata can be stored in the data store, and the tagged image data comprising the digital image content having a lower second image resolution and the associated metadata can be served to a client for viewing and/or editing. In this way, the high resolution version of the content is primarily made available when actually required, and lower resolution versions can be deployed during the tagging or post-tagging editing and review process. The centralised system allows for methods to deal with the boredom and brain freeze issues often associated with human tagging operators. For example, content to be tagged may be divided into sections and distributed between different members of a tagging “team”. In this way, an hour's worth of content to be tagged may be divided into five sections, for a team of five operators, meaning that each member of the team will only have to work on a maximum twelve minute section. Similarly, as the content is being metatagged in teams of five, with each completing a short section, the system will show each operator the tags being created by the other members of the team, some of whom may be tagging ahead, while others are behind. Whilst not always directly relevant this will aid lateral thinking. The present invention allows a service to be offered that, for the first time, will provide clients with storage online, and the ability to search and sell the thousands of video assets they create every year. The invention makes the process of adding keywords (or “metadata”) to content, so as to make it searchable, up six times faster than current methods, thereby facilitating a financially viable solution to the problem. Furthermore, the system may comprise a transcoder for transcoding the tagged image data for streaming to another device, such as a mobile device. In this way the image data can be coded in the appropriate format for a given browsing device. In some preferred embodiments of the invention, the system is adapted to: receive data identifying the physical location where received image content was first generated and also the time at which the received image content was generated; associate the identifying data synchronously with the relevant image content; determine, in dependence on the received identifying data, information about the physical location where the received image content was first generated; and, display, on the relevant tagging apparatus display means, said information about the physical location synchronously with displaying the image content. This functionality of the system can be utilised with any combination of tagging apparatus or can be used independently of the metadata tagging functionality to provided standalone geotagging of image content. Typically, the identifying data comprises GPS data identifying the physical location. According to a eighth aspect of the present invention, there is provided a user interface embodied on one or more computer readable media and executable on a computer, said user interface for use with meta-tagging of image content, said user interface comprising: an image content presentation area for displaying digital image content; a time line area for displaying a time line representation of a sequence of digital image content, including an indicator of the position in the timeline of the image content currently being displayed, the time line representation including a plurality of respective bars indicative of meta-tagging of the image content in the sequence, each bar indicative of the type of meta-tagging and the duration of the image content to which it applies. Typically, the width of each bar will be indicative of the duration of the image content to which the meta-tagging applies, and the colour of the bar will be indicative of the layer of meta-tagging to which the bar applies, for example the particular tagline type. In this way, the time line in the interface gives a ready visual indication to the operator of where in the sequence of image content the meta-tagging is concentrated, and also the richness and diversity of meta-tagging at any given point in the sequence. The interface may also have an item presentation area for displaying thumbnail images and associated descriptive metatags for particular image content in the sequence. This area may be interactive, allowing selection and display of a particular image. The user interface may also have a text presentation interface overlaying part of the image content presentation area, the text presentation interface for displaying the descriptive metatag keywords as the user selects a clip in the timeline and moves their mouse over the content as it plays. Typically, every keyword added to the clip will displayed opaquely over the content. The user interface of the eighth aspect of the present invention can advantageously be employed in the apparatus, system and method of the various aspects of the present invention. According to a ninth aspect of the present invention, a method of serving data comprises the steps of: receiving image data comprising digital image content having a first image resolution; storing the received image data having the first image resolution; tagging the stored image data with metadata descriptive of the image content; and, serving from a server the tagged image data comprising the digital image content having a second image resolution, wherein the second image resolution is lower than the first image resolution, and wherein the lower resolution image content of the served image data is editable while retaining the descriptive metadata tagging associated with the higher resolution image content. Typically, the high resolution meta-tagged image content will be stored electronically in the data storage of a central computer system and served by a central server at the lower resolution to one or more local computers for viewing and editing by a user. The important feature of this aspect of the invention is that the meta-tagging associated with the local low resolution version of the image content and with the centrally stored high resolution version of the image content remains linked. Thus, edits to the low resolution version of the image content can be replicated with associated metadata in a centrally-stored high resolution version of the image content. In this way, the central system is “watching” for changes or edits to the served low resolution version of the image content. In some embodiments, the tagged image data comprising the lower resolution image content is served over a web browser. Preferably, the lower resolution image content is searchable by reference to the associated metadata. Alternatively or additionally, the lower resolution image content is searchable semantically. Thus, in this aspect of the present invention, the lower resolution image content of the served image data may be edited whilst still retaining the associated metadata tagging. Modification data relating to the served image data may be received back at the server and automatically linked it to the stored tagged image data comprising the image content having the first resolution. In the case the image content has been edited, the modification data received back at the server may relate to edits of the served image data and may include new image content. In this way the lower resolution image content can be viewed, edited and augmented and modification data identifying the changes or selections is sent back to the server together with any associated metadata and is automatically linked to the high resolution version of the image content stored in a central data storage facility. Preferably, the tagged image data is served to an end user device in a format compatible with said device and comprising the image content having a resolution compatible with the end user device. The end user device could be a portable device, such as a lap top computer or PDA, including an iPhone or similar device. According to a tenth aspect of the present invention, a computer program product is provided comprising one or more computer-readable media having thereon computer-executable instructions that, when executed by one or more processors of a computer, causes a computer to execute the method steps the ninth aspect of the present invention. In the present invention, either via a central upload room or using their own links, client's raw footage will be uploaded to the image content management system, making it instantly secure. This content will then be metatagged, and low-resolution copies created, making it available to the client via a standard web browser. In this way, clients can interact with their footage within hours of filming. This possibility alone will change the way clients use their content, but via the web browser they can download it into the professional editing system of their choice, allowing them to create content without having to use a costly post production company. Once finished, the project files (not the data) are uploaded back to the system and re-united with the original footage. From here it can be sent, for example, to a special effects company for further work. The result is the creative company having total control, for the first time ever, of the creative process, but also for the first time, having an instantly available online, fully metatagged copy of their finished content. From the system, they can then send this worldwide to anyone they choose, create new copies for mobile, the web or international broadcast, and all without tying up their staff with tapes, couriers or post production facilities. Most significantly, via an online commerce presence, clients can sell their finished content direct to consumers, syndicate it to Internet broadcasters, and crucially, as it is metatagged, generate revenue from targeted advertising around it. Simultaneously, their unused footage, to which they may own the Intellectual property rights, and which currently is effectively valueless, can be sold as stock footage to a worldwide community of producers, realizing valuable extra revenue. Alongside this, clients archive material can be sent to a Digitizing factory, using robotic systems to upload tapes in extremely large quantities and at low cost. Since no company or archive can afford to use the teams in the call centre to add metadata, and the timescales will be longer, home based workers, served video via broadband to their web browser, will be used to add metadata, in a similar vein to Wikipedia. Such home based workers may be incentivised by a small micro payment initially, but in order to promote quality tagging, they may be offered a cut of the revenue if a clip sells. This will enable an army of people worldwide, complete with their specialist knowledge, to be utilised. As will be appreciated by those skilled in the art, the present invention provides a simple yet elegant solution to the problem of tagging image content with rich metadata, which in turn enables its searching. Moreover, an integrated system can be realized, which provides for the storage of tagged digital image content, with near immediate access to tagged raw footage for viewing and editing, and for easy searching and accessing of finalized footage, thereby allowing owners of rights to the footage to realize its commercial potential. The invention is not limited to applications in the shooting of commercial video or film footage, but could also be used for footage shot in non-commercial type environments, such as a hospital operating theatre. The invention could also find application in the tagging of still image content, such as photographs and the like. BRIEF DESCRIPTION OF THE DRAWINGS Examples of the present invention will now be described in detail with reference to the accompanying drawings, in which: FIG. 1 shows a schematic overview of the tagging system and procedure; FIG. 2 shows a client side overview of the tagging procedure; FIG. 3 illustrates the operation of the mobile Geo-positioning application; FIG. 4 shows a flow diagram of the tagging process; FIG. 5 shows an example of a tag pad for onscreen navigation and tag line selection; FIG. 6 shows an example of the tag screen; FIG. 7 shows an example of the dashboard screen; FIG. 8A shows a screenshot of the tagging user interface with keywords layered over a film clip; and, FIG. 8B shows a screenshot of the tagging user interface with a close up of the timeline and associated thumbnails. DETAILED DESCRIPTION FIG. 1 provides a schematic overview of a complete system according to the present invention. At the heart of the system is a Media Asset Management System (MAM) 100 , which is in communication with the other component parts and provides for central control of all data and processes. A suitable MAM system is the Artesia system provided by Open Text. The interface and editing management may be based on MXF Server provided by Film Partners and the server management might be run by IBM Vmware. In particular, the MAM is in communication with clients 101 from which it receives high resolution image content 102 and returns the content with synchronized metadata 102 . Tagging with metadata is consistently indicated throughout the figures by a small meta-tag symbol appended to the tagged item. Three such tag symbols are shown appended to element 153 in FIG. 1 . The high resolution image content may be downloaded 102 . However, as indicated, the tagged content may be returned as low resolution streaming media 103 , making it suitable for local searching and editing, or may be returned as a final high resolution streaming media version 104 . The client can interact with the system to obtain a tagged version of the raw video footage at low resolution 103 and perform post processing on it, before returning the finalized high resolution footage 102 for storage whilst maintaining the metadata synchronization. Clients can use any suitable editing system, such as Final Cut Pro provided by Apple, AVID or Adobe systems. The client may also be in communication with the MAM 100 via a management application running on a mobile device having GPS facility for pinpointing the location of the device. The application will be served for compatibility with the operating system of the mobile device in question. The real-time GPS data and associated time stamp can be then uploaded via the application and associated with the particular project. At a later time this identifying data can be reconciled with the footage shot at the location in a time synchronized manner. The original high resolution footage may be supplied by the client in various formats, which will often not be digital. In this case the footage is sent 105 to an ingest room 106 for digitizing prior to tagging. There will typically be a variety of different client types 101 , including those with their own servers and those whose connect directly. Other types may check in and out or may only be concerned with archive material (i.e. prosumer). Provision is made for all types of clients. In a preferred implementation, all image content will be received via the ingest room, 106 , 116 , whether delivered by courier or uploaded as data, as it provides a fast central repository. Any basic metadata already associated with the content is recorded under control of the MAM 100 . The digitized footage is stored in a primary data centre 110 , which is mirrored by one 120 or more 130 back-up data centres. These centres typically comprise a tape and/or disc storage system 111 , 121 , a redundant MAM 112 , 122 , and a transcoding engine 113 , 123 . A similar procedure can be used to digitize and store archive footage supplied by clients, and which can then be tagged as and when appropriate. The archive footage 115 is supplied to a digitizing factory 116 for digitizing, after which the high resolution digitized footage 118 can be downloaded for storage in the data centre 120 . The original tapes can be stored in a long term storage facility 117 . The MAM also mediates the delivery of tagged content 141 , 143 to end content customers 140 who may wish to search and obtain high resolution copies 143 of footage stored by the system. The Typically, the requested content is streamed at low resolution 141 via the web and can be searched with the aid of semantic assistance tools 144 , before the customer 140 requests and obtains a high resolution version 143 of particular footage. The provision of the low resolution footage may be via a sales front end 142 , which allows the customer 140 to browse and purchase media. The web portal will typically be implemented using a platform from either Microsoft or IBM web services. A separate payments system 145 manages the associated payments transactions, including processing payments received from the content customers 140 and passing on remuneration to the (client) owners of the footage with a suitable fee deduction for providing the service. A key component of the overall process is the army of human taggers 150 , who provide the input for the rich metadata tagging of the image content. The taggers 150 may be based locally in a more centralized tagging facility or may be distributed home workers. They may work individually on a given project or may be part of a team tagging a particular piece of footage. The MAM 100 is in communication with the tagging stations 150 via a tagging factory 151 , which supplies low resolution copies of digital image content 152 to the taggers 150 via their respective tagging station and receives back tags 153 for association with the content. The tagging factory 151 then adds the tags as metadata to the content, the metadata being synchronized with the content. The data is stored on a database, which will typically be a variant of SQL. FIG. 2 provides a schematic overview of the process from the perspective of a client 201 , starting with the initial interactions before any footage is shot 200 through the after shoot processing 210 , including tagging, and the post tagging editing process 220 , and on to the in post finalization of the tagged footage 230 and its provision to end content consumers 240 . Typically, before filming, the client 201 (for example a production manager) visits a website, signs up for the service and downloads and installs the management application 202 . After logging in, the client adds production details, such as title, number of hours of footage, characters, script and any associated media. In doing so, project file is set up 203 . Barcodes and/or QR codes may be generated for association with the project and materials 204 , and which may be printed out from the website 206 . Once a project file has been set up, the client goes “on set” to an actual shoot, subsequent to which all the raw image (e.g. video) footage shot during the shoot is delivered 207 to the ingest room 212 of a central processing facility via courier, where it is processed. The client receives notification of which tapes have been received 213 at the ingest facility. Subsequent to this, the client can request a review 214 if a tape is missing or if the information supplied is incorrect. Depending on the format in which the image content has been shot, the footage may then be digitized at the ingest facility 212 in an automated process. Media with machine readable codes 211 may also be inputted. The client 201 can log in to the web application 215 to view the progress of the digitising process for each individual media unit. The client is then notified that all of the media has been digitised 216 and can request a review 214 if something is not correct. The review can be performed online. The client chooses which files to start downloading and the Sync Manager 205 launches and begins downloading the selected files. The digitized footage is passed to the Tag Pipeline 217 and a tag team accepts the project. At some point the client receives a notification 218 of the scheduled start time of the metatagging process, after which the tagging process begins and metadata is generated and associated with the raw video content. The web application 215 may give an indication of time remaining until such time as the tagging is completed and notified as such 219 . In order to view and edit the digitized content, the client 221 opens their editing suite application 223 and creates a new edit project. The relevant file then appears in the client's ‘virtual drive’ 224 under that project name. At this point the client can pull clips into their edit and can also browse and edit the metadata that has been generated until such time as they complete the review/edit. The client builds edits using low resolution proxy files locally 225 . The Sync Manager 222 monitors the status of the edit project, synchronising updates on demand or automatically with the central server 226 . The client is able to view the full edit online, in a streaming mode, via the application 227 and can send the edit to others 229 to view. A notification 228 of the status of the project can be sent to multiple people for approval. Once satisfied with the edited raw footage, the client can pass the edit onto a Post house for finishing 230 . The Post house team member 231 interacts with the MAM 232 and downloads high resolution files 234 through their connection, again using a download manager 233 . Post production software may be used for graphics and finishing work 235 after which the edits to the high resolution footage 234 and materials are synchronized 236 . The footage and edit is checked out and checked back in once the post production process is completed. The client receives an email once the Post House has completed their edit and has access to a full resolution, metatagged copy of the image content via the web application 237 for downloading and distribution. A notification 238 of the status of the project may be sent to multiple people for approval 239 . At this point the client will typically decide how the finalised footage is to be commercialised. The client can choose to deliver it to a broadcaster 241 and/or syndicate via the web 242 or alternatives means. The client can also choose what they want to archive of the footage they have on the production servers. The client simply chooses the files they want to archive via a web interface and the selected files are backed up and stored on the long term Archive Storage 245 . Finally, the client receives a bill for the project and a payment is taken via direct debit 246 . During the actual shoot, the client may run the management application or some component thereof on a mobile device having GPS facility for pinpointing the location of the device. As illustrated in FIG. 3 , before the shoot 300 the client 301 accesses the web application to set up a new project 302 and enters the details of the new shoot 303 . The client may then download a particular mobile application 304 for interacting with the system. The mobile application will be served for compatibility with the operating system of the mobile device in question, whether it is an iPhone or an Android or MSWindows based mobile phone, or else some other type of mobile communication device. It is important to synchronise data/time settings on the camera(s) used for the shoot with the mobile device used for GPS tracking. The mobile application may generate a reminder for the user to do this, for example when the application is launched on the mobile device or a project selected for a new shoot. During the shoot 310 , the mobile application is launched 314 by the client team member 311 , the shoot project is selected 313 , and the application can run in the background or data can be checked in manually 312 . As the mobile device 305 moves from location to location with the shoot, the onboard GPS system monitors the position of the device until the application is deactivated 306 . The real-time GPS data and associated time stamp is broadcast or uploaded 307 via the application and associated with the particular specified project and stored 308 . After the shoot 320 the high resolution footage 321 is delivered to the ingest room 322 for digitizing. At a later time the MAM 323 communicates with the location data store 308 , sending the footage shoot ID and time 324 , and receiving back the relevant stored Geo Data 325 . This identifying data can be reconciled with the footage shot at the location in a time synchronized manner to provide a geotagged version 326 of the image content. As a consequence, the client can search their footage by street name, town and postcode immediately on it arriving into the system and being reserved to them. We now consider the actual tagging process in a little more detail with reference to FIGS. 4 to 7 . FIG. 4 provides a schematic overview of the tagging process and workflow, which is centred on the human tagger at their tagging station. FIG. 5 illustrates a tag pad (or console) for onscreen navigation and tag line selection by the human tagger. FIGS. 6 and 7 , respectively, show an example of the Tag screen and an example of the Dashboard screen, as displayed to the human tagger. As shown in FIG. 4 , initially a project of videos is uploaded into a web application and appears in the Tag Pipeline 401 on the Dashboard. Team leaders 402 from each available Tag Team bid on who can achieve the best results with the footage. The projects are allocated 402 and the clips are added into the Clip Queues for each winning team. Each Tag Team Tagger 420 is located in front of a computer display wearing a headset with directional microphone and holding a games console type controller. An example of the latter is shown in FIG. 5 . The Tagger logs into the Tagging software and is taken to the Dashboard 421 , shown in more detail in FIG. 7 . A variety of information useful to the Tagger is displayed on this screen. In particular, a visual display of the Tagline for the current user 702 is presented, including the last clip completed 701 , the next clip 702 awaiting tagging by the Tagger and subsequent clips 703 , 704 to be tagged. The Tagger can also see a list of team members with graphic avatars 705 , what his/her team is due to tag, the scores of other teams and of his/her team-mates 706 and more detailed statistics relating to his/her performance and the performance of the team 707 . Such information can act as incentive and motivator to the Tagger. To begin tagging, the Tagger is presented with the first clip 423 in the Tagger's Clip Queue in the Tagging Window, which is viewed as a video stream from the Media Asset Management (MAM) System 422 . Below the video currently playing is a bar, which will display numeric data relevant to the clip being shown. The application software sets up several empty Metadata Taglines 424 , and displays them on the screen next to the Tag Window. The five example Taglines illustrated in FIG. 4 are: Character, Location, Story, Object, Background, Emotion, and Action. Although not shown in FIG. 6 , these taglines would appear at the left hand side of the relevant tagline bar with the descriptive text (“John”, “Table” etc) entered for that tagline being shown further to the right. The snap shot of the Tag screen illustrated in FIG. 6 shows some typical Taglines 624 . The Tagger controls the playback of the video via the control pad 430 with functions which mimic standard video playback commands, such as fast forward, rewind, pause, play and a jog-wheel. FIG. 5 shows a games joy pad type console adapted for use with the invention. Navigation of the onscreen menu options 501 and jog control 502 is performed using the joystick type controllers. Certain buttons are programmed as shortcuts for certain onscreen functions or operations, such as pause 503 , dashboard 504 , confirm 505 , undo 506 , tag reference 507 and “mark as unknown” 508 . The remaining buttons 509 can be assigned to the different taglines a Tagger may typically be working with. The Tagger switches between Metadata Taglines by pressing the appropriate buttons 509 on the control pad. Whilst a Tagline is selected, the Tagger 431 speaks into the microphone to describe what he/she sees at the current point of playback of the currently playing movie 423 . If the image content is raw footage that has been geotagged in the manner described above with reference to FIG. 3 , then not only will the location and time data be available from the GPS location system, but that data can then be referenced against and linked to a resource such as Google Maps Enterprise. This allows the Tagger to see the location details of the image currently be viewed on a map on the tagging screen. Thus, for example, when the tagger sees a church on screen, the system can pick up the true name of the church using the location data. For example, the Tagger says “church”, and the system interrogates the map data and notes that there is only one church within 100 meters of location, named “St Matthews”, and tags the church as “St Matthews”. Voice Recognition Software 432 takes the audio stream of her recorded voice as an input, converting it into text or flagging it for disambiguation in the later quality assurance process. The Voice Recognition Software also removes extraneous sounds and optional words from a list stored in the Software Settings. If the Tagger is unable to recognise a given location, character or object he/she can assign a Tag Placeholder 425 , for instance “Character A”, which can then be corrected in the quality assurance process. The Tagger is also able to switch to the Tag Reference screen, thereby pausing the current playback and allowing the Tagger to browse stills from other Taggers' work 426 to find a definition for the item he/she is currently trying to tag. For example, characters will be displayed in a grid with their names below them based on having been successfully tagged by others. The Tagging Software takes the text versions of what has been said from the Voice Recognition Software and inserts them as Metadata Tags into the currently selected Metadata Tagline for the current clip at the point 427 that the word occurred in the audio stream, with adjustment for word length and the Tagger's ‘latency’, which is a setting that can be adjusted in the Software Settings. The tags are stored in a local database 433 . Each Tag is broadcast 434 to all of the other Taggers in the Tagger's team, as well as to any other user working on the project, including which Tagline it relates to, the position on that Tagline and its context within other Tags. As Tags are broadcast to other Taggers, the Software will recommend Tags 635 to each Tagger based on analysis of the tags that the Tagger has already added, tags that other Tag Team Members are using, and also recommendations based on dictionary or thesaurus look-ups and semantic analysis. The suggestions may be mediated by a Tag suggestion agent 435 . The tagging information is also sent to the Media Asset Management System (MAM) which stores each Tag in an SQL database and assigns it to the high resolution file. Once the Tagger has completed tagging the current clip, the next is automatically loaded from the Clip Queue and the process continues. The process is overseen by a Quality Controller 440 for the team who is logged in to the Admin Dashboard 441 . Once a given amount of video content has been tagged, the Quality Controller 440 is alerted and checks and corrects the content for errors. The Quality Controller uses Administration tools to approve tags 442 , request a rerun 443 and for disambiguation 444 . The Quality Controller signs off on the team's work, and the tags are committed to the main Media Asset Management System 445 , and also injected into the High Resolution media files. Once a piece of footage has been completed, a range of information relating to the tagging process is stored in the Tagging Software. Examples of such information include the accuracy of the Tagger's work, the density of keywords per minute, any unusual keywords used, and an indication if a given Tagger is the first to tag certain characters, objects and locations correctly. Other data about the Tagger and the Tag Team's performance may be stored in the Tagging Software, including scores 446 assigned to the Tag team members 447 . The Tagger can view his/her performance ranked against other team-mates and other teams in a High Score Table type display 448 on the Dashboard, and the system offers hints, tips and encouragement to the Taggers. FIGS. 8A and 8B are representative line drawings of actual screen shots, illustrating a user interface with a piece of video content being tagged. As illustrated in FIGS. 8A and 8B , the process of metadata being added is shown to the user via a unique display (user interface) 800 that is both qualititative and quantitative in form. As each keyword is added to the footage, a line 801 , 802 , 803 appears on the clip timeline 810 , which displays the exact timecode point at which the keyword has been added. The colour of the displayed line corresponds to the layer upon which the keyword has been placed, for example: Technical=grey line 801 , Action=yellow line 802 , Character=blue line 803 . Via this feature the user can immediately see the quantity of metadata that is being added to each clip in what may be a large volume of content. Simultaneously, as shown in FIG. 8B , a real-time display of every keyword added with a thumbnail 805 of the exact frame in the content scrolls across the bottom of the screen. This allows the user to see exactly what keywords are being added to what image so that they can accurately check the quality of the keywords. This means that via a single display, a large quantity of metadata becomes a meaningful and understandable dataset, which it previously has not been. Furthermore, as shown in FIG. 8B , if the user selects a clip in the timeline 810 , and moves their mouse over the content 820 as it plays, every keyword added to that clip will displayed 825 opaquely over the content 820 . Each of these keywords can be clicked upon, and in doing so will take the user to the exact timecode point in the video where that keyword was added. Similarly, if the user hovers their mouse over one of the thumbnails 805 as they scroll across the bottom of the screen, the act of clicking on it will take them to the exact point in the content that that keyword was added. Together, for the first time, these two powerful display innovations enable a user to be able to understand and interact with a high speed metadata process, as it happens in real time. As indicated above, the software element used to implement the invention will typically be coded as a web application, since it will be used both in the metatagging factory and also for remote, home based workers. The latter can be served video over broadband at lower resolution for archive footage tagging purposes. A variety of incentives can be supplied for remote workers including remuneration based on the quality of their tagging and the subsequent provision of the tagged content to paying end customers. The present invention provides an innovative method of tagging image content with rich metadata and serving the tagged data to clients and end consumers. The apparatus and system employs a number of readily available components, but also integrated in an innovative manner with proprietary interfaces. As will be appreciated by those skilled in the art, aspects of the invention can be implemented in a variety of different ways and the invention itself can be applied to a wide range of scenarios where image content can be usefully enhanced by the addition of metadata tags and the serving of the tagged content in searchable and editable form. The invention enables image content to be stored in a safe and readily accessible form and at a cost that is not prohibitive to the owners of the content. Moreover, the invention allows the creators or owners of the image content to edit and finalize raw content with increased functionality and also leverage the commercial worth of the finalized content through its enhanced searchability and provision when served over the web.
A method and apparatus for tagging image content with rich metadata is provided. The metadata is generated from keyword descriptions of image content spoken by human taggers while viewing the content. Voice recognition software is employed to identify the key keywords in an audio stream and the resultant metadata is associated in a synchronous manner with the relevant image content. A control console allows the human tagger to rapidly navigate onscreen menus and select different taglines for providing multilevel metadata tagging of the image content. An integrated system provides for the storage of tagged digital image content, with near immediate access to tagged raw footage for viewing and editing, and for easy searching and accessing of finalized footage. A method of serving the tagged content is also provide, which allows the content to be streamed over the web at an acceptable image resolution while maintaining the associated metatags.
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RELATED APPLICATION DATA [0001] This application claims the benefit of and priority under 35 U.S.C. §119(e) to U.S. Patent Application Ser. No. 60/344,927, filed Nov. 7, 2001, entitled “A Method for the Determination of the System Parameters of an Echo Measurement System,” which is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] This invention generally relates to time-domain reflectometry. In particular, this invention relates to systems and methods for calibrating a time-domain reflectometer to precisely determine the reflectometer's response when connected to an electrical network. [0004] 2. Description of Related Art [0005] Time-domain reflectometry (TDR) systems use electrical measurements to estimate the physical structure and electrical nature of a conducting medium, which will be referred to herein as the Device Under Test (DUT). An example of a DUT is a twisted pair subscriber line, which comprises one or more interconnected electrical transmission lines generally having unknown terminations. Features of the DUT that can be estimated include the length of the line, the existence of bridged taps, the bridged tap locations, the bridged tap lengths, changes in gauge, terminations, and the like. Exemplary DUTs, such as subscriber lines, are constructed of twisted pairs, which distort the amplitude and phase of electrical waveforms that propagate through the line. Since, the amplitude of the waveforms decrease exponentially with travel distance, the waveforms received from long subscriber lines are extremely weak and require a precise TDR system to capture minute variations that contain information about the characteristics of the subscriber line. SUMMARY OF THE INVENTION [0006] Identifying, measurizing and characterizing the condition of a transmission line is a key element of any Digital Subscriber Line (DSL) deployment. In cases where the transceiver connection is not performing as expected, for example, the data rate is low, there are many bit errors, a data link is not possible, or the like, it is important to be able to identify characteristics about the loop including the length of the loop, and the existence, location and length of any bridged taps without having to send a technician to a remote modem site to run diagnostic tests. In these cases a TDR system can be used to measure and characterize the transmission line in order to determine the problem with the connection. It is particularly desirable to implement the TDR system in the DSL transceiver that is already connected to the transmission line. This allows the DSL service provider to determine transmission faults without physically disconnecting the telephone line from the DSL transceiver, thus effectively converting the DSL transceiver into a TDR system. [0007] The TDR system discussed herein includes a three-port network, which will be referred to herein as the “front-end.” The TDR front-end is used to transmit signals and receive the corresponding reflected signals to obtain information about the characteristics of the DUT. As discussed above, one exemplary implementation of such a three-port device is the front-end of a DSL transceiver. [0008] A TDR front-end comprises numerous components. An artifact of these components is that information-bearing TDR signals are distorted as they pass through these components. With a perfect model of the response of the front-end, a TDR system can usually compensate for the artifacts introduced by the front-end components. In reality, however, the electrical characteristics of each component vary from design-to-design, board-to-board, slowly over time, and based on temperature. This is especially an issue when the TDR system is implemented in a DSL transceiver utilizing the DSL transceiver front-end. Since the DSL transceiver must also operate as a regular information transmission device, the transceiver is designed using different design criteria than a dedicated TDR system. For example, DSL transceivers are consumer devices that are produced in large volume at low cost and therefore the components used may not be as high a quality as dedicated TDR systems. The result is imperfect knowledge about the true response of the front-end, errors in the model of the front-end and degraded TDR performance. [0009] For at least this reason, it is important to precisely characterize the response of the TDR front-end. In particular, a front-end calibration method is required to determine the exact characteristics of the TDR system thereby removing the uncertainty of the electrical characteristics of the components in the TDR front-end. Since the TDR system is a three port system the calibration method determines the three independent parameters that completely specify any three port system. In the calibration process, the TDR system is connected to at least three predetermined DUTs and the TDR front-end is used to transmit signals and receive the corresponding reflected signals with each DUT connected. Next, the TDR system is calibrated by determining the three independent parameters of the three port TDR system using the transmitted and received waveforms along with the predetermined DUT characteristics. [0010] As an example, the TDR system can be implemented in a DSL transceiver and the DUT that needs to be characterized can be the transmission line that is causing problems in the DSL connection, e.g., bit errors. In this case, it is necessary to first calibrate the DSL transceiver front-end to characterize the electrical characteristics of all its components. Therefore, the DSL transceiver is connected to three known impedances and the DSL transceiver front-end is used to transmit signals and receive the corresponding reflected signals with each impedance connected. Next, the front-end is calibrated by determining the three independent parameters of the DSL front-end using the transmitted and received waveforms along with the known impedance values. Then, for example, as discussed in co-pending application Ser. No. 09/755,173, entitled “Systems and Methods for Establishing a Diagnostic Transmission Mode and Communicating Over the Same,” filed Jan. 8, 2001 and incorporated herein by reference in its entirety, one or more of the calibration information, characterization of the transmission line, or any other relevant information can be transmitted to a location, such as a central office modem. [0011] Accordingly, the systems and methods of this invention at least provide and disclose a model of the TDR front-end and a method for determining the parameters of the model using experimental measurements. [0012] Aspects of the invention also relate to a generalized model of the TDR front-end. [0013] Aspects of the invention further relate to modeling the behavior of a composite system where an arbitrary DUT is connected to port three of the TDR system. [0014] Aspects of the invention also relate to calibrating the TDR front-end model. [0015] Furthermore, aspects of the invention further relate to determining the TDR front-end model parameters. [0016] These and other features and advantages of this invention are described in, or apparent from, the following detailed description of the embodiments. BRIEF DESCRIPTION OF THE DRAWINGS [0017] The embodiments of the invention will be described in detail, with reference to the following figures, wherein: [0018] FIG. 1 is a functional block diagram illustrating an exemplary generalized model of a three port TDR front-end according to this invention; [0019] FIG. 2 is a functional block diagram illustrating an exemplary three-port TDR front-end model according to this invention; [0020] FIG. 3 illustrates a first exemplary method of characterizing a DUT according to this invention; [0021] FIG. 4 illustrates a second exemplary method of characterizing a DUT according to this invention; [0022] FIG. 5 illustrates a third exemplary method of characterizing a DUT according to this invention; [0023] FIG. 6 is a flowchart illustrating an exemplary method of calibrating the TDR front-end model according to this invention; and [0024] FIGS. 7-10 illustrate exemplary experimental results comparing the measured and predicted values. DETAILED DESCRIPTION OF THE INVENTION [0025] The exemplary embodiments of this invention will be described in relation to the application of a model to describe the TDR front-end and a method for determining the parameters of the model. However, it should be appreciated, that in general, the systems and methods of this invention will work equally well for modeling any type of three port TDR system. [0026] The exemplary systems and methods of this invention will also be described in relation to a TDR system that can be used in conjunction with a DUT such as a twisted-pair transmission line. However, to avoid unnecessarily obscuring the present invention, the following description omits well-known structures and devices that may be shown in block diagram form or otherwise summarized. [0027] For the purposes of explanation, numerous details are set forth in order to provide a thorough understanding of the present invention. It should be appreciated however, that the present invention may be practiced in a variety of ways beyond these specific details. For example, the systems and methods of this invention can generally be applied to any type of transmission line. [0028] Furthermore, while the exemplary embodiments illustrated herein show the various components of the TDR system collocated, it is to be appreciated that the various components of this system can be located at distant portions of a distributed network, such as a telecommunications network and/or the Internet, or within a dedicated TDR system. Thus, it should be appreciated that the components of the TDR system can be combined into one or more devices, such as a DSL transceiver, or collocated on a particular node of a distributed network, such as a telecommunications network. As will be appreciated from the following description, and for reasons of computational efficiency, the components of the TDR system can be arranged at any location within a distributed network without affecting the operation of the system. For example, the various components can be located in a CO modem, CPE modem, or some combination thereof. [0029] Furthermore, it should be appreciated that the various links connecting the elements can be wired or wireless links, or any combination thereof or any other know or later developed element(s) that is capable of supplying and/or communicating data to and from the connected elements. Additionally, the term module as used herein can refer to any known or later developed hardware, software, or combination of hardware and software that is capable of performing the functionality associated with that element. [0030] FIG. 1 illustrates an exemplary generalized model of the TDR front-end. The TDR front-end can be modeled as a linear, time-invariant three-port electrical network. Specifically, as illustrated in FIG. 1 , the TDR system 10 comprises a transmitter 100 , a receiver 110 , which may also include any necessary measurement components for measuring the received waveform as well processors and/or memory (not shown), a front-end 120 , a device under test (DUT) 130 , a first port 140 , a second port 150 , a third port 160 , a first voltage (v 1 ) 170 corresponding to the voltage across the first port 140 , a second voltage (v 2 ) 180 corresponding to a voltage across the second port, a third voltage (v 3 ) 190 corresponding to a voltage across the third port, a first current (i 1 ) 200 , a second current (i 2 ) 210 and a third current (i 3 ) 220 . In general, signals are transmitted from the transmitter 100 , such as a digital-to-analog converter or other waveform generator, at port 1 , reflections received by the receiver 110 , such as an analog-to-digital converter or other measurement device, on port 2 , with port 3 being connected to the DUT 130 , such as a subscriber line or other one-port electrical network. The TDR system 10 is also connected via link 5 to a transfer function module 20 , a storage device 30 and a parameter and matrix determination module 50 . [0031] This three-port model of the front-end captures any linear, time-invariant implementation that may be present within the front-end, including, but not limited to, transmit path filtering inside port 1 , receive path filtering inside port 2 , hybrid circuitry connecting the ports, output filtering inside port 3 , echo cancellers, or the like. Exemplary TDR front-ends that are characterized by the three-port model of the front-end include a wired or wireless modem, a DSL modem, an ADSL modem, a multicarrier transceiver, a VDSL modem, an SHDSL modem, and the like. [0032] FIG. 2 illustrates an exemplary configuration within the three-port TDR front-end model 120 . For this exemplary implementation, the front-end model 120 comprises a transmit path filter 230 , a receive path filter 240 , an analog hybrid circuit 250 and an output filter 260 . [0033] However, regardless of the specific implementation inside the front-end model, any linear time-invariant three-port network can be described by the matrix equation u=Yw, where [0000] Y = ( y 11 y 12 y 13 y 21 y 22 y 23 y 31 y 32 y 33 ) [0000] is an admittance matrix describing the relationships between currents and voltages of each port, and [0000] u = ( i 1 i 2 i 3 )   and   w = ( v 1 v 2 v 3 ) [0000] are vectors containing the currents and voltages, respectively, at each port. Further details regarding the vector relationship can be found in Microwave Engineering , Second Edition, by D. M. Pozar, Wiley, New York, 1998, which is incorporated hereby by reference in its entirety, and in particular pp. 191-193. [0034] In general, each of the quantities y ij are a complex function of frequency. Explicit notation of frequency dependence has been omitted for clarity. Therefore, it should be assumed that all parameters are complex functions of frequency unless noted otherwise. [0035] The DUT typically comprises one or more interconnected electrical transmission lines with unknown terminations. More generally, the DUT may be any linear, time-invariant, one-port electrical network. An exemplary DUT is a subscriber line. [0036] There are several exemplary ways to completely characterize the DUT including, for example: 1) As a complex, frequency-dependent input impedance Z, as shown in FIG. 3 . The input impedance includes all aspects of the DUT 130 and is not just limited to the characteristic impedance of the first section. 2) As a voltage impulse response v ir (t), also denoted h(t), when connected to a voltage source with source impedance Z source as shown in FIG. 4 , where δ(t) is an impulse voltage waveform. 3) As a complex, frequency-dependent one-port scattering parameter S 11 with respect to reference impedance Z ref as shown in FIG. 5 , where v + is the forward-traveling voltage wave, v − is the backward-traveling voltage wave and [0000] S 11 = v - v + . [0040] However, it is to be appreciated that while only three exemplary methods of characterizing a DUT are enumerated, there are an infinite number of ways to completely characterize a DUT. Each representation provides the same amount of information about the DUT such that each characterization is fundamentally equivalent. Therefore, changing the representation of the DUT does not change the behavior of the DUT, the representation merely changes the description of how the DUT behaves. [0041] Each of the various representations can be mapped to one another using transformations. For example, if the DUT is described by its voltage impulse response h(t), then it is related to input impedance Z of the DUT in accordance with: [0000] h  ( t ) = Z Z source + Z . [0042] Similarly if the DUT is described by its complex, frequency-dependent one-port scattering parameter S 11 , then it is related to the input impedance Z of the DUT in accordance with: [0000] S 11 = Z - Z ref Z + Z ref . [0043] For ease of understanding, the remaining disclosure will use the complex, frequency-dependent input impedance Z to describe the DUT. However, it should be appreciated, that any other equivalent representation can be substituted without changing the underlying behavior of the model. [0044] Specifically, the system attempts to model the behavior of the composite system when an arbitrary DUT is connected to port 3 of the TDR system 10 . The behavior of the system is described by the response at the receiver port 2 150 to a stimulus at transmitter port 1 140 . Either voltage or current can be applied at port 1 140 , and either voltage or current can be measured at port 2 150 . Therefore, there are at least four possible ways to obtain the system transfer function. However, it should be appreciated, that the system transfer function is but one or many equivalent ways to completely characterize the system. Any of these four methods provides the same information about the system, the choice of using one method over another depends, for example, on which one is more efficient to implement. [0045] As an example, voltages can be used at port 1 and port 2 so the voltage transfer function for the system is [0000] H = v 2 v 1 , [0000] which is a complex function of frequency. It should be appreciated however, that the models for each of the other three possible implementations are equivalent, so the analysis presented below applies equally to each. [0046] It can be assumed that the voltage is measured at port 3 160 using a device with infinite impedance, which yields i 2 =0. If the voltage measurement device at port 3 160 were not to have an infinite input impedance, then its finite input impedance could be absorbed into the three-port network. Therefore, there is no loss in generality by assuming that i 2 =0. [0047] The voltage transfer function of the TDR system is given by [0000] H = a   Z + b c   Z + 1 ( 1 ) [0000] where a, b and c are complex functions of frequency. Relating a, b, and c to y ij , [0000] a = y 23  y 31 - y 21  y 33 y 22 , b = - y 21 y 22 , c = y 22  y 33 - y 23  y 32 y 22 . [0000] Therefore, the three-port TDR front-end can be completely characterized by three independent parameters. Like the DUT, these three TDR front-end parameters can be represented in many different ways. For example, a, b, and c can be mapped to an alternative set of parameters as follows: [0000] a ~ = a   Z ref - b c   Z ref + 1 , b ~ = a   Z ref + b c   Z ref + 1 , c ~ = c   Z ref - 1 c   Z ref + 1 . [0000] This allows H to be expressed as a function of S 11 for the DUT as follows: [0000] H = a ~  S 11 + b ~ c ~  S 11 + 1 . [0000] Again, there are an infinite number of ways to completely characterize the three TDR front-end parameters. Each representation provides the same amount of information about the TDR front-end, so they are fundamentally equivalent. [0048] However, it should be noted that the system could be completely characterized by more than three parameters. Nevertheless, any representation that uses more than three parameters can be reduced to three independent parameters by the appropriate mapping. For example, [0000] H = a ′  Z + b ′ c ′  Z + d ′ [0000] can be reduced to the three independent parameters of Eq. 1 using: [0000] a = a ′ d ′ , b = b ′ d ′ ,  and   c = c ′ d ′ . [0049] Another example is: [0000] H = a ^  Z + b ^ c ^  Z + 1 + d ^ [0000] which can be reduced to three independent parameters using [0000] a=â+ĉ{circumflex over (d)},{circumflex over (b)}+{circumflex over (d)} ,and c=ĉ. [0050] The transfer function H has been formulated in terms of a three-port electrical network and the DUT 130 . Although the three-port representation is commonly used to characterize the loading effects of analog circuitry, the transfer function H may generally include the effects of digital signal processing. For example, digital filters and digital echo cancellers could be absorbed into the a, b, and c parameters. In this case, the transmitted signal v 1 is digital in nature and does not necessarily exist as a physical voltage, but eventually is converted to a voltage through a digital-to-analog converter (DAC). Similarly, the received digital signal corresponds to v 2 , which at some point was converted from a physical voltage to a digital signal using, for example, an analog-to-digital converter (ADC). [0051] As noted above, the models of the TDR front-end can be based on as few as three complex, frequency-dependent parameters. As discussed hereinafter, a technique for determining the value of these parameters based on actual measurements is illustrated. This technique will be referred to as “calibration.” [0052] The response of the front-end model must match the response of the actual front-end precisely enough to capture minute details of the waveforms that propagate through the actual front-end. Calibration is necessary since the electrical characteristics of the real front-end components can vary from design-to-design, and from board-to-board. Sometimes, component characteristics will vary slowly over time, which necessitates that the system be calibrated within a certain time period, for example during an initialization, before TDR measurements are performed on the DUT. [0053] As an example, the system could be calibrated by measuring each component individually, and incorporating the actual values into a complex system model that takes into account the relationships between each component. In reality, however, this approach would be time-consuming and impractical because systems typically contain hundreds of components with complex relationships. The front-end of a typical DSL modem exemplifies a system with numerous components. [0054] Using a model of the TDR front-end, such as the three-parameter model disclosed above, greatly simplifies the calibration process. The model allows a precise response of a front-end to be captured by taking far fewer measurements and combining them in a much simpler fashion. [0055] Since the model of H contains three independent parameters that describe the TDR front-end, not including the parameter that characterizes the DUT, then at least three different measurements with different known DUTs are required to solve for each of the independent parameters. [0056] If N measurements have been taken with N different DUTs, each with known impedance, then the TDR system transfer function can be determined for each of these N configurations. It is possible to determine values for a, b, and c that best fit Eq. 1 for the collection of all N configurations. The notion of “best fit” depends on the criterion chosen to quantify how well the measured values fit the data, such as minimizing some measure of error. One common criterion for establishing best fit is to minimize error in the least-squares sense. It should be noted however, that other optimization criteria are possible. If another optimization criterion is used, the underlying concept remains the same. [0057] The following example demonstrates optimization of a, b, and c in the least-squares sense. Assume that N measurements have been taken. Let Z n and H n denote the DUT impedance and TDR system transfer function, respectively, obtained for measurement n. Rearranging Eq. 1, aZ n +b−cZ n H n =H n for each n. This system of equations can be re-written in matrix form as Av=h where [0000] v = ( a b c ) [0000] contains the parameters to be determined and [0000] A = ( Z 1 1 - Z 1  H 1 Z 2 1 - Z 2  H 2 ⋮ ⋮ ⋮ Z N 1 - Z N  H N )   and   h = ( H 1 H 2 ⋮ H N ) . ( 2 ) [0058] If N=3, the values of a, b and c can sometimes be obtained by solving v=A −1 h. In practice, however, measurement errors sometimes cause this system of equations to be inconsistent. If N>3, the system of equations is over-specified and is usually inconsistent. [0059] Therefore, a solution for v can be found that minimizes some measure of the error. To minimize the error in the least-square sense, the optimal v, and thus the optimal a, b and c, can be found by satisfying the normal equations [0000] A* T Av opt =A* T h where *T denotes transposition followed by complex conjugation. See G. Strange, Linear Algebra and Its Application, 3 rd Ed., Harcourt Brace, San Diego, 1986, incorporated herein by reference in its entirety, and in particular pp. 154-156. It should be noted however, that other error minimization criterion are possible. If another error minimization is used, the underlying concept remains the same. This results in the following optimal value: [0000] v opt =[A* T A] −1 A* T h,   (3) [0000] Because a, b, and c are frequency-dependent, this equation must be solved separately for each frequency of interest. [0060] An exemplary technique for calibration according to this invention is accomplished with the aid of the transfer function module 20 , the storage device 30 and the matrix and parameter determination module 40 . [0061] In particular, a DUT 130 of known impedance Z n is connected to port 3 160 . The value of Z n should be known precisely and should be preferably chosen to maintain the front-end 120 within operational limits. A waveform v 1 is then generated and transmitted from the waveform generator 100 at port 1 . The transmitted waveform is received as the returned waveform v 2 at port 2 150 and consequently at the receiver 110 . [0062] The transfer function module 20 determines the transfer function of the TDR system for the current DUT, i.e., DUT n , in accordance with H n =v 2 /v 1 and stores the corresponding value pairs of Z n and H n in the storage device 30 . This process is repeated for each n with the corresponding value pairs of Z n and H n being stored in the storage device 30 . [0063] Having the pairs of Z n and H n , the matrix and parameter determination module 40 determines matrix A and vector h based on Eq. 2, as well as the parameters a, b, and c based on Eq. 3. The TDR system response H for any arbitrary DUT characterized by Z, can then be predicted by the transfer function module 20 based on the optimal parameters a, b, and c identified in Eq. 1. [0064] FIG. 6 illustrates an exemplary technique for calibration according to this invention. In particular, control begins in step S 100 and continues to step S 110 . In step S 110 , a DUT of a known impedance is connected to port 3 . The value of Z n should be known precisely. Ideally, Z n can be any value, but practical considerations dictate that care be taken to ensure that the front-end remains within its proper operating region. For example, port 3 should not be short-circuited if the short circuit would cause the front-end to exhibit non-linear behavior. The value of Z n can be complex and frequency-dependent, but usually a constant, real resistance is adequate. [0065] Next, in step S 120 , a waveform v 1 is transmitted at port 1 . Then, in step S 130 , the transmitted waveform is received as the returned waveform v 2 at port 2 . The transmitted waveform v 1 should be chosen such that it adequately illuminates all frequencies for which the transfer function of the TDR system is to be determined, and it should also adhere to the sampling rate and dynamic range limitations of the front-end. Otherwise, any arbitrary v 1 can be used. [0066] Furthermore, averaging can be performed to reduce uncorrelated background noise that might be present during each transmission. Control then continues to step S 140 . [0067] In step S 140 , the transfer function of the TDR system is determined for the current DUT in accordance with [0000] H n = v 2 v 1 . [0068] Only v 1 and v 2 are used in this calculation. Z 1 , a, b, and c are not used. [0069] Next, in step S 150 , the values of Z n and H n are recorded. Then, in accordance with step S 160 , for each n, steps S 110 -S 150 are repeated. It should be ensured that Z n covers at least three distinct values. It is desirable to have a range of Z n that approximates many possible DUTs. When this step is complete, N pairs of measurements for Z n and H n will have been recorded, where N is the number of complex impedances used, and N>3. Experiments have shown that results are improved by using more than three measurements, sometimes as many as ten (S 170 ). Control then continues to step S 180 . [0070] In step S 180 , the parameters a, b, and c are determined to best fit Eq. 1 for the collection of all N values of Z n and all N values of H n . One exemplary method for determining a, b, and c, is to minimize error in the least-squares sense using Eq. 2 and Eq. 3. Then, in step S 190 , the TDR system response H for any arbitrary DUT characterized by Z, is predicted using the optimal parameters a, b, and c used in Eq. 1. Control then continues to step S 200 where the control sequence ends. [0071] An experimental example of implementing the above calibration method was performed using a TDR system implemented on a DSL transceiver. In particular, three measurements on a particular DSL transceiver front-end were performed by connecting 10Ω, 51Ω, and 100Ω resistors to the DSL line interface port, i.e., port 3 . V L (f) was obtained by sampling the analog voltage waveform at a rate of 2204 k samples per second, since this corresponds to the standard DSL transceiver sampling rate. The final measurement of the response of the DSL front-end was obtained by dividing V L (f) into the input voltage waveform V s (f). The DSL front-end parameters a, b, and c were then determined in accordance with the above-described method. FIG. 7 shows the DSL front-end parameters obtained by solving Eq. 2. To test how well the given formulation can predict the actual echo responses, the measured and predicted echo responses were plotted in FIGS. 8-10 . The predicted echo responses were obtained by plugging in the determined DSL front-end parameters a, b, and c into Eq. 1 for Z=10Ω, 51Ω, and 100Ω. As observed, the exemplary measured and predicted echo responses very closely approximate each other confirming the model for the DSL front-end and validating that the approach of calibrating the transceiver by determining the parameters a, b, and c via experimental measurements is accurate. [0072] The above-described TDR modeling system can be implemented on a telecommunications device, such a modem, a DSL modem, an SHDSL modem, an ADSL modem, a multicarrier transceiver, a VDSL modem, or the like, or on a separate programmed general purpose computer having a communications device. Additionally, the systems and methods of this invention can be implemented on a special purpose computer, a programmed microprocessor or microcontroller and peripheral integrated circuit element(s), an ASIC or other integrated circuit, a digital signal processor, a hard-wired electronic or logic circuit such as discrete element circuit, a programmable logic device such as PLD, PLA, FPGA, PAL, modem, transmitter/receiver, or the like. In general, any device capable of implementing a state machine that is in turn capable of implementing the flowchart illustrated herein can be used to implement the various TDR modeling methods according to this invention. [0073] Furthermore, the disclosed methods may be readily implemented in software using object or object-oriented software development environments that provide portable source code that can be used on a variety of computer or workstation platforms. Alternatively, the disclosed TDR modeling system may be implemented partially or fully in hardware using standard logic circuits or VLSI design. Whether software or hardware is used to implement the systems in accordance with this invention is dependent on the speed and/or efficiency requirements of the system, the particular function, and the particular software or hardware systems or microprocessor or microcomputer systems being utilized. The TDR modeling systems and methods illustrated herein however can be readily implemented in hardware and/or software using any known or later developed systems or structures, devices and/or software by those of ordinary skill in the applicable art from the functional description provided herein and with a general basic knowledge of the computer and telecommunications arts. [0074] Moreover, the disclosed methods may be readily implemented in software executed on programmed general purpose computer, a special purpose computer, a microprocessor, or the like. In these instances, the systems and methods of this invention can be implemented as program embedded on personal computer such as JAVA® or CGI script, as a resource residing on a server or graphics workstation, as a routine embedded in a dedicated TDR modeling system, or the like. The TDR modeling system can also be implemented by physically incorporating the system and method into a software and/or hardware system, such as the hardware and software systems of a communications transceiver. [0075] It is, therefore, apparent that there has been provided, in accordance with the present invention, systems and methods for TDR modeling. While this invention has been described in conjunction with a number of embodiments, it is evident that many alternatives, modifications and variations would be or are apparent to those of ordinary skill in the applicable arts. Accordingly, it is intended to embrace all such alternatives, modifications, equivalents and variations that are within the spirit and scope of this invention.
A three-port TDR front end comprises numerous components. An exemplary three-port TDR front end is a DSL modem. Information-bearing TDR signals are distorted as they pass through these components. With a perfect model of the response of its front-end, a TDR system usually can compensate for the effects of its front-end. In reality, however, the electrical characteristics of each component vary from design-to-design, board-to-board, and slowly over time. The result is imperfect knowledge about the true response of the front-end, errors in the model of the front-end, and degraded TDR performance. At least for this reason it is important to precisely calibrate the response of the TDR front-end through the use of a TDR modeling system.
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RELATED PATENT DOCUMENTS Related documents are coowned U.S. Pat. No. 5,276,970 of Wilcox, and U.S. Pat. No. 4,789,874 of Majette—and also U.S. patent application Ser. No. 08/657,722 in the names of Armiñana et al., issued as U.S. Pat. No. 5,992,969. Each of these documents in its entirety is incorporated by reference into this present document. FIELD OF THE INVENTION This invention relates generally to machines and procedures for printing text or graphics on printing media such as paper, transparency stock, or other glossy media; and more particularly to a scanning thermal-inkjet machine and method that construct text or images from individual ink spots created on a printing medium, in a two-dimensional pixel array. It is most particularly applicable to large-format printer/plotters. BACKGROUND OF THE INVENTION (a) Encoders in incremental printing—Most large-format incremental printers use a linear encoder in determining and controlling printhead-carriage position and called “codestrip”, tensioned along the scan-axis structure, and an encoder sensor that is assembled on the carriage—with a groove for the strip. The sensor electrooptically reads markings on the taut strip. Associated electronics generates electronic pulses for interpretation by circuitry in the printer. Some early tensioned encoder strips were all plastic, adequate for small, desktop printers but not for larger printer/plotter machines. Other early strips were glued to the carriage-supporting “beam” structure, but such a solution gave up the advantages of a separate tensioned strip—including much easier assembly and disassembly, on the assembly line as well as in the field. Representative work of recent years in codestrip refinement appears in the Wilcox and Armiñana documents mentioned above. Such work in electronic interfacing appears in the Majette patent. (b) Alignment—Accurate readings, and also minimization of noise in operation, require good alignment between the strip and sensor. Maintaining such performance reliably over the life of a product requires avoiding friction and wear—which in turn makes alignment even more important. In the evolution of large-format printer/plotters, recent developments have tended toward use of these devices to print wider and wider mechanical drawings and posters. Of course these applications require wider-bed printing machines with correspondingly longer codestrips. Alignment, however, is progressively more difficult for longer codestrips, partly because of the tendencies to sag under the influence of gravity and twist slightly due to very small variations in mounting angle at each end of the strip. A particularly problematic cause of misalignment is vibration in the working environment. Vibration sources include impacts from nearby industrial construction, heavy motor traffic, elevators within the building and the like. Nevertheless, for codestrips of the type introduced in the Armiñana document, alignment has been under good control heretofore in systems having modest overall carriage travel—below about one meter (roughly three feet). (c) The one-meter barrier—More recently it has been noted that performance for strips spanning about 107 cm (3½ feet) is acceptable, but only marginally so. A current generation of these machines requires encoder strips with spans of 152 cm and 183 cm (five and six feet respectively). In a machine of this size the associated long dimensions of the strip cause failures in functional-vibration tests, particularly in large-amplitude harmonic movement near the middle of the strip. This vibration can produce bad readings from the sensor. For instance the counter may miss counting one or more scale graduations on the encoder strip. The result can be significant errors in a printed image. In cases that are even more serious, vibration causes complete disassembly of the sensor system—as the strip jumps entirely out of the sensor groove. In such cases trained service personnel may be required to restore normal operation. Damage to the strip can occur, and the sensor too may require repair. To prevent such problems the system is programmed to shut down the carriage servocontrol motor if the sensor system is able to detect that it has lost count of the encoder graduations—as for example if it loses the pulse train completely. If such a loss of count occurs while the carriage is near either end of the mechanism, and moving rapidly toward that end, this safety override may not have enough time to stop the carriage before it reaches the end bulkhead. Considerable damage to the carriage and other parts of the mechanism can result. For machines of modest size it is sufficient to provide a mechanical limiter that simply retains the strip within the sensor groove. The limiter and its installation represent undesirable added cost. This simple solution, moreover, has proven inadequate for a strip over 1½ m long. Even though retained within the sensor, the strip undergoes oscillations large enough to make sensor measurements erratic and unreliable. People familiar with this field will understand that the “barrier” suggested in the title of this subsection is not an abrupt step at precisely one meter. Rather the difficulty in achieving satisfactory codestrip arrangements increases progressively over a considerable range from, perhaps, less than one meter to two or possibly three meters. Nevertheless there is a clear qualitative difference, between lengths under one meter and lengths of, say, several meters. (d) An overconstrained problem—The encoder strip is a rather simple mechanical article, but those skilled in the art will recognize that this seeming simplicity may be very deceptive. The strip interacts in subtle ways with several different complex components of the system. As a result, it is not at all obvious how to overcome the difficulties outlined above. Some of the more-evident candidate solutions are impractical, due to certain persistent constraints. The progressively larger machine formats, even below the one-meter barrier suggested earlier, have called for greater tension in the strip. Beyond that barrier, simple increase of tension in the strip is unacceptable. One reason is that higher tension could potentially introduce safety concerns. Another reason is that higher tension in the strip can cause small twists and other irregular deformations in the associated mechanism. Even if microscopic, such interference with the straightness and structural integrity of the guide-and-support rods and beam can throw off the positional calibration of the whole carriage drive system. Such potential damage can be difficult to detect, and the design cost of reevaluating the entire mechanical system for such potential damage is in itself severe. If found, such a problem can be compensated only by strengthening the entire structure. Beefing up the mechanism in that way, in turn, would entail additional weight and cost. Another complication is that addition of stiffening elements or any other attachment to the strip itself would be extremely awkward, since the sensor groove is very narrow. Of course it is important not to add anything to the strip, or next to it, that might pose even greater risk of damage than the strip itself poses—that is to say, catastrophic failure modes must be evaluated as carefully as routine operation. Thus a supporting ledge below the codestrip (reasonably remote from the moving sensor) might be useful, although costly, but it would not resolve the problem of the strip moving upward. A “ceiling” strip immediately above the codestrip, to correct that deficiency, does not appear practical since the encoder sensor—moving at high speed—could strike such a component. It has been suggested to return to the approach of using adhesive to secure a strip to a solid beam structure. As mentioned earlier, however, that approach has associated inefficiencies and high costs. Such a beam-mounted encoder strip is also difficult to install and remove. Using small screws or bolts to fix a thin metal strip along the base would be even more undesirable. The assembly time required to thread in several screws is a significant cost in terms of modern production engineering. A separate rigid structure—to be bolted into place on the beam—would be still more impractical. Still another difficulty of earlier codestrip designs relates to the dimension stack. The dimension stack is the group of geometrical dimensions that must be algebraically added to calculate the relative position between two specified parts. Every dimension has a tolerance. If the number of dimensions is large—i. e. if the dimension stack is “long”—the tolerance can become very large, which is very undesirable. The pertinent parts in this case are the encoder strip and sensor, and the most problematic dimension is vertical alignment between the graduations and the sensor. For use of standardized parts and good performance, clearance between the top of the strip and the top of the sensor groove is only about two millimeters; and the graduations are roughly just four millimeters tall. Accordingly in one common failure mode the codestrip strikes the upper end of the groove. In another, as mentioned earlier, the downward-moving codestrip entirely leaves the groove. Making the groove substantially taller would result in greater noise levels in the electronics system. It would also implicate still further problems of mechanical alignment between parts. The encoder dimension stack for large-format printer/plotters is in fact undesirably lengthy. It is long primarily because of the tensioned mounting system—and also because the codestrip itself in these wide-bed systems is literally long, leading to large variations in vertical position at each point along the strip. In particular, the stack for the vertical relationship between the encoder-scale graduations and the immediately adjacent sensor includes the mounting tolerances within the sensor, and tolerances of the sensor mounting to its carriage. Next the stack continues through the carriage, and the carriage bushings, to the rods—then the beam, then the codestrip, and finally tolerances within the strip to the scale graduations. As a result, variation between machines, as to the vertical sensor-to-scale alignment, is very large. Mounting and configuration of the strip itself, however, accounts for much of this variation. Finally, an ideal solution should be one that is amenable to routine incorporation into not only 1½ to 2 m printers but also into both smaller and larger systems. For instance, a solution should be usable in 107-cm units previously described as “marginal” in encoder-strip performance, and also in 3 m or 7 m systems. It would be an added bonus to find a solution that could be implemented in a retrofit mode for any smaller systems installed in especially problematic (high vibration) environments. As this discussion shows, the codestrip problem is a particularly knotty one that defies easy solutions. (e) Conclusion—Codestrip instabilities have impeded the extension of uniformly excellent incremental printing to images well over a meter wide. Thus important aspects of the technology used in the field of the invention remain amenable to useful refinement. SUMMARY OF THE DISCLOSURE The present invention introduces such refinement. In its preferred embodiments, the present invention has several aspects or facets that can be used independently, although they are preferably employed together to optimize their benefits. In preferred embodiments of a first of its facets or aspects, the invention is an encoder strip for use in incremental printing. More specifically the strip is for use with mounting means that include a series of spaced pins for nonfastening support and alignment of the strip. The encoder strip includes an elongated member defining incremental-printer encoder indicia. It also includes a series of spaced apertures formed in the elongated member for nonclamping engagement with the spaced pins. The foregoing may constitute a description or definition of the first facet of the invention in its broadest or most general form. Even in this general form, however, it can be seen that this aspect of the invention significantly mitigates the difficulties left unresolved in the art. In particular, because it can be both supported and restrained vertically by the pin-and-aperture combinations, the novel codestrip can be mounted with much lower tension than earlier strips. The vertical support and restraint can be used to prevent the strip from bouncing downward out of the encoder groove—or upward and striking the end of the groove—particularly near the middle of the span, as well as from sagging and rotating. Nevertheless, since it is not to be fastened to its supports at the several pins, this codestrip is quickly and easily installed and replaced. It is also subject to substantially common tension all along its length and so behaves in a consistent fashion longitudinally. Although this aspect of the invention in its broad form thus represents a significant advance in the art, it is preferably practiced in conjunction with certain other features or characteristics that further enhance enjoyment of overall benefits. For example, it is preferred that the ends of the elongated member are for fastening to the mounting means, to secure and tension the elongated member. In this arrangement, at least one of the spaced apertures is spaced distinctly away from the fastening ends of the elongated member. Preferably the codestrip is a composite strip comprising a transparent member secured to a strength member. Also preferably the spaced apertures are shaped to constrain the elongated member with respect to exclusively one dimension; preferably they are slot-shaped (this allows for thermal expansion and contraction independently of the pins and mount). Preferably the elongated member exceeds approximately one meter (roughly forty inches) in length. Still more preferably the elongated member exceeds approximately 1.25 meter (approximately fifty inches) in length. The member is capable of use in spans of 1.5 and 1.75 meters (sixty and seventy) inches and longer, in which its use is still more preferable. The present novel codestrip escapes from the previously undesirable relationship between tension or positioning problems, on the one hand, and length on the other hand. Preferably the apertures are spaced to facilitate cutting elongated members in several different sizes from common, preapertured stock. More specifically, it is preferred that they be spaced at approximately thirty centimeters (11¾ inches) on centers to facilitate cutting spans of approximately 91½, 106½, 152½ and 183 centimeters (thirty-six, forty-two, sixty and seventy-two inches) from common, preapertured stock. Preferably at least one of the spaced apertures is positioned to prevent fundamental oscillation of the elongated member, due to environmental vibration, from moving the elongated member out of a specified operating position. Such positioning is especially effective in avoiding the vertical bouncing or sagging of previous codestrips, particularly in case of vibration from nearby equipment as mentioned earlier. In preferred embodiments of a second of its major aspects, the invention is a printer for use in incremental printing. The printer has an encoding system, and includes an elongated encoder strip defining encoder indicia—and having spaced apertures formed in the encoder strip. In preferred embodiments of a second of its major aspects, the invention is a printer for use in incremental printing. The printer has an encoding system, and includes an elongated encoder strip defining encoder indicia—and having spaced apertures formed in the encoder strip. The printer also includes some means for mounting the encoder strip. For purposes of generality and breadth in discussing the invention, these means will be called simply the “mounting means”. The mounting means in turn include some means for nonclamping protrusion through the spaced apertures of the encoder strip to support and align the encoder strip. Again for breadth and generality these means will be called the “nonclamping protrusion means”. The nonclamping protrusion means include a series of spaced pins. Also part of the printer are some means for responding to the encoder indicia (the “responding means”) to control printing. The foregoing may constitute a description or definition of the second facet of the invention in its broadest or most general form. Even in this general form, however, it can be seen that this aspect of the invention too significantly mitigates the difficulties left unresolved in the art. In particular, the incremental printer of this second aspect of the invention is capable of forming drawings or photographic-quality pictures on paper of virtually unlimited width, since the printer itself can now be manufactured essentially as wide as desired. Although this second aspect of the invention in its broad form thus represents a significant advance in the the “supporting and tensioning means” or in shorthand form the “end-supporting means”. In this case, at least one of the spaced pins is spaced distinctly away from the end-supporting means. Another preference, particularly if the printer includes a scanning printhead carriage that moves substantially parallel to the encoder strip, is that the printer further have a sensor disposed adjacent to the encoder strip and carried on the scanning printhead carriage. Here it is preferable that the previously mentioned responding means include means for developing signals representative of position and velocity of the sensor and carriage relative to the encoder strip. These signal-developing means are responsive to the sensor. Yet another preference is that the printer include printheads carried on the carriage and forming colorant patterns on the printing medium—to construct an image on the medium—and a printing-medium advance mechanism providing relative motion, perpendicular to the scanning printhead carriage, between the carriage and the printing medium. In this case the responding means further include a digital processor to coordinate the printheads and the advance mechanism in forming the image. The processor is responsive to the position- and velocity-representative signals. In this novel printer, not only the required tension but also the scale-to-sensor dimension stack is essentially independent of codestrip length. The tension need only be high enough to hold the vertical positioning of the strip within a rather tight specification over the relatively short distance between two adjacent pins—a very easy task. With this condition specified, that severe specification is the only number in the stack that importantly relates to sagging of the strip. That specification is substantially unrelated to the overall strip length. In preferred embodiments of a third of its basic aspects or facets, the invention is a method for preparing and using an encoder strip, for use in incremental printing. The strip itself includes a thin, narrow, elongated member. The method includes the steps of mounting the strip in tension with respect to its elongated dimension; and constraining the strip at multiple points spaced apart along its elongated dimension, for alignment with respect to its narrow dimension. The method also includes the step of leaving the strip substantially unconstrained with respect to its thin dimension; this last step, however, is not applied with respect to the ends of the strip, where in fact the strip is constrained with respect to its thin dimension. Again this aspect of the invention, even as couched in these broad terms, significantly advances the art of incremental printing. This is so because, by the steps stated, the method establishes an encoding function that is essentially immune to displacement of the codestrip entirely out of operating position in its encoder, and also to lesser displacements sufficient to throw off the automatic counting of encoder indicia. Yet this method maintains uniform tension along the codestrip span, allows for natural thermal response, and leaves the strip sufficiently independent of its mounts for very easy installation, disassembly and reassembly. Nevertheless it is preferable to use this novel method in conjunction with certain further features or characteristics that additionally enhance enjoyment of the benefits of the invention. For example, preferably the constraining step includes providing spaced-apart restraints for the strip, along the elongated dimension; and the mounting step comprises disposing the strip to engage the spaced-apart restraints. Another preference is that the constraining step include providing apertures in the strip, spaced apart along the elongated dimension; and providing pins to protrude through the apertures without fastening the strip to the pins. In this case certain further preferences apply, particularly if the method is for use with an encoder sensor that undergoes relative motion with respect to the strip, along the elongated dimension. Among those preferences are these three: the mounting step comprises disposing the strip in a functional positioning with respect to the sensor; in operation the strip is subject to vibration that tends to disturb that functional positioning; and the pins maintain the functional positioning. In this case, particularly if the system includes an encoder sensor that has a channel for the strip, it is yet further preferable that the mounting step include disposing the strip to extend through the channel in the sensor; and that the pins prevent the strip from leaving the channel. All of the foregoing operational principles and advantages of the present invention will be more fully appreciated upon consideration of the following detailed description, with reference to the appended drawings, of which: BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an isometric or perspective view, taken from right rear and above, of a carriage and carriage-drive mechanism according to a preferred embodiment of apparatus aspects of the present invention; FIG. 2 is a like view, but very greatly enlarged, of locating pins and slots at the exemplary five positions marked “LPS” in FIG. 1; FIG. 3 is a view like FIG. 1 but enlarged and taken along the lines 3 — 3 (i. e. from left rear and above) in FIG. 1; FIG. 4 is a left end elevation, taken along the lines 4 — 4 in FIG. 1; FIG. 5 is a right end elevation, taken along the lines 5 — 5 in FIG. 1; FIG. 6 is an isometric or perspective exterior view of a large-format printer-plotter which is a preferred embodiment of the present invention, and which includes mechanisms closely similar to those of FIGS. 1 through 5; FIG. 7 is a view like FIG. 1 but of the FIG. 6 machine and taken from front above left; FIG. 8 is a like view of a printing-medium advance mechanism which is mounted within the case or cover of the FIG. 6 device, in association with the carriage as indicated in the broken line in FIG. 8; FIG. 9 is a like but more-detailed view of the FIG. 7 carriage, showing the printheads or pens which it carries; FIG. 10 is a bottom plan of the printheads or pens, showing their nozzle arrays; FIG. 11 is a detail view like FIG. 1 but enlarged and showing the region in the sight marked 11 — 11 in FIG. 1; FIG. 12 is a view like FIG. 4 but enlarged and showing the region within the sight marked 12 — 12 in FIG. 4; FIG. 13 is a conceptual block diagram of the printers of FIGS. through 12 ; and FIG. 14 is a flow chart representing a preferred form of method aspects of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 1. Encoder Strip with Support and Alignment a. Pin support and guidance—Preferred embodiments of the invention provide a novel way to hold and reference the encoder strip 33 (FIG. 1 ). The new system is remarkably very simple and elegant. As taught in the Armiñana document mentioned earlier, the strip 33 is made up of a metal strength member 33 m (FIG. 3) and a plastic scale 33 p. Also as explained by Armiñana the plastic piece 33 p has the function of guarding the fine metal edges of the metal member 33 m. Mounted along the scan-axis beam 38 , spaced longitudinally are locating pins 60 (FIG. 2 ). Correspondingly spaced slots 61 , 62 are punch-formed along the two-piece encoder strip 33 . When all assembled to the beam 38 , the pins 60 and slots 61 , 62 form spaced-apart sets of locating pins and slots LPS. The strip 33 at assembly is tensioned from its ends as before but also positioned on the pins 60 —i. e. so that the pins 60 extend through the slots 61 , 62 in the strip 33 . The plastic scale 33 p has alternating transparent and opaque portions forming graduations, as fully detailed Armiñana. This scale passes through a groove 133 g (FIGS. 5 and 12) in the sensor 133 . The sensor 133 has a light source at one side of the groove and a detector at the other. The pins 60 prevent the previously troublesome vertical movement. They locate the strip 33 in a very accurate position for the sensor 133 to read the graduations. More specifically, mounting holes 68 for the locating pins 60 are formed along the beam 38 . The pins 60 are inserted into the mounting holes 68 and extend from the beam 38 toward the position of the encoder strip 33 , 33 m, 33 p. A plastic spacer 66 stands off the strip 33 from the beam 38 , to the correct location within the sensor groove 133 g. As formed in the metal portion 33 m of the strip 33 , the slots 61 (FIG. 2) are in a close clearance fit with the pins 60 . Ordinarily the exact clearance is not extremely critical since the strip 33 is under some tension and therefore tends to pull the slot edges of the thin metal strength member 33 m into position as required even in case of some very slight degree of interference fit. As formed in the plastic scale 33 p, the slots 62 are larger than those in the strength member 33 m. The point is to ensure that the locating action, and any necessary straightening forces, bear upon the strength member 33 m, rather than the relatively compliant plastic scale 33 p. A small area of the metal member 33 m thus is seen in the illustration, through the slot 62 serving as a window in the plastic scale 33 p. Slots 61 , 62 rather than circular holes are formed in the codestrip 33 to accommodate very slightly different thermal deformation behaviors of the strip 33 and beam 38 . Preferably at least one set LPS of locating pins and mating slots is relatively near the center of the strip, longitudinally, so as to deter vibration in a fundamental mode. The concern is vibrational amplitude, not particular harmonics; therefore it has proven unnecessary to space the pins-and-slot sets LPS according to any special harmonic analysis. This freedom is advantageously exploited to enable manufacture of the codestrips for different machine sizes from common stock. The pin mounting holes 68 and the slots 61 , 62 are accordingly spaced for manufacturing convenience at a uniform distance of approximately 30 cm on centers (11¾ inches). That spacing has been found to provide suitable clear lengths at the ends of the strip for mounting, in every machine size now contemplated. Preferably one end 33 m ″ of the strength member 33 m is bolted 69 to a solid mount, and the other end 33 m ′ (FIGS. 3 and 4) clamped or bolted to a spring plate 63 —on the end bulkhead 65 —that provides a calibrated tension. A retaining pin 64 projects from the spring plate 63 , and positively locates that end 33 m ′ of the strength member longitudinally. b. Tension—In current products, tension levels are similar to those in previous units. Much of the earlier design of the spring 63 is being reused; the tensioning holder is very rigid and can effectively resist the tension. For future models with larger scan-axis dimensions it will not be necessary to increase the tension at all, because cause the encoder weight is supported by the pins. In smaller products—unless they are modified to incorporate the present invention—the strip weight must be compensated with tension, exerting relatively high force on the tensioned holder. Thus for example in earlier designs the encoder-strip tension for a machine with printing area 91 cm (3 foot) wide the tension is 36 newtons—but for a machine with 137 cm (4½ foot) printing area, 5 newtons. With the current invention, the tension for the 91 cm machine can still be 36 N, and a 152 cm (5 foot) machine, too, is only 36 N. Such low tension causes no problems. Nevertheless if desired the tension in both machine sizes could be reduced from 36 to, say, 25 N. Perhaps most important in this regard, required tension is now independent of codestrip length. The tension need only be sufficient to maintain good vertical-positioning tolerance over the span between any two adjacent pins—i. e., only about 30 cm. c. Straightness—The straightness of the current encoder is just the straightness of the pin locations on the rod beam. In the current best implementation it is less than ±0.15 mm. With no pins the natural deformation of the encoder is much greater, on the order of ±0.8 mm, and can vary with time, from lot to lot, etc. d. Dimensional stack—As noted earlier, codestrip designs heretofore have suffered from an unduly long dimension stack. The present invention permits a major reduction in the stack, and makes the stack—like the tension—in essence independent of codestrip length. Height variation in the encoder-strip scale is now only the tolerance for a short span of 30 cm between pins. That is determined by the codestrip properties and the tension—which as already noted has also been made independent of the strip length. In consequence, tolerances of every related dimension can be smaller. A much more robust design has resulted. e. Slot-and-threaded-support variant—In practice of the present invention, pressed-in pins are greatly preferred to screw-in elements such as studs and screws. With proper installation equipment, pins are much faster to install in the base. Screw-in-elements, however, are entirely usable in place of pins, and may be substituted if desired for whatever reason. One possible situation in which screws or studs may be helpful is field retrofit of older machines. As noted earlier, such products may be advantageously retrofitted with slot support according to the present invention. Retrofit is useful if operation is affected by nearby construction, passing trucks, railway or subway lines, heavy industry or buildings with active freight elevators and the like. Trained field-service personnel using suitable special jigs or fixtures can drill and tap precisely positioned holes in the base. Studs or screws are then readily installed to support the codestrip. f. Representative dimensions—The accompanying specifications are typical of a now-preferred embodiment. Except to the extent incorporated into the accompanying claims, they should be considered merely exemplary. dimensions (mm) slot strip overall strip length on portion height thickness centers diameter metal 8 0.1  3 2.1  plastic 14  0.18 3 3.75 4A length spacing embed project tot. diameter pins 300 3 9 12 2 overall approx. width in FIGS. 4 & 5 carriage 250 g. Relationship to the prior art—The present invention enables strips with spans of 152 cm and 183 cm (five and six feet respectively) to be assembled into a large-format printer/plotter in a completely routine way. Yet it substantially eliminates previously pervasive failures in functional-vibration tests—near the middle of the strip as well as elsewhere. Vibration-induced bad readings from the sensor, such as miscounting by one or more scale graduations, have become essentially historical phenomena. The strip never jumps out of the sensor groove and accordingly never threatens to drive into the end bulkheads or in any other way to damage nearby components. No support ledge, “ceiling” element, or limiter is used. Tension in the strip is essentially as low as could be desired, substantially obviating safety concerns in this regard—as well as all potential for related deformations and calibration problems. It has not been necessary to strengthen the beam or any other part of the mechanism to achieve these goals. No stiffening element or other attachment to the strip itself is used, and nothing is added to the strip or immediately next to it that might pose a risk of damage. No adhesive, screw or bolt is needed to fix the strip to the base; rather the pins are simply pressed into place, significantly restraining assembly cost. Required tension is dramatically reduced. Perhaps more importantly, the tension is now substantially independent of the codestrip length. The tension need only be sufficient to provide good straightness over the roughly 30 cm span between adjacent pins. The encoder dimension stack, too, is correspondingly reduced, and also essentially independent of the encoder-strip length. Therefore the invention can be routinely incorporated into the present generation of 1½ to 2 m printers—and also into smaller systems, and even much larger systems, with equal ease. It can be implemented in a retrofit mode for smaller systems in problematic environments. In other words, the present system not only resolves the problems described in the “BACKGROUND” section of this document for strips one to two meters long, but actually appears to remove the length barrier entirely. With the present invention, strips under modest tension can be supported with reliable orientation and positional stability at practically any length desired. The pin-located codestrip has resolved every aspect of the defiant, knotty problems detailed earlier. 2. Other Hardware Components As noted earlier, the present invention is compatible equally well with the present generation of 1½ m and 2 m printer/plotters and earlier basic designs, some of which remain in production. This is emphasized by showing a different model, to illustrate general features of the preferred printer/plotter, from the unit appearing in FIGS. 1 through 5, and FIGS. 11 and 12. Thus some preferred embodiments include a main case 1 (FIG. 6) with a window 2 , and a left-hand pod 3 that encloses one end of the chassis. Within that pod are carriage-support and -drive mechanics and one end of the printing-medium advance mechanism, as well as a pen-refill station containing supplemental ink cartridges. The printer/plotter also includes a printing-medium roll cover 4 , and a receiving bin 5 for lengths or sheets of printing medium on which images have been formed, and which have been ejected from the machine. A bottom brace and storage shelf 6 spans the legs which support the two ends of the case 1 . Just above the print-medium cover 4 is an entry slot 7 for receipt of continuous lengths of printing medium 4 . Also included are a lever 8 for control of the gripping of the print medium by the machine. A front-panel display 11 and controls 12 are mounted in the skin of the right-hand pod 13 . That pod encloses the right end of the carriage mechanics and of the medium advance mechanism, and also a printhead cleaning station. Near the bottom of the right-hand pod for readiest access is a standby switch 14 . Within the case 1 and pods 3 , 13 the carriage assembly 20 (FIG. 7) is driven in reciprocation by a motor 31 —along dual support and guide rails 32 , 34 —through the intermediary of a drive belt 35 . The motor 31 is under the control of signals 57 from a digital electronic microprocessor (essentially all of FIG. 13 except the print engine 50 ). In the block-diagrammatic showing, the carriage assembly 20 travels to the right 55 and left (not shown) while discharging ink 54 . A very finely graduated encoder strip 33 is extended taut along the scanning path of the carriage assembly 20 , and read by an automatic optoelectronic sensor 133 , 233 to provide position and speed information 52 for the microprocessor. (In FIG. 13, signals in the print engine are flowing from left to right except the information 52 fed back from the encoder sensor 233 —as indicated by the associated leftward arrow.) The codestrip 33 thus enables formation of color ink-drops at ultrahigh resolution (typically 24 pixels/mm) and precision, during scanning of the carriage assembly 20 in each direction. A currently preferred location for the encoder strip 33 is near the rear of carrisge tray (remote from the space into which a user's hands are inserted for servicing of the pen refill cartridges). Immediately behind the pens is another advantageous position for the strip 36 (FIG. 3 ). The encoder sensor 133 (for use with the encoder strip in its forward position 33 ) or 233 (for rearward position 36 ) is disposed with its optical beam passing through orifices or transport portions of a scale formed in the strip. A separate line sensor 37 (FIGS. 5, 7 and 8 ) also rides on the carriage 20 , for reading test patterns or other information from the printing medium. A cylinder platen 41 (FIG. 8 )—driven by a motor 42 , worm 43 and worm gear 44 under control of signals 46 from the processor 15 —rotates under the carriage-assembly 20 scan track to drive sheets or lengths of printing medium 4 A in a medium-advance direction perpendicular to the scanning. Print medium 4 A is thereby drawn out of the print-medium roll cover 4 , passed under the pens on the carriage 20 to receive inkdrops 54 for formation of a desired image, and ejected into the print-medium bin 5 . The carriage assembly 20 includes a previously mentioned rear tray 21 (FIG. 9) carrying various electronics. It also includes bays 22 for preferably four pens 23 - 26 holding ink of four different colors respectively—preferably cyan in the leftmost pen 23 , then magenta 24 , yellow 25 and black 26 . In the illustrations of the current model (FIGS. 1 through 5 ), the pens are not shown installed. When in place they are under the cartridge retainer latch 67 and project downward slightly beyond the bottom of the line sensor 37 . Each of the pens, particularly in a large-format printer/plotter as shown, preferably includes a respective ink-refill valve 27 . The pens, unlike those in earlier mixed-resolution printer systems, all are relatively long and all have nozzle spacing 29 (FIG. 10) equal to one-twelfth millimeter—along each of two parallel columns of nozzles. These two columns contain respectively the odd-numbered nozzles 1 to 299 , and even-numbered nozzles 2 to 300 . The two columns, thus having a total of one hundred fifty nozzles each, are offset vertically by half the nozzle spacing, so that the effective pitch of each two-column nozzle array is approximately one-twenty-fourth millimeter. The natural resolution of the nozzle array in each pen is thereby made approximately twenty-four nozzles (yielding twenty-four pixels) per millimeter, or 600 per inch. Preferably black (or other monochrome) and color are treated identically as to speed and most other parameters. In the preferred embodiment the number of printhead nozzles used is always two hundred forty, out of the three hundred nozzles (FIG. 10) in the pens. This arrangement allows for software/firmware adjustment of the effective firing height of the pen over a range of ±30 nozzles, at approximately 24 nozzles/mm, or ±30/24=±1¼ mm. This adjustment is achieved without any mechanical motion of the pen along the print-medium advance direction. Alignment of the pens can be automatically checked and corrected through use of the extra nozzles. As will be understood, the invention is amenable to use with a very great variety in the number of nozzles actually operated. 3. Microprocessor Hardware Data-processing arrangements for the present invention can take any of a great variety of forms. To begin with, image-processing and printing-control tasks 332 , 40 can be shared (FIG. 13) among one or more processors in each of the printer 320 and an associated computer and/or raster image processor 30 . A raster image processor (“RIP”) is nowadays often used to supplement or supplant the role of a computer or printer—or both—in the specialized and extremely processing-intensive work of preparing image data files for use, thereby releasing the printer and computer for other duties. Processors in a computer or RIP typically operate a program known as a “printer driver”. These several processors may or may not include general-purpose multitasking digital electronic microprocessors (usually found in the computer 30 ) which run software, or general-purpose dedicated processors (usually found in the printer 320 ) which run firmware, or application-specific integrated circuits (ASICs, also usually in the printer). As is well-understood nowadays, the specific distribution of the tasks of the present invention among all such devices, and still others not mentioned and perhaps not yet known, is primarily a matter of convenience and econoics. On the other hand, sharing is not required. If preferred the system may be designed and constructed for performance of all data processing in one or another of the FIG. 13 modules—in particular, for example, the printer 320 . Regardless of the distributive specifics, the overall system typically includes a memory 232 m for holding color-corrected image data. These data may be developed in the computer or raster image processor, for example with specific artistic input by an operator, or may be received from an external source. Ordinarily the input data proceed from image memory 232 m to an image-processing stage 332 that includes some form of program memory 333 —whether card memory or hard drive and RAM, or ROM or EPROM, or ASIC structures. The memory 333 provides instructions 334 , 336 for automatic operation of rendition 335 and printmasking 337 . Image data cascades through these latter two stages 335 , 337 in turn, resulting in new data 338 specifying the colorants to be deposited in each pixel, in each pass of the printhead carriage 20 over the printing medium 41 . It remains for these data to be interpreted to form: actual printhead-actuating signals 53 (for causing precisely timed and precisely energized ink ejection or other colorant deposition 54 ), actual carriage-drive signals 57 (for operating a carriage-drive motor 35 that produces properly timed motion 55 of the printhead carriage across the printing medium), and actual print-medium-advance signals 46 (for energizing a medium-advance motor 42 that similarly produces suitably timed motion of the print-medium platen 43 and thereby the medium 41 ). Such interpretation is performed in the printing control module 40 . In addition the printing control module 40 may typically be assigned the tasks of receiving and intepreting the encoder signal 52 fed back from the encoder sensor 233 . The printing-control stage 40 necessarily contains electronics and program instructions for interpreting the colorant-per-pixel-per-pass information 338 . Most of this electronics and programming is conventional, and represented in the drawing merely as a block 81 for driving the carriage and pen. That block in fact may be regarded as providing essentially all of the conventional operations of the printing control stage 40 . 4. Method As suggested in FIG. 14, which will be self explanatory to people skilled in this field, method aspects of the present may be conceptualized as having two main steps. One of these is functional mounting 201 of the codestrip through the sensor groove, in tension. The other is constraint 202 of the strip at multiple longitudinally spaced points for transverse alignment—i. e., in the previous illustrations, alignment vertically. In some sense perhaps a third major step is the result, namely stable operation 208 of the encoder sensor system. For preferred embodiments, in the first step 201 the strip is mounted in functional positioning with respect to sensor. The second step 202 includes provision 203 of longitudinally spaced restraints. Although disposition 206 of the strip to engage those restraints could be regarded as part of the constraint-providing step 202 , it is perhaps more logical—or at least equally so—to consider that disposition part of the mounting step 201 . Therefore in FIG. 14 (note dashed arrow) and certain of the appended claims, disposition of the strip to engage the restraints is conceptualized as part of or associated with the mounting step 201 . The restraint provision 203 may be seen as further subdivided to include provision 204 of apertures in the strip, and provision 205 of pins to protrude through the apertures—without fastening of the strip to the pins. Another significant preference is a step of omission, namely refraining 207 from acting to constrain the encoder strip with respect to its thin dimension. This step refers only to constraint at the locating pins, and thus is not absolute: at both its ends, the strip is constrained in that direction. The above disclosure is intended as merely exemplary, and not to limit the scope of the invention—which is to be determined by reference to the appended claims.
Spaced pins support and align the strip. Apertures in the strip engage the pins with no fastening. The strip—best a transparent member and glued strength member—is end-mounted and -tensioned. Ideally the apertures are slots to constrain the strip as to only one dimension, and spaced (ideally about 30 cm on centers) to facilitate cutting various-size strips (e. g. for spans of roughly 91½, 106½, 152½ and 183 cm) from common, preapertured stock. The strip is longer than a meter; the invention is progressively more valuable for 1¼ m or longer strips. At least one pin is placed to keep fundamental oscillation of the strip, due to environmental vibration, from moving the strip out of position. The invention can take the form of the strip only, for use with the pins; or a printer with encoding system having the strip and pins—and a sensor responsive to the encoder to control printing; or a method of preparing a system for use. The pins prevent the strip from leaving the sensor and permit use of very low tension—only that needed to hold up the strip, within its vertical-alignment tolerance, over a short span between pins. The tension, and thereby the vertical-dimension stack from encoder scale to sensor, are thus made virtually independent of encoder-strip length. Such a printer ideally has a printhead carriage that scans parallel to the strip; the sensor (adjacent to the strip and carried on the carriage) develops signals representing position and velocity of the sensor and carriage relative to the strip. Printheads on the carriage form color marks to construct an image on a print medium. A medium-advance mechanism provides relative motion between carriage and medium. A processor responds to the position/velocity signals, and coordinates the printheads and advance mechanism to form the image.
49,476
BACKGROUND OF THE INVENTION A. Field of the Invention The present invention relates to a water-proof structure, more specifically the present invention relates to a spinning reel having a water-proof structure that prevents liquid from entering a reel main body of the spinning reel. B. Description of the Background Art A spinning reel generally includes a reel main body having a complex combination of mechanisms disposed therein. A rotor is disposed at a front portion of the reel main body and is rotatably supported by the reel main body. A spool is supported on the reel main body, with portions of the rotor extending radially outwardly from the spool such that a fishline may be wound by movement of the rotor around a fishline receiving portion of the spool. The spool is disposed on a front portion of the rotor and supported by the reel main body such that the spool may undergo oscillations back and forth along an axis of rotation of the rotor. A handle is rotatably supported on a side of the reel main body. Within the reel main body are the following: a rotation transmission mechanism for rotating the rotor about the spool, an oscillating mechanism for causing the spool to oscillate along the rotor's axis of rotation, and a control device that prevents reverse rotation of the rotor. The rotation transmission mechanism includes a master gear shaft, a master gear fixed to the master gear shaft, and a pinion gear. The master gear shaft is supported in the reel main body and extends laterally between opposite sides of the reel main body (left and right sides of the reel main body). The master gear is disposed within the reel main body. The pinion gear has gear teeth engaged with corresponding gear teeth formed on the master gear. The rotor is fixedly coupled to an end of the pinion gear for rotation therewith. The oscillating mechanism includes, for instance, an intermediate gear, a threaded shaft, a slider, and a sliding guide. The intermediate gear is coupled with the pinion gear for rotation in response to rotation of the pinion gear. The threaded shaft is disposed parallel to a spool shaft, with the intermediate gear coupled to one end thereof. The slider is engaged with the threaded shaft via the sliding guide such that the slider moves in response to rotation of the threaded shaft. The spool shaft is axially coupled to the slider such that the spool shaft oscillates back and forth with the slider. Grease is applied to each of the above mentioned moving members to reduce friction, whereby members move more efficiently. The reverse rotation prevention mechanism is located toward a front portion of the reel main body. One end of the spool shaft and an end of the pinion gear extend out of the front of the reel main body through a bore in the reel main body such that the spool and the rotor may be supported thereon, respectively. Ends of the master gear shaft extend out of bores in the opposite sides of the reel main body such that the handle may be attached to the master gear shaft from either of the two opposite ends of the master gear shaft. As described above, many moveable members such as the spool shaft, the master gear shaft, and the pinion gear extend out from the reel main body through bores. The bores are formed such that there are gaps between the bores and the moveable members that pass through the bores to allow smooth movement of the moveable members. There are also gaps between the reel main body and stationary members such as the reverse rotation prevention mechanism. It is possible for liquid such as water to enter the reel main body through the gaps between the bores and the moveable members, and between the stationary members and the reel main body. When the reel main body is being cleaned, it is also possible for water and/or detergent to enter the reel main body. The grease applied to the conventional moveable members has been relatively highly viscous and durable and usually continues to provide lubrication even when liquid enters inside the reel main body from the gaps. PROBLEM TO BE SOLVED BY THE INVENTION Since highly viscous and durable grease is applied to rotation transmission mechanisms and oscillating mechanisms of conventional spinning reels, it is difficult to improve the efficiency in rotating the handle because of the resistance of the grease. Specifically, it is difficult to reduce the amount of energy necessary to rotate the handle in part because of the viscosity of the grease. Also, once seawater that entered inside the reel main body dries, deposits such as crystals of salts remain. When the deposits are trapped between gears or between rollers of a bearing, smoothness of rotation is affected. SUMMARY OF THE INVENTION The object of the invention is to improve the efficiency in rotary action of a handle of a spinning reel while maintaining smoothness of rotation. In accordance with one aspect of the present invention, a water-proof spinning reel prevents liquid from entering an interior space thereof. The interior space is defined with a reel main body of the spinning reel. The water-proof spinning reel includes a moveable member that extends outward from within the reel main body. A stationary member is fixed to the reel main body. A seal member is disposed about the movable member contacting the moveable member and at least one of the reel main body and the stationary member. Preferably, the seal member is made of an elastic material. Preferably, the moveable member is a master gear shaft of the spinning reel. A pair of bearings support opposite ends of the master gear shaft within the reel main body. A pair of the seal members are supported on the reel main body, the seal members being disposed adjacent to respective ones of the pair of bearings on opposite sides of the reel main body such that the seal members each contact respective portions of the master gear shaft, the reel main body, and respective ones of the bearings. Preferably, each of the bearings is a rotary bearing having an outer race coupled to the reel main body, an inner race supporting the master gear shaft, and a roller supported between the outer race and the inner race for rolling therebetween. Preferably, the seal member has an outer diameter that is slightly smaller than an outer diameter of the outer race. Preferably, the master gear shaft is formed with a pair of seal contacting portions that contact respective ones of the seal members, the seal contacting portions having an outer diameter that is smaller than an inner diameter of the inner race. Preferably, the master gear shaft is formed with a hollow interior having a first threaded portion and a second threaded portion, the first threaded portion being a right handed thread and the second threaded portion having a left handed thread. The spinning reel includes a handle assembly that includes a shaft having a first threaded portion and a second threaded portion. The first threaded portion of the master gear shaft is a right handed thread and the second threaded portion of the master gear shaft has a left handed thread. The first threaded portion of the master gear shaft is engageable with the first threaded portion of the handle assembly, and the second threaded portion of the master gear shaft is engageable with the second threaded portion of the handle assembly. Preferably, one of the seal members is disposed between the outer race of the bearing and the reel main body. The other of the seal members is disposed between the other of the outer race and a lid member that is fixed to the reel main body. Preferably, the moveable member is a shaft pivotally supported by the reel main body for controlling a one-way clutch of the spinning reel. The seal member encircles a portion of the shaft and contacts the shaft and the reel main body. Alternatively, the moveable member is a rotor and the stationary member is a reverse rotation prevention mechanism fixedly supported on the reel main body. The seal member is supported between the rotor and the reel main body so as to contact both the rotor and the reel main body. Preferably, a cylindrical elastic member adapted to encircle a flange portion formed at a front side of the reel main body and an outer peripheral surface of the reverse rotation prevention mechanism. In accordance with another aspect of the present invention, a water-proof spinning reel prevents liquid from entering an interior space of a reel main body of the spinning reel. The water-proof spinning reel includes the reel main body and a spool shaft movably supported within the reel main body. A rotor is rotatably supported in the reel main body and a seal member made of an elastic material is disposed between the spool shaft and an end of the rotor contacting the spool shaft and the end of the rotor. In accordance with yet another aspect of the present invention, a water-proof spinning reel for prevents liquid from entering an interior space of a reel main body of the spinning reel. The water-proof spinning reel includes the reel main body, a member adapted for connection to the reel main body and a seal disposed between the reel main body and the member. Preferably, the seal is made of an elastic material. Preferably, the reel main body is formed with a first flange portion that has a semi-cylindrical shape. The member is formed with a second flange portion having semi-cylindrical shape, the first and second flange portions together define a single cylindrical shape. The seal is disposed between contacting surfaces of the first and second flange portions. Preferably, the reel main body is formed with an opening, and the member is a lid adapted to cover the opening, the seal being disposed between contacting surfaces of the member and the reel main body. Preferably, the reel main body is formed with an opening and a first flange portion that has a semi-cylindrical shape. The member is formed with a second flange portion having semi-cylindrical shape, the first and second flange portions together define a single cylindrical shape. The spinning reel further includes a lid adapted to cover the opening, the seal being disposed between contacting surfaces of the member and the reel main body, and the first and second flange portions. In accordance with yet another aspect of the present invention, a water-proof spinning reel for preventing liquid from entering an interior space of a reel main body of the spinning reel. The water-proof spinning reel includes a spool shaft supported within the reel main body, the spool shaft defining a spool axis. The water-proof spinning reel also includes an oscillation movement mechanism for moving the spool axis back and forth along the spool axis. The oscillation movement mechanism is disposed within the reel main body. A portion of the oscillation movement mechanism is supported within bore formed on a rear portion of the reel main body. A seal member disposed on the rear portion of the reel main body prevents water from entering the reel main body via the bore. With the above water-proof structure for a spinning reel, gaps between the moveable members and the reel main body and/or a stationary member attached to the reel main body is sealed with a seal member. Therefore, it is less likely that liquid enters the interior space of the fishing reel through gaps between the moveable member and the reel main body and/or the stationary member. As a result, grease having a lower viscosity can be utilized to lubricate the various elements within the interior space. Accordingly, resistance from the grease is smaller, whereby efficiency in rotation of the handle is improved. Also, since less liquid enters the interior space, there is a reduction in deposits left when liquid dries. Accordingly, there are fewer deposits trapped between gears and between rollers. Therefore, smoothness of rotation of the handle of the spinning reel can be maintained. These and other objects, features, aspects and advantages of the present invention will become more fully apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings where like reference numerals denote corresponding parts throughout. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a side plan view of a spinning reel in accordance with one embodiment of the present invention showing a handle assembly attached to right side of a reel main body of the spinning reel; FIG. 2 is a side cross-sectional view of the spinning reel in accordance with the present invention; FIG. 3 is a back side cross-sectional view of the spinning reel depicted in FIG. 1 with the handle assembly attached on a left side of the reel main body; FIG. 4 is a fragmentary perspective, exploded view of the reel main body of the spinning reel depicted in FIG. 1; FIG. 5 is a fragmentary cross-sectional view of a master gear of the spinning reel depicted in FIG. 1 on a slightly enlarged scale; FIG. 6 is a fragmentary, cross sectional side view of a front portion of the spinning reel depicted in FIG. 1 on a slightly enlarged scale; and FIG. 7 is a fragmentary, cross sectional side view of a rear portion of the spinning reel depicted in FIG. 1 on a slightly enlarged scale. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT OVERALL STRUCTURE A spinning reel in accordance with a first embodiment of the present invention is described below with reference to FIGS. 1 and 2. The spinning reel shown in FIGS. 1, 2 , 3 and 4 is, relative to most spinning reels, a large spinning reel that is able to hold about 200 m of size 8 fishline, with the fishline wound about a spool 4 , described in greater detail below. The spinning reel includes a reel main body 2 , a rotor 3 that is supported on the reel main body 2 about an axis A (FIG. 2 ), the spool 4 , and a handle assembly 1 that is rotatably supported on the reel main body 2 . As is described in greater detail below, rotation of the handle assembly 1 with respect to the reel main body 2 causes the rotor 3 to rotate and causes the spool 4 to undergo oscillations along the axis A (FIG. 2) in order to receive the fishline. The rotor 3 is rotatably supported by a front portion of the reel main body 2 and is rotatable about the above mentioned axis A. The spool 4 has an outer peripheral surface about which the fishline is wound, and is disposed on a front portion of the rotor 3 so as to be movable back and forth (oscillate) along the axis A. STRUCTURE OF THE HANDLE ASSEMBLY As shown in FIG. 3, the handle assembly 1 is threaded into a master gear shaft 10 , as is described below. As shown in FIG. 1, the handle assembly 1 includes a T-shaped handle portion 1 a and a L-shaped crank arm 1 b. The handle portion 1 a is rotatably attached to an end of the crank arm 1 b. With reference again to FIG. 3, the crank arm 1 b includes an arm portion 7 a, a shaft portion 7 b, and an attachment portion 7 c. A base end of the arm portion 7 a is pivotally coupled to the shaft portion 7 b. The attachment portion 7 c has a cup-like shape and extends around a portion of the shaft portion 7 b, as is described in greater detail below. The attachment portion 7 c is substantially concentric with the shaft portion 7 b with the shaft portion 7 b extending beyond the end of the attachment portion 7 c such that the distal end of the shaft portion 7 c is threaded into the master gear shaft 10 . The shaft portion 7 b has a rod-shaped cross section. On the distal end (toward the right side of FIG. 3) of the shaft portion 7 b, a first male screw portion 8 a and a second male screw portion 8 b are formed concentrically and axially next to each other. The first male screw portion 8 a is a right-handed screw (a screw that is threaded in when it rotates in a clockwise direction). The second male screw portion 8 b is a left-handed screw (a screw that is threaded in when it rotates in a counter-clockwise direction) that has a larger diameter than the first male screw portion 8 a. Accordingly, the handle assembly 1 can be attached to either the right side of the reel main body 2 as shown in FIGS. 1 and 2, or the left side of the reel main body 2 as shown in FIG. 3 . On a base end of the shaft portion 7 b, flat surfaces 8 c are formed parallel to each other. A bore 8 d is formed on the flat surfaces 8 c for receiving therein a pivot pin 8 e which pivotally supports the arm portion 7 a on the shaft portion 7 b. The arm portion 7 a is pivotally coupled to the shaft portion 7 b via the pivot pin 8 e. The attachment portion 7 c includes a contacting portion 9 a, a shaft cover 9 b, and a pressure member 9 c. The contacting portion 9 a defines an end surface of the arm portion 7 a. The shaft cover 9 b has a cylindrical-shape that encircles an outer periphery of a portion of the shaft portion 7 b but is spaced apart from the shaft portion 7 b. The pressure member 9 c surrounds a portion of the shaft portion 7 b and is located between the outer surface of the portion of the shaft portion 7 b and the shaft cover 9 b. The contacting portion 9 a of the attachment portion 7 c is formed with an opening that engages the flat surfaces 8 c of the shaft portion 7 b such that the shaft cover 9 b cannot rotate relative to the shaft portion 7 b. In this way, the shaft portion 7 b can be rotated by rotation of the shaft cover 9 b such that the shaft portion 7 b may be threaded into the master gear shaft 10 and later removed (unthreaded) from the master gear shaft 10 by rotation of the shaft cover 9 b. An end of the shaft cover 9 b extends around a tubular cover 19 b that is supported on the reel main body 2 . The pressure member 9 c is tubular in shape and is coupled to the shaft portion 7 b but is rotatable and axially movable with respect to the shaft 7 b, as is described further below. The end of the pressure member 9 c contacts the master gear shaft 10 while the handle assembly 1 is attached thereto. On the outer periphery of the shaft portion 7 b between the pressure member 9 c and the contacting portion 9 a of the shaft cover 9 b there are four plate springs 9 d that are arranged as two pairs of plate springs. Further, between the contacting portion 9 a and the plate springs 9 d a washer 9 e is disposed encircling the shaft portion 7 b. The two pairs of plate springs 9 b contact each other at outer peripheries thereof. When the handle assembly 1 is attached to the master gear shaft 10 the plate springs 9 d are compressed between the pressure member 9 c and the washer 9 e such that the biasing force of the plate springs 9 d biases the pressure member 9 c into firm engagement with the master gear shaft 10 thereby preventing the shaft portion 7 b from becoming unscrewed from the master gear shaft 10 . Specifically, the biasing force that urges the pressure member 9 c against the master gear shaft 10 helps to retain one of the first male screw 8 a or the second male screw 8 b in threaded engagement with the corresponding threads in the master gear shaft 10 . As well, with the plate springs 9 c under compression, the contacting portion 9 a further contacts an end surface of the arm portion 7 a such that the arm portion 7 a is not able to pivot about the pin 8 e. When the handle assembly 1 is to be removed from the master gear shaft 10 , the shaft cover 9 b is rotated to loosen the threaded engagement between the shaft portion 7 b and the master gear shaft 10 . As the shaft portion 7 b begins to become unscrewed (unthreaded) from the master gear shaft 10 , the plate springs 9 d expand and are no longer compressed, and the contacting portion 9 a becomes separated from the shaft cover 9 b. The contacting portion 9 a also comes out of contact with the end surface of the arm portion 7 a of the crank arm 1 b. Accordingly, the crank arm 1 b can easily pivot about the pivot pin 8 e. When the handle assembly 1 is threaded in by rotating the shaft cover 9 b, the contacting portion 9 a contacts the end surface of the arm portion 7 a whereby the handle assembly 1 is retained rigidly in an attachment state where the crank arm 1 b cannot pivot about the pivot pin 8 e. While the handle assembly 1 is attached to the master gear shaft 10 , the plate springs 9 d bias the pressure member 9 c towards the master gear shaft 10 , whereby the attachment of the handle assembly 1 to the master gear shaft 10 does not come loose easily. STRUCTURE OF REEL MAIN BODY As is shown in FIGS. 1, 2 and 3 , the reel main body 2 includes a reel body 2 a and a leg 2 b. The reel body 2 a has an opening 2 c on a side portion thereof (the opening 2 c is open toward the left side of FIG. 3 ). The leg 2 b has a shape resembling the letter T and is shaped to connect the reel main body to a portion of a fish rod (not shown). The leg 2 b is formed on the reel body 2 a integrally therewith, and extends in an upward direction therefrom. The opening 2 c is shaped to receive a lid member 2 d thereby closing the reel main body. As shown in FIG. 2, inside the reel body 2 a there is a space for many elements which define several mechanisms. The space within the reel body 2 a is accessed via the opening 2 c by removing the lid member 2 d. Within the space within the reel body 2 a are a rotor driving mechanism 5 for rotating the rotor 3 in response to rotation of the handle assembly 1 , and an oscillating mechanism 6 that moves the spool 4 back and forth along the axis A such that the fishline (not shown) may be uniformly wound around the spool 4 by rotation of the rotor 3 . As shown in FIG. 3, the opening of the reel body 2 a is closed and sealed by a lid member 2 d. The lid member 2 d is fixedly connected to an outer periphery of the opening 2 c by bolts. On a peripheral portion of the opening 2 c, a liquid gasket 80 is applied as shown in FIG. 4 in hatched shading, to seal a gap between the lid member 2 d and the opening 2 c, thereby preventing liquid from entering the reel body 2 a and contaminating the moving elements of the mechanism therein. It should be appreciated that the hatched shading in FIG. 4 representing the liquid gasket 80 is not an indication of a cross-section, but rather is an indication of the liquid gasket 80 . FIG. 4 shows a first flange portion 2 e formed on a front portion of the reel body 2 a. The first flange portion 2 e generally has a semi-cylindrical shape, or in other words is approximately half of a cylinder in shape. The first flange portion 2 e is formed on the reel body 2 a and extends forward in front of the opening 2 c. A second flange portion 2 f is fixed to the first flange portion 2 e and the reel body 2 a. The second flange portion 2 f has a semi-cylindrical shape and completes a cylinder shape with first flange portion 2 e. A one-way clutch 51 of a reverse rotation prevention mechanism 50 is fixed to the first flange portion 2 e (and second flange portion 2 f, as shown in FIG. 2 . The one-way clutch 51 allows the rotor 3 to rotate in one direction, but prevents the rotor 3 from rotating in an opposite direction. As is indicated in FIG. 4, the second flange portion 2 f is a separate member from the reel body 2 a and makes it easy to install the various elements that are retained within the reel body 2 a. The configuration of the second flange portion 2 f is such that the master gear 11 is closer to a front of the interior of the reel body 2 a than in prior art configurations. A water repellent seal 81 made of an elastic material is disposed on surfaces of the second flange portion 2 f that contact the first flange portion 2 e and the lid member 2 d. As shown in FIG. 4, the water repellent seal 81 is disposed in a semi-circular shape on a rear surface of the second flange portion 2 f facing the lid member 2 d. The water repellent seal 81 is also disposed on surfaces that contact the first flange portion 2 e. The one-way clutch 51 has a shape corresponding to the cylinder defined by the combination of the first flange portion 2 e and the second flange portion 2 f. A tubular seal ring 82 made of an elastic material such as NBR is disposed on an outer periphery of the one-way clutch 51 and the first and second flange portions 2 e and 2 f, as shown in FIG. 6, such that any outer peripheral gaps formed on the one-way clutch 51 and the first and second flange portions 2 e and 2 f, along with a gap formed between the one-way clutch 51 and the first and second flange portions 2 e and 2 f are all sealed. As shown in FIGS. 3 and 5, a cylindrical boss portion 17 a is formed on one side of the reel body 2 a (toward the right side of FIG. 5 ). The boss portion 17 a extends inwardly within the reel body 2 a for supporting a bearing 16 a which supports one end of the master gear shaft 10 . Another boss portion 17 b is formed on the lid member 2 d opposing the boss portion 17 a, and with the lid member 2 d fixed in the opening 2 c, the boss portion 17 a and boss portion 17 b are axially aligned. The boss portion 17 b extends both inward and outward from the space within the reel body 2 a for supporting a bearing 16 b which further supports another end of the master gear shaft 10 (on the left side of FIG. 5 ). The boss portion 17 a of the reel body 2 a is covered by a shaft cover 19 a. However, the shaft cover 19 a can be removed and the handle assembly 1 may be threaded into the master gear shaft 10 via the opening defined by the bearing 16 a. The tubular cover 19 b may be coupled to either of the boss portions 17 a or 17 b on opposite sides of the reel body 2 a, depending upon which side of the reel body 2 a the handle assembly 1 is attached to (i.e. for a left-handed user or a right handed user). The tubular cover 19 b prevents water from entering the reel main body 2 a. As shown in FIG. 1, the shaft cover 19 a and tubular cover 19 b are oval members, both adapted to be coupled to either boss portion 17 a and 17 b by two small bolts 19 c. The surface of the reel body 2 a around the boss portion 17 a is formed with an oval recess 17 c for attachment of either the shaft cover 19 a or the tubular cover 19 b. STRUCTURE OF THE ROTOR DRIVING MECHANISM As shown in FIG. 3, the rotor driving mechanism 5 includes a master gear 11 to which the handle assembly 1 is non-rotatably attached via the master gear shaft 10 . The rotor driving mechanism 5 also includes the pinion gear 12 that has gear teeth engaged with corresponding gear teeth formed on the master gear 11 . As shown in FIG. 5, the master gear 11 includes the master gear shaft 10 , a gear attachment portion 11 a integrally formed with the master gear shaft 10 , and the gear member 11 b detachably coupled to the gear attachment portion 11 a. The master gear shaft 10 is a hollow member made of a stainless steel material. Both ends of the master gear shaft 10 are rotatably supported by the reel body 2 a and the lid member 2 b via the bearings 16 a and 16 b. The bearings 16 a and 16 b are rotary bearings, each having an inner race 20 a, an outer race 20 b, and ball bearings 20 c. Seal rings 18 a and 18 b made of an elastic material such as NBR are disposed adjacent to the outer peripheral surface of the master gear shaft 10 , and axially outward from the internal space of the reel body 2 a, the inner race 20 a and the outer race 20 b of the bearings 16 a and 16 b, respectively. The seal rings 18 a and 18 b are washer-like members, tightly retained within seal coupling recesses 18 c and 18 d, which are formed in the lid member 2 d and reel body 2 a, respectively, axially outward from the bearings 16 a and 16 b. Inner radiuses of the seal coupling recesses 18 c and 18 d (outer radiuses of the seal rings 18 a and 18 b ) are smaller than outer radiuses of the bearings 16 a and 16 b. Axial lengths of the seal coupling recesses 18 c and 18 d are slightly smaller than thicknesses of the seal rings 18 a and 18 b. Inner peripheries of the seal rings 18 a and 18 b are disposed adjacent to seal surfaces 10 e and 10 f of the master gear shaft 10 . Outer radiuses of the seal surfaces 10 e and 10 f are smaller than the radiuses of the portion of the main gear shaft 10 that contacts the bearings 16 a and 16 b. Small bolts 18 e and 18 f are threaded into the boss portions 17 a and 17 b contacting the outer races 20 b of the bearings 16 a and 16 b. The small bolts 18 e and 18 f through the outer races 20 b force the seal rings 18 a and 18 b into firm engagement with the seal coupling recesses 18 c and 18 d such that the seal rings 18 a and 18 b seal outer peripheral portions thereof without rotating with the master gear shaft 10 . Since the seal surfaces 10 e and 10 f have smaller radiuses than the bearing attachment surfaces, it is less likely that the seal surfaces 10 e and 10 f are damaged. Further, after repeated attachment and detachment of the handle assembly 1 , if the master gear shaft 10 should be deformed thereby extending farther in a radially outward direction, the seal rings 18 a and 18 b may still provide a reliable seal. Also, since the seal coupling recesses 18 c and 18 d have smaller radiuses than the outer races 20 b, thrust forces that are applied to the bearings 16 a and 16 b can be directly supported by the reel body 2 a and the lid member 2 d. As shown in FIG. 5, the master gear shaft 10 is formed with a first through bore 10 a, a first female screw portion 10 b, a second through bore 10 c, and a second female screw portion 10 d all formed concentrically and axially aligned in the above recited order from the right side of FIG. 4 to the left side of FIG. 5 . The second female screw portion 10 d opens to the left end of the master gear shaft 10 . The axial length of the first through bore 10 a is substantially the same as the axial length of the second female screw portion 10 d. The first through bore 10 a has a larger radius than the second female screw portion 10 d, such that the second male screw portion 8 b of the shaft portion 7 b can be inserted therethrough. The first female screw portion 10 b is formed with right-handed screw threads, into which the first male screw portion 8 a of the shaft portion 7 b can be threaded. The axial length of the first female screw portion 10 b is slightly longer than the axial length of the first male screw portion 8 a. The axial length of the second through bore 10 c is substantially the same as the axial length of the first female screw portion 10 b. The second through bore 10 c has a larger diameter than the first female screw portion 10 b, such that the first male screw portion 8 a can be inserted therethrough. The second female screw portion 10 d is threaded with left-handed screw threads, into which the second male screw portion 8 b of the shaft portion 7 b can be threaded. On portions of the outer surface of the master gear shaft 10 are flat surfaces 10 g formed parallel to each other for engagement with corresponding surfaces of the gear attachment portion 11 a. The gear attachment portion 11 a is formed on the flat surfaces 10 g integrally with the master gear shaft 10 by press fitting the master gear shaft 10 into the gear attachment portion 11 a or other means. The gear attachment portion 11 a is made of a zinc alloy, which can be molded integrally with a stainless alloy easily. The gear attachment portion 11 a includes a boss portion 11 c and a flange portion 11 d. The boss portion 11 c is fixedly coupled to the master gear shaft 10 , as described above. The flange portion 11 d is formed on an outer periphery of the boss portion 11 c. The gear member 11 b is detachably coupled to the flange portion 11 d by a plurality of bolts 13 . The gear member 11 b is a disk shaped member made by forging an aluminum alloy. Therefore, the gear member 11 b is relatively light. The gear member 11 b includes a disk portion 11 e and the face gear portion 11 f. The disk portion 11 e is non-rotatably coupled to the flange portion 11 d. The face gear portion 11 f is formed on the outer peripheral portion of the disk portion 11 e, and is adapted to engage gear teeth formed on the pinion gear 12 . As shown in FIG. 2, the pinion gear 12 is a tubular member disposed extending around a portion of the axis A in a generally central portion of the reel body 2 a. The pinion gear 12 is restrained within the reel body 2 a against axial movement along the axis A, but rotates about a spool shaft 15 . A front portion 12 a of the pinion gear 12 extends through a central portion of the rotor 3 . The front portion 12 a is fixed to the rotor 3 by a nut 33 . The pinion gear 12 is rotatably supported by the reel body 2 a at two spaced axially spaced apart portions via bearings 14 a and 14 b, respectively. The spool shaft 15 extends completely through the pinion gear 12 . The pinion gear 12 is formed with gear teeth engaged with the gear teeth on the master gear 11 and further engaged with gear teeth on an intermediate gear 23 of an oscillating mechanism 6 , described in greater detail below. ROTOR STRUCTURE As shown in FIG. 2, the rotor 3 includes a cylindrical portion 30 fixed to the pinion gear 12 , first and second rotor arms 31 and 32 , and a bail arm 40 . The first and second rotor arms 31 and 32 are formed on side portions of the cylindrical portion 30 opposed to and parallel to each other. The bail arm 40 is a mechanism for guiding the fishline on to the spool 4 as the rotor 3 rotates about the spool 4 . The cylindrical portion 30 and the rotor arms 31 and 32 are made of a material such as an aluminum alloy, and are formed integrally together as a one-piece unit. A front central portion of the cylindrical portion 30 is non-rotatably fixed to the front portion 12 a of the pinion gear 12 by the nut 33 , as described above. A rotor bearing 35 is fitted between the nut 33 and the spool shaft 15 . The outer race of the rotor bearing 35 is held in a recess in the nut 33 , and the inner race of the bearing 35 is fixedly mounted to the shaft 15 . A seal 34 is fitted into a recess in the nut 33 that is axially outward from and diametrically larger than the recess for the bearing 35 . A locking cap 33 a is fastened over the nut 33 to the front wall and retains the seal 34 . A front wall 41 is formed on a front portion of the cylindrical portion 30 . A boss portion 42 is formed on a central portion of the front wall 41 . The boss portion 42 has a through bore formed in the center thereof. The front portion 12 a of the pinion gear 12 and the spool shaft 15 extend through the through bore of the boss portion 42 , such that the pinion gear 12 is non-rotatably coupled to the through bore. A reverse rotation prevention mechanism 50 is disposed within the cylindrical portion 30 , adjacent to the boss portion 42 . The reverse rotation prevention mechanism 50 includes a one-way clutch 51 and a switching mechanism 52 . The one-way clutch 51 is a roller type one-way clutch, in which an inner race 51 a, which is non-rotatably coupled to the pinion gear 12 , freely rotates. The switching mechanism 52 switches the one-way clutch 51 between an active state, in which reverse rotation is prevented, and an inactive state, in which reverse rotation is allowed. As shown in FIG. 6, a sleeve 43 made of a stainless alloy is retained between the inner race 51 a and the boss portion 42 of the rotor 3 . The sleeve 43 is a thin tubular member having a large diameter portion 43 a, a small diameter portion 43 b, and a disk portion 43 c extending therebetween. The large diameter portion 43 a is coupled to an outer periphery of the boss portion 42 , while the small diameter portion 43 b is coupled to the inner race 51 a and the pinion gear 12 . The disk portion 43 c that connects the large portion 43 a and the small portion 43 b is disposed between the boss portion 42 and the inner race 51 a. A shaft seal 85 having a lip is retained on a front portion of the one-way clutch 51 . The lip contacts an outer peripheral surface of the large diameter portion 43 c of the sleeve 43 . Since the disk portion 43 c is disposed between the boss portion 42 and the inner race 51 a, it is unlikely that liquid can enter the cylindrical member 30 (FIG. 2) through a gap formed in the inner periphery of the sleeve 43 . Therefore, by sealing with the shaft seal 85 an outer peripheral surface of the sleeve 43 , liquid does not enter inside the reel main body 2 through gaps around the one-way clutch 51 . The sleeve 43 allows a precise positioning of the shaft seal 85 relative to the rotor 3 . Without the sleeve 43 , if the rotor 3 is offset from the shaft seal 85 while the rotor is coupled to the pinion gear 12 , the shaft seal 85 cannot seal properly. By utilizing the sleeve 43 , the shaft seal 85 can be more easily positioned relative to the rotor 3 such that the shaft seal 85 can seal properly. As shown in FIGS. 2 and 4, the reel body 2 a includes a switching mechanism 52 that has a stopper shaft 53 . The stopper shaft 53 is pivotably coupled to the reel body 2 a so as to be able to move between an inactive position and an active position. As shown in FIG. 7, the stopper shaft 53 has a stopper handle 53 a, a shaft portion 53 b, and a cam portion 50 c. The stopper handle 53 a projects in a rearward direction through the reel body 2 a. The stopper handle 53 a is fixedly connected to the shaft 53 b. The cam portion 50 c is fixedly coupled to a front end of the shaft portion 53 b. An O-shaped ring 86 is installed on the shaft portion 53 b, at an inward portion relative to the stopper handle 53 a. The O-shaped ring 86 prevents liquid from entering the reel main body 2 a through gaps that may exist around the stopper shaft 53 . A front portion of the cam portion 53 c contacts the one-way clutch 51 , so as to switch the one-way clutch 51 between the inactive position and the active position according to pivoting of the stopper shaft 53 . STRUCTURE OF THE OSCILLATING MECHANISM As shown in FIG. 7, the oscillating mechanism 6 includes a threaded shaft 21 disposed below and parallel to the spool shaft 15 , a slider 22 adapted to move back and forth along the threaded shaft 21 , and an intermediate gear 23 fixed to a front end of the threaded shaft 21 . A rear end of the threaded shaft 21 is rotatably supported via the bearing 25 in a support bore 2 g that is formed on a rear portion of the reel body 2 a. The support bore 2 g is sealed by a pressure lid 88 . A planar seat packing member 87 is disposed on a rear portion of the reel body 2 a to prevent liquid from entering inside the reel main body 2 a through a gap between the pressure lid 88 and the reel body 2 a. The seat packing member 87 is disposed between the pressure lid 88 and the rear portion of the reel body 2 a, and is fixedly coupled to the rear portion of the reel body 2 a by the pressure lid 88 which is fixedly coupled the rear portion of the reel body 2 a by a small bolt 89 . The rear portion of the reel body 2 a is covered by a protection cover 90 . The slider 22 is movably supported by two guide shafts 24 that are disposed parallel to the threaded shaft 21 . A rear end of the spool shaft 15 is non-rotatably coupled to the slider 22 . The intermediate gear 23 couples with the pinion gear 12 . SPOOL STRUCTURE As shown in FIG. 2, the spool 4 is disposed between the first rotor arm 31 and the second rotor arm 32 of the rotor 3 . A central portion of the spool 4 is coupled to the front end of the spool shaft 15 via a drag mechanism 60 . The spool 4 includes a winder body 4 a, a skirt portion 4 b, and a flange board 4 c. The fishline is wound about an outer periphery of the winder body 4 a. The skirt portion 4 b is formed integrally with a back portion of the winder body 4 a. The flange board 4 c is fixed to a front end of the winder body 4 a. The winder body 4 a is a cylindrical member, having the outer peripheral surface that is parallel to the spool shaft 15 . As shown in FIG. 6, the winder body 4 a is rotatably coupled to the spool shaft 15 by two bearings 56 and 57 . The skirt portion 4 b is disk shaped and extends in a radially outward direction from a rear end portion of the winder body 4 a. A thread through bore 93 is formed on a portion of the skirt portion 4 b adjacent to the winder body 4 a. One end of the fishline (not shown) wound around the winder body 4 a extends through the bore 93 and is anchored to the skirt portion 4 b by tying the fishline to a projection 92 formed on a rear surface of the skirt portion 4 b radially outward from the bore 93 . By tying an end of the fishline to the projection 92 , a knot at the end of the fishline is not wound in the winder body 4 a. Therefore, the fishline can be wound evenly about the winder body 4 a when a thin fishline is used. As a result, the fishline can be pulled out from the spool smoothly, with an improved smoothness of rotation. The flange board 4 c is an annular ring-shaped member having an outer peripheral portion that projects in a front direction relative to the reel main body 2 a. The flange board 4 c is fixedly coupled to the winder body 4 a by a spool ring collar 55 that is threaded to an inner periphery of the winder body 4 a. The spool 4 is supported on the bearing 57 that is retained in position at one end thereof on the spool shaft 15 by a positioning washer 54 that is coupled to the spool shaft 15 . A seal ring 91 made of an elastic material is disposed between the positioning washer 54 and the bearing 57 , adjacent to inner and outer races of the bearing 57 and a portion of the spool 4 where the bearing 57 is retained. The seal ring 91 is a washer-shaped member for preventing liquid from entering the drag mechanism 60 through a rear portion of the spool 4 . DRAG MECHANISM STRUCTURE As shown in FIGS. 2 and 6, an adjustable drag mechanism 60 is disposed between the spool 4 and the spool shaft 15 for applying a drag force to the spool 4 . As shown in FIG. 6, the drag mechanism 60 includes a handle portion 61 and a friction portion 62 . The handle portion 61 allows the amount of drag force to be controlled manually. The friction portion has a plurality of disks that are pressed into friction engagement with one another and further coupled to the spool 4 . The handle portion 61 includes a first member 63 , a second member 64 , and a sound mechanism 65 . The first member 63 is rotatably and axially movably coupled to the spool shaft 15 . The second member 64 is disposed at an axially front position with respect to the first member 63 . The spool shaft 15 is threaded into the second member 64 . The sound mechanism 65 is coupled between the first member 63 and the second member 64 . The first member 63 is a cylindrical member with a flange, having a cylindrical portion 63 a and a flange portion 63 b is a ring having a larger diameter than the cylindrical portion 63 a. An oval coupling bore 66 is formed on an inner peripheral portion of the cylindrical portion 63 a for non-rotatably coupling with the spool shaft 15 . A rear end surface of the cylindrical portion 63 a of the first member 63 is disposed adjacent to a friction surface 62 . A seal plate 71 is coupled between the cylindrical portion 63 a of the first member 63 and an inner peripheral surface of the spool ring collar 55 for preventing liquid from entering inside the spool 4 . The seal plate 71 is a seal member made by inserting a ring-shaped member made of a stainless material into a plate-shaped elastic member made of NBR. The seal plate 71 has a lip on an outer peripheral portion thereof. The seal plate 71 is biased by a snap ring 79 in a direction shown as a leftward direction in FIG. 6. A ring-shaped projection 71 c is formed on the seal plate 71 , which extends to the left side of FIG. 6 . The projection 71 c contacts a cover member 68 , which is described below, for preventing the liquid from entering from outside the spinning reel. The second member 64 is disposed opposite the first member 63 so as to be rotatable relative to the first member 63 . The second member 64 includes a handle body 67 and a cover member 68 . The handle body 67 is disposed on a front end of the spool shaft 15 (to the left side of FIG. 6 relative to the first member 63 ). A front end of the cover member 68 is fixedly coupled to the handle body 67 . The first member 63 is relatively rotatably disposed within the cover member 68 . The handle body 67 is a disk-shape member having a trapezoid-shaped handle 67 a which is formed on a front surface thereof and extends toward the front of the spinning reel (the left side of FIG. 6 ). A nut 69 , which is threaded into the front end of the spool shaft 15 , is non-rotatably and axially movably coupled to an inner periphery of the handle body 67 . A coil spring 70 is disposed in a compressed manner on an outer periphery of the spool shaft 15 , between the second member 64 and the nut 69 . The cover member 68 is cylindrically shaped having a bottom portion 68 b and a cylindrical portion 68 a. The cylindrical portion 63 a of the first member 63 passes through the bottom 68 b of the cover member 68 . The projection 71 c of the seal plate 71 contacts the bottom portion 68 b of the cover member 68 . The cylindrical portion 68 a of the cover member 68 is coupled to an outer peripheral surface of the handle body 67 via screws (not shown). An annular seal ring 72 is disposed between the bottom 68 b of the cover member 68 and a rear end surface of the cylindrical portion 63 a of the first member 63 . An O-shaped ring 73 is coupled between a front end of the cylindrical portion 68 a of the cover member 68 and the handle body 67 . The seal ring 72 and the O-shaped ring 73 are both made of an elastic material such as NBR, and prevent liquid from entering inside the spool 4 through gaps between the first member 63 and the cover member 68 , and between the handle body 67 of the second member 64 and the cover member 68 . In prior art configurations, once liquid enters inside the spool 4 through these gaps (in the absence of sealing members), the liquid reaches the friction portion 62 through the gap between the first member 63 and the spool shaft 15 , even with the seal plate 71 . As a result, drag force may fluctuate due to the wet friction portion 62 . The friction portion 62 includes a first disk 101 , a second disk 102 , and a drag sound mechanism 103 . The first disk 101 contacts the first member 63 . The second disk 102 contacts the first disk 101 with a felt material therebetween. The drag sound mechanism 103 contacts the second disk 102 with a felt material therebetween. An inner peripheral portion of the first disk 101 is coupled to the spool shaft 15 , so as to rotate together therewith. An outer peripheral portion of the second disk 102 is coupled to the spool 4 , so as to rotate together therewith. The drag sound mechanism 103 generates a sound when the spool shaft 15 and the spool 4 rotate relative to each other, in other words, while the drag mechanism is active. OPERATION OF THE REEL In the above described spinning reel, the bail arm 40 is pivoted into a casting position so that the fishline can be released during casting. As a result, the fishline is let out from the front end of the spool 4 due to the weight of a lure (not shown). When the fishline is to be wound up, the bail arm is turned back to a fishline wind-up position. The bail arm comes back to the fishline wind-up position automatically when the handle assembly 1 rotates in a direction that winds up the fishline, because of a bail reverse mechanism which is not shown in the drawings. Rotational torque of the handle assembly 1 is transmitted to the pinion gear 12 , via the master gear shaft 10 and the master gear 11 . Once torque is transmitted to the pinion gear 12 , the torque is further transmitted to the rotor 3 from the front portion 12 a of the pinion gear 12 , and also to the oscillating mechanism 6 via the intermediate gear 23 which couples to the pinion gear 12 . As a result, the rotor 3 rotates in the direction that winds the fishline around the spool 4 while the spool 4 moves back and forth repeatedly to evenly allow winding of the fishline. During fishing, water spray and waves occasionally splash on a reel, and the reel becomes wet. Even when the reel becomes wet, since the drag mechanism 60 is equipped with the seal plate 71 , the seal ring 72 , and the O-shaped ring 73 , and also since the spool 4 is equipped with the seal ring 91 , water entering inside the reel from front and rear portions thereof is not likely to reach the friction portion 62 . Therefore, once a drag force is adjusted, the drag force will not be changed because of the wet friction portion 62 . Also, seal members such as the seal rings 18 a and 18 b, the shaft seal 34 , the liquid gasket 80 , the water repellent sealing 81 , the seal ring 82 , the shaft seal 85 , the O-shaped ring 86 , the seal plate 87 are disposed between the reel body 2 a and mobile, stationary, and constituting members, liquid is prevented from entering inside the reel main body 2 a. Therefore, it is unlikely that seawater enters inside the reel. Accordingly, deposits such as crystals of salt will not remain inside the bearings or guide portion. Therefore, there is no need to apply a highly viscous grease inside the reel. Also, it is less likely that deposits will be trapped between the gears and rollers, whereby the handle rotates more smoothly. ALTERNATE EMBODIMENTS (a) Although a front-drag type spinning reel was described in the above embodiment, the present invention can be applied to water-proof structures of other types of spinning reels, including a rear-drag type spinning reel, a spinning reel without a drag, and a lever-drag type spinning reel. (b) Although seal members were disposed on constituting members and stationary members, not only on moveable members such as a master gear, seal members can be applied to only one of the constituting, stationary, and moveable members. EFFECT OF THE INVENTION According to the present invention, since liquid can be prevented from entering the reel main body through gaps between moveable members, stationary members, and a reel body, grease with low viscosity can be utilized. Therefore, resistance due to viscosity of the grease decreases, thereby improving the efficiency of winding a handle. Also since liquid is prevented from entering the interior spaces of the reel main body, there are less deposits which remain after liquid evaporates, whereby deposits are less likely to be trapped between gears and rollers. In this way, rotation of the handle will be smooth. Various details of the invention may be changed without departing from its spirit nor its scope. Furthermore, the foregoing description of the embodiments according to the present invention is provided for the purpose of illustration only, and not for the purpose of limiting the invention as defined by the appended claims and their equivalents.
Configuration for waterproofing rotary mechanism shafts protruding from the compartments in which they are housed in a spinning reel main unit. In each case the shafts are supported on ball bearings, but in some cases the outer race and its mounting are fitted to be stationary in the compartment with respect to the compartment, and the shaft and the inner race supporting are rotatable. In other cases, the shaft and the inner race supporting it are stationary, and the outer race and its mounting in the compartment rotate about the shaft. Shaft seals are furnished to seal respective protruding shafts. In all cases, the seal is retained by the compartment mounting axially outward with respect to the compartment and contacts both the stationary and at least either the rotary component or the rotary mechanism shaft. Washers, caps, or lids retain and position the shaft seals against the shaft bearing stationary components.
53,962
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to a device for straightening and stabilizing the vertebral column, particularly for stabilizing broken vertebrae. [0003] 2. Description of the Related Art [0004] Devices for straightening and stabilizing broken vertebrae are known to be used. These devices include a catheter which can be inserted into the interior of the vertebra through a duct drilled into the pedicle of the broken vertebra. A pressure line pushed through the catheter into the interior of the vertebra has at the end thereof an expandable pressure balloon which makes it possible to expand once again and return into its original shape a vertebra which has been compressed and possibly broken. The balloon which has subsequently been decompressed and pulled out together with the pressure line leaves a hollow space into which a bone filler material can be introduced through the catheter. SUMMARY OF THE INVENTION [0005] It is the primary object of the present invention to provide a novel device for stabilizing the vertebral column, particularly for straightening and stabilizing broken vertebrae, which makes it possible to achieve a higher degree of stabilization more quickly than by using the known devices, wherein the required operation is simpler. [0006] In accordance with the present invention, the device for straightening and stabilizing the vertebral column is characterized by a supporting implant which is plastically expandable by internal pressure. [0007] Such a supporting implant, which is preferably provided for being arranged in the interior of a vertebral body fractured under compression or also, for example, after an intervertebral disc resection for arrangement between adjacent vertebral bodies, can be easily moved to the implantation location because of its small dimensions. After the expansion has been effected, a preliminary stabilization is ensured immediately because the supporting implant maintains its final shape obtained during the plastic expansion. A filler material which is initially present in liquid form can be introduced under slight pressure into the created hollow space and can harden in the hollow space. Because of the action of the supporting implant, it is not necessary to wait until the filler material has hardened completely. [0008] While mechanical tools for producing the internal pressure are conceivable, a preferred embodiment of the invention provides for a device which produces the internal pressure by means of a pressure fluid. [0009] The pressure fluid can be introduced directly into the supporting implant, which requires that the supporting implant and the supply connections are pressure tight. However, in accordance with a preferred embodiment, a pressure balloon is provided which is arranged in the interior of the supporting implant and into which the pressure fluid can be introduced. [0010] The expandable supporting implant may include a weakened wall, or a wall which is perforated in the manner of expanded metal and/or folded in the manner of a bellows. [0011] This type of supporting implant can be expanded with relatively low internal pressure, wherein the stability of the expanded implant is reduced by the weakened or folded portions, however, the implant can still carry out a sufficient supporting function. [0012] The wall of the expandable supporting implant may have weak portions and/or folds arranged in such a way that the supporting implant expands into a desired shape. For example, if such a supporting implant is arranged between adjacent vertebrae, the desired shape is approximately that of a parallelepiped. [0013] In accordance with a preferred embodiment of the invention, the expandable supporting implant has an oblong shape so that it is suitable for being arranged at the implantation location by means of a catheter or a guide sleeve. In particular, the expandable supporting implant, and possibly the pressure balloon, may be placed in the manner of a stocking on a pressure line which can be introduced through the guide sleeve, wherein the pressure balloon is arranged between the supporting implant and the pressure line and, in the non-expanded state, forms a hose-type sleeve which surrounds the pressure line and which is connected at its ends in a pressure-tight manner by being placed around the circumference of the pressure line. [0014] The pressure fluid is preferably not compressible, and a device for measuring the supplied amount of pressure fluid is provided. This makes it possible to control the degree of expansion through the supplied quantity. [0015] In accordance with another advantageous embodiment of the invention, a monitoring device is provided which monitors changes over time of the fluid pressure and the supplied fluid quantity so that the pressure application can be interrupted when predetermined relative values of these changes are exceeded. Such a monitoring device prevents fluid which is under high pressure from being released into the body when the supporting implant is destroyed, for example, as a result of a material defect. [0016] The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of the disclosure. For a better understanding of the invention, its operating advantages, specific objects attained by its use, reference should be had to the drawing and descriptive matter in which there are illustrated and described preferred embodiments of the invention. BRIEF DESCRIPTION OF THE DRAWING [0017] In the drawing: [0018] [0018]FIG. 1 is a schematic sectional view of a device according to the invention with a supporting implant placed on a pressure line; [0019] [0019]FIG. 2 is an illustration of a detail of the supporting implant of FIG. 1; [0020] [0020]FIG. 3 is an illustration, on a smaller scale, showing the device of FIG. 1 inserted into a broken and compressed vertebral body; [0021] [0021]FIG. 4 shows the vertebral body of FIG. 3 which has been expanded by means of the device of FIG. 1; and [0022] [0022]FIG. 5 is an illustration of another embodiment of the supporting implant which can be used in a device of the invention. DETAILED DESCRIPTION OF THE INVENTION [0023] [0023]FIG. 1 of the drawing shows a guide sleeve 1 and a pressure line 2 extending through the guide sleeve 1 , wherein the pressure line 2 is provided with an opening 3 for releasing a pressure fluid. [0024] An elastic hose-type sheath 4 is placed in the manner of a stocking and flush at the ends thereof on the circular cylindrical pressure line 2 . The sheath 4 is glued in a pressure-tight manner at its ends to the circumference of the pressure line 2 at 5 and 6 . Instead of providing a glued connection, it would also be possible to press the elastic sheath 4 at the ends thereof by means of rings against the pressure line. [0025] A hollow-cylindrical supporting implant 7 is placed around the elastic sheath 4 . As can be seen in FIG. 2, the cylindrical wall 8 of the implant 7 is a mesh-like material with openings 9 , wherein wires of the mesh extend at an acute angle relative to each other. The wall 8 can be tangentially expanded in the manner of expanded metal in the direction of double arrow 21 , so that the supporting implant 7 is radially expanded. [0026] At its end opposite the sheath 4 or the supporting implant 7 , the pressure line 2 is in connection with a schematically illustrated device 10 for supplying an incompressible pressure fluid 11 , wherein this device 10 includes a pressure cylinder 12 and a piston 13 . The piston 13 may be movable manually, preferably by means of a screw-type pressure gauge, or by means of a motor drive. [0027] Reference numeral 14 denotes a schematically illustrated control and monitoring device which includes a pressure indicator 16 and a display 17 for the supplied quantity of pressure fluid. [0028] The manner of operation of the device is shown in FIGS. 1 and 2 and shall now be explained in connection with FIGS. 3 and 4. [0029] For stabilizing a broken vertebra, initially a duct 18 is drilled through the pedicle 20 , wherein a catheter and a drilling tool extending through the catheter can be used for this purpose. As shown in FIGS. 3 and 4, the guide sleeve 1 is now placed in the duct 18 and the pressure fluid 2 with the supporting implant 7 can be forwardly pushed into the interior of the compressed vertebra which has compression folds at 19 . [0030] The incompressible pressure fluid 11 is pressed by means of the device 10 into the pressure line 2 , the pressure fluid 11 emerges from the opening 3 and the elastic sheath 4 is expanded into a balloon. The expanding sheath or balloon 4 expands the supporting implant 7 , as illustrated in FIG. 4, wherein the wall 8 of the supporting implant 7 is plastically deformed in the direction of arrow 21 shown in FIG. 2 and the acute angles between the mesh wires at 17 are widened. [0031] The quantity of supplied pressure fluid during the expansion can be read at the display 17 of the control and monitoring device 14 and, thus, the extent of the achieved expansion can be determined. The expansion or supply of pressure fluid is stopped when a predetermined value of the supplied pressure fluid quantity has been reached. [0032] The control and monitoring device 14 further ensures that the application of pressure is stopped immediately if the balloon 4 ruptures during the expansion, for example, due to a material defect, and pressure fluid is released from the vertebra; this is the case when the supplied pressure fluid quantity increases significantly over time, while the pressure stays constant or increases only slightly. [0033] After the required expansion has been achieved, the pressure fluid is withdrawn through the opening 3 which is located near the lowest point of the balloon 4 . The pressure line 2 with the empty pressure balloon or the empty sheath 4 can now be pulled back through the guide sleeve 1 . [0034] The plastically deformed supporting implant 7 maintains its shape and supports the vertebra in such a way that it maintains the shape shown in FIG. 4 and the damage shown at 19 can heal. A filler material is introduced into the interior of the supporting implant. [0035] [0035]FIG. 2 is a cross-sectional view of another embodiment of a supporting implant 7 a according to the invention. The supporting implant 7 a has in its wall 8 a folds 22 , wherein the folds on opposite sides have different lengths, so that the expanded implant has a rectangular shape in cross-section. [0036] In the embodiment described above, a salt solution containing an x-ray contrast agent is used as the pressure fluid. [0037] Of course, two of the above-described supporting implants can be and are usually inserted into a broken vertebra, wherein ducts are drilled in both pedicles for inserting a catheter. [0038] While specific embodiments of the invention have been shown and described in detail to illustrate the inventive principles, it will be understood that the invention may be embodied otherwise without departing from such principles.
A device for straightening and stabilizing the vertebral column, particularly for stabilizing broken vertebrae, includes a supporting implant which is plastically expandable by internal pressure. The supporting implant can be placed into the interior of a vertebral body which has been fractured under compression or between adjacent vertebral bodies. A pressure balloon to which pressure fluid can be admitted may be arranged in the interior of the supporting implant for producing the internal pressure.
11,932
BACKGROUND OF THE INVENTION The present invention relates generally to diastereomeric mono- and di-hydroxylated diamino cyclohexane compounds and the methods for preparing them in a sterocontrolled manner. The invention also relates to the use of such compounds as synthons in the preparation of platinum complexes for such pharamceutical uses ana antitumor agents. Vicinal, 1,3-, and 1,4-relationships of O and N functions in pharmacologically active compounds are of particular interest in drug design. In particular, appropriately functionalized aminocyclitols of the cyclohexane diol diamine type serve as synthons for cyclic and acyclic compounds. The synthons are useful for mechanism-based stereostructure-activity investigations in numerous biological systems. A synthon is a structural unit within a molecule which is formed and/or assembled by conceivable synthetic operations. These operations refer not to laboratory manipulations, but to structural transformations in the molecular sense. A synthon is an idealized fragment produced by bond disconnection during a retrosynthetic analysis. Synthons also serve as the focal point for the facile elaboration of compounds with a diversity of pharmacological activity. Thus, a single generic synthon provides avenues for entry into a range of biological areas. A number of synthons have been produced from such compounds as carbohydrates and amino acids which permit the implementation of this conceptual strategy in the organic synthesis of cyclic and acyclic compounds. To be useful for biological investigations, the synthon must provide isomeric compounds since many pharmacological systems display enantio- and diastereo- meric preferences. Incorporation into a pharmacological system of functional substituents which are suitable for conversion into various targets of biological interest in an important factor in selecting a synthon. The functional substituents must be able to impose a high degree of either enantio- or diastereo- meric control during key reactions. To be most useful, the synthon must be able to strike a positional balance in a particular synthetic scheme, by sufficiently complex in structure, and be available in sufficient quantity so that divergent syntheses may be completed. In addition, synthons useful in medicinal chemistry must be convertible to several biologically different targets, have a wide isomeric pool, and be readily available and facilitate inexpensive preparation. In particular, cyclohexane diol-diamine types of aminocyclitols serve as synthons and are found in such substances as streptamine, epistreptamine, 2-deoxystreptamine, 2,5- and 2,6-dideoxystreptamine, actinamine and fortamine. While these substances occupy an important place in antimicrobial chemotherapy, the cyclohexane diol-diamines, as a group, have received relatively little attention. Although there are eleven possible regioisomeric cyclohexane diol-daimines 1 - 11, as shown below, previous synthetic efforts have centered mainly on regioisomers 5-10. Selected diastereomers of the 5-10 compounds have been employed as mutasynthons for the preparation of new antibiotics having altered sensitivity to plasmid- and nonplasmid- mediated bacterial resistance. Also, one stereoisomer, reported in Kuglov et al., Vesti. Akad. Navak BSSR, Ser. Khing Navuk, 1981, 5, 66-71, of compound 7 possesses antihypertensive activity. ##STR1## Only certain regioisomers of cylohexane diol-diamines have been synthesized and biologically investigated for use as synthons. In particular, only the synthesis of derivatives of compound 1 has been performed, as reported in Kresze, G. and Melzer, H., Justus Liebige Ann. Chemie, 1874, (1981). While this cyclohexane diol-diamine nucleus is useful as a synthon, the synthon capabilities embodied in 4 have not been previously investigated, nor has there been any investigation into the use of synthons such as the cyclohexane diol diamine nucleus as a synthon for the synthesis of analogs of the organo platinum antitumor agent, cisdiammin dichloro platinum II (cisplatin). Cisplatin is used for patients with a variety of terminal malignancies. However, the clinical utility of the antitumor agent cisplatin is limited by severe nephrotoxicity where damage is directly correlated with the dosage and ranges from tubular swelling to total necrosis. Other side-effects include ototoxicity leading to high frequency hearing loss and mental confusion. Therefore, while cisplatin has shown to be beneficial in a broad spectrum of antitumor activity, there is a need for continued research for improved congeners of cisplatin with reduced nephrotoxic and emetic effects. One successor to cisplatin is the dichloro trans-1,2-diaminocyclohexane Pt(II) complex 13a which displays high activity against a broader range of tumors than cisplatin, and a lack of cross resistance without significant nephrotoxicity. However, this compound 13a has a low therapeutic index which imposes dosage limits on the course of therapy. Also, since the 13a compound lacks sufficient aqueous solubility it is very difficult to make pharmaceutical formulations for intravenous administration. ##STR2## In an effort to overcome these problems, modifications to 12 focus primarily on the chloride leaving groups such as substitution of either malonate, 13b or sulfate, 13c for the chloride ions. The sulfato analog 13c is very water soluble and high reactive. However, 13c retains a high degree of toxic potential and suffers from stability problems in aqueous formulations as a result of this chemical lability. Bidentate carboxylate ligands, such as malonate 13b are at the other end of the reactivity spectrum. Much higher doses of 13b are needed than would otherwise be employed and such higher doses lead to neurological and otological toxicities as well as significant myelosuppression. In light of the importance of developing synthons useful in biological investigations, it can readily be appreciated that a need exists for the development of novel synthons which provide isomeric compounds capable of being converted to several biologically active pharmaceutical compounds. There is a need for synthons which are capable of imposing a high degree of enantio- and/or diastereomeric control during various key reactions in the synthesis of the pharmaceutical compounds. There is a further need for the development of synthons useful in medicinical chemistry which are readily available and which facilitate inexpensive preparation of the desired pharmaceutical compounds. It can also readily be appreciated that a need exists for the development of new organoplatinum chemotherapeutic compounds less toxic than the known cisplatin compound which can be readily prepared from synthons capable of imposing diastereomeric control during the synthesis of such chemotherapeutic compounds. There is a further need for organoplatinum compounds which are more active than cisplatin and have a greater spectrum of anti-tumor efficacy than cisplatin. There is another need for organoplatinum compounds which show a wide range of activity and which do not lead to additive toxicity when used alone or in combination with other therapeutic agents. There is still another need for attractive synthetic routes for the preparation of such synthons and the novel organoplatinum compounds prepared therefrom. SUMMARY OF THE INVENTION One aspect of the present invention relates to a process of making cyclohexane-1,2-di(O)-4,5-di(N) diastereomers of 4 which are useful as synthons for various diastereoisomeric pharmaceutical systems. The present invention also relates to the stereoisomer compounds 4 which are derived from retro- synthetic analysis. ##STR3## In another aspect, the present invention relates to novel antineoplastic Pt(II) complexes 14 derived from the stereoisomers 4 and the processes for making such Pt(II) complexes 14a, 14b and 14c. Mono- and di-hydroxyl substitution on the cyclohexane ring renders the organoplatinum complex relatively more water soluble, thereby facilitating intravenous administration. The Pt(II) complexes 14 of the present invention are less nephrotoxic than cisplatin and are readily excreted via the kidney due to their enhanced water solubility. In a composition aspect, the present invention encompasses novel pharmaceutical compositions comprising the novel Pt(II) complexes 14a, b and c in an amount sufficient to have an antineoplastic effect in an animal or patient. ##STR4## The present invention provides a process for preparing a diastereomeric 1,2-dihydroxylated-4,5-diaminocyclohexane compound which comprises dihydroxylating a bis[benzylcarbamate](Cbz) compound of the formula ##STR5## to give the corresponding dihydroxylated benzylcarbamate-protected diamine compound of the formula ##STR6## and thereafter liberating, by catalytic hydrogenation, the diastereomeric SP-1,2-dihydroxylated-4,5-diamino cyclohexane compound of the formula ##STR7## The present invention further provides a process, as described above, wherein the diastereomeric 1,2-dihydroxylated-4,5-diaminocyclohexane synthon compound of the formula 4, immediately after hydrogenation is platinated to form a SP-4,2-dichloro(4,5-dihydroxy-1,2-cyclohexane diamine-N,N')-platinum compound of the formula ##STR8## The present invention further provides a process wherein a bis[benzylcarbamate] compound prior to catalytic hydrogenation, is catalytically esterified to give a compound of the formula wherein R is an ester or organic acetate group having from 2 to 22 carbon atoms ##STR9## and, following catalytic hydrogenation, platinating the compounds of the formulae 54, 55 and 36 to give the corresponding SP-4,2-dichloro(4,5-di-substituted-oxy-1,2-cyclohexanediamine-N,N')-platinum compound of the formula wherein R is an organic acetate, or ester, group having from 2 to 22 carbon atoms ##STR10## The present invention further provides a process for preparing a diastereomeric SP-4,2-dichloro(4-hydroxy-1,2-cyclohexanediamine-N,N')-platinum compound which comprises the steps of the monohydroxylating the bis[benzylcarbamate](Cbz) compound to give the corresponding monohydroxylated benzylcarbamate-protected diamine compound of the formula: ##STR11## catalytically hydrogenating, and thereafter platinating to give the corresponding diastereomeric SP-4,2-dichloro(4-hydroxy-1,2-cyclohexanediamine N,N')-platinum compound of the formula ##STR12## The present invention further provides a diastereomeric 1,2-dihydroxylated-4,5-diaminocyclohexane compound defined according to the generic formula: ##STR13## The present invention further provides a diasteromeric SP-4,2-dichloro(4,5-dihydroxy-1,2-cyclohexane diamine-N,N')-platinum compound defined according to the generic formula: ##STR14## The present invention further provides a diastereomeric S,P-4,2-dichloro-(4,5-di-substituted-oxy-1,2-cyclohexane diamine-N,N')-platinum compound defined according to the generic formula wherein R is an organic acetate, or ester, group having from 2 to 22 carbon atoms: ##STR15## The present invention further provides a diastereomeric SP-4,2-dichloro(4,hydroxy-1,2-cyclohexanediamine-N,N')-platinum compound defined according to the generic formula: ##STR16## The present invention further provides a pharmaceutical composition comprising at least one of the diastereomeric SP-4,2-dichloro(4,5-dihydroxy-1,2-cyclohexane diamine-N,N')-platinum compounds or pharmaceutically acceptable salts thereof, in an amount sufficient to have an antineoplastic effect in an animal or patient together with at least one pharmaceutically acceptable excipient. The invention further provides a pharmaceutical composition comprising at least one of the diastereomeric S,P-4,2-dichloro(4,5-diacetyloxy-1,2-cyclohexane diamine-N,N')-platinum compounds or pharmaceutically acceptable salts thereof, in an amount sufficient to have an antineoplastic effect in an animal or patient together with at least one pharmaceutically acceptable excipient. The invention further provides a pharmaceutical composition comprising at least one of the diastereomeric S,P-4,2-dichloro(4-hydroxy-1,2-cyclohexane diamine-N,N')-platinum compounds or pharmaceutically acceptable salts thereof, in an amount sufficient to have an antineoplastic effect in an animal or patient together with at least one pharmaceutically acceptable excipient. DETAILED DESCRIPTION OF THE INVENTION Novel stereocontrolled pathways lead to the six aminocyclitol diastereomers 4a-f which belong to the cyclohexane-1,2-di(O)-4,5-di(N) series of the present invention. The relative stereochemical relationships of the diastereomers 4a-f are defined as follows: ##STR17## Compounds 4a-4f are named according to IUPAC nomenclature. For convenience, the stereochemical relationships between the hydroxyl and amino groups are described as follows: the "front" hydroxyl function bonded to C-1 (as arbitrarily designated by IUPAC convention) its relationship to the vicinal alcohol is specified as cis or trans (c or t). The orientation of the "C-2" OH group to the 4-amino group is described as syn or anti (s or a) and the vicinal amine stereochemistry follows the cis/trans convention. Proceeding clockwise from the lower left of the molecule, isomer 4a is designated as cis-syn-cis (csc) and 4d as cis-anti-trans (cat), etc. The generic structure of the cyclohexane diol-diamine stereoisomers 4a-4f of the present invention are attractive synthons because, according to the present invention, all six diastereomers are now available via short stereocontrolled pathways employing readily available reagents. Diastereomers 4a-4f are useful in the preparation of novel hydroxylated organoplatinum complexes 14 for antitumor evaluation. Oxygenation of the diaminocyclohexane ligand provides sites for metabolism and further chemical derivatization to improve the water solubility of the organoplatinum complex. Access to the complete series of the organoplatinum complexes affords a spectrum of agents which show unique stereoisomeric differences in solubility and antineoplastic properties. The amelioration of toxicity and improving hydrophilicity of organoplatinum complexes is achieved by making modifications on the diamine ligand of the diastereomer synthons 4a-4f of the present invention. Addition of one or more hydroxyl functions to the cyclohexane diamine portion of the organoplatinum complex provides a means by which these improvements are made. The hydroxyl groups serve as sites for chemical derivatization with sugars or dicarboxylic acids to increase aqueous solubility, if the parent system is insufficiently soluble in water. Furthermore, metabolic modification of the drug at the glycol moiety by glucuronidation, sulfate or phosphate formation is another choice by which the hydrophilicity of the complex is improved and toxicity lessened. The following diol-diamine Pt(II) complexes 44-49 are prepared according to one aspect of the present invention: ##STR18## In addition, the four stereoisomeric hydroxy-diamine analogs 50-53 derived from an olefinic intermediate in the synthetic sequence serve as additional probes of the stereospecific effects of hydroxyl substitution on the antineoplastic activity of the diaminocyclohexane-Pt nucleus. ##STR19## Further, three corresponding complexes, 56-58 wherein R is an ester or organic acetate group having from 2 to 22 carbon atoms, serve as additional probes of the stereospecific effects of further substitutions on the antineoplastic activity of the diaminocyclohexane-Pt nucleus. ##STR20## The syntheses of the novel compounds of the invention are based upon oxidative manipulation of the suitably protected diaminocyclohex-4-enes 15 and 16. Stereocontrolled glycol formation via mild, inexpensive and readily available reagents provides the target diol diastereomers. ##STR21## Stepwise Curtius rearrangement, as reported in Kricheldorf, H. R., Chem. Ber., 1972, 105, 3958-3965, and shown in scheme 1 below, and hydrolysis in situ of the intermediate bis(isocyanate) 19 affords cis-15 .2HCl in 50% overall yield from tetrahydrophthalic anhydride 17. Similarly, bis(acylchloride) 21 is converted to trans-16 2HCl in 59% net yield. Respective bis[benzylcarbamates (Cbz)] 20 and 22 are desired, since subsequent applications of cyclohexane diol-diamines require facile removal without inorganic by-products. Use of 1,2,2,6,6-pentamethylpiperidine (PMP) in aqueous THF provides bis(Cbz) 20 and 22 in excellent yield by recrystallization of the crude reaction mixtures. Excess benzyl alcohol addition to the Curtius intermediate bis(isocyanates) affords the respective isomers 20 and 22 in approximately 30% yield. Additional chromatographic procedures are required to separate desired materials from complex mixtures. ##STR22## Catalytic osmylation of trans-22 affords cis-anti-trans 23 (98%) which serves as a stable source of 4d as shown in Scheme 2 below. The 1 H NMR spectrum differs from the spectra for the remaining five diastereomers as shown in Table 1 below. Exclusive formation of 23 from 22 during osmylation from either side of the Pi system is a function of the 2-fold axis of symmetry in the product. Similar osmylation of cis-22 at room temperature for 16 h proceeds with little stereocontrol, and a 90% yield of a 1.3:1.0 ratio of 24 to the sterically more congested isomer 25 is obtained. At -20° C. (5 da) a modest increase (2.1:1.0, respectively) in stereoselectivity is achieved. Unexpectedly, these results indicate that the pseudoaxial carbamate presents only a minor degree of steric impedance to OsO 4 for approach to the Pi system. ##STR23## TABLE 1______________________________________500 MHz .sup.1 H NMR Resonance Signals (δ) Assignments forcyclohexane diol-diamines diastereomers 4a-f. compd.______________________________________4a 3.75- 1.82- 1.98-2.20 3.65-3.75 1.82-1.98 1.98-2.20 3.95 1.984b 3.86- 1.88- 2.00-2.08 3.80-3.86 1.88-1.96 2.00-2.08 3.96 1.964c 3.72 1.82 2.07-2.16 3.80 3.67 1.86 2.07-2.16 3.834d 3.73 1.68 2.22 3.52 3.42 1.82 2.02 3.954e 3.52- 1.55- 2.28-2.34 3.43-3.50 1.55-1.63 2.28-2.34 3.60 1.634f 3.89- 1.95- 2.02-2.10 3.60-3.64 1.95-2.02 2.02-2.10 3.93 2.02______________________________________ .sup.a Compounds 4a-f are numbered starting with the carbon bearing hydroxyl group as No. 1 in the lower left part of the ring. Notable differences in the 500 MHz 1 H spectra of the cis-anti-cis 24 and cis-syn-cis 25 compounds support the diastereomeric assignments proposed on the basis of mechanistic principles. At identical concentrations in acetone-d 6 solution, the NH (6.45 δ) and OH (4.14 δ) proton resonance signals in 25 are downfield to those of 24 (6.27 and 3.70 δ, respectively). Intramolecular hydrogen bonding owing to the 1,3-diaxial relationship of OH and NH functions in 25 (and in its flip conformation) account for the downfield shift. Furthermore, the NH protons in 25 exchange with D 2 O at a much faster rate (15 min) than those in 24 (exchange not observable after 30 min.). Hydroxyl proton exchange with D 2 O proceeds equally rapidly for both isomers. Confirmation of the relative stereochemical assignments for these isomers is provided by X-ray analysis of the dichloro Pt(II) complex of 4a derived from 25 which clearly showed the cis-syn-cis arrangement of OH and NH 2 functions. Epoxidation of olefins 20 and 22 is carried out at room temperature with two equivalents of freshly purified m-chloroperbenzoic acid (MCPBA) and each affords a single epoxide 26 (86%) and 29 (73%), respectively, as shown in Scheme 3 below. Lower oxirane yields result when commercially available technical grade or less peracid (1.2-1.5 equivalents) is employed. Unlike 29, which has a C 2 axis of symmetry and whose 500 MHz 1 H NMR spectrum is first order, 26 displays a deceptively simple spectrum with insufficiently resolved two-proton multiplet resonance signals at δ 3.85 (H-3 and H-4), 3.2 (H-1 and H-6) and 2.35 (H2e and H5e). As such, the oxirane configuration of 26 is determined chemically. NaBH 4 reduction (or use of LiBH 4 in THF) of 26 affords a single alcohol 27 (72%) identical in all respects to the major diastereomer [3.5 (27): 1.0 (28)] resulting from exposure of 20 to excess B 2 H 6 /alkaline peroxide, as shown in Scheme 3 below. Since diborane is known to hydroborate the sterically most accessible face of a Pi system, the major component should be 27. Thus, delivery oxygen of MCPBA to 20 is mainly influenced by steric rather than electronic factors. ##STR24## Acid-catalyzed hydrolysis, as shown in Scheme 4 below, of epoxides 26 and 29 at room temperature afford trans-anti-cis 30 (73%) and trans-anti-trans 31 (69%), respectively, which in turn serve as stable precursors to diol-diamines 4c and 4e. Formation of 31 from 29 is accompanied by bicyclo [3.3.1] oxazolidone 32 (16%). The ratio of 31:32 is unchanged at temperatures between 0°-65° C. Treatment of 29 with glacial HOAc in the presence or absence of NaOAc or with H 2 O 2 /HCO 2 H mainly affords 32 and traces 31. ##STR25## Formation of the bicyclo [3.3.1] system 32 via proposed intermediate 33 results from preferred anchimerically assisted proton catalyzed diaxial opening of epoxide 29. This pathway should be favored over formation of the bicyclo [3.2.2] skelton 34 wherein the carbocyclic ring is forced into a diaxially substituted boat conformation even though transition states leading to each are allowed processes. However, 1 H NMR double resonance experiments do not distinguish between these two possibilities. Correlation of long-range H-C couplings (by COLOC) carried out on the hydrogenolysis (debenzylated) compound clearly establishes structure 32 as the product. Correlation between the proton resonance signals at δ 3.78 and 4.55 with the carbonyl resonance signal at δ 156 indicates that the proton signals are attributable to H-5 and H-1, respectively. Observation of a similar 3-bond J C-H correlation between the resonance signals for H-1 and C-5 (δ 46) and H-5 and C-1 (δ 75) can only take place in the debenzylated bicyclo [3.3.1] product of 32. Facilitation of hydrolysis by a neighboring axial carbamate functionality as in 29 is not possible during oxirane hydrolysis of 26. Whereas cleavage of 29 is complete after two hours at room temperature, 26 requires six hours and no bicyclic product formed. ##STR26## 32 can not be converted to trans-syn-trans cyclohexane diol-diamine 4f under a variety of conditions. The synthesis for 4f is achieved from cis-anti-trans 23. Regioselective monoacetylation (1.1 equivalents of Ac 2 O with 4-dimethylaminopyridine as catalyst) in THF at -25° C. furnished 35 (73%) contaminated with diacetate 36 (8%) (independently prepared in 92% yield using excess Ac 2 O at room temperature). Anticipated equatorial acetylation in 35 is in agreement with 1 H NMR analysis confirming the relative downfield shift from the H-4 or H-5 resonance signals in 23 of the H 4 axial proton (δ 5.10). Decoupling of equatorial H-5 (α to the OH group in 35) reveals the requisite axial-equatorial and diaxial coupling constants of 5 and 12 Hz between H-4 and the C-3 methylene protons. Jones oxidation of 35 affords keto acetate 37 (87%). Reduction (NaBH 4 ) and acetylation affords diacetates 38 (65%) and 36 (9%) separable by chromatography. Deacetylation (MeOH, K 2 CO 3 ) affords 39, as stable precursor to the cyclohexane diol-diamine 4f. The cyclohexane diol-diamines 4a-f form hygroscopic salts (HCl or dicarboxylates). Free amines are characterized by 500 MHz 1 H NMR spectroscopy and/or by conversion in situ to their Pt(II) complexes following treatment with K 2 PtCl 4 . ##STR27## The synthesis of the four hydroxy-diastereomers 27-28 and 40-41 from olefins 20 and 22 is achieved nonstereoselectively using diborane. Three molar equivalents of the reagent are required for complete hydroboration of the starting materials. In the case of cis-20, a 3:1 ratio of alcohols 27 and 28 is obtained in 91% yield. The same ratio of products results when the reaction is carried out at room temperature or at 0° C. or with up to five molar equivalents of diborane. Trans olefin 22 provides a 1.4:1 ratio of alcohols 40 and 41 in 78% yield when treated with diborane under similar conditions. ##STR28## Stereoselective reduction of the ketones derived from these alcohols is as follows: trans diamino-ketone 42 is prepared in 87% yield by Jones oxidation of a diastereomeric mixture of 40 and 41. Treatment of 42 with 1.3 molar equivalents of NaBH 4 at -20° C. gives primarily the expected equatorial alcohol 40 in 65% yield, accompanied by only a small amount of 41. This ratio is improved by performing the reaction at -78° C. Conversely, exposure of 42 at low temperature (-78° C.) to 1.2 equivalents of K-Selectride in THF furnishes a 20:1 ratio of axial:equatorial alcohols in 86% yield. These results confirm the structural assignments made as a result of the hydroboration-oxidation of 22. ##STR29## Cis diamino-ketone 43 is prepared in 94% yield by Jones oxidation of alcohol 27. Unlike 42, two conformations are available to 43 which differ only slightly in energy at room temperature. ##STR30## In β-substituted cyclohexanones, the usual stereochemical outcome of NaBH 4 reductions is often reversed. The presence of an axial β-substituent leads to predominant equatorial delivery of hydride as opposed to normal axial attack. The eventual result of this reduction indicates that the axial nitrogen substituent does not coordinate with the reducing agent facilitating an axial vector for delivery of hydride from the sterically more hindered side of 43. The diastereomeric outcome is dependent upon temperature, and amount and mode of addition of the reducing agent. Good results are achieved at -78° C. using 0.6 molar equivalents of NaBH 4 . At higher temperatures or when the reducing agent is added all at once, less stereoselection is observed. The results of these experiments are tabulated in Table II below. TABLE II______________________________________Effect of temperature, amount of NaBH.sub.4, andmode of addition on reduction of ketone 43. ##STR31## ##STR32## Mode of MolarTemp. Addition Equiv. NaBH.sub.4 Ratio of 28:27______________________________________-78° divided 0.6 18:10° C. divided 0.6 3:125° C. divided 0.6 1.5:1-78° 1 portion 0.6 4:10° C. 1 portion 0.6 1.8:125° C. 1 portiopn 0.6 1.2:1-78° divided 1 9:10° C. divided 1 1.5:125° C. divided 1 1.2:1______________________________________ Treatment of ketone 43 with a slight excess of K-Selectride at -78° C. in THF leads to the formation of alcohols 28 and 27 in a ratio of 1.3:1. Alcohol 28 is the product arising from preferred equatorial attack on the predicted favored conformation, while the less sterically hindered 27 arises from the less favorable 43b, indicating that even at low temperature, substantial amounts of this conformer are present. ##STR33## The six dihydroxy diamines 4a-4f and four diamine alcohols derived from 27-28 and 40-41 are prepared by catalytic hydrogenation of the protected species in methanol at 20 psi for two hours. NMR analysis at 90 or 270 MHz shows that each isomer is generated in yields of at least 90%. Attempted isolation of the diol-diamines as salts (HCl, oxalate, succinate, citrate) is frustrated by their hydroscopic nature while the free bases darkened on standing. Therefore, the platination of all diamines is carried out immediately following hydrogenation, as shown in Tables III and IV below. TABLE III______________________________________ ##STR34## ##STR35##Pt % H.sub.2 Ocomplex yield hydration______________________________________45 cac 43 144 csc 37 146 tac ? ?47 cat 73 148 tst 61 149 tat <5 --______________________________________ TABLE IV______________________________________ ##STR36## ##STR37##Pt % H.sub.2 Ocomplex yield hydration______________________________________50 ac 37 --51 sc 37 --52 st 65 1/253 at 48 1______________________________________ Platinum complexes formation is carried out according to the method of Connors, et al., Chem-Biol. Interact., 5, 415 (1972). After standing at room temperature for 24 hours, the precipitate is collected by filtration. Precipitation of the complex is observed within one to two hours for the trans analogs. In contrast, the cis derivatives often require five to six hours for noticeable complex formation. The diol-diamine complexes 44, 45, and 46 and hydroxy-diamine complex 53 co-crystallize with one mole of water, as shown by elemental analysis. The X-ray structure of 44 shows the water to be bound between the two hydroxyl groups. Corresponding diacetates of the diols 23, 25 and 24 are prepared and serve as potential prodrugs for the diol-diamine complexes. These diacetate complexes 56-58 are synthesized as shown in Table V below. TABLE V______________________________________ ##STR38## ##STR39## ##STR40## ##STR41## ##STR42## ##STR43## Pt % complex yield______________________________________ 56 csc 49 57 cac 65 58 cat 73______________________________________ The compounds of the present invention and their salts can be used as pharmaceuticals. Among other things, they have antineoplastic activity and are suitable for inhibiting or preventing cell division in neoplasms. They have enhanced water solubility allowing for facile excretion via the kidney and thus also have reduced nephrotoxicity. They are useful, for example, as a chemotherapeutic alternative to the drug cisplatin in the treatment of various neoplasms. The antineoplastic activity of the compounds of the present invention was determined using the following procedure: Female DBA/2 and DFA 1 , mice were obtained from Harlan Labs, Indianapolis, Ind. The mice were housed in gang stainless steel cages in environmentally controlled animal facilities and fed Purina Mouse Chow #5015. Water and food were available ad libitum and all mice were allowed at least 1 week for adaptation to their surroundings before being assigned to a study. Antitumor experiments were conducted against P388 and/or L1210 leukemias using the experimental protocols developed by the National Cancer Institute (NCI). P388 and L1210 tumors were maintained by continuous passage in the DBA/2 mice. On day 0, ascitic fluid was removed from the peritoneum of a DBA/2 mouse, diluted with Hank's balanced salt solution, cell concentration determined on a Coulter Counter (Model MHR) and 10 6 P388 cells or 10 5 L1210 cells were implanted intraperitoneally (0.2 ml) into CDF 1 recipient test mice. After the mice were weighed and implanted with tumor, they were randomly distributed into treatment groups of 7 animals each. Drugs were administered in a single dose. Drugs were evaluated by median survival time (MST). Percent treated to control (T/C) were calculated for each group according to the NCI protocols. Dosing solutions were prepared by dissolution of drug into 0.9% physiological saline or 0.3% Klucel in sterile water. Over a dosage range of 5 mg/kg to 40 mg/kg, the cis-anti-cis complex 45 displays significant activity as shown in the examples below. At 40 mg/kg 45 has a T/C of 157 while the cis-syn-cis diastereomer shows somewhat less antitumor effects. The trans diamine isomer 47 is toxic at doses above 20 mg/kg. The Pt complex 46 derived from the trans-anti-cis diol also demonstrates antineoplastic activity when given in crude form at a dose as low as 20 mg/kg. The following examples illustrate the biological antitumor activity of the platinum (II) complex compounds provided by the present invention. All compounds are injected intraperitoneally on a day one schedule. The toxicity levels are defined as toxic if T/C<85. The toxicity levels are defined as active if T/C>120 for the test system P388, and T/C>125 for the test system L1210. ______________________________________ mg/kgCompound No. Test System Dose MST T/C______________________________________Example A ˜45 P388 40 16.50 157 20 14.00 133 10 12.50 119 5 11.83 113Example B ˜47 P388 40 3.00 29 20 4.50 43 10 12.83 122 5 12.50 119Example C ˜44 P388 40 14.50 138 20 12.00 114 10 12.50 119 5 11.17 106Example D ˜56 P388 40 11.3 103 20 11.3 103 10 11.1 101 5 11.0 100Example E ˜58 P388 40 12.17 111 20 12.0 109 10 11.5 105 5 10.85 99Example F ˜57 P388 40 11.25 102 20 11.0 100 10 11.1 101 5 10.5 95Example G ˜46 P388 80 14.5 141 60 16.0 155 40 13.8 134 20 14.0 136 10 12.5 121Example H ˜50 P388 80 4.2 42 40 8.5 86 20 16.5 168 10 15.2 154Example I ˜51 P388 80 13.5 137 40 18.0 183 20 15.0 153 10 13.8 141Example J ˜52 P388 80 2.2 22 40 3.2 32 20 3.3 34 10 15.8 161Example K ˜52 L1210 20 4.0 50 10 5.5 69 5 11.5 144 2.5 10.5 131Example L ˜53 P388 80 2.2 22 40 5.0 51 20 14.5 147 10 16.5 168Example M ˜53 L1210 20 7.5 94 10 12.5 156 5 12.5 156 2.5 10.5 131Example N ˜48 P388 40 6.00 55 20 10.83 98 10 6.00 55 5 12.50 137 2.5 12.50 137Example Ocisplatin P388 6 24.5 249 3 18.5 188 1.5 15.5 158Example Pcisplatin L1210 6 18.5 180 3 18.2 176 1.5 16.0 155______________________________________ The compounds of the present invention and their salts can be used as medicaments; for example, in the form of pharmaceutical preparations which contain them in association with a compatible pharmaceutical excipient or carrier material. The carrier material can be an organic or inorganic inert carrier material suitable for enteral or parenteral administration such as, for example, water or saline solutions. The pharmaceutical preparations can be made up in a liquid form (e.g. as solutions, suspensions or emulsions). The pharmaceutical preparations may be sterilized and/or may contain adjuvants such as preserving, stabilizing, wetting or emulsifying agents, salts for varying the osmotic pressure or buffers. They can also contain still other therapeutically valuable substances. The medicaments can be produced in a manner known per se by mixing a compound of the present invention or a salt thereof with a non-toxic, inert, liquid carrier material customary per se in such preparations and suitable for therapeutic administration (e.g. the aforementioned carrier materials) and, if desired, bringing the mixture into the desired dosage form. The following examples illustrate the processes provided by the present invention: Melting points were determined in open capillaries with a Thomas-Hoover Uni-Melt apparatus and are uncorrected. Infrared spectra were recorded with a Beckman model 4230 spectrophotometer. Nuclear magnetic resonance spectra were recorded using either a Bruker WP-80, HX-90E, 300 MHz or 500 MHz spectrometer. TMS (CDCl 3 , DMSO, acetone or pyridine) or TSP (D 2 O) were used as internal standards. Chemical shifts are reported on the scale with peak multiplicities: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; dd, doublet of doublets; dt, doublet of triplets. THF was freshly distilled from Na/benzophenone ketyl. Dioxane was distilled first from CaH 2 then from Na/benzophenone ketyl. Elemental analyses were performed by Galbraith Laboratories, Inc., Knoxville, Tenn. EXAMPLE 1 Diastereomeric 1,2-Dihydroxy-3,4-diaminocyclohexanes 4a-f. Deprotection of the respective Cbz-protected diol-diamines. The respective Cbz-protected diamines (100 mg; 0.242 mmol; 23→4d, 24→4b, 25→4a, 30→4c, 31→4e, 39→4f are dissolved in 5 ml of MeOH. Catalyst (10% Pd/C; 20 mg) is added and the bottle alternatively evacuated (H 2 O aspirator) and refilled to 20 psi with H 2 five times. The suspension is shaken under 20 psi for 2 h. Following filtration (Celite) the colorless filtrate is concentrated in vacuo routinely affording 90% of the free diamines 4a-f whose NMR spectra are recorded in Table V below. EXAMPLE 2 cis-4-cyclohexene-1,2-diamine Dihydrochloride (15 2 HCl). Acid chloride 18b (12.61 g, 68 mmol) is dissolved in 40 ml of dry dioxane under argon in an oven-dried 250 ml round bottom flask. TMSN 3 (11.03 g; 95 mmol) is added at room temperature by pipette to the stirred solution which is subsequently heated to 80°-85° C. in an oil bath. N 2 evolution begins within 5-10 min and continues for 20-30 min. The reaction is cooled to 35°-40° C. and diluted with 24 ml of Me 2 CO. Concentrated HCl (17 ml) is added cautiously through the top of the condenser. Stirring is continued until CO 2 formation ceased (approximately 30 min). The precipitate is filtered and washed with Me 2 CO and Et 2 O providing 7.5 g (60%) of the diamine salt as a white powder mp 255°-265° C. IR (KBr) 2800 and 1460 cm -1 ; NMR (90 MHz, CDCl 3 ) δ 5.62 (deceptively t, 2H, olefinic), 3.75-3.9 (m, 2H, methines), 2.0-2.6 (m, 4H, methylenes). Anal. calc for C 6 H 14 N 2 Cl 2 : C, 38.93; H, 7.62; N, 15.13; Cl, 38.31. Found: C, 39.08; H, 7.44; N, 15.12; Cl, 38.00. EXAMPLE 3 trans-4-cyclohexene-1,2-diamine Dihydrochloride (16 2 HCl). Trans bis(acid chloride) 21 (4.7 g, 23 mmol) is dissolved in 10 ml of dry dioxane under argon in an oven dried 50 ml round bottom flask. Me 3 SiN 3 (5.85 g; 50 mmol) is added by pipette at room temperature. The flask is immersed in an oil bath preheated to 80° C. Vigorous N 2 evolution begins within 10 min after which time the heating bath is removed. When N 2 evolution subsides, the orange solution is reheated for ca. 10 min to 80° C. to ensure completion of the rearrangement. The reaction is cooled to 35°-40° C. and diluted with 15 ml of Me 2 CO followed by cautious addition of 7 ml of conc. HCl. CO 2 evolves immediately, and vigorous stirring is continued until gas generation ceases. The precipitate is collected by filtration and washed with Me 2 CO and Et 2 O affording 2.6 g (61%) of white powder, mp>280° C.; lit. 25 mp>320° C. IR (KBr) 2820, 1600 and 1515 cm -1 ; NMR (90 MHz, D 2 O δ 5.6-5.7 (m, 2H, olefinic), 3.6-3.8 (m, 2H, methines), 2.0-2.7 (m, 4H, methylenes). Anal. calc for C 6 H 14 N 2 Cl 2 : C, 38.93; H, 7.62; N, 15.13; Cl, 38.31. Found: C, 38.67; H, 7.42; N, 15.22; Cl, 37.34. EXAMPLE 4 cis-3-cyclohexene-1-carboxylic acid-6-isocyanato-trimethylsilylester (18a) is prepared according to the method of Kricheldorf, H. R., Chem. Ber., 1972, 105, pp. 3958-3965. cis-1,2,3,6-tetrahydrophthalic anhydride (Aldrich, recrystallized from toluene, 15.0 g; 99 mmol) is dissolved in 90 ml of dry dioxane under argon in an oven-dried 250 ml round bottom flask. Trimethylsilylazide (TMSN 3 , 16.0 g; 138 mmol) is added by pipette to the stirred solution held at room temperature. The gently stirring solution is immersed in an oil bath preheated to 80°-85° C. N 2 evolution ceases after 30-45 min. The solution is cooled to 35°-40° C. and concentrated in vacuo (bath temp<35° C.) to a slightly yellow oil that is purified by distillation under reduced pressure to furnish 19.36 g (82%) of a colorless liquid bp 80°-84° C. (0.4 torr); lit. 26 bp 82°-84° C. (0.4 torr). IR (neat) 2250 and 1720 cm -1 . NMR (90 MHz, CDCl 3 ) δ 5.5-5.59 (m, 2H, olefinic), 4.2-4.3 (m, 1H, H-6), 2.5-2.8 (m, 1H, H-1), 2.3-2.5 (m, 4H, methylenes) and 0.3 (s, 9H, SiMe 3 ). EXAMPLE 5 cis-3-cyclohexene-1-carbonyl chloride-6-isocyanate (18b) is prepared by a modification of the method of Kricheldorf, supra, wherein use of a catalytic amount of DMF provides an improved yield at lower temperature: Trimethylsilyl ester 18a (19.36 g; 81 mmol) is dissolved in 40 ml of CCl 4 . DMF (10 drops) is added followed by freshly distilled SOCl 2 (15.18 g; 113 mmol). The reaction mixture is heated to 40°-50° C. in an oil bath. Gas evolution begins within 5-10 min. The reaction is maintained at approximately 50° C. until the infrared absorption at 1720 cm -1 (ester) has disappeared (30-45 min). The solution is cooled to room temperature and concentrated in vacuo to a viscous yellow liquid that is distilled under reduced pressure to furnish 12.61 g (84%) of 18b as a colorless liquid, bp 60°-62° C. (0.15 torr); lit. 26 bp 70°-72 ° C. (0.2 torr). IR (neat) 2260 and 1790 cm -1 ; NMR (90 MHz, CDCl 3 ) δ 5.5-5.9 (m, 2H, olefinic), 4.4-4.5 (m, 1H, H-6), 3.0-3.2 (m, 1H, H-1), 2.4-2.6 (m, 4H, methylenes). This compound is used immediately for the next reaction. EXAMPLE 6 Bis(phenylmethyl) cis-4-cyclohexene-1,2-diyl-bis(carbamate) (20). Dihydrochloride 15 2 HCl (2.35 g; 13 mmol) is dissolved in 40 ml of THF and 5.0 ml of distilled H 2 O and cooled in an ice bath. 1,2,2,6,6-Pentamethylpiperidine (PMP; 7.87 g; 58 mmol) is added by pipette. After 10 min, a cold (0° C.) solution of benzyl chloroformate (4.34 g; 25 mmol) in 10 ml of THF is added dropwise over 15 min. Vigorous stirring is maintained for 1 h at ice bath temperature. The reaction is diluted with 100 ml of EtOAc and washed with 3×10 ml of 10% HCl solution. The acidic aqueous layer is back-extracted with 3×20 ml of EtOAc. The combined organic layers are washed with 3×25 ml of brine, dried (MgSO 4 ) and concentrated in vacuo affording a viscous, faintly yellow oil which is purified by flash chromatography (pet ether:EtOAc 3:1) providing the biscarbamate 20 as a thick colorless liquid. The liquid is induced to solidify when treated with Et 2 O:hexane affording 4.25 g (88%) of a white powder mp 80°-81° C. which resisted further recrystallization. IR (KBr) 3380, 3360, 1720 and 1680 cm -1 ; NMR (90 MHz, CDCl 3 ) δ 7.34 (s, 10H, aromatic), 5.6 (m, 2H olefinic), 5.2-5.4 (m, 2H, NH), 5.09 (s, 4H, benzylic), 3.9-4.2 (m, 2H methines), 2.4-2.7 (m, 2H, pseudoequatorial methylenes), 1.8-2.2 (m, 2H pseudoaxial methylenes). Anal. Calcd for C 22 H 24 N 2 O 4 : C, 69.46; H, 6.36; N, 7.36. Found: C, 69.24; H, 6.34; N, 7.32. EXAMPLE 7 trans-4-Cyclohexene-1,2-dicarbonyl Dichloride (21). Freshly distilled fumaryl dichloride (3.7 g; 24 mmol) is dissolved in 10 ml of dry Et 2 O in an oven dried 20-neck 50 ml round bottom flask, fitted with a gas inlet and dry ice Dewar condenser. The stirred solution is cooled to approximately -50° C. (dry ice/CH 3 CN). Butadiene (ca. 3 ml) is condensed into the flask and the cooling bath removed. Within 25-30 min the exothermic reaction ceases. After an additional 10 min the excess butadiene and solvent are removed in vacuo to furnish 4.7 g (approx 95%) of the Diels-Alder adduct as a colorless liquid which is used immediately without further purification. IR (neat) 3140 and 1785 cm -1 . EXAMPLE 8 Bis(phenylmethyl) trans-4-Cyclohexene-1,2-diyl-bis(carbamate) (22). Trans bis(benzylurethane) 22 is prepared in 94% yield from 16.2HCl using methodology identical to the one used for the synthesis of the corresponding cis isomer. The white solid obtained after chromatography is recrystallized from toluene:hexane affording fine white needles mp 144°-145° C. IR (KBr) 3320 and 1685 cm -1 ; NMR (90 MHz, CDCl 3 ) δ 7.3 (s, 10H, aromatic), 5.67 (d, 2H, NH, J=2.6 Hz), 5.07 (s, 4H, benzylic), 3.6-3.9 (m, 2H methines), 2.3-2.7 (m, 2H, pseudoequatorial methylenes), 1.8-2.2 (m, 2H, pseudoaxial methylenes). Anal. calc for C 22 H 24 N 2 O 4 : C, 69.46; H, 6.36; N, 7.36. Found: C, 69.61; H, 6.27; N, 7.35. EXAMPLE 9 Bis(phenylmethyl) (1α, 2β, 4α, 5α)-(4,5-Dihydroxy)-1,2-cyclohexanediyl)-bis(carbamate) (23). Olefin 22 (2.0 g, 5.3 mmol) is added to a mixture of Me 2 CO (40 ml), distilled H 2 O (3 ml) and tBuOH (2 ml). N-methylmorpholine-N-oxide (NMO) monohydrate (0.8 g; 5.9 mmol) and OsO 4 (0.009 g; 3.6×10 -2 mmol) in CCl 4 are added, and the reaction is stirred at room temperature under dry argon for 16 h. Me 2 CO (50 ml) is added, and white precipitate dissolved. Solid NaHSO 3 (ca. 0.2 g) is added, and the mixture is stirred for 15 min. The suspension is filtered, and the filtrate is concentrated in vacuo providing a tan solid which is purified on silica gel by eluting with CHCl 3 :Me 2 CO 1:1 affording 2.13 g (98%) of white solid mp 172°-173° C. Ir (KBr) 3460 (shoulder), 3320, 1680, 1070 and 1025 cm -1 ; NMR (500 MHz, pyridine-d 5 ) δ 8.40 (d, 1H, aromatic, J=8 Hz), 8.04 (d, 1H, aromatic, J=8 Hz), 7.30-7.40 (m, 4H, aromatic), 7.20-7.30 (m, 4H, aromatic), 6.31 (s, 1H, NH), 6.24 (s, 1H, NH), 5.31 (H A , of A'B' q, 1H, benzylic, J=12.6 Hz, 5.29 (H B' of A'B' q, 1H, benzylic, J=12.6 Hz), 5.22 (H A of AB q, 1H, benzylic, J=12.9 Hz), 5.19 (H B of AB q, 1H benzylic, J=12.9 Hz), 4.65-4.72 (m, 1H, H-2), 4.35-4.38 (m, 1H, H-4), 4.16-4.26 (m, 1H, H-1), 4.00-4.08 (m, 1H, H-5 ), 2.63 (deceptively simple d, 1H, H-3a, J=12.5 Hz), 2.48-2.60 (m, 2H, H-6a and H-6e), 1.84 (deceptively simple d, 1H, H-3a, J=12 Hz). Anal. calc for C 22 H 26 N 2 O 6 : C, 63.76; H, 6.32; N, 6.76. Found: C, 63.44; H, 6.42; N, 6.62. EXAMPLE 10 Bis(phenylmethyl) 1α, 2α, 4α, 5α)-(4,5-Dihydroxy-1,2-cyclohexanediyl)-bis(carbamate) (23), and bis(phenylmethyl) (1α, 2α, 4α, 5β)-(4,5-Dihydroxy-1, 2-cyclohexanediyl-bis(carbamate) (24). Olefin 20 (2.00 g; 5.3 mmol) is dissolved in 16 ml of Me 2 CO, 3.2 ml of distilled H 2 O and 2.1 ml of t-BuOH at room temperature. MNO monohydrate (0.80 g; 5.9 mmol) and OsO 4 (0.0091 g; 0.036 mmol) in 0.91 ml of CCl 4 are added and stirring is continued under argon for 16 h. Excess OsO 4 is decomposed by addition of approximately 0.2 g of NaHSO 3 . The suspension is stirred for 15-20 min and filtered through MgSO 4 . The filtrate is concentrated in vacuo affording a tan solid. Chromatography over 120 g of silica gel using CHCl 3 :Me 2 CO 3:2 as eluant affords 1.14 g (52%) of 24, mp 142°-144° C. and 0.86 g (39%) of 23 mp 157°-158° C. in a ratio of 1.34:1, respectively. For 24 IR (KBr) 3460 (br), 1715, 1680, 1080 and 1020 cm -1 ; NMR (500 Hz, acetone-d 6 ) δ 7.3-7.35 (m, 10H, aromatic), 6.27 (br s, 2H, NH), 5.05 (s, 4H, benzylic), 4.16-4.19 (m, 2H, H -4 and H -5 ), 3.95-3.97 (m, 2H, H -1 and H -2 ), 3.70 (d, 2H, OH, exch. with D 2 O, exch. with D 2 O, J=3.9 Hz), 1.86-1.97 (m, 4H, methylenes). Anal. calc for C 22 H 26 N 2 O 6 : C, 63.76; H, 6.32; N, 6.76. Found: C, 63.55; H, 6.40; N, 6.62. For 23 IR (KBr) 3380, 3320, 1710, 1700, 1100 and 1035 cm -1 NMR (500 MHz acetone-d 6 ) δ 7.28-7.40 (m, 10H, aromatic), 6.3-6.5 (br s, 2H, NH), 5.06 (s, 4H, benzylic), 4.14 (s, 2H, OH, exch with D 2 O), 3.8-4.1 (broad m, 4H, methines), 1.9-2.0 (m, 2H, equatorial methylenes), 1.81 deceptively simple d, 2H, axial methylenes, J gem =13 Hz). Anal. calc for C 22 H 26 N 2 O 6 : C, 63.76; H, 6.32; N, 6.76. Found: C, 63.60; H, 6.33; N, 6.60. EXAMPLE 11 Bis(phenylmethyl) (1α, 3β, 4β, 6α)-7-Oxabicyclo(4.1.0)heptane-3,4-diylbis(carbamate) (26). Olefin 20 (1.4 g, 3.9 mmol) is dissolved in 15 ml of CH 2 Cl 2 at room temperature and NaHCO 3 (0.31 g; 3.9 mmol) is added. m-Chloroperoxybenzoic acid (freshly purified, 0.63 g; 7.8 mmol) in 10 ml of CH 2 Cl 2 is added dropwise over 10 min to the vigorously stirred suspension. After 3 h, EtOAc (50 ml) is added, and the solution is washed with 3×15 ml portions of 10% NaHSO 3 and 5% NHCO 3 solutions and brine. The organic layer is dried (Na 2 SO 4 ) and concentrated in vacuo affording a colorless oil. Four hours following addition of 25 ml of Et 2 O, colorless needles (1.09) g. are collected by filtration. Flash chromatography of the mother liquor (pet ether:Me 2 CO 3:1) provides an addition 0.18 g of product (mp 107°-108.5° C.) for a combined yield of 1.27 g (86%). IR (KBr) 3420, 3300, 1725, 1690 and 1320 cm -1 ; NMR (500 MHz, CDCl 3 ) δ 7.29-7.35 (m, 10H, aromatic), 5.57 (d, 2H, NH, J=6.4 Hz), 5.10 (H A of AB q, 2H, benzylic, J=12 Hz), 5.06 (H B of AB q, 2H, benzylic, J=12 Hz), 3.85 (deceptively simple dd, 2H, H-3 and H-4, J=6 and 13 Hz), 3.21 (s, 2H, H-1 and H-6), 2.35 (deceptively simple d, 2H, H-2e and H-5e, J=13 Hz), 2.02 (dd, 2H, H-2a and H-5a, J=7 and 13 Hz). Anal. Calc for C 22 H 24 N 2 O 5 : C, 66.65; H, 6.10; N, 7.07. Found: C, 66.71; H, 6.11; N, 7.21. EXAMPLE 12 Bis(phenylmethyl) (1α, 2α, 4β)-(4-Hydroxy-1,2-cyclohexanediyl)-bis(carbamate) (27) and Bis(phenylmethyl) (1α, 2α, 4α)-4-Hydroxy-1,2-cyclohexanediyl)-bis(carbamate) (28). Olefin 20 (1.5 g, 3.95 mmol) is dissolved in 50 ml of dry THF under argon and cooled in an ice bath. Diborane (1M in THF, 12 ml, 12 mmol) is added dropwise by syringe. After 6 h at 0° C., the reaction is cooled to -20° C. (ice-salt bath). NaOH (12 ml of a 6N solution) and 30% H 2 O 2 (8 ml) are added cautiously. The reaction is allowed to warm to room temperature over three hours. The aqueous phase is saturated with K 2 CO 3 and separated from the organic layer. The aqueous solution is extracted with 4×25 ml of Et 2 O. The combined organic extracts are dried (Na 2 SO 4 ) and concentrated in vacuo to yield a thick oil which is purified by flash chromatography (Et 2 O:Me 2 CO; 20:1) affording 0.35 g of 28 and 1.07 g of 27 for a total yield of 91%. Both compounds are obtained as clear oils which solidified after treatment with Et 2 O/hexane. For 28: mp 82°-86° C., IR (KBr) 3460 (sh), 3380, 3340, 1695, 1685, 1265, 1070, and 1040 cm -1 ; NMR (500 MHz, CDCl 3 ) δ 7.34 (s, 10H, aromatic), 6.27 (s, 1H, NH), 5.41 (s, 1H, NH), 5.08 (s, 4H, benzylic), 4.00-4.10 (m, 2H), 3.66-3.72 (m, 1H), 1.60-1.92 (m, 6H, methylene). Anal calc for C 22 H 25 N 2 O 7 : C, 66.48; H, 6.34; N, 7.05. Found: C, 66.28; H, 6.50; N, 6.83. For 27: mp 163°-164 ° C., IR (KBr) 3460 (sh), 3320, 1725, 1700, 1675, 1270, 1245 and 1015 cm -1 ; NMR (500 MHz, CDCl 3 ) δ 7.34 (s, 10H, aromatic), 5.09 (br s, 6H, 2NH and benzylic), 4.15-4.20 (m, 1H, H-4), 3.85-3.91 (m, 2H, H-1 and H-2) 1.4-2.1 (m, 6H, methylene). Anal. calc for C 22 H 25 N 2 O 7 : C, 66.48; H, 6.34; N, 7.05. Found: C, 66.46; H, 6.48; N, 6.93. EXAMPLE 13 Bix(phenylmethyl) (1α, 3α, 4β, 6α)-7-Oxabicyclo(4.1.0)heptane-3,4-diyl-bis(carbamate) (29). Olefin 22 (500 mg, 1.4 mmol) is treated with MCPBA in NaHCO 3 -buffered CHCl 3 for 4 hours at room temperature as described for the preparation of 26. Flash chromatography affords epoxide 29 as a white solid which is recrystallized from CCl 4 yielding 380 mg (73%) of fine white needles mp 168°-169° C. IR (KBr) 330, 1685 and 1290 cm -1 ; NMR (500 MHz, CDCl 3 ) δ 7.31 (s, 10H, aromatic), 4.99-5.10 (m, 5H, 4 benzylic and 1 NH), 4.84 (s, 1H, NH), 3.71-3.74 (m, 1H, H-4), 3.53-3.57 (m, 1H, H-3), 3.21 (s, 1H, H-1), 3.13 (deceptively simple t, 1H, H-6, J=4 Hz) 2.55 (deceptively simple dd, 1H, H-5e, J=2, and 15 Hz), 2.46 (deceptively simple dt, 1H, H-2e, J=4, 10 and 15 Hz), 1.83 (deceptively simple dd, 1H, H-2a, J=10 and 15 Hz), 1.74 (ddd, 1H, H-5a, J=2, 10 and 15 Hz). Anal. calc for C 22 H 24 N 2 O 5 : C, 66.65; H, 6.10; N, 7.07. Found: C, 66.26; H, 6.16; N, 6.90. EXAMPLE 14 Bis(phenylmethyl)(1α, 2α, 4α, 5β)-(4,5-Dihydroxy-1,2-cyclohexanediyl)-(bis(carbamate) (30). METHOD A: Epoxide 26 (300 mg, 0.76 mmol) is dissolved in 4 ml of THF at room temperature. Two ml of 1% (V/V) aqueous H 2 SO 4 is added, and the reaction mixture is stirred for 8 hours at room temperature. The solution is diluted with 25 ml of EtOAc and extracted with 2×5 ml portions of 5% NaHCO 3 solution and brine. The organic layer is dried (Na 2 SO 4 ) and concentrated to an oil that is purified by flash chromatography (CHCl 3 :Me 2 CO; 3:2) to furnish 231 mg (74%) of the trans diol as a white solid, mp 141°-142° C. IR (KBr) 3360, 1735, 1680 and 1065 cm -1 ; NMR (500 MHz, pyridine-d 5 ) δ 8.06 (d, 1H, NH, J=8 Hz), 7.95 (br s, 1H, NH), 7.35-7.43 (m, 4H aromatic), 7.22-7.31 (m, 6H, aromatic), 5.12-5.27 (m, 4H, benzylic), 4.51-4.63 (m, 1H, H-4), 4.40-4.51 (m, 1H, H-2), 4.05-4.18 (m, 1H, H-1), 2.41-2.60 (m, 2H, H-3e and H-6e), 2.18-2.30 (m, 1H, H-6a), 2.01-2.16 (m, 1H, H-3a). Anal. calcd for C 22 H 26 N 2 O 6 : C, 63.76; H, 6.32; N, 6.76. Found: C, 63.62; H, 6.43; N, 6.58. METHOD B: Epoxide 26 (300 mg, 0.76 mmol) is dissolved in a mixture of 5 ml of dry THF and 1 ml of distilled deionized H 2 O. Nafion-H (35-60 mesh powder; 60 mg) is added, and the reaction mixture is heated at reflux with vigorous stirring for 36 hours. The reaction mixture is cooled and the catalyst is removed by filtration. The filtrate is concentrated in vacuo affording a clear oil which is purified as in Method A to furnish 264 mg (84%) of diol 30. EXAMPLE 15 Bis(phenylmethyl) (1α, 2α, 4α, 5β)-(4,5-Dihydroxy-1,2-cyclohexanediyl)-bis(carbamate) (31) and Phenylmethyl (1α,5α,6β, 8β)-(8-Hydroxy-3-oxo-2-oxo-4-azabicyclo[3.3.1]non-6-yl)-carbamate (32). Epoxide 29 (50 mg, 0.13 mmol) is dissolved at room temperature in 1.5 ml of Me 2 CO with stirring. Aqueous H 2 SO 4 (1% V/V, 0.5 ml) is added, and the solution is stirred at room temperature for two hours. Solid NaHCO 3 is added to pH 7 (pH paper). The reaction is concentrated affording a white solid which is purified by preparative tlc (silica gel, 2 developments with CHCl 3 :Me 2 CO, 3:2) yielding 6 mg (16%) of the bicyclic 32 mp 214°-215° C. and 36 mg (69%) of diol 31 mp 171°-172° C. For 32, IR (KBr) 3420, 3300, 1735, 1680 and 1065 cm -1 ; NMR (500 MHz, pyridine-d 5 ) δ 8.91 (s, 1H), 7.43 (d, 2H, J=7 Hz), 7.30-7.35 (m, 2H), 7.27 (d, 1H, J=7 Hz), 6.94 (d, 1H, J=7.6 Hz), 5.31 (H A of AB q, 1H, benzylic, J=12.3 Hz), 5.25 (H B of AB q, 1H, benzylic, J=12.3 Hz), 4.64-4.70 (m, 1H), 4.32-4.38 (m, 1H), 4.22-4.30 (m, 1H), 3.90-3.96 (m, 1H), 2.71 (deceptively simple doublet, 1H, J=13.8 Hz), 2.32 deceptively simple dt, 1H, J=3.9, 4.5 and 14 Hz), 1.82 (deceptively simple d, 1H, J=15 Hz), 1.74 (deceptively simple d, 1H, H-7a, J=13.8 Hz). Anal. calc for C 15 H 18 N 2 O 5 : C, 58.82; H, 5.92; N, 9.15. Found: C, 59.01; H, 5.99; N, 9.07. For 31 IR (KBr) 3360, 3290, 1685 and 1035 cm -1 ; NMR (270 MHz, acetone-d 6 ) δ 7.28-7.33 (m, 10H, aromatic), 6.15 (d, 2H, NH, J=7 Hz), 5.02 (s, 4H, benzylic), 4.01 (d, 2H, OH, exch with D 2 O, J=3 Hz), 3.80-3.88 (m, 4H, methine), 1.90-1.97 (m, 4H, methylene). Anal. calc for C 22 H 26 N 2 O 6 : C, 63.76; H, 6.32; N, 6.76. Found: C, 64.05; H, 6.24; N, 6.65. EXAMPLE 16 Bis(phenylmethyl) (1α, 2β, 4α, 5α)-(4-Acetyloxy)-5-hydroxy-1,2-cyclohexanediyl)-bis(carbamate) (35) and Diacetate 36. Diol 23 (1.0 g, 2.42 mmol) is dissolved in 50 ml of THF and cooled to -25° C. in dry ice --CCl 4 . Et 3 N (0.27 g; 2.4 mmol), DMAP (0.03 g; 0.24 mmol) and Ac 2 O (0.27 g; 2.66 mmol) are added. After standing for 24 hours in the freezer at -25° C., the solution is concentrated to afford a white solid which is partitioned between EtOAc (100 ml) and 5% HCl solution (20 ml). The organic layer is washed with 20 ml of dlute HCl and 2×20 ml portions of brine and dried (Na 2 SO 4 ). Concentration furnishes a white solid which is crystallized from CHCl 3 to afford 0.61 g of the hydroxy-acetate as a white solid mp 199°- 201° C. Flash chromatography (Et 2 O) of the mother liquor gives 0.095 g (8%) of 36 and another 0.024 g of 35 for a total yield of 74% IR (KBr) 3520, 3310, 1720, 1680, 1265 and 1030 cm -1 ; NMR (500 MHz, pyridine d 5 ) δ 8.55 (s, 1H, aromatic), 8.21 (s, 1H, aromatic), 7.39 (dd, 4H, aromatic, J=7 and 18 Hz), 7.20-7.30 (m, 4H, aromatic), 6.84 (s, 1H, NH), (H A of AB q, 1H, benzylic, H=12.6 Hz), 5.28 (H A ' of A'B' q, 1H, benzylic, J=12.7 Hz), 5.22 (H B' of A'B' q, 1H, benzylic, J=12.7 Hz), 5.18 (H B of AB q, 1H, benzylic, J=12.6 Hz), 5.10 (deceptively simple dt, 1H, H-4, J= 5 and 12 Hz), 4.7-4.8 (m, 1H, H-1), 4.50-4.53 (m, 1H, H-5), 4.2-4.3 (m, 1H, H-2), 2.55-2.67 (m, 2H, H-3and H-6e), 2.40-2.48 (m, 1H, H-3a), 1.80-1.90 (m, 4H, OAc and H-6a). Anal. calc for C 24 H 28 N 2 O 7 : C, 63.15; H, 6.18; N, 6.14. Found: C, 62.88; H, 6.24; N, 5.97. EXAMPLE 17 Bis(phenylmethyl) (1α, 2β, 4α, 5α)-(4,5-Diacetyloxy-1,2-cyclohexanediyl)-bis(carbamate) (36). Diol 23 (350 mg, 0.845 mmol) is dissolved in 20 ml of THF and cooled in an ice bath. Et 3 N(171 mg; 1.69 mmol), DMAP (21 mg; 0.169 mmol) and Ac 2 O (345 mg; 3.38 mmol) are added. The reaction is allowed to warm slowly to room temperature. After 22 hours the solution is evaporated to dryness. The residual white solid is dissolved in 25 ml of EtOAc and washed with 2×10 ml portions each of 5% HCl solution and brine. The organic layer is dried (Na 2 SO 4 ) and concentrated in vacuo to an oil. Upon addition of Et 2 O (10 ml) and hexane (5 ml), small white rosettes form slowly. After standing for 2 hours, the crystals (349 mg) are collected by filtration. Preparative tlc (Et 2 O) of the mother liquor affords an additional 40 mg for a total of 392 mg (92%), mp 122°-123° C.; IR (KBr) 3360, 3300, 1740, 1690 and 1250 cm -1 ; NMR (80 MHz, CDCl 3 ) δ 7.29 (s, 10H, aromatic), 4.7-5.3 (m, 8H, benzylic, NH, H-4 and H-5), 3.4-3.9 (m, 2H, H-1 and H-2), 1.5-2.3 (m, 10H, methylene and CH 3 ). Anal. calc for C 26 H 30 N 2 O 8 : C, 62.64; H, 6.07; N, 5.62. Found: C, 62.44; H, 6.06; N, 5.40. EXAMPLE 18 Bis(phenylmethyl) (1α, 2β, 4β)-(4-Acetyloxy)-5-oxo-1,2-cyclohexanediyl)-bis(carbamate) (37). The pure hydroxy-acetate 35 (632 mg, 1.38 mmol) is dissolved at room temperature in 40 ml of Me 2 CO and cooled in an ice bath. Jones reagent (1.7 ml of a solution diluted to 2.5 m in Cr +6 ) is added dropwise. The reaction is stirred for 2 hours at ice bath temperature. Isopropanol is added to destroy the excess oxidant, and the Cr salts are removed by filtration. The filtrate is concentrated in ca. 5 ml in vacuo and partitioned between EtOAc (50 ml) and H 2 O (10 ml). The organic layer is washed with 10 ml of H 2 O, 2×10 ml of brine and dried (Na 2 SO 4 ). Concentration in vacuo affords a white solid which is purified by flash chromatography (CHCl 3 :Et 2 O; 1:1) to afford 547 mg (87%) of 37, mp 163°-164° C. Ir (KBr) 3350, 3280, 1765, 1720, 1690, 1230, 1060 and 1040 cm -1 , NMR (500 MHz, CDCl 3 ) δ 7.3 (s, 10H, aromatic), 5.2-5.3 (m, 1H, H-4), 5.0-5.15 (m, 4H, benzylic), 4.0-4.1 (m, 1H, H-2), 3.75-3.85 (m, 1H, H-1), 2.85 (dd, 1 H, H-6e, J=3 and 11 Hz), 2.50-2.56 (m, 1H, H-3e), 2.45 (deceptively simple t, 1H, H-6a, J=13 Hz), 2.12 (s, 3H, OAc), 1.72 (deceptively simple q, 1H, H-3a, J=13 and 25 Hz). Anal. calcd. for C 24 H 26 N 2 O 7 : C, 63.43; H, 5.77; N, 6.16. Found: C, 63.39; H, 5.82; N, 5.92. EXAMPLE 19 Bis(phenylmethyl) (1α, 2β, 4β, 5α)-(4,5-Diacetyloxy-1,2-cyclohexanediyl)-bis(carbamate) (38). Keto-acetate 37 (250 mg, 0.551 mmol) is dissolved in THF (8 ml) and absolute ETOH (2 ml) and cooled to -78° C. NaBH 4 (total of 12.5 mg; 0.330 mmol) is added in three portions every 10 min. After 1 hour at -78° C., the solution is concentrated in vacuo to furnish a white solid which is partitioned between EtOAc (25 ml), THF (5 ml) and 5 ml of H 2 O. The organic layer is washed with 5 ml of H 2 O and dried (Na 2 SO 4 ). Concentration in vacuo affords a white solid which is dissolved in 10 ml of THF and cooled in an ice bath. Et 3 N (110 mg; 1.10 mmol), DMAP (13 mg; 0.110 mmol) and Ac 2 O (168 mg; 1.65 mmol) are added. The reaction is allowed to warm slowly to room temperature, and after 1 hour is concentrated in vacuo to furnish a white solid. CHCl 3 (25 ml) is added, and the solution is washed with 3×5 ml of 5% HCl solution, 2×10 ml of brine, and dried (Na 2 SO 4 ). The solvent is removed in vacuo and the white solid crystallized from CHCl 3 /CCl 4 to provide 135 mg of the product. Preparative tlc (CHCl 3 :Et 2 O; 5:1, 2 developments) of the mother liquor furnishes another 30 mg for a total of 165 mg (65%) of 38 mp 220°-221° C.; IR (KBr) 3320, 1730, 1680, 1290, 1250, 1240, 1070 and 1020 cm -1 ; NMR (500 MHz CDCl 3 ) δ 7.31 (s, 10H, aromatic), 5.10-5.09 (m, 6H, 2 NH, and 4 benzylic), 4.89-4.91 (m, 2H, H-4 and H-5), 3.58-3.66 (m, 2H, H-1 and H-2), 2.39 (deceptively simple d, 2H, H 3e and H 6e , J=12 Hz) 2.01 (s, 6H, 2 OCH 3 ), 1.43 (deceptively simple d, 2H, H3a and H6a, J=11 Hz). Anal. calc for C 26 H 30 N 2 O 8 : C, 62.64; H, 6.07; N, 5.62. Found: C, 62.82; H, 6.09; H, 5.61. EXAMPLE 20 Bis(phenylmethyl) (1α, 2β, 4β, 5α)-(4,5-Dihydroxy-1,2-cyclohexanediyl)-bis(carbamate) (39). Diacetate 38 (100 mg, 0.201 mmol) is suspended in 7 ml of MeOH at room temperature. K 2 CO 3 (61 mg; 0.442 mmol) was added, and the reaction mixture is heated to reflux (diacetate dissolves). After one hour the reaction is cooled to room temperature and stirred for another 1.5 hours. The solvent is removed in vacuo according a white solid which is recrystallized from MeOH/H 2 O affording 65 mg (78%) of diol 39 mp 197°-198° C. IR (KBr) 3400(sh) 3300, 1680, 1280, 1240, 1065 and 1030 cm -1 ; NMR (500 MHz, pyridine d 5 ) δ 8.30 (s, 2H, aromatic), 7.37 (d, 4H, aromatic, J=7.2 Hz), 7.2-7.3 (m, 4H, aromatic), 6.64 (s, 2H, NH), 5.30 (H A of AB q, 2H, benzylic J=12.6 Hz), 5.21 (HB of ABq, 2H, benzylic, J=12.8 Hz), 4.19-4.26 (m, 2H, H-4 and H-5), 3.93 (deceptively simple d, 2H, H-1 and H-2, J=9.2 Hz), 2.76 (deceptively simple d, 2H, H-6e and H-3e, J=12.7 Hz), 1.9-2.0 (m, 2H, H-6a and H-3a) anal. calc for C 22 H 26 N 2 O 4 : C, 63.76; H, 6.32; N, 6.76. Found: C, 63.84; H, 6.42; H, 6.61. EXAMPLE 21 Bis(phenylmethyl) (1α, 2β, 4α,)-(4-hydroxy-1,2-cyclohexanediyl) bis(carbamate) (41) and Bis(phenylmethyl) (1α, 2β, 4β)-(4-hydroxy-1,2-cyclohexanediyl) bis(carbamate) (40). Hydroboration-oxidation method. Trans olefin 22(1.5 g, 3.95 mmol) is treated as described for cis 20. Flash chromatography of the mixture (Et 2 O:Me 2 CO; 25:1) afford 0.52 g of 41 and 0.71 g of 40 for a total yield of 78%. For 41: mp 142°-143° C., IR(KBr) 3390, 3280, 1695, 1270, 1120 and 990 cm -1 ; NMR (500 MHz, CDCl 3 ) δ 7.30 (s, 10H, aromatic), 5.30 (d, 1H, NH, J=7.6 Hz), 5.14 (d, 1H, NH, J=7.5 Hz), 5.00-5.12 (m, 4H, benzylic), 4.13-4.18 (m, 1H, H 4 ), 3.84-3.92 (m, 1H, H 2 ), 3.40-3.50 (m, 1H, H 1 ), 2.19 (deceptively simple d, 1H, H 3e , J=13 Hz), 1.70-1.90 (m, 3H, H 5e , H 6e and H 6a ), 1.53 (deceptively simple t, 1H,H 5a , J=12 Hz), 1.42 (deceptively simple t, 1H, H 3a , J=12.6 Hz.) Anal. calc for C 22 H 25 N 2 O 7 : C, 66.48; H, 6.34; N, 7.07. Found: C, 66.22; H, 6.58; N, 7.13. For 40: mp 184°-185° C., IR(KBr) 3320, 1680, 1280, 1070 and 1020 cm -1 ; NMR (500 Mhz, CDCl 3 ) δ 7.32 (s, 10H, aromatic), 5.00-5.18 (m, 6H, 2NH and benzylic), 3.68-3.76 (m, 1H, H 4 ), 3.45-3.52 (m, 1H, H 2 ), 3.36-3.45 (m, 1H, H 1 ), 2.3 (deceptively simple d, 1H, H 3e , J=10 Hz), 2.07 (deceptively simple dd, 1H, H 5e , J=2 and 8 Hz), 1.98 (deceptively simple d, 1H, H 5a , J=9 Hz), 1.2-1.4 (m, 3H, H 6e , H 3a and H 6a ). Anal. calc for: C 22 H 25 N 2 O 7 : C, 66.48; H, 6.34; N, 7.07. Found: C, 66.17; H, 6.34; N, 6.84. NaBH 4 reduction method. Ketone 42 (100 mg, 0.263 mmol) is dissolved in 5 ml of absolute ethanol then cooled to -20° C. (dry ice-CCl 4 ). NaBH 4 (13 mg; 0.341 mmol) is added in three portions over 30 minutes. After one hour at -20° C., the reaction is concentrated to dryness. The residue is dissolved in 10 ml of EtOAc and washed with 2×5 ml each of H 2 O and brine, then dried (Na 2 SO 4 ). The mixture is purified by flash chromatography as described above to afford 68 mg of 40 and 7 mg of 41 for a total yield of 72%. K-Slectride reduction. Ketone 42 (100 mg, 0.263 mmol) is dissolved in 5 ml of dry THF under argon, and cooled to -78° C. K-Slectride (0.3 ml of a 1M solution in THF) is added dropwise by syringe. After 30 minutes at -78° C., excess hydride is quenched by addition of 20 ml of Et 2 O saturated with H 2 O. The solution is concentrated in vacuo and the residue dissolved in 25 ml of Et 2 O, and washed with 2×5 ml each of H 2 O and brine. The organic layer is dried (Na 2 SO 4 ) and concentrated to an oil which is purified as described above, affording 82 mg of 41 and 4 mg of 40 for a total yield of 86%. EXAMPLE 22 Bis(phenylmethyl) (1α, 2β)-(4-oxo-1,2-cyclohexanediyl) bis(carbamate) (42). Alcohol 41 (100 mg, 0.251 mmol) is dissolved in 5 ml of Me 2 CO and cooled in an ice bath. Jones reagent (0.3 ml of a 2.5M solution) is added dropwise. After two hours at 0° C., isopropanol is added to quench excess oxidant. The Cr salts are filtered and washed with Me 2 CO. The blue-green filtrate is concentrated in vacuo to a green and white solid. The residue is partitioned between 25 ml of EtOAc and 10 ml of H 2 O. The organic layer is washed with 10 ml of H 2 O, 2×10 ml of brine and dried (Na 2 SO 4 ). EtOAc is removed in vacuo to afford a white solid which is recrystallized from CCl 4 to afford 87 mg (87%) of the ketone as a white powder mp 135°-136° C., IR(KBr) 3220, 1725, 1685, 1280, 1240 and 1020 cm -1 ; NMR (500 MHz, CDCl 3 ) δ 7.31 (s, 5H, aromatic), 7.30 (s, 5H, aromatic), 5.28 (d, 2H, NH, J=6.1 Hz), 5.00-5.10 (m, 4H, benzylic), 3.75-3.90 (m, 2H, H 1 and H 2 ), 2.76 (dd, 1H, H 3e , J=3.8 and 14.3 Hz), 2.45-2.55 (m, 2H, H 5e and H 5a ), 2.34 (deceptively simple t, 1H, H 3a , J=12.2 Hz), 2.20-2.30 deceptively simple d, 1H, H 6e , J=7.6 Hz), 1.50-1.60 (m, 1H, H 6a ). Anal. calc for C 22 H 24 N 2 O 5 : C, 66.65; H, 6.10; N, 7.07. Found: C, 66.40; H, 6.02; N, 6.86. EXAMPLE 23 Bis(phenylmethyl) (1α,2α)-(4-oxo-1,2-cyclohexanediyl) bis(carbamate) (43). Alcohol 27 (300 mg, 0.754 mmol) is dissolved in 15 ml of Me 2 CO and cooled in an ice bath. Jones reagent (1.5 ml of a 2.5M solution) is added dropwise. After 30 minutes at 0° C., isopropanol is added to destroy excess Cr +6 , the solids are removed by filtration and washed with Et 2 O. The blue-green filtrate is concentrated to an oil which is dissolved in 40 ml of Et 2 O ml portions each of H 2 O and brine. The dried (Na 2 SO 4 ) organic layer is reduced in vacuo to a clear oil which is crystallized from Et 2 O/hexane to afford 281 mg (94%) of 43 as fine white needles mp 105°-106° C., IR(KBr) 3310, 1695, 1260, 1245 and 1090 cm -1 ; NMR (500 MHz, δ 7.30-7.36 (m 10H, aromatic), 5.52 (br s, 1H, NH), 5.08-5.12 (m, 3H, NH and benzylic), 4.30-4.38 (m, 1H, H 2 ), 4.15-4.23 (m, 1H, H 1 ), 2.68-2.78 (m, 1H, H 6e ), 2.43 (dd, 1H, H 3e , J=5 and 12 Hz), 2.32-2.40 (m, 2H, H 5a and H 6e ), 1.82-1.91 (m, 1H, H 6a ). Anal. calc for C 22 H 24 N 2 O 5 : C, 66.65; H, 6.10; N, 7.07. Found: C, 66.86; H, 6.00; N, 7.12. EXAMPLE 24 (SP-4,2-(1α, 2α, 4α, 5α))-dichloro(4,5-dihydroxy-1,2-cyclohexanediamine-N,N')-platinum 44. Diol 25 (100 mg, 0.242 mmol) is added to a suspension of 20 mg 10% Pd/C in 5 ml of MeOH. The Parr bottle is alternatively evacuated (water aspirator) and refilled five times to 20 psi with H 2 gas. The suspension is shaken at room temperature for two hours under 20 psi H 2 . The catalyst is removed by filtration and the filtrate concentrated in vacuo to afford a clear oil. Distilled deionized H 2 O (5 ml) is added followed by K 2 PtCl 4 (100 mg; 0.242 mmol). The flask is swirled to dissolve the salt, stoppered, covered with foil and allowed to stand at room temperature for 24 hours. The yellow-green crystals that form are collected by filtration and recrystallized from H 2 O to afford 45 mg (43%) of 44 as small yellow-green cubes. Anal. calc for C 6 H 14 N 2 O 2 PtCl 2 -H 2 O: C, 16.75; H, 3.75; N, 6.51; Pt, 45.35; Cl, 16.48. Found: C, 16.39; H, 4.16; N, 6.59; Pt, 44.91; Cl, 16.45. EXAMPLE 25 (SP-4,2(1α, 2α, 4β, 5β))-dichloro(4,5-dihydroxy-1,2-cyclohexanediamine-N,N')-platinum 45. Diol 24 (100 mg, 0.242 mmol) is treated as described for the synthesis of 44, affording yellow crystals which are recrystallized from H 2 O-MeOH to deliver 38.7 mg (37%) of 45 as yellow crystals. Anal. calc for C 6 H 14 N 2 O 2 PtCl 2 -H 2 O: C, 16.75; H, 3.75; N, 6.51; Pt, 45.35; Cl, 16.48. Found: C, 16.81; H, 3.28; N, 6.54; Pt, 45.21; Cl, 16.75. EXAMPLE 26 (SP-4,2-(1α, 2β, 4α, 5α))-dichloro(4,5-dihydroxy-1,2-cyclohexanediamine-N,N')-platinum 47. Diol 23 (100 mg, 0.242 mmol) is treated as described for the synthesis for 44. The resulting bright yellow powder is recrystallized from H 2 O affording 69 mg (69.5%) of 47 as a bright yellow powder. Anal. calc for C 6 H 14 N 2 O 2 PtCl 2 -H 2 O: c, 16.75; H, 3.75; N, 6.51; Pt, 45.35; Cl, 16.48. Found: C, 16.80; H, 3.26; N, 6.45; Pt, 45.49; Cl, 16.35. EXAMPLE 27 (SP-4,2-(1α, 2β, 4β, 5α))-dichloro(4,5-dihydroxy-1,2-cyclohexanediamine-N,N')-platinum 48. Diol 39 (100 mg, 0.242 mmol) is treated as described for the synthesis for 44. The resulting bright yellow solid is recrystallized from H 2 O affording 22 mg (22%) of 48 as small bright yellow needles. Anal. calc for C 6 H 14 N 2 O 2 PtCl 2 : C, 17.48; H, 3.42; N, 6.80; Pt, 47.33; Cl, 17.20. Found: C, 17.39; H, 3.31; N, 6.59, Pt, 47.03; Cl, 16.98. EXAMPLE 28 (SP-4,2-(1α, 2α, 4β))-dichloro(4-hydroxy-1,2-cyclohexanediamine-N,N')-platinum 50. Diol 27 (300 mg, 0.756 mmol) is treated as described for the synthesis for 44. The canary yellow precipitate is filtered and washed with 5% HCl solution, Me 2 CO and Et 2 O, affording 112 mg (37%) of 50 as a yellow powder. Anal calc for C 6 H 14 N 2 OPtCl 2 : C, 18.19; H, 3.56; N, 7.07; Pt, 49.24; Cl, 18.10. Found: C, 17.93; H, 3.72; N, 6.91; Pt, 48.93; Cl, 18.10. EXAMPLE 29 (SP-4,2-(1α, 2α, 4α))-dichloro(4-hydroxy-1,2-cyclohexanediamine-N,N')-platinum 51. Alcohol 28 (125 mg, 0.314 mmol) is treated as described for the synthesis for 44. After 24 hours the greenish yellow crystals are recrystallized from H 2 O affording 46 mg (37%) of 51. Anal calc for C 6 H 14 N 2 OPtCl 2 : C, 18.19; H, 3.56; N, 7.07; Pt, 49.24; Cl, 17.90. Found: C, 18.25; H, 3.62; N, 7.05; Pt, 49.07; Cl, 17.95. EXAMPLE 30 (SP-4,2-(1α, 2β, 4β))-dichloro(4-hydroxy-1,2-cyclohexanediamine-N,N')-platinum 52. Alcohol 40 (100 mg, 0.252 mmol) is treated as described for the synthesis for 44. The precipitate is collected and recrystallized from H 2 O affording 52 as bright yellow needles, 65 mg (65%). Anal calc for C 6 H 14 N 2 OPtCl 2 -1/2 H 2 O: C, 17.79; H, 3.73; N, 6.91; Pt, 48.15; Cl, 17.50. Found: C, 17.77; H, 3.85; N, 6.71; Pt, 48.31; Cl, 16.98. EXAMPLE 31 (SP-4,2-(1α, 2β, 4α))-dichloro(4-hydroxy-1,2-cyclohexanediamine-N,N')-platinum 53. Alcohol 41 (200 mg, 0.503 mmol) is treated as described for the synthesis for 44, affording 99 mg (48%) of 53 as yellow-green needles. Anal. calc for C 6 H 16 N 2 O 2 PtCl 2 : C, 17.40; H, 3.89; N, 6.76; Pt, 47.10; Cl, 17.12. Found: C, 17.44; H, 3.82; N, 6.63; pt, 46.68; Cl, 17.38. EXAMPLE 32 Bis(phenylmethyl) (1α, 2α, 4β, 5β)-(4,5-diacetyloxy-1,2-cyclohexanediyl)bis(carbamate) (55) and Bis(phenylmethyl) (1α, 2α, 4α, 5α)-(4,5-diacetyloxy-1,2-cyclohexanediyl)bis(carbamate) (54). Olefin 20 (1.00 g, 2.6 mmol) is treated with OsO 4 and N-methylmorpholine-N-oxide as described for the synthesis of diols 25 and 24. The crude reaction mixture is suspended in ice-cold CHCl 3 (40 ml). Et 3 N (532 mg; 5.3 mmol), DMAP (96 mg; 0.79 mmol) and Ac 2 O (1.074 g; 11 mmol) are added, respectively. The reaction is allowed to warm slowly to room temperature. After 5.5 hours, the solution is washed with 3×10 ml portions each of 5% HCl solution and brine, then dried (Na 2 SO 4 ). The solution is concentrated in vacuo and the mixture is purified by flash chromatography (CHCl 3 :Et 2 O; 5:1) to afford 320 mg of 54, 356 mg of 55 plus 370 mg of a mixture for a total of 1.046 g (80%). For 54: mp 84°-86° C., IR(KBr) 3300, 1730, 1705, 1250, 1235, 1055 and 1030 cm -1 ; NMR (90 MHz, CDCl 3 ) δ 7.34 (s, 10H, aromatic), 5.0-5.2 (m, 8H, benzylic, NH, H 4 and H 5 ), 4.0-4.3 (m, 2H, H 1 and H 2 ), 1.7-2.1 (m, 10H, methylene and 2 CH 3 ). For 55: mp 129°-130° C., IR(KBr) 3300, 1730, 1690, 1245, 1055 and 1020 cm -1 ; NMR (90 MHz, CDCl 3 ) 7.33 (s, 10H, aromatic), 5.0-5.5 (m, 8H, benzylic, NH, H 4 and H 5 ), 3.9-4.1 (m, 2H, H 1 and H 2 ) 1.8-2.1 (m, 10H, methylene and 2CH 3 ). Anal. (of mixture) calc for: C 26 H 30 N 2 O 8 : C, 62.64; H, 6.07; N, 5.62. Found: C, 62.37; H, 6.21; N, 5.40. EXAMPLE 33 (SP-4,2-(1α, 2α, 4α, 5α))-dichloro(4,5-diacetyloxy-1,2-cyclohexanediamine-N,N')-platinum 57. Diacetate 54 (100 mg, 0.201 mmol) is added to a suspension of 10% Pd/C in 5 ml of MeOH. The bottle is alternatively evacuated (water aspirator) and refilled to 20 psi with H 2 gas. The suspension is shaken under 20 psi of H 2 for two hours at room temperature. The catalyst is filtered and the filtrate concentrate in vacuo to afford a clear oil. The residue is dissolved in 5 ml of distilled deionized H 2 O and K 2 PtCl 4 (83 mg; 0.201 mmol) is added. The flask is swirled to dissolve the salt, stoppered and covered with foil. After standing at room temperature for 24 hours, the yellow precipitate is filtered and washed with 5% HCl solution, Me 2 CO and Et 2 O to afford 64 mg (65%) of 57. Anal. calc for C 10 H 18 N 2 O.sub. 4 PtCl 2 : C, 24.20; H, 3.66; N, 5.64; Pt, 39.31; Cl, 14.29. Found: C, 24.33; H, 3.69; N, 5.50; Pt, 39.11; Cl, 13.94. EXAMPLE 34 (SP-4,2-(1α, 2α, 4β, 5β))-dichloro(4,5-diacetyloxy-1,2-cyclohexanediamine-N, N')-platinum 56. Diacetate 55 (100 mg, 0.201 mmol) is treated as described for the synthesis of 57. The brown precipitate is washed with 5% HCl solution, Me 2 CO and Et 2 O to afford 49 mg (49%) of 56. Anal calc for C 10 H 18 N 2 O 4 PtCl 2 : C, 24.20; H, 3.66; N, 5.64; Pt, 39.31; Cl, 14.29. Found: C, 23.98; H, 3.79; H, 5.50; Pt, 39.98; Cl, 13.94. EXAMPLE 35 (SP-4,2-(1α, 2β, 4α, 5α))-dichloro(4,5-diacetyloxy-1,2-cyclohexanediamine-N, N')-platinum 58. Diacetate 36 (100 mg, 0.201 mmol) is treated as described for the synthesis of 57. The bright yellow precipitate is washed with 5% HCl solution, Me 2 CO and Et 2 O to afford 73 mg (73%) of 58 as a bright yellow powder. Anal calc for C 10 H 18 N 2 O 4 PtCl 2 : C, 24.20; H, 3.66; N, 5.64; Pt, 39.31; Cl, 14.29. Found: C, 24.46; H, 3.75; N, 5.58; Pt, 39.03; Cl, 13.97.
One aspect of the present invention relates to a process of making cyclohexane-1,2-di(O)-4,5-di(N) diastereomers which are useful as a synthons for various diastereoisomeric pharmaceutical systems. The present invention also relates to the stereoisomer compounds which are derived from retro-synthetic analysis. In another aspect, the present invention relates to novel antineoplastic Pt(II) complexes derived from the stereoisomers and the processes for making such Pt(II) complexes. Mono- and di-hydroxyl substitution on the cyclohexane ring renders the organoplatinum complex relatively more water soluble, thereby facilitating intravenous administration. The Pt(II) complexes of the present invention are less nephrotoxic than cisplatin and are readily excreted via the kidney due to their enhanced water solubility. In a composition aspect, the present invention encompasses novel pharmaceutical compositions comprising the novel Pt(II) complexes in an amount sufficient to have an antineoplastic effect in an animal or patient.
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[0001] This application is a continuation of International Application No. PCT/JP2005/020399 filed on Nov. 1, 2005, which claims the benefit of Japanese Patent Application No. 2004-319737 filed on Nov. 2, 2004. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates to an organic transistor having an organic semiconductor material and a manufacturing method thereof, and specifically to an organic transistor formed by ink-jet drawing process and a manufacturing method thereof. [0004] 2. Related Background Art [0005] In recent years, research on organic electronic devices using organic materials has been flourishing. Realization of costly inexpensive organic electronic devices that are excellent in lowering process temperature and portability is expected by applying thin film formation of organic materials to devices. [0006] For example, research on organic electronic devices such as organic ELs and organic transistors etc. is flourishing. Among them, since a semiconductor material itself which is the most vital part of functions of the organic transistor is an aggregate of organic molecules, and partially covalently-bonded and comparatively weak bonded body, the organic transistor is promising in lowering process temperature and abundant in flexibility to enable reduction in weight, whereby it is excellent in portability. Hence, there is a possibility of application to liquid crystal displays as well as paper-like displays, rapidly making such research active in recent years. As a method for realizing application of organic electronic devices to such a field of electronic devices, a method of making organic transistors utilizing an ink-jet drawing process is nominated, and applications to next-generation low-temperature process and highly portable electronic devices are expected. [0007] With respect to making organic transistors, a variety of methods are nominated, and for example, a method of making organic transistors in use of surface mapping by way of a piezoelectric ink-jet drawing process and surface free energy control by Seiko Epson Corporation is described in “Science” 280, 2123 in 2000 and “Tech Digest of IEDM”, p. 623 in 2000 and the like. [0008] On the other hand, “Extended Abstracts of the 2003 International Conference on Solid State Devices and Materials” p. 222 to 223 in 2003 discloses a process of making organic transistors with short channels, including the steps of using a self-assembled monolayer (SAM), increasing the surface free energy of a portion irradiated with UV light by exposure of UV light from substrate back surface, mapping the surface of the self-assembled monolayer (SAM) by giving contrast against the low surface free energy of non-exposed portions, causing Ag ink to drop to portions having a high surface free energy to draw source and drain electrodes, and making an organic transistor with short channels. [0009] In addition, “Digest of technical papers AM-LCD 04 OLED-4” p. 37 to 40 discloses a process of manufacturing transistors with short channels by increasing the surface free energy of a portion irradiated with light by mask exposure of UV light using polyimide as an insulating film, mapping a polyimide surface by giving contrast against the low surface free energy of non-exposed portions and drawing source and drain electrodes to portions having high surface free energy. [0010] According to the above-described report on “Extended Abstracts of the 2003 International Conference on Solid State Devices and Materials” p. 222 to 223 in 2003, the method of mapping a self-assembled monolayer (SAM) with UV light makes it impossible to vary the surface free energy of the self-assembled monolayer (SAM) by using UV light other than the vacuum ultraviolet light of 200 nm or less. Accordingly, in order to implement highly fine patterning of a surface free energy, significantly expensive stepper using a vacuum UV light of 200 nm or less has to be used, which is unrealistic as a process of manufacturing an organic transistors. [0011] In addition, as reported by “Extended Abstracts of the 2003 International Conference on Solid State Devices and Materials” p. 222 to 223 in 2003, any back-surface exposure makes it possible to carry out patterning of surface free energy of a self-assembled monolayer (SAM), but because of utilizing a gate electrode in order to implement patterning, a gate electrode has to be formed with photolithography. In addition, due to implementation of back surface exposure, a substrate material is expected to be limited due to the light-absorbing property of the substrate. Moreover, highly fine patterning is slightly difficult due to implementation of exposure using the gate electrode as a mask in the back surface exposure. [0012] On the other hand, in the method of mapping a polyimide insulating film with UV light according to “Digest of technical papers AM-LCD 04 OLED-4” p. 37 to 40, the material existing on the channel interface and the insulating film are integral. In this case, in case of applying an orientated organic semiconductor to a channel portion, orientation cannot be controlled and sufficient electric performance that the semiconductor material has cannot be drawn out. In addition, it is possible to design polyimide so that patterning of a surface free energy is implemented with UV light of 254 nm, which however occasionally gives rise to decrease in insulating performance. SUMMARY OF THE INVENTION [0013] In a mode of the present invention, an object of the present invention is to realize an organic transistor having a short channel and high electric characteristics, which is formed by patterning of surface free energy with general UV light of 254 nm as UV light wavelength of an exposure system and, consequently, implements highly fine patterning of surface free energy with an inexpensive aligner. Moreover, another object of the present invention is to realize an organic transistor having a short channel and high electric characteristics and including a layer having a function of controlling orientation and a material excellent in insulating performance which are separated. [0014] In addition, in another mode of the present invention, an object of the present invention is to accurately form a gate electrode by providing a substrate insulating layer on a substrate, subjecting the substrate insulating layer to highly fine patterning of surface free energy with UV light of 254 nm without using vacuum process or photolithography. [0015] At least one among the above-described objects is achieved by any one of the following inventions. [0016] Firstly, the present invention provides an organic transistor having a bottom gate structure, including a substrate, a gate electrode, a gate insulating layer, source and drain electrodes, and an organic semiconductor layer, wherein the gate insulating layer has a low surface energy in a portion thereof in proximity to the source and drain electrodes and a relatively high surface energy in a portion thereof in proximity to the gate electrode, and has different compositions in a layer thickness direction. [0017] In such an organic transistor, the above-described gate insulating layer having different compositions in a layer thickness direction preferably has a double layer structure composed of an upper layer having a relatively low surface energy and a lower layer having a relatively high surface energy. [0018] In addition, the above-described gate insulating layer, the upper layer preferably has a surface free energy of 40 mN/m or less and the lower layer has a surface free energy of 45 mN/m or more. [0019] A portion of the upper insulating layer of the gate insulating layer upper layer in contact with a part or all of the source and drain electrodes preferably has a surface free energy of 50 mN/m or more. [0020] In addition, the present invention provides the above-described organic transistor, wherein in a portion of the above-described gate insulating layer having a double layer structure composed of the upper layer and the lower layer, a hydrogen bonding component of surface free energy of the above-described upper insulating layer is 1.0 mN/m or less, and a hydrogen bonding component of surface free energy of the above-described lower insulating layer 2.0 mN/m or more, and a hydrogen bonding component of surface free energy of a portion of an insulating layer connected continuously with the above-described upper insulating layer and adjacent to a part or all of the source and drain electrodes is 5.0 mN/m or more. [0021] In addition, the present invention provides the above-described organic transistor, wherein in a portion of the gate insulating layer having a double layer structure composed of the above-described upper layer and lower layer, the above-described upper insulating layer is polyimide containing an alkyl group in a side chain thereof, and the above-described lower insulating layer is polyimide having no alkyl group. [0022] In addition, the present invention provides the above-described organic transistor, wherein in a portion of the gate insulating layer having a double layer structure composed of the above-described upper layer and lower layer, the above-described upper insulating layer is polyimide containing an alkyl group in a side chain thereof, and the above-described lower insulating layer is made of an inorganic insulating material. [0023] In addition, the present invention provides the above-described organic transistor, wherein a portion of the gate insulating layer having a double layer structure composed of the above-described upper layer and lower layer, the film thickness of the above-described upper insulating layer is thinner than the thickness of the above-described lower insulating layer. [0024] In addition, the present invention provides the above-described organic transistor, wherein a portion of the gate insulating layer having a double layer structure composed of the above-described upper layer and lower layer, the film thickness of the above-described upper insulating layer is 2 nm or more and 200 nm or less, and the above-described lower insulating layer is 100 nm or more. [0025] In addition, the present invention provides a method of manufacturing an organic transistor including a substrate, a gate electrode, a stacked gate insulating composed of two or more layers, source and drain electrodes, and an organic semiconductor layer, which method includes the steps of: [0026] subjecting the above-described stacked gate insulating layer composed of two or more layers to mask exposure with ultraviolet rays having a wavelength band of 200 nm or more and 300 nm or less, [0027] discharging an electrode material for forming source and drain onto a portion subjected to the above-described mask exposure by an ink-jet method, and [0028] separating the electrode material difference in surface free energy between the portion subjected to the mask exposure and the other portion not subjected to the mask exposure to form a channel. [0029] In addition, the present invention provides the above-described method of manufacturing an organic transistor, wherein prior to the step of subjecting the above-described stacked gate insulating layer composed of two layers to mask exposure with ultraviolet rays having a wavelength band of 200 nm or more and 300 nm or less, the above-described stacked gate insulating layer composed of two or more layers is subjected to a rubbing treatment. [0030] In addition, the present invention provides the above-described method of manufacturing an organic transistor, wherein prior to or after the step subjecting the above-described stacked gate insulating layer composed of two or layers to the mask exposure with ultraviolet rays having a wavelength band of 200 nm or more and 300 nm or less, the above-described stacked gate insulating layer composed of two or more layers is subjected to irradiation of polarized ultraviolet light. [0031] In addition, the present invention provides an organic transistor having a bottom gate structure with a plurality of insulating layers, including a substrate, a gate electrode, a substrate insulating layer located between the substrate and the gate electrode, a gate insulating layer, source and drain electrodes, and an organic semiconductor layer, wherein the gate insulating layer has a low surface energy being in a portion in proximity to the source and drain electrodes and a high surface energy in a portion in proximity to the gate electrode, and has different compositions in a layer thickness direction, and a surface free energy of the substrate insulating layer is lower than a surface free energy in a portion in proximity to the gate electrode. [0032] In addition, the present invention provides the above-described organic transistor having a bottom gate structure, including a substrate, a gate electrode, a substrate insulating layer located between the substrate and the gate electrode, a gate insulating layer, source and drain electrodes, and an organic semiconductor layer, wherein the gate insulating layer consists of an upper layer having a low surface energy and a lower layer having a high surface energy, and a surface free energy of the substrate insulating layer is lower than the high surface free energy of the lower layer of the above-described gate insulating layer. [0033] In addition, the present invention provides the above-described organic transistor, wherein the upper layer of the above-described gate insulating layer has a surface free energy of 40 mN/m or less, the lower layer of the gate insulating layer has a surface free energy of 45 mN/m or more, and the above-described substrate insulating layer has a surface free energy of 45 mN/m or more. [0034] In addition, the present invention provides the above-described organic transistor, wherein the upper layer of the above-described gate insulating layer is an insulating layer having a surface free energy of 50 mN/m or more adjacent to a part or all of the source and drain electrodes, and the above-described substrate insulating layer is an insulating layer having a surface free energy of 50 mN/m or more adjacent to a part or all of the gate electrode. [0035] In addition, the present invention provides the above-described organic transistor, wherein in the above-described gate insulating layer, a hydrogen bonding component of surface free energy of the above-described upper insulating layer is 1.0 mN/m or less and a hydrogen bonding component of surface free energy of the above-described lower insulating layer is 2.0 mN/m or more, and a hydrogen bonding component of surface free energy of a portion of an insulating layer connected continuously with the above-described upper insulating layer and adjacent to a part or all of the above-described source and drain electrodes is 5.0 mN/m or more; and wherein in the above-described substrate insulating layer, a hydrogen bonding component of surface free energy is 1.0 mN/m or less, and a hydrogen bonding component of surface free energy of a portion of an insulating layer connected continuously with the above-described substrate insulating layer and adjacent to a part or all of the above-described gate electrode is 5.0 mN/m or more. [0036] Here, the surface free energy is stipulated by three components, i.e., dispersion component, polarity component and hydrogen bonding component from the extended Fowkes equation. [0037] In addition, the present invention provides the above-described organic transistor wherein in the above-described substrate insulating layer and the above-described gate insulating layer, the substrate insulating layer and the upper layer of the gate insulating layer are polyimide containing an alkyl group in a side chain, and the lower layer of the gate insulating layer is polyimide containing no alkyl group in a side chain. [0038] In addition, the present invention provides the above-described organic transistor wherein in the above-described substrate insulating layer and the above-described gate insulating layer, the substrate insulating layer and the upper layer of the gate insulating layer are polyimide containing an alkyl group in a side chain, and the lower layer of the gate insulating layer is made of an inorganic insulating material. [0039] In addition, the present invention provides the above-descried organic transistor wherein in the above-described substrate insulating layer and the above-described gate insulating layer, the layer thickness of the substrate insulating layer and the layer thickness of the upper layer of the gate insulating layer are thinner than layer thickness of the lower layer of the gate insulating layer. [0040] In addition, the present invention provides the above-described organic transistor wherein in the above-described substrate insulating layer and the above-described gate insulating layer, the layer thickness of the substrate insulating layer and the layer thickness of the upper layer of the gate insulating layer are 2 nm or more and 200 nm or less, and the layer thickness of the lower layer of the gate insulating layer is 100 nm or more. [0041] In addition, the present invention provides a method of manufacturing an organic transistor including a plurality of insulating layers and including a substrate, a gate electrode, a substrate insulating layer located between the substrate and the gate electrode, a stacked gate insulating layer composed of two or more layers, source and drain electrodes, and an organic semiconductor layer, which method comprises the steps of: [0042] subjecting the above-described substrate insulating layer and the above-described gate insulating layer to mask exposure with ultraviolet rays (UV light) having a wavelength band of 200 nm or more and 300 nm or less; [0043] discharging an electrode material for forming a gate electrode onto a part or all of a portion subjected to the mask exposure of the substrate insulating layer by an ink-jet method such that the electrode material expands to the portion subjected to the mask exposure to form a gate electrode; and [0044] discharging an electrode material for forming source and drain electrodes to the portion subjected to the mask exposure of the gate insulating layer by an ink-jet method, separating the electrode material by a difference in surface free energy between the portion subjected to the mask exposure and the other portion not subjected to the mask exposure to form a channel. [0045] In addition, the present invention provides the above-described method of manufacturing an organic transistor, wherein prior to the step of subjecting the above-described stacked gate insulating layer composed of two or more layers to the mask exposure with ultraviolet rays having a wavelength band of 200 nm or more and 300 nm or less, the stacked gate insulating layer composed of two or more layers is subjected to a rubbing treatment. [0046] In addition, the present invention provides the above-described method of manufacturing an organic transistor, wherein prior to or after subjecting the above-described stacked gate insulating layer composed of two or more layers to the mask exposure with ultraviolet rays having a wavelength band of 200 nm or more and 300 nm or less, the stacked gate insulating layer composed of two or more layers is subjected to irradiation of polarized ultraviolet light. [0047] Here, the above-described inventions can be appropriately combined to a not contradictory extent. [0048] In addition, it goes without saying that, among those of the above-described inventions based on the premise of the stacked gate insulating layer, for those irrelevant to thickness, “upper layer” and “lower layer” read respectively as “portion of a gate insulating layer in proximity to source and drain electrodes of the gate insulating layer” and “portion of a gate insulating layer in proximity to a gate electrode of the gate insulating layer” to enable to regard as an invention relating to an organic transistor including no stacked gate insulating layer. BRIEF DESCRIPTION OF THE DRAWINGS [0049] FIG. 1 is a sectional diagram of an organic transistor of a bottom gate type in case of including double insulating layer structure consisting of an insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide containing no alkyl group, as an example of the present invention; [0050] FIG. 2 is a conceptual diagram of orientation control by rubbing applicable to the present invention; [0051] FIG. 3 is a conceptual diagram of orientation control by polarized UV light applicable to the present invention; [0052] FIG. 4 is a graph showing variations in contact angle of water of polyimide containing an alkyl group in a side chain against 254 nm UV light irradiation amount, which is applied for description of experiments of the present invention; [0053] FIG. 5 is a graph showing changes in total surface free energy of polyimide containing an alkyl group in a side chain against 254 nm UV light irradiation amount, which is applied for description of experiments of the present invention; [0054] FIG. 6 is a graph showing variations in each component of surface free energy of polyimide containing an alkyl group in a side chain against 254 nm UV light irradiation amount, which is applied for description of experiments of the present invention; [0055] FIG. 7 is a graph showing a relationship between a stock solution concentration of polyimide containing an alkyl group in a side chain and a film (layer) thickness, which is applied for description of experiments of the present invention; [0056] FIG. 8 is a graph showing dependency of change in contact angle of water of polyimide containing an alkyl group in a side chain on film (layer) thickness against 254 nm UV light irradiation, which is applied for description of experiments of the present invention; [0057] FIG. 9 is an optical microscope photograph showing a particle structure after ink-jet drawing of Au nano ink onto polyimide with surface free energy subjecting to mapping so as to set channel length=5 μm with 254 nm UV light irradiation, which is applied for description of embodiments of the present invention; [0058] FIG. 10 is a graph showing a result of experiments having checked influence to Vth by forming the insulating film of a transistor with a stacked structure of polyimide containing an alkyl group in a side chain and polyimide containing no alkyl group and causing respective film thickness to vary; [0059] FIGS. 11A and 11B are diagrams showing steps of implementing surface energy control of orientated film with UV light according to the present invention; [0060] FIG. 12 is a sectional diagram of an organic transistor of a bottom gate type in case of including a double insulating layer structure consisting of an insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide containing no alkyl group and a substrate insulating layer, as an example of the present invention; [0061] FIG. 13 is a conceptual diagram of orientation control by rubbing applicable to the present invention; [0062] FIG. 14 is a conceptual diagram of orientation control by polarized UV light applicable to the present invention; [0063] FIGS. 15A and 15B are diagrams showing steps of implementing surface energy control of a substrate insulating layer with UV light according to the present invention; and [0064] FIGS. 16A, 16B , 16 C and 16 D are diagrams showing steps of forming a gate electrode with an ink-jet subject to surface energy control of a substrate insulating layer with UV light according to the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0065] According to a preferable embodiment of the present invention, in the configuration of an organic transistor, by forming a double insulating layer structure consisting of an insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide containing no alkyl group and subjecting a channel portion on its insulating layer to masking to undergo irradiation with Deep UV light, surface free energy can be controlled to become low in channel portion and high in non-channel portion, and precise control of a channel becomes feasible with an ink-jet method using its surface free energy distribution. [0066] In addition, by the insulating layer made of polyimide containing no alkyl group, decrease in breakdown voltage of an insulating layer made of polyimide containing an alkyl group in a side chain and increase in Vth are covered so that highly reliable transistor with a high breakdown voltage and a low leak current and high performance can be realized. [0067] In addition, a rubbing treatment or irradiation of polarized UV light is carried out for an insulating film made of polyimide containing an alkyl group in a side chain to arrange organic semiconductor layers formed onto an orientated film in channel portions in one direction, an orientated structure that can realize extremely high mobility can be realized. [0068] According to a preferable embodiment of the present invention, in a structure of an organic transistor, by forming, as the substrate insulating film, an organic insulating layer made of polyimide containing an alkyl group in a side chain, subjecting a portion other than a gate on this substrate insulating layer to masking, and subjecting only the gate portion to irradiation with Deep UV light, whereby surface free energy of the gate portion can be controlled high and surface free energy of the portion other than the gate can be controlled low, and precise control of the gate becomes feasible with an ink-jet method using its surface free energy distribution. [0069] In addition, by forming, as a gate insulating layer, a double insulating layer structure of an organic insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide not containing it, masking a channel portion on this gate insulating layer, and carrying out irradiation with Deep UV light, surface free energy of the channel portion can be controlled low and surface free energy of the portion other than the channel portion can be controlled high, and precise control of the channel becomes feasible with an ink-jet method using its surface free energy distribution. [0070] In addition, by an insulating layer made of polyimide containing no alkyl group, decrease in breakdown voltage of an insulating layer made of polyimide containing an alkyl group in a side chain and increase in Vth are covered so that highly reliable transistor with a high breakdown voltage and a low leak current and high performance can be realized. In addition, the implementing rubbing treatment or the irradiation of polarized UV light onto an insulating film made of polyimide containing an alkyl group in a side chain makes it possible to arrange organic semiconductor layers formed in one direction on an alignment film in channel portions, whereby an orientated structure that can realize extremely high mobility can be realized. [0071] In addition, utilizing this structure, excellent organic transistor can be realized. In addition, an organic transistor of the present invention can be expected to be applied to a variety of electronic devices such as a paper-like display, an organic ID tag, an organic EL. [0072] As a technique of forming channels and improving mobility of an organic transistor, the present inventors focused attention on an organic substance having a low surface free energy that was decomposable with ultraviolet rays. This is to derive surface free energy becoming low prior to decomposition with ultraviolet rays and derive surface free energy becoming high after the decomposition. Keeping a low surface free energy by protecting an organic substance on a gate with a mask and deriving a high surface free energy by decomposing an organic substance in the vicinity thereof with ultraviolet rays makes it possible to dam ink in portions with low surface free energy at the time of drawing source and drain electrodes with an electrically conductive ink with drawing method such as ink-jet, whereby extremely accurate gate-likewise, as for organic substance in portions corresponding to a gate on a substrate, the organic substance is decomposed with ultraviolet rays to make its surface free energy high, a portions in the vicinity thereof are protected with a mask to keep its surface free energy low, and therefore ink spreads over portions with high surface free energy at the time of drawing a gate electrode and is dammed in portions with low surface free energy, whereby an extremely accurate gate-electrode can be formed. [0073] As wavelength of ultraviolet rays used in the present invention, any wavelength that can decompose organic substance may be used, but ultraviolet rays having wavelength around 254 nm are preferably used, considering that fine patterns can be made and from a point of view of costs of apparatus. [0074] Among these organic substances, an alignment film comprising a polymeric compound gives rise to alignment regulation force by rubbing treatment or polarized ultraviolet rays irradiation, and the force can orient organic semiconductor molecules on a gate (channel portion interface), whereby this enables planning of improvement in organic transistor properties such as improvement in mobility and therefore is preferable. An example of the alignment film comprising a polymeric compound used in the present invention includes polyimide containing an alkyl group in a side chain. [0075] On the other hand, an alignment film comprising a polymeric compound such as polyimide containing an alkyl group in a side chain is the one having been developed by focusing attention on orientation control, and there are quite a few cases that performance as a gate insulating layer is insufficient. [0076] Therefore, it has been found to be possible to satisfy improvement in transistor properties in terms of the above-described insulation, highly precise gate length stipulation and orientation control by forming, on the gate, insulating film of a polymeric system such as polyimide and polyolefin containing no alkyl group in a side chain and insulating film of inorganic oxide system such as SiO 2 and Ta 2 O 5 , that are excellent in insulation, and stacking thereon polymeric orientation film such as polyimide containing an alkyl group in a side chain as a low surface free energy organic substance that is decomposable with ultraviolet rays. Moreover, it has been found to be possible to satisfy improvement in transistor properties in terms of the above-described highly precise gate electrode formation, insulating property, highly precise channel length stipulation and orientation control, by stacking also on substrate an alignment film comprising a polymeric compound such as polyimide containing an alkyl group in a side chain as a low surface free energy organic substance that is decomposable with ultraviolet rays. [0077] Among them, a polymeric insulating film having a skeleton like an alignment film comprising a polymeric compound provides good tight contact with the alignment film comprising a polymeric compound, and therefore can be used preferably in case of forming an organic transistor onto a flexible substrate. [0078] The present inventors hereof have implemented experimental study as follows for reaching the present invention, and details thereof will be described. [0000] (Experiment 1) [0079] Relationship of density of alkyl group, surface free energy (surface E), surface free energy hydrogen bonding term, water repellency and leak current will be described in the following Table 1. Table 1 shows relationship of density of alkyl group, surface free energy, hydrogen bonding term, water repellency and leak current in respective kinds of insulating films which are applied for describing experiments of the present invention. TABLE 1 Hydrogen Insulating Alkyl Surface E bonding Water film group (mN/m) (mN/m) repellency Leak A None 50 3.1 x B None 49 2.5 x ∘ C None 45 2.0 x Δ D Small 40 1.0 ∘ x density E Middle 37 0.2 ∘ x density F Large 35 0.0 x density (Note 1:) Evaluation of water repellent reads as follows. : extremely well water-repellent. ∘: comparatively water-repellent. x: not water-repellent. (Note 2:) Evaluation of leak reads as follows. : Leak current is extremely small and gives rise to no problem as an insulating layer. ∘: Leak current is comparatively small and gives rise to no problem as an insulating layer. Δ: Leak current is comparatively large but is barely usable as an insulating layer x: Leak current is significant and not usable as an insulating layer. [0080] When surface free energy becomes small, leak current tends to become large, and around 45 mN/m for surface free energy was a limit value that will not give rise to a problem. In this case, as for respective components of surface free energy, as the hydrogen bonding term becomes smaller, the leak current tends to become larger, and around 2.0 mN/m for hydrogen bonding term is a limit value that will not give rise to a problem. In addition, all the insulating layers that have not given rise to any problem with leak current contained no alkyl group. On the other hand, an insulating layer having a low surface free energy gave rise to a problem with leak current, but in order to strike electrodes differently by way of patterning of surface free energy, surface free energy needs to be sufficiently low and around 40 mN/m was the limit. At this time, the hydrogen bonding term decreases as surface free energy becomes low, and in order to strike electrodes differently by way of patterning of surface free energy, around 1.0 mN/m for hydrogen bonding term was the limit and the lower than this was desirable. Materials having a low surface free energy contained alkyl groups, and by increase in the alkyl groups, surface free energy decreased and the hydrogen bonding term tended to decrease. The surface free energy for materials with the least alkyl group density was 40 mN/m, and the hydrogen bonding term thereof was 1.0 mN/m. [0081] As described above, a preferable example of an organic transistor in the present invention is stipulated to be a double structure consisting of an insulating layer with 40 mN/m or less and an insulating layer with 45 mN/m or more for surface free energy, a double structure consisting of an insulating layer with 1.0 mN/m or less and an insulating layer with 2.0 mN/m or more for a hydrogen bonding term of surface free energy, and moreover, a double structure consisting of an insulating layer containing an alkyl group in a side chain and an insulating layer containing no alkyl group, in channel portions having undergone no change in structure with UV light. In addition, for striking gate electrodes differently, in the gate portions, a substrate insulating layer provided between a substrate and a gate electrode derives surface free energy of 40 mN/m or less and hydrogen bonding term of surface free energy is stipulated to be 1.0 mN/m or less. [0000] (Experiment 2) [0082] Surface free energy of an insulating layer consisting of polyimide containing an alkyl group in a side chain was caused to undergo partial change, and an experiment on striking water droplets differently was implemented with an ink-jet method. Onto a portion of an insulating layer with surface free energy being sufficiently low and showing an initial contact angle of 95 degrees which was subjected to irradiation of UV light to partially increase surface free energy and decrease the contact angle, water droplets were made to drop by an ink-jet method, and it was determined whether or not the droplets after landing went over a portion having a low surface free energy. Table 2 shows a result thereof. Table 2 shows relationship between contact angle of water of polyimide after 254 nm UV light irradiation and the state of striking droplets differently, to be applied to description of an experiment of the present invention. TABLE 2 Contact angle of water (subject to UV irradiation) 10° 20° 30° 40° 50° 60° 10° 80° 90° State of striking ∘ ∘ Δ x x x droplets differently [0083] As shown in Table 2, in case of contact angle of water in the UV light irradiated portion being not more than 30 degrees, they stopped completely in the portion having a low surface free energy so as to allow different strokes sufficiently (in the table). Even 40 degrees and 50 degrees allowed to strike differently, but the case of droplets to go beyond after landing occurred (∘ in the table). With 60 degrees, the case of droplets to go beyond after landing increased, but there was a case where differentiation of striking was barely feasible (Δ in the table), and with not less than 70 degrees almost all droplets went beyond the portion having a low surface free energy (x in the Table). Accordingly, 60 degrees or less of contact angle of water is set as a limit that can stop the droplets after landing. [0084] Accordingly, 60 degrees or less of contact angle of water is set as a limit that can stop the droplets after landing. 254 nm UV light irradiation amount at the time when the contact angle of water becomes 60 degrees or less is approximately 10 J/cm 2 based on an extrapolated value as shown in FIG. 4 , and surface free energy at this time is approximately 50 mN/m or more in total based on an extrapolated value as shown in FIG. 5 and approximately 5 mN/m or more in the hydrogen bonding term as shown in FIG. 6 . [0085] As described above, the surface free energy of an insulating layer in contact with source and drain electrodes and a gate electrode of an organic transistor in a preferable example of the present invention is defined as 50 mN/m or more and the hydrogen bonding term is defined as to be 5 mN/m or more. [0000] (Experiment 3) [0086] Based on a result of Experiments 1 and 2, a substrate insulating layer with surface free energy of 40 mN/m or less was subjected to patterning thereon with UV light to form a portion to become a gate electrode with surface free energy of 50 mN/m or more and to consider to what extent gate electrode width can be struck differently. Consideration was implemented with water as solvent. As in FIG. 16 , a gate electrode portion of a substrate insulating layer-coating part 23 on a glass substrate 22 and, at the same time, portions sufficiently larger in width than the gate electrode on both sides of the gate electrode was subjected to UV exposure so as to make the surface free energy of the portions high to carry out patterning, and water was caused to drop with ink jet in the portions on both sides of the gate electrode. Since surface free energy in the portion to become the gate electrode is sufficiently high than its circumference, water soaks the gate electrode portion and spreads. When the gate electrode width was about 20 μm, patterning was sufficiently feasible, but as the gate electrode width became thinner, good patterning became less feasible. In the experiment, when it was up to around 3 μm, the dropped water soaked and spread, but when it was 1 μm, the dropped water could not soak and spread skillfully. [0000] (Experiment 4) [0087] As shown in FIG. 7 , as the concentration of polyimide was caused to decrease, the film thickness of an insulating layer made of polyimide containing an alkyl group in a side chain decreased, thereby a thin film could be formed up to 2 nm. In addition, as shown in FIG. 8 , the insulating layer having undergone changes in film thickness was irradiated with 254 nm and 30 J/cm UV light, then also a sufficient contact angle of water at a film thickness of 2 nm could be observed. Based on this, the thickness of the insulating layer containing alkyl group in side chain is stipulated to be 2 nm or more that enables thin film formation. [0088] In addition, as for the insulating layer made of polyimide containing no alkyl group in a side chain, as shown below in Table 3, in order to derive sufficient performance on insulating breakdown voltage, a film thickness of 100 nm or more was required. [0089] Table 3 shows relationship between the film thickness of polyimide containing an alkyl group in a side chain and the breakdown voltage, to be applied to description of experiments of the present invention. TABLE 3 Film thickness of Insulating layer 50 nm 100 nm 200 nm 300 nm 400 nm 500 nm Insulating No Good Good Good Good Good Breakdown good Voltage In Table 3, “Good” means sufficient in practical use, and “No good” means insufficient in practical use. (Experiment 5) [0090] By changing the film thickness of an upper insulating layer made of polyimide containing an alkyl group in a side chain and a lower insulating layer polyimide containing no alkyl group, electric properties of TFT were evaluated. For a semiconductor layer, P3HT was used. Setting the total film thickness of the insulating film at 500 nm, proportion of the upper layer to the lower layer was changed. FIG. 10 shows relationship between the film thickness of respective insulating layers and Vth. It is apparent that the upper insulating layer made of polyimide containing an alkyl group in a side chain exceeds 200 nm, then Vth steeply becomes large. Next, showing embodiments, the present invention will be described in detail. [0091] The present invention is to make an organic transistor having excellent functions, including an organic semiconductor layer, an insulating layer and a plurality of electrodes, wherein the insulating layer has a stacked body of an insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide containing no alkyl group. Composition of this stacked body of insulating layers may vary continuously in the film thickness direction, or may be a separated multi-layer structure. [0092] The present embodiment exemplifies production of an excellent organic transistor having a staked body of an insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide containing no alkyl group. [0093] Here, for the lower layer, without limiting to an insulating layer made of polyimide containing no alkyl group in the present embodiment, but a variety of insulating layers made of materials containing no alkyl group can be used. Disregarding whether materials in that case are organic or inorganic, all materials presenting insulation can be used, and in particular, in case of an organic system, polyimide, polyamide, polyamideimide and polyolefin containing no alkyl group, and for inorganic system, a highly insulating material such as SiO 2 and Ta 2 O 5 are desired to be used. [0094] In addition, as for an upper layer, instead of an organic insulating layer made of polyimide containing an alkyl group in a side chain, an insulating layer made of the other materials can be used as well. In that case, a material showing insulation, in particular with surface free energy being low, generating single axis alignment regulating force by rubbing treatment and polarized ultraviolet rays, and being caused to derive variations in surface free energy, and having bonding being destructible with ultraviolet rays in order to make mapping easy at the time of electrode drawing is preferably used. For example, organic system polymeric material such as polyimide, polyamide, polyamideimide and PVP (polyvinyl phenol) containing bonding being destructible by ultraviolet rays is desired to be used. [0095] For forming a double layer structure of the gate insulating layer used in a preferable mode of the present invention, with variety of methods such as a spin coat method, an ink-jet drawing method, offset printing, screen printing and the like, it can be made easily. In addition, a gate electrode, source and drain electrodes can be formed with a variety of methods such as an ink-jet drawing method, a screen printing method. Any film forming method can make thin film sufficiently functionable in an organic transistor of the present invention. [0096] The double insulating layer structure used in a preferable mode of the present invention is desired to be formed as thinner as possible within such a range that can retain insulation sufficiently from a knowledge on device properties. The insulating layer made of polyimide containing no alkyl group is desired to be about 1 μm or less in order to be used effectively with a low gate voltage. On the other hand, an insulating layer made of polyimide containing an alkyl group in a side chain is satisfactory if it has a sufficient thickness required for alignment regulating force and surface free energy patterning, 2 nm or more is desired which is formable as film. In addition, an insulating layer containing an alkyl group in a side chain is desired to be 200 nm or less in consideration of electric properties. [0097] Moreover, as for an insulating layer in a double structure used in a preferable mode of the present invention, in consideration of its role, an insulating layer made of polyimide containing no alkyl group is required to be highly insulating, and therefore, an insulating layer made of polyimide containing no alkyl group is desired to be thicker than an insulating layer containing an alkyl group in side chain. [0098] As for an organic semiconductor layer in the present invention, a variety of materials such as low-molecular system and polymeric system can be nominated, and any known material can be used, but a polymeric system semiconductor material such as P3HT (poly(3-hexylthiophene)) and F8T2 (Fluorene-bithiophene) and the like in particular is comparatively easily soluble with an organic solvent and easily undergoes drawing with an ink-jet method, and is arranged in a single axis direction, whereby its improvement in properties can be expected and suitable for use in a process of the present invention. In addition, low-molecular material such as pentacene, rubrene and porphyrin showing high mobility in the case where hopping conduction is main and molecules are arranged perpendicularly also dissolves by causing precursor solution to dissolve into an organic solvent or by treating the low molecules themselves with a special organic solvent, and can be used in the process of the present invention. [0099] With referring to the drawings, an organic transistor provided with a double insulating layer structure consisting of an organic insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide containing no alkyl group will be described briefly as a preferable example of the present invention. FIG. 1 is a sectional diagram of an embodiment of an organic transistor structure of a bottom gate type showing the present invention. As shown in FIG. 1 , a gate electrode 12 is formed only in a portion on a substrate 10 . Thereon, an insulating layer 13 made of polyimide containing no alkyl group is formed, and thereon an insulating layer 14 made of polyimide containing an alkyl group in side chain is formed. Thereon, source and drain electrodes 15 are particularly stacked at a distance of the channel length, and moreover an organic semiconductor layer 16 is partially formed so as to cover the channel part. Reference numeral 21 denotes a gate insulating film consisting of the insulating layer 13 and the insulating layer 14 . FIG. 2 is an explanatory diagram showing a rubbing treatment method of giving alignment regulating force. FIG. 3 is a conceptual diagram of polarized UV light irradiation of giving alignment regulating force. As follows, another embodiment of the present invention will be described. [0100] The present embodiment is to make an organic transistor having excellent functions, including a substrate, a substrate insulating layer, a gate electrode, a gate insulating layer, source and drain electrodes and an organic semiconductor layer, wherein the gate insulating layer is a stacked body of an insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide containing no alkyl group. Composition of this stacked body of gate insulating layer may vary in a continuous fashion in the film thickness direction, or may be a separated multi-layer structure. [0101] The present embodiment exemplifies production of an organic transistor having excellent functions, including an insulating layer made of polyimide containing an alkyl group in a side chain for a substrate insulating layer, and, for a gate insulating layer, a stacked body of an insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide containing no alkyl group. [0102] Forming of a substrate insulating layer and a double layer structure of the gate insulating layer in the present embodiment can be made easily by a variety of methods such as a spin coat method, an ink-jet drawing method, offset printing screen printing and the like. In addition, a gate electrode, source and drain electrodes can be formed by a variety of methods such as an ink-jet drawing method and a screen printing method. Any film forming method can make thin film sufficiently functionable in an organic transistor of the present invention. [0103] The substrate insulating layer in the present embodiment may be provided with any thickness, but the thickness is desired to such an extent that will not deteriorate flexibility of a device. In addition, a double layer structure of the gate insulating layer of the present invention is desired to be formed as thinner as possible within such a range that can retain insulation sufficiently from a knowledge on device properties. The insulating layer made of polyimide containing no alkyl group is desired to be around 1 μm or less in order to be used effectively with the gate voltage being a low voltage. On the other hand, an insulating layer made of polyimide containing an alkyl group in a side chain is satisfactory if it has a sufficient thickness required for alignment regulating force and surface free energy patterning, and the thickness is desired to be 2 nm or more which is formable as film. In addition, an insulating layer made of polyimide containing an alkyl group in a side chain is desired to be 200 nm or less in consideration of electric properties. [0104] Moreover, as for a gate insulating layer in a double structure in the present invention, in consideration of its role, an insulating layer made of polyimide containing no alkyl group is required to be highly insulating, and therefore, an insulating layer made of polyimide containing no alkyl group is desired to be thicker than an insulating layer made of polyimide containing an alkyl group in side chain. [0105] Other points are likewise the above-described embodiment. [0106] With referring to the drawings, an organic transistor, in the present invention, provided with a substrate insulating layer of an organic insulating layer made of polyimide containing an alkyl group in a side chain, and provided with a double layer structure of the gate insulating layer consisting of an organic insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide containing no alkyl group will be described briefly. FIG. 12 is a sectional diagram of an embodiment of an organic transistor structure of a bottom gate type showing the present invention. As shown in FIG. 12 , a substrate insulating layer 11 made of polyimide containing an alkyl group is provided on a substrate 10 , and thereon a gate electrode 12 is formed only in a portion. Thereon, a gate insulating layer 13 made of polyimide containing no alkyl group is formed, and thereon a gate insulating layer 14 made of polyimide containing an alkyl group in a side chain is formed. Thereon, source and drain electrodes 15 are particularly stacked at a distance of the channel length, and moreover an organic semiconductor layer 16 is partially formed so as to cover the channel part. FIG. 13 is an explanatory diagram showing a rubbing treatment method of giving alignment regulating force, and FIG. 14 is a conceptual diagram of polarized UV light irradiation of giving alignment regulating force. [0107] With referring to the following examples, the present invention will be described further particularly. EXAMPLE 1 [0108] An example of having employed an ink-jet drawing method as a method of forming source and drain as well as an organic semiconductor layer to make a bottom gate type organic transistor provided with a double insulating layer structure consisting of an insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide containing no alkyl group will be nominated. [0109] On a glass substrate, Al for forming a gate was formed, which underwent patterning with a photolitho process to form a gate electrode. Thereon, polyimide (SE812 produced by NISSAN CHEMICAL INDUSTRIES, LTD.) was coated with a spinner to obtain a thickness of approximately 300 nm and underwent firing with 300° C. for 30 minutes to form an insulating layer made of polyimide containing no alkyl group. Hereon, as an insulating layer containing an alkyl group in a side chain, polyimide containing a side chain of an alkyl group with low surface energy was formed with offset printing to obtain a thickness of 30 nm and underwent firing with 210° C. with an oven for 60 minutes. After forming a double insulating layer structure, in a rubbing apparatus as shown in FIG. 2 , with a rubbing roller made of cotton, rubbing treatment at 1000 rpm and orientation treatment were implemented. [0110] After rubbing was over, the substrate was cleansed, and subsequently the surface of polyimide containing an alkyl group in a side chain underwent masking with a metal mask, and the portion where a channel was desired to be formed as in FIG. 11 underwent pattern exposure across the 5 μm width with an aligner (UX3000 produced by USHIO INC.) with Deep UV light of 254 nm. Implementing exposure with 254 nm UV light, polyimide incurs significant changes in surface energy. In particular, polyimide containing an alkyl group in a side chain with a low surface free energy incurs significant changes thereof. [0111] FIGS. 5 and 6 show relationship between the 254 nm UV light irradiation amount and the surface free energy of polyimide containing an alkyl group in a side chain. According to UV light irradiation amounts, hydrogen bonding term in particular increases by large margin. FIG. 4 shows relationship between the 254 nm UV light irradiation amount and the contact angle of water. By UV light irradiation as shown in FIG. 4 , the contact angle of water varies from 95 degrees to 10 degrees. [0112] Shielding only the portion for forming a channel with a mask, exposure with 254 nm UV light was implemented, and thereafter, source and drain electrodes were formed with an ink-jet drawing method. For an electrode material, the one with gold nano particles having been dispersed in a solution of an acqueous system was used (hereinafter to be referred to as “gold nano ink”), and when this solution was coated onto both sides of polyimide with low surface energy to become a channel by ink-jet drawing, the gold nano ink was dammed with polyimide to become a channel since surface energy was 38 mN/m that was extremely low, soaked/spread in both sides of the upper layer and was stabilized. FIG. 9 shows a photograph after gold nano ink was brought into drawing with an ink-jet method. As in FIG. 9 , it is apparent that, even with 5 μm channel length, gold nano ink to become source and drain spreads in both sides of a channel and the channel is formed beautifully. [0113] Under this state, implementing firing with 210° C. with an oven for 120 minutes, gold nano particles for forming source and drain were fused themselves with each other and metalized to form electrodes. Subsequently, on polyimide with low surface energy to become a channel, as a semiconductor layer, a porphyrin precursor, which was dissolved into a toluene solvent, was jetted for drawing with an ink jet method, underwent firing with 200° C. with an oven for 60 minutes and was crystallized. Film thickness of the semiconductor layer was set at 100 nm. An orientation state of the semiconductor film was confirmed with a polarized microscope to note that bright and dark difference appeared and orientation in a direction of rubbing was derived. In addition, channel length was 5 μm. Moreover, the same polyimide as the one used for the insulating layer was formed thereon as a protection film of 500 nm with spin coating and underwent firing with 250° C. with an oven for 60 minutes. [0114] Wiring was implemented in the gate and the source and drain on the formed organic transistor of a bottom gate type. Measurement on properties of the formed organic transistor with a semiconductor parameter analyzer in a vacuum showed high mobility in the order of 0.2 cm 2 /Vs and good saturation characteristic to the gate voltage. EXAMPLE 2 [0115] Except that, as the lower insulating layer on the Al gate wiring, polyimide was replaced with SiO 2 of plasma CVD, a bottom gate type organic transistor was made likewise Example 1. Film forming conditions of SiO 2 were set at TEOS/He/O 2 =185 sccm/100 sccm/3500 sccm, reaction pressure of 800 mtorr, substrate temperature of 330° C. and film thickness of 300 nm. [0116] Measurement on properties of the formed organic transistor with a semiconductor parameter analyzer in a vacuum showed a mobility of 0.3 cm 2 /Vs. [0117] In the present example, a glass substrate is used, but all the other inorganic system materials such as a Si substrate can be used. In addition, polymeric system materials may be used, and, in particular, liquid crystal polymer and the like are suitable to an organic transistor of the present invention due to its nature of thermal expansion and high heat resistance. [0118] In the present example, Al is used as a gate electrode material, and a gate electrode is formed with photolithography, but an electrically conductive metal material can be formed by an ink-jet method or a screen printing method to implement printing directly onto a required places. As the electrically conductive metal material, low temperature firing type Ag nano ink or nano paste in use of Ag nano particles or low temperature firing type Ag ink or paste in mixture of silver oxide and organic silver compounds utilizing occurrence of oxidation-reduction reaction of Ag at 150° C. are nominated. These materials show sufficient low resistance similar to metal Ag after firing with 150° C. for around 60 minutes and are desirable as materials at the time of forming a gate electrode with printing process such as an ink-jet method or a screen printing method. In addition, besides Ag, there may be used low temperature type electrically conductive ink or paste by use of all electrically conductive materials capable of undergoing low temperature firing with nano particle formation of Au, Pt and the like. [0119] In the above-described two examples, polyimide and SiO 2 are used for an insulating layer containing no alkyl group, but inorganic system insulating materials such as Al 2 O 3 and Ta 2 O 5 can also be used. In addition, in the present invention, SiO 2 undergoes film formation under vacuum, but a method of coating inorganic system coating type insulating film by spin coating, offset printing or the like and firing it can be used. In addition, as organic system insulating material, polyamide, polyamideimide and the like besides polyimide can be coated by spin coating, offset printing, etc, are highly insulating with low leak current and are usable. [0120] In the present example, in order to arrange organic semiconductor layers, the polyimide film containing an alkyl group in a side chain undergoes rubbing, but organic semiconductor layers can also be arranged by using polarized ultraviolet ray equipment as shown in FIG. 3 to irradiate polarized ultraviolet rays onto the polyimide film. Polyimide film incurs a cleavage in imide structure of the main chain skeleton by ultraviolet rays, and therefore irradiation of polarized ultraviolet rays causes imide structure to remain in the bias direction of light to generate alignment regulating force in one direction. Irradiating polarized ultraviolet rays onto film of polyimide containing an alkyl group in a side chain subject to source and drain electrodes formation, organic semiconductor layers formed onto polyimide film will become arrangeable in one direction. [0121] In addition, in the present example, a solution obtained by dispersing gold nano particles into an electrically conductive material of source and drain electrodes is used, but nano particle dispersed solutions which include any highly electrically conductive metals, such as Pt, which can be shrunk down to nano size to undergo low temperature firing, can also be used. In addition, organic system electrically conductive materials such as PEDOT•PSS solution capable of being brought into coating with ink-jet drawing can be used. [0122] In the present example, porphyrin is used for semiconductor layers, but soluble precursor of low molecule semiconductor material of pentacene and rubrene or low molecule semiconductor materials that are soluble themselves can be used. In case of a low molecule system material, hopping conduction is main, and with molecules being perpendicular to a substrate, overlapping of π electrons results in increase in probability in electron hopping and conductivity tends to increase further. On the other hand, as an organic semiconductor material of a polymeric system P3HT, F8T2, etc. can be used, but will give rise to effects a little bit smaller than the materials of a low molecule system from the point of view of orientation. COMPARATIVE EXAMPLE 1 [0123] Except that an insulating layer made of polyimide containing no alkyl group was not provided on a substrate, a bottom gate type organic transistor was made likewise Example 1. On a glass substrate, Al for forming a gate was formed, which underwent patterning with a photolitho process to form a gate electrode. Thereon, polyimide containing an alkyl group in a side chain with low surface free energy (preproduction sample) was formed with offset printing to derive 300 nm and underwent firing with 210° C. with an oven for 60 minutes. After forming a double insulating layer structure with a rubbing roller made of cotton, rubbing treatment was implemented at 1000 rpm and orientation treatment was implemented. [0124] After rubbing was over, the substrate was cleansed, and subsequently the surface of polyimide containing an alkyl group in a side chain underwent masking with a metal mask, and the portion where a channel was desired to be formed underwent pattern exposure across the 5 μm width with an aligner with Deep UV light of 254 nm. Shielding only the portion to become a channel with a mask, exposure with 254 nm UV light was implemented, and thereafter, source and drain electrodes were formed with an ink-jet drawing method. For an electrode material, the one with gold nano particles having been dispersed in a solution of an acqueous system was used, and when this solution was coated onto both sides of polyimide with low surface energy to become a channel with ink-jet drawing, the gold nano ink was dammed with polyimide to become a channel since surface energy was 38 mN/m that was extremely low, soaked/spread in both sides of the surface layer and was stabilized, under the state of which, implementing firing with 210° C. with an oven for 120 minutes, gold nano particles to become source and drain were fused themselves with each other and metalized to form electrodes. [0125] Subsequently, on polyimide with low surface energy to become a channel, as a semiconductor layer, a toluene solution of a porphyrin precursor was formed to derive 100 nm with ink jet drawing, underwent firing with 200° C. with an oven for 60 minutes and was crystallized. Moreover, a protection film was formed with spin coating and underwent firing with 200° C. with an oven for 60 minutes. [0126] Wiring was implemented in the gate and the source and drain on the formed organic transistor of a bottom gate type. As the result of measurement on properties of the formed organic transistor with a semiconductor parameter analyzer in a vacuum, the organic transistor having a large leak current and sufficient transistor properties were not obtained. COMPARATIVE EXAMPLE 2 [0127] Except that polyimide of orientated film did not undergo rubbing, a bottom gate type organic transistor was made likewise Example 1. An orientation state of the semiconductor film was confirmed with a polarized microscope to note that bright and dark difference appeared but a minute particle state was observed and no orientation was confirmed. [0128] Measurement on properties of the formed organic transistor with a semiconductor parameter analyzer in a vacuum showed a mobility of 0.03 cm 2 /Vs. EXAMPLE 3 [0129] An example of having employed an ink-jet drawing method as a method of forming gate electrode, source and drain electrodes as well as an organic semiconductor layer to make a bottom gate type organic transistor provided with, as a substrate insulating layer, an insulating layer made of polyimide containing an alkyl group in a side chain and provided with, as a gate insulating layer, a double insulating layer structure consisting of an insulating layer made of polyimide containing an alkyl group in a side chain and an insulating layer made of polyimide containing no alkyl group will be nominated. [0130] On a glass substrate, polyimide containing a side chain of an alkyl group with low surface energy was formed with spin coating to obtain a thickness of 30 nm and underwent firing with 210° C. with an oven for 60 minutes. Subsequently the surface of polyimide containing an alkyl group in a side chain underwent masking with a photo mask, and the portion where a gate was desired to be formed as in the sectional drawing of FIG. 15 underwent pattern exposure across 20 μm width of the gate electrode and 1.5 mm length of the gate electrode with an aligner (UX3000 produced by USHIO INC.) with Deep UV light of 254 nm. Implementing exposure with 254 nm UV light, polyimide incurs significant changes in surface energy. In particular, polyimide containing an alkyl group in a side chain with surface free energy being low incurs significant changes thereof. [0131] FIGS. 5 and 6 show relationship between the 254 nm UV light irradiation amount and the surface free energy of polyimide containing an alkyl group in a side chain. According to UV light irradiation amounts, particularly hydrogen bonding term increases by large margin. FIG. 4 shows relationship between 254 nm UV light irradiation amount and contact angle of water in the same polyimide material. By UV light irradiation as shown in FIG. 4 , the contact angle of water varies from 95 degrees to 10 degrees. [0132] Shielding the portions other than the portion to become a gate with a mask, the portion to become the gate underwent exposure with 254 nm UV light, and thereafter, the gate electrode was formed with an ink-jet drawing method. For an electrode material, the one with gold nano particles having been dispersed in a solution of an acqueous system was used (hereinafter to be referred to as “gold nano ink”), and the gold nano ink was coated onto the polyimide with low surface energy to become a gate with ink-jet drawing as shown in FIG. 16 , the gold nano ink soaked/spread over the surface of the polyimide to become a gate since surface energy was 38 mN/m that was extremely low, and uniformly spread only over the gate portion since surface free energy in the circumference of the gate was held low, and was stabilized. [0133] Under this state, implementing firing with 210° C. with an oven for 120 minutes, gold nano particles to become a gate electrode were fused themselves with each other and metalized to form an electrode. On this gate electrode, polyimide (SE812 produced by NISSAN CHEMICAL INDUSTRIES, LTD.) was coated with a spinner to obtain thickness of approximately 300 nm and underwent firing with 300° C. for 30 minutes to form a gate insulating layer containing no alkyl group. Hereon, as a gate insulating layer containing an alkyl group in a side chain, polyimide containing an alkyl group in a side chain with low surface energy (preproduction sample) was formed with offset printing to derive 30 nm and underwent firing with 210° C. with an oven for 60 minutes. [0134] After forming the double layer structure of the gate insulating layer, in a rubbing apparatus as shown in FIG. 13 , with a rubbing roller made of cotton, rubbing treatment was implemented at 1000 rpm and orientation treatment was implemented. After rubbing was over, the substrate was cleansed, shielding only the portion to become a channel with a mask, exposure with 254 nm UV light was implemented, and thereafter, source and drain electrodes were formed with an ink-jet drawing method. For an electrode material, gold nano particle ink was used, and when this solution was coated onto both sides of polyimide with low surface energy to become a channel with ink-jet drawing, the gold nano ink was dammed with polyimide to become a channel since surface energy was 38 mN/m that was extremely low, soaked/spread in both sides of the upper layer and was stabilized. Under this state, implementing firing with 210° C. with an oven for 120 minutes, gold nano particles to become source and drain were fused themselves with each other and metalized to form electrodes. [0135] Subsequently, on polyimide with low surface energy to become a channel, as a semiconductor layer, a porphyrin precursor, which was dissolved into a toluene solvent, was brought into drawing with ink jet, underwent firing with 200° C. with an oven for 60 minutes and was crystallized. Film thickness of the semiconductor layer was set to 100 nm. An orientation state of the semiconductor film was confirmed with a polarized microscope to note that bright and dark difference appeared and orientation in a direction of rubbing was derived. In addition, channel length was 5 μm. Moreover, the same polyimide as the one used for the insulating layer was formed thereon as a protection film of 500 nm with spin coating and underwent firing with 250° C. with an oven for 60 minutes. [0136] Wiring was implemented in the gate and the source and drain on the formed organic transistor of a bottom gate type. Measurement on properties of the formed organic transistor with a semiconductor parameter analyzer in a vacuum showed a high mobility in the order of 0.2 cm 2 /Vs and a good saturation characteristic to the gate voltage. EXAMPLE 4 [0137] Except that, as the lower layer insulating film on the gate wiring, polyimide was replaced with SiO 2 of plasma CVD, a bottom gate type organic transistor was made likewise Example 1. Film forming conditions of SiO 2 were set at TEOS/He/O 2 =185 sccm/100 sccm/3500 sccm, reaction pressure of 800 mtorr, substrate temperature of 330° C. and film thickness of 300 nm. [0138] Measurement on properties of the formed organic transistor with a semiconductor parameter analyzer in a vacuum showed a mobility of 0.3 cm 2 /Vs. [0139] For the present embodiment, a glass substrate is used, but all the other inorganic system materials such as a Si substrate can be used. In addition, polymeric system materials may be used, and in particular liquid crystal polymer and the like are suitable to an organic transistor of the present invention due to its nature of thermal expansion and high heat resistance. [0140] In the present embodiment, Au is used as a gate electrode material, and Au nano ink undergoes printing directly onto required places by an ink-jet method to form a gate electrode, and as the electrically conductive metal material, low temperature firing type Ag nano ink in use of Ag nano particles or low temperature firing type Ag ink etc. in mixture of silver oxide and organic silver compounds utilizing occurrence of oxidation-reduction reaction of Ag at 150° C. are also nominated. These materials show a sufficiently low resistance similar to metal Ag after firing with 150° C. for around 60 minutes and are desirable as materials at the time of forming a gate electrode by printing process such as an ink-jet method or a screen printing method. In addition, besides Au and Ag, there may be used low temperature type electrically conductive ink or paste in use of all electrically conductive materials capable of undergoing low temperature firing by nano particle forming of Pt and the like. [0141] In the above-described two embodiments, the two kinds of polyimide and SiO 2 are used for an insulating layer containing no alkyl group, but inorganic system insulating materials such as Al 2 O 3 and Ta 2 O 5 can also be used. In addition, in the present invention, SiO 2 undergoes film forming with vacuum film forming, but a method of coating an inorganic system coating type insulating film by spin coating, offset printing, etc. and undergoing firing can be used. In addition, as organic system insulating material, polyamide, polyamideimide and the like besides polyimide can be coated by spin coating, offset printing or the like are highly insulating with low leak current and are usable. [0142] In the present embodiment, in order to arrange organic transistor layers, the polyimide film containing an alkyl group in a side chain undergoes rubbing, but organic transistor semiconductor layers can also be arranged by using polarized ultraviolet ray equipment as shown in FIG. 14 to irradiate polarized ultraviolet rays onto the polyimide film. Polyimide film incurs a cleavage in the imide structure of the main chain skeleton by ultraviolet rays, and therefore irradiation of polarized ultraviolet rays causes the imide structure to remain in the bias direction of light to generate alignment regulating force in one direction. After source and drain electrodes formation, irradiation of polarized ultraviolet rays onto film of polyimide containing an alkyl group in a side chain makes it possible to arrange organic transistor layers formed on a polyimide film in one direction. [0143] In addition, in the present embodiment, a solution derived by dispersing gold nano particles into electrically conductive material of source and drain electrodes is used, but nano particle dispersed solutions which include any highly electrically conductive metals, such as Pt, which can be shrunk down to nano size to undergo low temperature firing, can also be used. In addition, organic system electrically conductive materials such as PEDOT•PSS solution capable of being brought into coating with ink-jet drawing can be used. [0144] In the present embodiment, porphyrin is used for semiconductor layers, but soluble precursor of low molecule semiconductor material of pentacene and rubrene or low molecule semiconductor materials that are soluble themselves can be used. In case of low molecule system material, hopping conduction is main, and with molecules being perpendicular to a substrate, overlapping of π electrons results in increase in probability in electron hopping and conductivity tends to increase further. On the other hand, as an organic semiconductor material of a polymeric system P3HT, F8T2, etc. can be used, but will give rise to effects a little bit smaller than the materials of a low molecule system from the point of view of orientation. COMPARATIVE EXAMPLE 3 [0145] Except that an insulating layer containing an alkyl group was not provided as a substrate insulating layer on a substrate, a bottom gate type organic transistor was made likewise Example 3. On a glass substrate, Au ink for forming a gate was directly brought into drawing with ink jet, and a gate electrode was formed. Due to lack of the substrate insulating layer containing an alkyl group and of patterning of surface free energy, Au ink did not soak/spread, giving rise to dot shapes in size of around 30 μm connected in a sequential fashion, and height fluctuated significantly and never became constant. Under this state, implementing firing with 210° C. with an oven for 120 minutes, gold nano particles to become a gate electrode were fused themselves with each other and metalized to form an electrode. [0146] On this gate electrode, polyimide (SE812 produced by NISSAN CHEMICAL INDUSTRIES, LTD.) was coated with a spinner to derive thickness of approximately 300 nm and underwent firing with 300° C. for 30 minutes to form a gate insulating layer containing no alkyl group. Hereon, as a gate insulating layer containing an alkyl group in a side chain, polyimide containing an alkyl group in a side chain with low surface energy (preproduction sample) was formed with offset printing to derive 30 nm and underwent firing with 210° C. with an oven for 60 minutes. After forming a double layer structure of the gate insulating layer, in a rubbing apparatus as shown in FIG. 13 , with a rubbing roller made of cotton, rubbing treatment was implemented at 100 rpm and orientation treatment was implemented. After rubbing was over, the substrate was cleansed, shielding only the portion to become a channel with a mask, exposure with 254 nm UV light was implemented, and thereafter, source and drain electrodes were formed with an ink-jet drawing method. For an electrode material, gold nano particle ink was used, and when this solution was coated onto both sides of polyimide with low surface energy to become a channel by ink-jet drawing, the gold nano ink was dammed with polyimide to become a channel since surface energy was 38 mN/m that was extremely low, soaked/spread in both sides of the upper layer and was stabilized. Under this state, implementing firing with 210° C. with an oven for 120 minutes, gold nano particles to become source and drain were fused themselves with each other and metalized to form electrodes. [0147] Subsequently, on polyimide with low surface energy to become a channel, as a semiconductor layer, a porphyrin precursor, which was dissolved into a toluene solvent, was brought into drawing with ink jet, underwent firing with 200° C. with an oven for 60 minutes and was crystallized. Film thickness of the semiconductor layer was set to 100 nm. An orientation state of the semiconductor film was confirmed with a polarized microscope to note that bright and dark difference appeared and orientation in a direction of rubbing was derived. In addition, channel length was 5 μm. Moreover, the same polyimide as the one used for the insulating layer was formed thereon as a protection film of 500 nm with spin coating and underwent firing with 250° C. with an oven for 60 minutes. [0148] Wiring was implemented in the gate and the source and drain on the formed organic transistor of a bottom gate type. Properties of the formed organic transistor with a semiconductor parameter analyzer in a vacuum were measured, but since width and height of the gate electrode fluctuated significantly and were not constant, no constant electric field could be applied, and stable transistor properties were not derived. [0149] An organic transistor of the present invention can realize as a highly reliable transistor with a high breakdown voltage and a low leak current and high performance, and therefore can be utilized to electronic devices such as a paper-like display, an organic ID tag, an organic EL, etc. [0150] This application claims priority from Japanese Patent Application No. 2004-319737 filed on Nov. 2, 2004, which is hereby incorporated by reference herein.
There is provided an organic transistor having a bottom gate structure, composed of a substrate, a gate electrode, a gate insulating layer, source and drain electrodes and an organic semiconductor layer, wherein the gate insulating layer is formed so as to have a low surface energy in a portion thereof in proximity to the source and drain electrodes and a relatively high surface energy in a portion in proximity to the gate electrode, and consist of different compositions in a layer thickness direction, whereby an organic transistor has a short channel and high electric characteristics; as well as a method of manufacturing the organic semiconductor.
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CROSS-REFERENCE TO PRIOR APPLICATIONS This application is the U.S. National Phase application under 35 U.S.C. §371 of International Application No. PCT/IB2012/052763 filed on Jun. 1, 2012, which claims the benefit of European Patent Application No 11169391.7, filed on Jun. 10, 2011. These applications are hereby incorporated by reference herein. FIELD OF THE INVENTION The invention relates to a system, a control unit for a segment controller and a method for secure protocol execution in a network. BACKGROUND OF THE INVENTION Recently, wireless mesh networks attract more and more attention, e.g. for remote control of illumination systems, building automation, monitoring applications, sensor systems and medical applications. In particular, a remote management of outdoor luminaires, so-called telemanagement, becomes increasingly important. On the one hand, this is driven by environmental concerns, since telemanagement systems enable the use of different dimming patterns, for instance as a function of time, weather conditions or season, allowing a more energy-efficient use of the outdoor lighting system. On the other hand, this is also driven by economical reasons, since the increased energy efficiency also reduces operational costs. Moreover, the system can remotely monitor power usage and detect lamp failures, which allows for determining the best time for repairing luminaires or replacing lamps. Current radio-frequency (RF) based wireless solutions preferably use a mesh network topology, e.g. as shown in FIG. 1 . The wireless network comprises a central controller or segment controller 60 and a plurality of nodes 10 (N) being connected among each other by wireless communication paths 40 in a mesh topology. Thus, the nodes 10 and the central controller 60 may comprise a transceiver for transmitting or receiving data packets via wireless communication paths 40 , e.g. via RF transmission. In the backend, a service center 80 is situated and serves for system management. This entity normally communicates with one or more central controllers 60 of a corresponding network as a commissioning tool in charge of controlling or configuring this network over a third party communication channel 70 , such as the Internet or mobile communication networks or other wired or wireless data transmission systems. In case of a lighting system or any other large wireless network, a network can also be divided into segments, so that a node 10 belongs to exactly one segment having one segment controller 60 . Therefore, the terms “segment controller” and “central controller” should be seen as exchangeable throughout this description. In general, any node 10 of the mesh network can communicate with the service center 80 via the segment controller 60 . However, in some situations, high security standards have to be fulfilled in order to provide basic security services. An example is protection against a man-in-the-middle attack, i.e. preventing sensitive information being provided to non-authorized nodes 10 or preventing manipulation of the information provided to the nodes 10 . For instance, outdoor lighting control involves the remote management of lighting nodes requiring a communication link between the service center 80 and the nodes 10 themselves through a controlling device such as a segment controller 60 . In contrast to the service center 80 and the nodes 10 , the segment controller 60 , which is in the middle, is often not fully trusted since it may be managed and manipulated by third parties such as installers or customers. Thus, a segment controller 60 may act as a man-in-the-middle and manipulate some messages. This makes the execution of security protocols challenging. For instance, keying material cannot be provided to the segment controller 60 , since it may be misused. Therefore, it is required to find means that allow to upgrade and/or activate software functionalities of the network nodes 10 or the like without being afraid of an intruder being able to put malware on the nodes 10 . For this, it is important to ensure that a protocol for performing such actions is correctly performed by the segment controller 60 . Traditional end-to-end security protocols that allow for an end-to-end authentication between two trusted entities require the interactive exchange of messages between the service center 80 and the nodes 10 , e.g., based on a challenge-response authentication handshake. Although such a procedure provides high security, it poses severe requirements regarding the usage of the GPRS link 70 as shown in FIG. 1 and regarding the service center 80 in the backend, since it involves continuous connections, more bandwidth and more operations at the service center 80 . Thus, an end-to-end security handshake from the service center 80 to the nodes 10 ensuring, e.g., mutual authentication, is expensive and involves a lot of data traffic, continuous connection with the backend, more bandwidth and more operations at the backend. Hence, it is desired to find means for communicating with network nodes 10 from the backend via an intermediate controlling device, providing a reasonable trade-off between security and operational needs suitable for the respective application. SUMMARY OF THE INVENTION In view of above disadvantages and problems in the prior art, it is an object of the present invention to provide a system, a control unit for a segment controller and a method for secure protocol execution in a wireless network, allowing for the secure configuration of network nodes from a backend, while minimizing connectivity requirements and workload at the backend and reducing the communication overhead. The invention is based on the idea to force a controlling device, which serves as an intermediate entity between network nodes and a service center, to carry out a particular protocol with at least one of the nodes by providing the controlling device with corresponding protocol information, wherein the controlling device requires a predetermined response message from the respective node(s) in order to carry out a next step of the protocol. It is to be understood that the service center as well as the controlling device or segment controller may also be represented by a certain network node, respectively. The predetermined response message may relate to a correct response(s) from the respective node(s), which can only be given by the node in case that the protocol is performed correctly. Thus, the protocol may be performed by the intermediate controlling device without causing extensive data traffic as it would be involved, e.g., in a common security handshake, thereby reducing the communication overhead. Moreover, by making the protocol execution dependent on a valid answer of the node to be controlled, manipulation of information provided to the node or misuse of the information by the controlling device may be prevented. Therefore, features of an end-to-end handshake between the nodes and the backend can be realized with respect to security. In one example, the protocol may relate to at least one of configuring the network nodes, updating node software, activating node features and commissioning of the nodes. Then, e.g., software update information may be provided to the nodes via the controlling device, while preventing manipulation of this information and preventing the information being provided to other nodes than the target nodes. Since the controlling device may only be able to proceed with the protocol having valid response messages from the right target node(s), correct protocol-based operation of the controlling device can be enforced. According to one aspect of the present invention, a system for ensuring correct protocol execution in a network, such as a wireless mesh network, having one or more nodes is provided. The system comprises a service center and a segment controller, wherein the service center provides protocol information to the segment controller for carrying out a protocol with at least one particular node of the network nodes. In order to be able to use the protocol information, the segment controller may need information provided by this node in a response message. The response message may be sent by the node, after having received a message from the segment controller, e.g. announcing a particular information or execution of a particular protocol. Preferably, the node provides a valid response message to the segment controller only after successful verification of a previous message or information received from the segment controller. Therefore, the segment controller may be forced to provide the right protocol information to the right node in order to receive a valid response message for performing a further, following or subsequent step of the protocol. By these means, correct operation of the segment controller may be supervised by the node to be controlled, i.e. the target node, thus preventing misuse of the protocol information. Likewise, this prevents malware to be successfully installed on the node. Hence, it may be guaranteed without control by the service center that only information authorized by the service center is distributed to network nodes and that only parties authorized by the service center have access to the distributed information. Since no continuous communication with the service center may be required in this process, the service center may be partially offline. In one embodiment, the response message of the node includes information about an identity of the node and/or about an identifier of the message received from the segment controller, to which the node is responding with the response message. The identifier of the message may be a string or value derived from the received message, e.g. a fingerprint of the message from the segment controller. Here, a fingerprint refers to uniquely identifying data by extracting from it a small key. Thus, the identifier of the message may relate to a function of a content of the message sent from the segment controller. The node identity may relate to an individual key of the node. In this case, it may also be ensured that the segment controller performs the protocol with the correct target node. However, the node identity may also relate to a symmetric key common to all nodes of the network, e.g. a commissioning key. This key or the node identity is preferably not known to the segment controller. Thus, the node may generate a check value or string depending on the content of the received message and/or based on its identity. By these means, the response message indicates the identity of the receiving node as well as the content of the received message, so that a correct protocol execution can be easily verified. Preferably, the response message from the node (or parts thereof) is required in order to decrypt at least a part of the protocol information provided by the service center to the segment controller. Thus, the segment controller may generate a key for decryption based on the response message from the node. For instance, the segment controller may be provided by the service center with an at least partially encrypted configuration message for configuring at least one of the network nodes. In order to proceed with the configuration of the node, the segment controller may require the response message for decryption. The response message may include a security key of the node, e.g. node identity or commissioning key, a message fingerprint or the like in an inseparable or coded way, so that the segment controller or eavesdropping entities cannot derive the original security keys. Therefore, the segment controller can be enforced to carry out a specific protocol with specific nodes by providing the segment controller with correspondingly encrypted protocol information. Thus, the segment controller can neither misuse the nodes nor transmit the protocol information to non-authorized nodes, since the segment controller can only decrypt and use the protocol information, when following the protocol. If it does not follow the protocol correctly, it cannot decrypt the information and thus cannot misuse the information. After the segment controller has decrypted at least a part of the protocol information using the response message, the segment controller may forward some or all of the decrypted protocol information to the node or nodes in the network. Preferably, the protocol information is encoded based on different keys. In this embodiment, the node(s) in a network may return (a) response messages corresponding to the last received message from the segment controller. These/this response messages (or party of them/it) may be used in turn by the segment controller to generate the next key for decrypting the next part of protocol information. For instance, information for a subsequent protocol step may be encoded with an expected valid response message of the node to a message from the segment controller relating to a previous protocol step. Thus, the protocol information may be iteratively decrypted. By these means, the correct operation of the segment controller is observed and ensured step by step. In a preferred embodiment, the segment controller is provided with the protocol information for all steps of the protocol. In this case, the protocol information may be encoded based on different keys. This allows executing the protocol by involving mainly interactions between the segment controller and the nodes, since the security is already guaranteed by the requirement of the correct response message. Hence, the connectivity with the backend required for performing the protocol as well as the number of operations at the backend can be decreased. Additionally, the segment controller may send a request for protocol information related to a subsequent protocol step to the service center, wherein the request message is based on the response message received from the at least one node. Thus, the service center may verify using the information about the response message of the node included in the request message that the segment controller has performed the previous protocol step with the correct node and/or in a correct way. Then, the service center may provide the segment controller with further protocol information required for performing a next protocol step. In case that more than one node is controlled with the protocol, the segment controller may aggregate information about all response messages (or a subset of them) from the respective nodes in the request message to the service center. Here, the service center may in addition check, whether all of the nodes to be controlled have been successfully addressed in the previous protocol step. Preferably, the service center and a node of the network share at least one of a common security key, a commissioning key, a cryptographic function such as hash function, an iteration number of a hash function and a current hash value. The service center may know a security key individual for each network node or a security key common to all network nodes or for one or more groups of network nodes. Alternatively or additionally, the service center may keep a hash chain or hash function for each network or network segment and a start value a 0 thereof. Then, a node may be initialized with the anchor of the respective hash chain or function. The hash function may be replaced by another one-way function or chain, wherein an iterative application of the function gives chain links or elements derived from a starting string or starting value, e.g. a i =HASH(a i−1 ). Preferably, the protocol and/or the response message is at least partially based on a hash function such as a hash algorithm SHA-2. By these means, a node, which is initialized with the anchor of the hash chain and which keeps track of the current hash chain element can verify a received message by checking, whether the hash element a i−1 included in the received message satisfies the condition: a i =HASH(a i−1 ). Hence, using hash chains or other one-way function allows authentication without public-key cryptography. In some embodiments, the protocol may include providing information to one ore more nodes of the network. Then, the information is preferably protected based on a secret key derived from a master secret and an information identity number. The information may be transmitted from the service center via the segment controller to the node. Thus, in order to secure the information, the secret key may be based on a master secret, i.e. a string or value only known to the node and the service center, but not to the segment controller. For instance, a master secret may relate to a security key of the node or a commissioning key of the node. Moreover, the secret key may additionally include an information identity number, e.g. a random number, a nonce or a salt set by the service center. Thus, in the example that the information relates to a software update, the information identity number may correspond to a software update number or software number. By these means, sensitive information can be protected and features of an end-to-end security handshake between the service center and the node can be mimicked. In one embodiment, the service center may provide a random number, a salt or a nonce specific for the protocol to the node. This may be required at the node as an input in a one-way function such as a hash function. Preferably, the salt or nonce is at least 16 bytes long. The random number, salt or nonce may relate to the information identity number described above. At least one of these protocol steps may include providing configuration information to a node or reconfiguration a node or rebooting a node or any combination thereof. Preferably, a reboot step may be additionally protected by means of an authentication token, e.g., a new hash chain link. Thus, a current or valid hash chain link has to be provided to the node in order to admit permit rebooting. The service center may therefore provide the segment controller with the current hash chain link, which may be the same for several nodes, so that rebooting in a synchronized manner is possible. This may enable a more secure and stable network operation, in particular, when providing a software update to a plurality of nodes. When completing the protocol, the segment controller may send a confirmation message to the service center. The confirmation message may be based on at least one response message received at the segment controller from the respective nodes. Thus, the confirmation message may include information about the identity of the respective node(s) and/or about the content of the last message from the segment controller received at the respective node(s). In the example of a software update, the last message, which the node receives from the segment controller, may include a software image, possibly encoded by a secret key. Therefore, the corresponding response message from the node to the segment controller may comprise information about the node identity and/or a fingerprint of the software image, so that the service center may verify that the right node is updated and/or that the node is updated with the right software. Therefore, the service center may be only involved in the protocol, when providing the protocol information to the segment controller and when receiving the confirmation message from the segment controller. Thus, communication with the service center is reduced, while still enabling secure controlling of the network nodes via an intermediate entity, i.e. the segment controller. In a preferred embodiment of the present invention, the system is applied for telemanagement of a lighting system. For instance, the node of the wireless network may correspond to a luminaire of the lighting system, such as a street lighting system or any other lighting system. In such systems, communication between the segment controller and the service center may rely on third party structures, while communication between the segment controller and the nodes are based on the wireless transmission within the network. Therefore, reducing communication with the service center results in lower maintenance costs. According to another aspect of the present invention, a control unit for a segment controller is provided allowing for secure protocol execution in a wireless network one or more nodes. By means of the control unit according to the present invention, the segment controller is adapted to perform a protocol based on protocol information provided by a service center in order to control at least one of the network nodes, wherein the execution of the protocol depends on at least one response message of the controlled node. Thus, the control unit for the segment controller according to the present invention can be applied to a segment controller of any above-described embodiment for a system according to the present invention. The control unit may be incorporated, integrated, mounted to or operatively coupled to the segment controller. According to a further aspect of the present invention, a method for secure protocol execution in a wireless network having one or more nodes is provided. According to the method, protocol information is provided to a segment controller of the network for control of at least one of the network nodes. The segment controller performs the protocol based on the received protocol information. For this, the segment controller needs at least one response message of the at least one node in order to carry out the protocol. Hence, the method according to the present invention is adapted to be performed by the system or the control unit of a segment controller according to any of the above-described embodiments of the present invention. These and other aspects of the invention will be apparent from and elucidated with reference to the embodiments described hereinafter. The invention will be described in more detail with respect to exemplary embodiments that are illustrated by the accompanying figures. However, the invention is not limited to these exemplary embodiments. BRIEF DESCRIPTION OF THE DRAWINGS In the figures: FIG. 1 illustrates an example of a wireless mesh network; FIG. 2 shows a flow diagram illustrating an embodiment of the present invention; FIG. 3 shows a schematic view of the process of FIG. 2 ; FIG. 4 shows a diagram for a process according an embodiment of the present invention; FIG. 5 illustrate the principle of a HASH chain; FIG. 6 shows a flow diagram illustrating another embodiment of the present invention; FIG. 7 shows a schematic view of the process of FIG. 6 ; and FIG. 8 shows a flow diagram illustrating an embodiment of the present invention. DETAILED DESCRIPTION Preferred applications of the present invention are actuator networks, sensor networks or lighting systems, such as outdoor lighting systems (e.g. for streets, parking and public areas) and indoor lighting systems for general area lighting (e.g. for malls, arenas, parking, stations, tunnels etc.). In the following, the present invention will be explained further using the example of an outdoor lighting system for street illumination, however, without being limited to this application. In the field of lighting control, the telemanagement of outdoor luminaires via radio-frequency network technologies is receiving increasing interest, in particular solutions with applicability for large-scale installations with segments of above 200 luminaire nodes. Since radio frequency (RF) transmissions do not require high transmission power and are easy to implement and deploy, costs for setting up and operating a network can be reduced. However, the data packet transmission may alternatively use infrared communication, free-space-visible-light communication or power line communication. In a telemanagement system for lighting control, the number of luminaire nodes 10 is extremely high. Hence, the size of the network is very large, especially when compared to common wireless mesh networks, which typically contain less than 200 nodes. In addition, the nodes 10 typically have limited processing capabilities due to cost considerations, so that processing and memory resources in the luminaire nodes 10 will be limited. Thus, security measures and communication protocols for transmitting data packets between single nodes 10 should consider the limited resources for efficient and secure data packet transmission. Finally, compared to other so-called ad-hoc mesh networks, the telemanagement system for an outdoor lighting control network is stationary, i.e. the luminaire nodes 10 do not move. Since the luminaire nodes 10 (e.g. the lamp poles) are stationary, node positions will not change over time. Thus, the physical positions of the nodes 10 , for instance GPS-coordinates or other position data, may be known in the system, enabling geographic or position-based routing using pre-programmed or predefined positions. In the following, embodiments of the present invention will be described using the example of a protocol for software updates. However, the present invention is not limited thereto and the protocol to be performed by the segment controller 60 may also relate to activation of node features and the like. In FIG. 2 , a first embodiment for ensuring secure protocol execution by the segment controller 60 is shown. In FIG. 3 , the data traffic of the example shown in FIG. 2 between the service center 80 , the segment controller 60 and the network node 10 is schematically illustrated. The arrows in FIG. 3 indicate the direction of communication, while time can be considered to run in the downward direction. In a first step S 200 , the service center 80 provides information for executing a protocol to the segment controller 60 . Receiving this information, the segment controller 60 starts to perform the corresponding protocol. Thus, the segment controller 60 transmits a first message to one or more nodes 10 (S 210 ), e.g. for announcing the start of the protocol. Each node 10 acknowledges the message received from the segment controller 60 with a response message including an index or identifier of the content of the received message and an identifier or key indicating the node identity (S 220 ). In step S 230 , the segment controller 60 collects the response messages from the nodes 10 and forwards them in a compressed form, e.g. aggregated in a batch message, to the service center 80 . By these means, the service center 80 can verify that the segment controller 60 has performed the first steps of the protocol correctly and successfully. This may include verifying that the first message included the correct content, that the first message was successfully received by the nodes 10 or that the segment controller 60 has transmitted the first message to the correct nodes 10 , i.e. to the target nodes of the protocol. After having determined that at least one verification was successful, the service center 80 transmits information for further steps of the protocol to the segment controller 60 (S 240 ). Thus, in step S 250 , the segment controller 60 can perform the next step of the protocol, e.g. transmitting a second message to the nodes 10 . Preferably the second message comprises the software image of the software update, which is stored by the nodes 10 in step 260 . In addition, some identifying means may be included in the first message and the second message, so that the nodes 10 can verify the content of the received second message before storing it (S 260 ). Then, in step S 270 , the nodes 10 transmit to the segment controller 60 second response messages, which dependent on the received content and the respective node identity like the first response messages. In step S 280 , the segment controller 60 aggregates the second response messages into a batch of messages and forwards it to the service center 80 . After successful verification by the service center 80 , the service center 80 provides a reboot key to the segment controller 60 for activating the new software (S 290 ). When receiving and successfully verifying the reboot key, the nodes 10 are rebooted in step 2100 . Optionally, the segment controller 60 may receive confirmation messages from the nodes 10 after rebooting and forward them in a further message batch to the service center 80 . For increasing security, also certain time intervals may be set for receiving expected messages. For instance, a maximum time interval may be set at the service center 80 for the initiation of the protocol in step S 200 and the provision of the reboot key in step S 290 . It is also to be understood that more than two steps of the protocol are controlled in this way, i.e. that there are further iterations like the steps S 200 to S 230 or S 240 to 280 . Therefore, according to the embodiment shown in FIGS. 2 and 3 , the nodes 10 report to the service center 80 via the segment controller 60 , which of the nodes 10 has received the message from the segment controller 60 and what they have received. Only after the service center 80 has verified correct protocol execution, it provides the segment controller 60 with information for further steps of the protocol. Since the segment controller 60 bundles the response messages of the single nodes 10 and forwards them in a batch message, the data traffic between the segment controller 60 and the service center 80 can be reduced. Thus, due to the dependence of the response messages of the nodes 10 on the node identity and on the content of the message received from the segment controller 60 , the segment controller 60 will only receive valid response messages, when performing the protocol correctly. Therefore, although the protocol is performed by a not fully trusted entity, i.e. the segment controller 60 , correct protocol execution can be stepwise enforced without requiring high data load on the connection to the service center 80 . In FIG. 4 , a more detailed example for the first embodiment of the present invention is shown. In this example, the service center 80 knows a commissioning key K com common to all nodes of the network, node identities or node specific keys K node of the network nodes 10 , a HASH-function such as SHA256 is used by the nodes in the network, a start value of the HASH-function a 0 , and at least one of an iteration number 1 of the HASH-function and a last used HASH-chain element a L . The network nodes 10 , in contrast, know the commissioning key K com , the HASH-function SHA256 of the network, a last element or anchor a N of the HASH-chain and the last HASH-chain element a L that has been disclosed. In FIG. 5 , the principle of a HASH-chain is illustrated. The HASH-chain includes N elements a i that are generated using a one-way HASH-function with a L =HASH(a L−1 ). Thus, each element a i of the HASH-chain can only be generated based on the preceding HASH-chain element a i−1 . Since only the service center 80 knows the initial HASH-chain element a 0 , only the service center 80 can generate the next HASH-chain element a i+1 . For authentication of an information, the service center 80 uses the HASH-chain elements a i in the opposite direction, as shown in FIG. 5 . For instance, the service center 80 includes the current HASH-chain element a L−1 in a message to the node 10 . Then, the node 10 , which only knows the last used HASH-chain element a L , can verify the message by checking whether a L =HASH(a L−1 ). By these means, information can be authenticated without need for public-key cryptography. As shown in FIG. 4 , the service center 80 initiates the execution of a software updating protocol performed by the segment controller 60 by transmitting a first message M 1 to the segment controller 60 . The first message M 1 includes a preack, the preack being the value of a function such as a message authentication-code function depending on a current HASH-chain element a L−1 and a fingerprint of the software update. Here, the fingerprint can also refer to a value of a function or a string. For instance, the preack may be obtained using the following expression: M 1:preack= HMAC ( SHA 256( E k ( SW ))∥salt, a L−1 ), wherein the two upright lines indicate concatenation, HMAC relates to a keyed HASH-message authentication-code, SHA256 is a HASH-function SHA-2 with a 256-bit fingerprint, E K relates to an encryption function based on an encryption key K, SW denotes the software update, salt is an at least 16 byte nonce specific for the software update and a L−1 is the current HASH-chain element. The encryption key K may be derived from the commissioning key K com and the salt, e.g. as K=HMAC(salt, K com ). The segment controller 60 forwards the message M 1 to the node 10 , which stores the preack. The preack is used for enabling verification of the software update and the origin of the message content in a subsequent step. Since the preack has only very small information amount, memory at the nodes can be saved. Then, the node 10 creates a response message M 2 based on the message content of the received message M 1 and the node specific key K node . For instance, the response message M 2 of the node 10 may include the result of following expression: M 2: SHA 256( M 1∥ K node ) In general, a message authentication code is derived from M 1 and K node . If the segment controller 60 does not receive a response message M 2 from an addressed node 10 , the segment controller 60 may request this node 10 to sent the response message M 2 . Possibly, a certain time interval is set at the segment controller 60 for defining a maximum time interval for receiving the response messages. After the segment controller 60 has received the response messages M 2 node _ 1 , . . . , M 2 node _ N from the respective nodes 10 , it transmits a message M 3 to the service center 80 based on the received response messages M 2 node _ 1 , . . . , M 2 node _ N . For instance, the segment controller 60 aggregates the response messages M 2 node _ 1 , . . . , M 2 node _ N , e.g. using the HASH-function: M 3: SHA 256( M 2 node _ 1 ∥ . . . ∥M 2 node _ N ) If the service center 80 has not received the message M 3 within a predetermined time, the service center 80 may request the message M 3 from the segment controller 60 . When receiving the message M 3 , the service center 80 can verify using the message M 3 that the correct target nodes 10 have been addressed and that all target nodes 10 have successfully received the first message M 1 . Then, the service center 80 transmits a message M 4 to the segment controller 60 including the encrypted software update E K (SW), the salt and the current HASH-chain-element a L−1 . The segment controller 60 calculates a fingerprint of the encrypted software update, e.g. SHA256(E K (SW)), and transmits a message M 5 to the node 10 including the fingerprint of the encrypted software update, the salt and the current HASH-chain element a L−1 . Then, the node 10 determines whether the value of the preack received in the message M 1 is identical to the result of a predefined function, when inputting parameters received with the message M 5 . Hence, in the example shown in FIG. 4 , the node 10 checks whether: preack== HMAC ( SHA 256( E K ( SW ))∥salt, a L−1 )) In addition, the node 10 determines whether the last used HASH-chain element a L can be derived by applying the HASH-function to the HASH-chain element a L−1 included in the message M 5 , e.g. whether SHA256(a L−1 )=a L . If both of these verification processes are successful, the node 10 accepts the fingerprint of the encrypted software update and the salt, which were received with the message M 5 , and switches to a software update mode. Moreover, the node 10 can now calculate the encryption key K based on the salt and the commissioning key K com . Meanwhile or afterwards, the segment controller 60 transmits a further message M 6 to the node 10 including the encrypted software update. If the node 10 can verify that the previously accepted fingerprint is identical to the calculated fingerprint of the encrypted software update received with the message M 6 , it will accept the software update and store the same. Instead of transmitting the messages M 5 and M 6 , however, the segment controller 60 may also just forward the message M 4 to the node 10 . Anyway, the node 10 will return a second response message M 7 to the segment controller 60 including a fingerprint of the received encrypted software update, the salt, the current HASH-chain element a L−1 and the node specific key K node . For instance, the message M 7 may include: M 7: SHA 256( SHA 256( E K ( SW ))∥salt∥ a L−1 ∥K node ) The segment controller 60 collects the response messages M 7 node _ 1 , . . . , M 7 node _ N from all nodes 10 and aggregates them into a batch message M 8 , which is transmitted to the service center 80 . After having received and verified that the message M 8 is correct, i.e. that the segment controller 60 has executed the protocol steps correctly, the service center 80 provides the segment controller 60 with message M 9 including the next HASH-chain element a L−2 . This is used by the segment controller 60 as a reboot key for rebooting the target nodes 10 and activating the new software. Thus, in the last step, the segment controller 60 forwards the message M 9 including the reboot key or HASH-chain element a L−2 to the network nodes 10 . When verifying that the HASH-chain element key a L−2 is valid, the network nodes 10 can be rebooted in a synchronized manner and the new software on the network nodes 10 is activated. Possibly, a confirmation of the successful update and rebooting is sent from the nodes via the segment controller 60 to the service center. It should be noted that instead of the HASH-function SHA256, any other cryptographic function can be used to generated a message authentication code. Thus, a fingerprint of a software update can be distributed to predetermined target nodes 10 or to all nodes 10 of the network and the nodes 10 can be rebooted in a synchronized manner. This approach uses two links of the HASH-chain to sign the software fingerprint and the rebooting message, respectively. Moreover, the software update itself is protected with a secret encryption key K specific for the software update, so that the segment controller 60 has no access to the software update. Therefore, according to the first embodiment of the present invention, a secure and economic protocol for software updates can be provided without the need of public key cryptography. However, this embodiment has a few limitations. For instance, it requires that the service center 80 is online, since a software update can only be finished after providing the reboot key in the message M 8 . Moreover, the protocol can be manipulated in order to store another software on the network nodes 10 , yet without being able to activate this software. This fake software upload attack may occur as follows: After reception of message M 4 , the manipulated segment controller 60 can send a number of fake messages M 1 , so that the nodes 10 have to drop the actual message M 1 provided by the service center 80 . Then, the segment controller 60 can generate a fake message M 5 based on a fake software update. If the segment controller has even access to the commissioning key K com , the segment controller 60 may be able to generate a valid software encryption key K using the salt received with the message M 5 from the service center 80 and put another software on a node 10 . Generally, however, the segment controller 60 will have no access to the commissioning key K com and can hence create no valid encryption key K. In this case, the segment controller 60 can only fill the memory of the node 10 with useless information. Yet, in any of these cases, the segment controller 60 cannot activate the fake software, because it lacks the HASH-chain element a L−2 as reboot key. In FIG. 6 , a second embodiment of the present invention is illustrated, which can overcome at least some of these drawbacks of the first embodiment. FIG. 7 is a schematic view of the embodiment described with respect to FIG. 6 indicating the direction of communication between the different entities. The main difference of this embodiment to the first embodiment is that the segment controller 60 is provided with all information for protocol execution with a first message from the service center 80 , wherein the information for different protocol steps is encrypted based on different keys. By these means, the data traffic between the service center 80 and the segment controller 60 can be minimized, so that the service center 80 only has to trigger the software update protocol and optionally receive an acknowledgement, once the protocol is finished. Thus, this allows for offline operation of the service center 80 , since the service center 80 only has to provide the first message M 0 and can then be offline for the rest of the time. In a first step S 500 of FIG. 6 , the service center 80 provides the segment controller 60 with all information required to execute a software update protocol. Yet, only a first part of this information is not encoded and can thus be used by the segment controller 60 . The segment controller 60 forwards this part of information to the respective target nodes 10 (S 510 ). Each node 10 returns a response message based on the received message content and its node identity (S 520 ). Using the response messages from the nodes 10 , the segment controller 60 is now able to generate a first encryption key (S 530 ) in order to decode a further part of protocol information. Since the response messages depend on the node identity and on the message content transmitted to the node and since the segment controller 60 is only able to decode the next part of protocol information with valid response messages, the segment controller 60 is forced to provide the correct content to the correct nodes 10 in order to be able to proceed with the protocol. Using the generated encryption key, the segment controller 60 can decode the second part of the protocol information and forward it to the network nodes 10 in step S 540 . Possibly, the network nodes 10 verify the second part of the protocol information before storing it (S 550 ). In step S 560 , the nodes 10 transmit second response messages to the segment controller 60 . Based on the second response messages, the segment controller 60 can generate the second encryption key (S 570 ) and decode a further part of the protocol information. These steps may be repeated, until the segment controller 60 can decode a reboot key included in the protocol information received from the service center 80 and forward the reboot key to the nodes (S 580 ). If the reboot key is determined to be valid, the nodes 10 are rebooted and the new software is activated (S 590 ). Preferably, the protocol is completed by transmitting a conformation message to the service center 80 in step S 5100 . This confirmation message may relate to acknowledgements of the nodes 10 aggregated by the segment controller 60 , which may respectively include the node identity or a node specific key and a fingerprint of the activated software. By means of this confirmation message, the service center 80 can verify whether all nodes 10 have been successfully updated and whether the correct software has been used. Hence, also in this embodiment, correct protocol execution by the segment controller 60 is enforced step by step and activation of new node software is only possible after successful verification of the single protocol steps. In FIG. 8 , an example for the second embodiment according to the present invention is illustrated in more detail. Similar to the example illustrated in FIG. 4 , the service center 80 knows the commissioning key K com of the network, the node specific keys K node or node identities, the HASH-function of the network, e.g. SHA256, the initial HASH-chain element a 0 and the last used HASH-chain element a L or an iteration number of the HASH-function 1 . The node 10 knows about its node specific key K node or its node identity, the commissioning key K com , the HASH-function SHA256, the last element or anchor of the HASH-chain a N and the last used HASH-chain element a L . For starting the protocol, the service center 80 transmits a first message M 0 including the preack and at least two further information blocks, which are encrypted based on different encryption keys K i . In the example shown, only two further information parts are shown, encrypted with encryption key K 1 and K 2 , respectively. Thus, the message M 0 may comprise: M 0:preack; E K1 ( SHA 256( E k ( SW )),salt, a L−1 ,E k ( SW )); E K2 ( a L−2 ) With the message M 0 , the segment controller 60 should be able to execute the protocol, e.g. for updating software on the nodes 10 , without further interference from the backend. However, since only the preack is not encoded, the segment controller 60 can only use the preack in the beginning. Thus, the segment controller 60 transmits a message M 1 including the preack to the node 10 . The preack value has been generated by the service center 80 based on the salt or random number specific for the software update, the current HASH-chain element a L−1 and the fingerprint of the encrypted software update. For instance, the preack value may be derived as described above for the first embodiment. After receiving the preack with the message M 1 , the nodes 10 store the preack and return a first response message M 2 that might be dependent of a fingerprint of the content of the message M 1 and the respective node specific key K node . For instance, the message M 2 may include the value of the function SHA256(M 1 ∥K node ). As described above, predefined time intervals may be set also in this embodiment for defining a maximum time interval between two messages or protocol steps. For instance, if the segment controller 60 does not receive the response messages M 2 node _ 1 , . . . , M 2 node _ N from all the nodes 10 within a predefined time interval, the segment controller 60 may request the response message M 2 from the corresponding node 10 . When having received all response messages M 2 node _ 1 , . . . , M 2 node _ N , the segment controller 60 can determine a first encryption key K 1 , e.g. using a key derivation function as the next one: K 1= SHA 256( M 2 node _ 1 ∥ . . . ∥M 2 node _ N ), Using this encryption key K 1 , the segment controller 60 can decrypt the second part of the protocol information, in the above example relating to the fingerprint of the encrypted software update SHA256(E k (SW)), the salt, the current HASH-chain element a L−1 and the software update E k (SW) encrypted with the encryption key K. The encryption key K can be based on the commissioning key K com and the salt, as described above. Then, the segment controller 60 forwards the decrypted fingerprint of the encrypted software update SHA256(E k (SW)), the salt and the current HASH-chain element a L−1 in a message M 3 to the node 10 . After having received the message M 3 from the segment controller 60 , the node 10 determines whether the preack value received with the message M 1 is identical to a predetermined function of the fingerprint of the encrypted software update, the salt and the current HASH-chain element a L−1 and whether the HASH-chain element included in the message M 3 is valid. If this is the case, the node 10 accepts the salt and the fingerprint of the encrypted software update included in the message M 3 as software fingerprint and switches to the software update mode. Based on the salt and the commissioning key K com , the node 10 can calculate the encryption key K. Then, the segment controller 60 transmits a further message M 4 including the software update encrypted with the encryption key K to the node 10 . If the result of a given fingerprint function of the received encrypted software update is identical to the previously defined fingerprint, e.g. if fingerprint=? SHA256(E K (SW) received )), the node 10 accepts the software update. Instead of transmitting two messages M 3 and M 4 to the node 10 , the segment controller 60 can also transmit only one message including the fingerprint of the encrypted software update, the salt, the current HASH-chain element a L−1 and the encrypted software update. In any case, the node 10 transmits a response message M 5 to the segment controller 60 including a value calculated based on the fingerprint of the encrypted software update, the salt, the current HASH-chain element a L−1 and the node specific key K node . For instance, the value may be calculated based on the following expression: SHA 256( E K ( SW ))∥salt∥ a L−1 ∥K node ) In case the segment controller 60 does not receive the response message M 5 from the respective mode 10 within a predefined time interval, the segment controller 60 may request this response message M 5 . Using the received response messages M 5 node _ 1 , . . . , M 5 node _ N , the segment controller 60 can compute the second encryption key K 2 and decrypt the third part of protocol information that was included in the message M 0 from the service center 80 . For instance, the encryption key K 2 can be calculated based on the following expression: K 2= SHA 256( M 5 node _ 1 ∥ . . . ∥M 5 node _ N ) Optionally, the second encryption key K 2 may also be used by the segment controller 60 as a conformation message to be transmitted to the service center 80 . In a final step, the segment controller 60 transmits a message M 7 to the node 10 including a next HASH-chain element a L−2 , which is used as a reboot key and was included in the third part of protocol information. The node 10 verifies the reboot key by determining whether the HASH-chain element is correct, e.g. by determining whether: SHA 256( a L−2 )== a L−1 If this is the case, the node 10 is rebooted and the new software is activated. The gist of this embodiment relies on the fact that the information that the segment controller 60 has to distribute to the network nodes 10 in messages M 3 , M 4 and M 7 is encrypted with different keys K 1 and K 2 . These encryption keys depend on the acknowledgements from the respective network nodes 10 . Thus, the segment controller 60 can only decrypt and therefore use the next protocol information, if all network nodes 10 send the expected acknowledgements or response messages. In this way, correct operation is enforced and ensures the right behavior of the segment controller 60 : If the segment controller 60 does not follow the protocol, it cannot use the protocol information for the next protocol steps because the information is encrypted. If the segment controller 60 behaves in the right way, it can decrypt the information and follow the expected protocol operation. Moreover, communication with the service center 80 can be reduced, since the communication takes mainly place between the partially trusted segment controller 60 and the nodes 10 without reducing system security. This allows off-line operation of the service center 80 . Therefore, according to the present invention, services from the backend can be provided by enforcing correct operation of an intermediate entity that is not fully trusted. Moreover, data traffic to the backend and operations at the backend can be minimized, thus simplifying the network management. Since the communication link between the segment controller 60 of the network and the service center 80 at the backend often relies on third party infrastructures such as GPRS, this also reduces maintenance costs of a network. The embodiments of the present invention are in particular suitable for large wireless networks such as outdoor lighting systems for enabling services from the service centre 80 , e.g. for updating dimming patterns of luminaire nodes 10 in a street lighting system or for transmitting other configuration or commissioning information. Here, it is important to ensure that only nodes 10 of the network receive the information. However, the embodiments of the present invention are also applicable to any other protocol, application, system or network exhibiting a communication and trust pattern as described above, e.g. a lightweight ZigBee-IP.
For secure configuration of network nodes from a backend with low connectivity requirements and workload at the backend and reduced communication overhead, a system, a control unit for a segment controller and a method for secure protocol execution in a network are provided, wherein protocol information is provided to a segment controller ( 60 ) for controlling a node ( 10 ) and a protocol is performed based on the protocol information to control the node ( 10 ), at least one response message of the node ( 10 ) being required at the segment controller ( 60 ) for performing one or more steps of the protocol.
53,787
TECHNICAL FIELD This invention relates generally to gas burners, and more particularly gas burners having burner elements made of woven ceramic fibers. BACKGROUND OF THE INVENTION Gas burners having radiant burner elements have long been used to heat fluids in commercial, industrial and residential applications. Such applications include areas as diverse as home heating and commercial deep fat fry cookers. In one known form of gas burner, a combustible gas or air-gas mixture is passed through a burner element including one or more flat plenum clay tiles. The gas is burned on the surface of the element. Such burners have sometimes been found to be undesirable for many purposes, because they are inefficient as they often loose heat to the environment and undesirably heat incorrect sections of the apparatus in which they are employed. U.S. Pat. No. 4,919,609 (Sarkisian et al., Apr. 24, 1990) and U.S. Pat. No. 4,397,299 (Taylor et al., Aug. 9, 1983) disclose two examples of gas burners employing gas-permeable tiles. It has also been found that, under some circumstances, gas burners more efficiently consume the fuel gas when their burner elements are configured as cylinders. While various methods have been employed to construct cylindrical burner elements, their use has been found to require a careful balance of pressurized gases to ensure that the supplied pressure is uniform, so that the flame on the surface of the burner element does not creep back into the burner, particularly into any mixing chamber contained within the burner element, and explode or backflash. The following criteria are believed to be important in selecting the material to be used for distributing gas in a gas burner element: 1. The material needs to permit a low pressure drop across the burner element. 2. The material must have uniform openings for evenly distributing the gas mixture at the surface of the burner element. 3. The material must have good insulative properties in order to prevent backflashing. 4. The material must support ignition and combustion only on its downstream surface, typically its outer surface. This criterion is particularly important when the combustion gas is propane. Propane gas has a higher flame velocity than natural gas (about 2.85 feet per second to about 1 foot per second), so that its flame has a higher tendency to creep into the pores of a burner element. Some prior attempts to meet these criteria have involved the use in burner elements of ceramic fibers in various configurations, such as in felts, sintered webs, random orientations and ceramic fiber filters. Such attempts often encountered drawbacks such as non-uniform pore sizes, high backpressures, and backflashing when flames crept back into the mixing chamber or other source of the combustion gas. The last-mentioned type of ceramic fiber burner element, the filter, is conventionally made by placing short, wetted ceramic fibers, and (optionally) a binder, over a screen of a particular mesh size, and vacuuming out the moisture to form a cylinder of fibers. Such a construction is subject to several of its own particular drawbacks. Such fibrous elements lack integrity. Moreover, because the fiber matrix must be thin enough to allow gas to pass through it, the strength of the matrix is compromised and the material degrades during use. Furthermore, with both filter-like constructions and constructions such as felts, the burner elements easily clog with dust and other impurities carried by the air and combustion gas, so that the filters require increased pressures to insure an adequate flow of combustion gas through the elements in which they are employed. Felt-type ceramic fiber burner elements are shown in U.S. Pat. No. 4,604,054 (Smith, Aug. 5, 1986), U.S. Pat. No. 3,425,675 (Twine, Feb. 4, 1969), U.S. Pat. No. 3,208,247 (Weil et al., Sep. 28, 1965) and U.S. Pat. No. 3,191,659 (Weiss, Jun. 29, 1965). Burner elements constructed from vacuum-drawn ceramic fibers are disclosed in U.S. Pat. No. 4,883,423 (Holowczenko, Nov. 28, 1989), U.S. Pat. No. 4,809,672 (Kendall et al., Mar. 7, 1989), U.S. Pat. No. 4,746,287 (Lannutti, May 24, 1988), U.S. Pat. No. 3,275,497 (Weiss et al., Sep. 27, 1966), and U.S. Pat. No. 3,179,156 (Weiss et al., Apr. 20, 1965). A burner element incorporating sintered reticulated ceramic webs is shown in U.S. Pat. No. 4,568,595 (Morris, Feb. 4, 1986), while U.S. Pat. No. 4,519,770 (Kesselring et al., May 28, 1985) and U.S. Pat. No. 4,416,618 (Smith, Nov. 22, 1983) disclose burner elements including ceramic fibers in random orientations. Other burner element constructions are shown in U.S. Pat. No. 4,898,151 (Luebke et al., Feb. 6, 1990) and U.S. Pat. No. 3,726,633 (Vasilakis et al., Apr. 10, 1973), as well as in Japanese published applications JP 61-143613 (NGK lnsulators Ltd., published Dec. 18, 1984) and JP 61-070313 (NGK Insulators KK, published Apr. 11, 1986), and in French Patent No. FR 1,486,796 (Sangotoki Kabushiki Kaisha, Jun. 30, 1967). One recent attempt at obviating the problems encountered with these or similar burner elements has been to construct burner elements from ceramic foams. Ceramic foams are made by soaking a polyurethane foam or other combustible foam material with a liquid ceramic material, drying off the mixture, and burning off the foam material, leaving a porous ceramic structure. The number of pores per inch in the resulting burner element can be selected by choosing the proper pore size of the precursor foam. While ceramic foam materials were first developed for filtering high temperature casting alloys, the use of such ceramic foams as burner elements is described in the present Applicant's prior U.S. Pat. No. 4,900,245 (issued Feb. 13, 1990). Applicant's device as disclosed in that patent has found significant utility in devices such as commercial deep fat fryers. The burner element is made from a reticulated ceramic foam having a porosity of about 40 to about 100 pores per linear inch, formed about a perforate cylindrical metal diffuser. A high emissivity coating is placed on the reticulated ceramic foam burner element for substantially decreasing the likelihood of backflashing. Applicant's prior burner element functions admirably for its intended purpose. However, its use in practice has been found to be subject to some drawbacks. Like other ceramic foam elements, some shrinkage and brittleness has been encountered. When the burner elements need to be replaced due to routine maintenance, moving, or unrelated repair of the fryers in which they are employed, the elements sometimes break because of this brittleness. Moreover, control of the pore size is perhaps not as precise as would be desired in order to insure that enough air is supplied to the combustion gas and avoid backflashing. Even when these problems are not encountered, the ceramic foam eventually melts down and becomes more brittle when the supply of air decreases, as it periodically may do. As a practical matter, once the ceramic foam elements are removed a single time from the device in which they are employed, they are often not subject to ready reuse. Accordingly, it is an object of the present invention to provide a highly efficient radiant heat burner element for a fluid immersion apparatus or other device, which will uniformly burn combustion gases without backflashing. It is another object of the present invention to provide a radiant heat burner element of lower shrinkage and lower brittleness than encountered with prior ceramic burner elements. It is a further object of the present invention to provide a ceramic burner element which is readily subject to reuse and which does not easily break during replacement. It is also yet another object of the present invention to provide a radiant heat burner element which is more reliable and less subject to clogging than have been past ceramic burners. SUMMARY OF THE INVENTION In accordance with the preferred embodiment of the invention, these and other objects and advantages are addressed as follows. The present invention solves the problems of control of pore size and breakage of brittle ceramic burner elements by providing a gas burner comprising a hollow burner element made from woven ceramic fibers. The weave of the element is selected to have a predetermined gas permeability which matches the flow rate, composition and backpressure of the combustible gas being burned, so as to allow burning of the combustible gas on a surface of the burner element, without significant backflashing. The ceramic fibers are preferably formed as a cloth of fibers of materials such as a metal oxide, alumina, quart, or vitreous silica, most preferably of alumina-boria-silica. The cloth is preferably about 0.1 to 4.0 millimeters thick and is characterized by a pore size of 0.01 to 0.06 inches, so as to have a gas permeability of about 25 to 500 cubic feet per square foot per minute. In a first preferred embodiment, the woven fibers of the burner element are supported by a metallic layer support, such as a coil spring or a wire mesh cylinder, about which the cloth is wrapped. The open end of the coil spring or mesh cylinder is closed by a ceramic cap sealed to the cylinder or coil spring by a liquid ceramic. When the ceramic fibers are configured as a sheet of cloth, the abutting ends of the cloth are together by ceramic fiber threads, preferably of the same composition as the cloth itself, to form a seam. In another preferred embodiment of the present invention, the woven ceramic fiber is formed into a self-supporting element, for example, as a plurality of cloth layers joined together by ceramic fiber threads, so as to prevent movement of the layers relative to one another. Preferably, the ceramic fiber threads are composed of the same ceramic fiber as the cloth itself. While a plurality of individual, discrete ceramic fiber layers can be employed in this fashion, most conveniently the burner element can be formed as a spiral wrap of a single piece of cloth, forming plural layers. The open end of the element is again closed by a ceramic cap and sealed to the woven fiber with a liquid ceramic, or can be pinched closed by tacking with ceramic fiber or other heat-resistant threads. A variety of burner element shapes are contemplated within the invention, including cylindrical, tubular, and relatively flattened shapes. The present invention also encompasses a gas burner including a burner element of the type disclosed, as well as an ignition element positioned adjacent a surface of the burner element through which the combustible gas passes, and means adapted to supply combustible gas and air to the burner element. The invention is also directed to an infrared heater fueled by a flowing combustible gas, which comprises the burner and ceramic fiber element described above, the disclosed ignition element and gas and air supply means, and a metal tube disposed about and spaced from the burner element, so as to define a plenum (between the burner element and the tube) to which either air or combustion gas is supplied. In yet another embodiment, the invention comprises a fluid immersion apparatus such as a deep fat fryer in which the metal tube of the heater forms part of the fluid tank of the apparatus, preferably part of one of the walls of the fluid tank. The present invention enjoys significant advantages due to its use of a woven ceramic fiber burner element. The use of such a burner element provides a significant cost saving throughout the lifetime of the apparatus in which the burner and burner element are used. One way in which cost should be saved is in an anticipated reduction in the need for periodic maintenance of the burner; since the woven ceramic fiber burner element has a pore size greater than the pore size of prior ceramic felts or vacuum-drawn fiber elements, less clogging of the burner element from contaminants in the combustible gas will be encountered. A second way in which cost is saved lies in the flexibility of the ceramic woven fibers making up the burner element with respect to one another, so that the brittleness encountered in prior ceramic foam burner elements is avoided. The woven ceramic fiber burner elements can be withdrawn from a fluid apparatus such as a commercial deep fat fryer without damage; even if the burner element is knocked against a hard object, the worst that should usually happen is that the element or its supporting wire coil or mesh needs to be pushed back into its original shape. The impact, which would otherwise irreparably damage a ceramic foam burner element, is rendered of no consequence. The use of the woven fiber ceramic burner element also allows a burner, heater or fluid apparatus incorporating the burner element to achieve the other advantages and objects described above. BRIEF DESCRIPTION OF THE DRAWINGS The nature and extent of the present invention will be clear from the following detailed description of the particular embodiments thereof, taken in conjunction with the appendant drawings, in which: FIG. 1 is a perspective view of the preferred embodiment of the present invention; FIG. 2 is a cross-sectional view of the embodiment shown in FIG. 1; FIG. 3 is a partial, perspective view of a portion of the preferred embodiment of the present invention; FIG. 4 is a partial, perspective view of another preferred embodiment of the present invention, similar to FIG. 3; FIG. 5 is a perspective view of a portion of another preferred embodiment of the present invention; FIG. 6 is a perspective view of a portion of another preferred embodiment of the present invention; and FIG. 7 is a perspective view of a portion of another preferred embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION With reference first to FIGS. 1 and 2, a burner 10 according to the present invention is shown in conjunction with a fluid immersion apparatus such as a deep fat fryer 12. The fryer includes a walled tank 14 defining a chamber 16 containing a fluid 18 therein, such as liquefied fat. The fryer 12 includes an infrared heater 20 which incorporates the burner 10 and which has an outer metal tube 22 positioned adjacent to and preferably forming part of one of the walls 24 of the tank 14. The burner 10 is positioned within the tube 22 so as to heat the tube 22, which in turn heats the fluid 18 contained in the tank 14. With reference now to FIG. 3, the burner 10 includes a burner element 23 formed as a piece of a woven ceramic fiber cloth 24 wrapped about a support 26 such as a wire mesh cylinder 27. The cloth piece 24 is rectangular in shape and has abutted edges 28 connected together at spaced locations by ceramic fiber threads 30, preferably of the same composition as the cloth piece 24. Alternatively, the threads 30 can be made of a different non-reactive, heat-resistant material, or a metal wire. The burner 10 also comprises a base 21 to which the wire mesh cylinder 27 and the woven ceramic cloth piece 24 are affixed. The base 21 is preferably composed of reinforced ceramic. The woven ceramic fiber burner element 23 is sealed to the base 21 by a layer of a conventional liquid ceramic 32. The burner 10 further includes a cap 34 sealed to the cloth 24 by another layer 36 of a conventional liquid ceramic. The metal tube 22 of the infrared heater 20 is disposed about and spaced from the burner element 23 so as to define a plenum 38 between the woven ceramic burner element 23 and the metal tubes 22. The burner 10 includes supply means such as ports 40 and 42 formed in the base 21 for supplying combustion gas and air, respectively, to the interior 44 of the burner element 23 and to the plenum 38. The ports are connectable to conventional gas and air supply lines (not shown), for example, to tanks of air and combustible gas. An ignitor element 45 is carried by the burner 10 and is located closely adjacent to one surface of the burner element 23, for example, its outer surface 46. Upon activation of the ignitor element 45, combustion of the supplied gas will occur on the outer surface 46 of the burner element 23. The gas and air supplies to the ports 40 and 42 can of course be reversed, and the ignitor element 45 positioned closely adjacent to an interior surface 48 of the burner element 23, to yield combustion on the interior surface 48. The gas permeability of the ceramic fiber weave making up the burner element 23 is selected to prevent any appreciable or significant backflashing during combustion. The gas permeability of a woven cloth made of ceramic fibers is determined by the pore size and the thickness of the cloth. The pore size and cloth thickness will affect the backpressure in the combustion gas supply required for operation. The gas permeability must be selected to match this backpressure, as well as the composition and the combustion gas flow rate. For example, when a burner element in accordance with the present invention is used in a conventional deep fat fryer of a size useful for restaurant service, the gas permeability of the burner element is preferably between 25 and 500 cubic feet per square foot per minute measured at 0.5 inches of water column pressure (w.c.), depending upon the gas employed. Multiplying the gas permeability (in cubic feet per square foot per minute) by 32.05 yields an approximate value for the maximum useful heat output from the burner element 23 in btu-hours per square inch. The useful range of gas permeabilities of the burner element 23 varies with the particular gas combusted because different gases have different flame velocities; different gases therefore require different mixture velocities in order to prevent backflashing (the unintended creeping of the flame back into the burner element 23). However, the gas mixture velocity at a given pressure depends upon and can thus be controlled by the gas permeability of the burner element 23. The gas permeability of a burner element 23 useful for combusting natural gas is a convenient reference for permeabilities useful with other gases. For example, it is desirable that when natural gas is to be combusted, the gas permeability of the burner element 23 is between 25 and 500 cubit feet per square foot per minute (0.5 inches water column), and preferably about 118 cubic feet per square foot per minute. Natural gas has a flame velocity of about 1 foot per second. Combustion gases containing molecular hydrogen, in contrast, have flame velocities on the order of 9 feet per second. Accordingly, a burner element 23 useful for combusting a hydrogen-containing gas mixture such as manufactured gas (a commercially available mixture containing about 50 percent molecular hydrogen plus some natural gas and carbon dioxide) preferably has a gas permeability of no more than 42 percent of the gas permeability of a comparable element used for combusting natural gas. Thus, when manufactured gas is used, it is desirable that the gas permeability of the burner element 23 is no more than 210 cubic feet per square foot per minute, and preferably about 50 cubic feet per square foot per minute. The desirable and preferred permeabilities for a burner element 23 for combusting propane are between those of natural gas and manufactured gas, since its flame velocity is between their flame velocities. These gas permeabilities can typically be achieved in a burner element constructed from a woven ceramic fiber cloth having a pore size of 0.01 to 0.06 inches and a thickness of 0.1 to 4.0 millimeters. The mesh size of the support 26 should be selected so that it has at most an inconsequential effect on the gas permeability of the burner element 23, as long as it provides adequate support to the burner element 23. For example, the mesh size of the cylindrical screen 27 should preferably be at least a few times greater than the pore size of the cloth 24 wrapped about it. Above such a mesh size, the mesh size is not critical. The ceramic fibers which are woven to form the burner element 23 of the present invention can be composed of metal oxide, alumina, quartz, vitreous silica, or other heat resistant ceramic that can withstand up to 2300° F. It is particularly preferred that the fibers are made of a specific alumina-boria-silica ceramic fiber, incorporated into a ceramic fabric and sold under the brand name "Nextel 312" by 3-M Company, St. Paul, Minn. "AMISIL" brand (Auburn Manufacturing Corporation), "Fiberfrax Woven Textile" brand and "Flexweave" brand (both from Carborundum Corporation) fabrics are also preferred woven cloths for constructing the burner element 23. Four preferred varieties of Nextel brand ceramic fabrics are woven as double layer weave, five harness satin weave, crow foot satin weave and plain weave, all of which are useful in the present invention. The thread counts for these varieties range from 19 to 40 per inch warp, and 17 to 20 per inch fill, yielding air permeabilities of from 36 to 240 cubic feet per square foot per minute, depending upon the denier of the ceramic yarn employed in making the fabrics. The tensile strength of the ceramic fibers used to make the woven burner element 23 are not believed to be critical to the utility of the fibers in the present invention, so long as the brittleness encountered with ceramic foams or the like is avoided. The fibers of the preferred Nextel 312 brand ceramic cloths have a tensile strength of 250,000 psi. The preferred Nextel fabrics also have a continuous use temperature of 2200° F. and a short term use temperature of 2600° F., with a melt temperature of about 3272° F. The physical configuration of the burner element 23 can be chosen as may be advantageous for the particular environment of use contemplated. When disposed about a support 26, the burner element 23 will preferably conform to the shape of that support 26. Although the support 26 has been disclosed in the first preferred embodiment of the invention as a wire mesh cylinder 27, as shown in FIG. 4, the support 26 can alternatively comprise a wire coil spring 50 instead of the cylinder 27. Moreover, with either the cylinder 27 on the spring 50, the burner element 23 can alternatively be configured as a woven ceramic fiber cloth tape 52 wrapped at a diagonal pitch on the support 26, such as the spring 50. Adjacent edges 54 of the cloth tape 52 abut one another and are joined at spaced locations by threads 56, again, of the same or a different ceramic fiber as the cloth tape 52, or of wire or other heat resistant material. Of course, the shape of the support 26 allows other shapes to be employed for the burner element 23, for example, closed, pinched-end tubular 64 (FIG. 6) or relatively flattened 66 (FIG. 7) shapes. The support 26 can be rigid, as when the coil spring 50 is stiff, or the support 26 can be semi-rigid, as when the mesh cylinder 27 is used. Indeed, the burner 10 need not include any support 26 at al. For example, in another preferred embodiment of the present invention as disclosed in FIG. 5, the burner element 23 can be configured as a plurality of layers 58 of a woven ceramic fiber cloth, such as provided by the spiral wrapping of a single piece 60 of woven ceramic fiber cloth upon itself. The layers 58 are fixed with respect to one another at spaced locations by threads 62 like those described earlier. Movement of the layers 58 with respect to one another thus being prevented, the burner element 23 so formed possesses adequate ridigity for use. Its open ends are preferably closed by the ceramic base 21 and the end cap 34 disclosed above, and sealed to them in the fashion described before. The present invention thus provides a woven ceramic burner element, an infrared heater including the burner element, and a fluid immersion apparatus incorporating the heater, which address and meet the objects mentioned above, and which achieve superior efficiency, uniformity, reliability and durability in combusting fuel gas for heating. While the invention has been described in terms of several specific embodiments, it must be appreciated that other embodiments could readily be adapted by one skilled in the art. Accordingly, the scope of the invention is to be limited only by the following claims.
An infrared heater for a fluid immersion apparatus such as a commercial deep fat fryer includes a burner whose burner element is made from woven ceramic fibers, preferably formed as a cloth. The burner can also include a wire mesh or screen for supporting the cloth; alternatively, the cloth can be made self-supporting through the wrapping or affixing of several cloth layers together. The burner element possesses a predetermined gas permeability adequate to avoid any significant backflash during the use of the burner. The gas permeability is selected to match the flow rate, composition and backpressure of the selected gas, and takes into account the insulative capacity of the fiber weave employed. The resulting burner construction is substantially more durable and resistant to damage during replacement or inspection than are burners having conventional ceramic elements, such as foams, felts, or the like.
24,661
FIELD OF THE INVENTION [0001] The present invention relates to high-content cellular screening assays, and more particularly to assays for screening for cell stimulation agents and employing multiplex monitoring of reporters in single cells or single populations of cells. BACKGROUND TO THE INVENTION [0002] The process of discovering a new therapeutic agents, traditionally involves the following stages: i) identification of a drug target, ii) validation of the target, iii) screening for compounds that affect the activity of the target, iv) testing lead compounds for toxicity, v) testing lead compounds for side effects, and vi) examining the metabolism and stability of lead compounds, in the patient or in an appropriate model system. Once a potential therapeutic target has been identified and validated, the initial stage of drug discovery requires the screening of often hundreds of thousands of compounds to identify those that regulate the target in the appropriate therapeutic manner. This screening process requires the development of assay techniques which can quickly and inexpensively measure the potency of compounds that regulate the target factor of interest. These high-throughput screening assays can take various forms that include either cell-based or biochemical assays that often rely on colorimetric, fluorescence, radiometric or luminescence-based detection in order to measure receptor activation, RNA, protein concentration, enzyme activity or the physical interaction of proteins to form a functional complex. A constant challenge facing the drug discovery field is to increase the speed and efficiency by which potential lead compounds are identified from the tens of thousands of chemical compounds tested in compound library screens, and thereafter optimised into new pharmacological agents. A common problem encountered during lead optimisation is that the drug candidate originally identified by virtue of its ability to modulate the activity of one or a few specific target proteins also often has one or more contra-indications. Detrimental effects can be caused by the lack of specificity of a compound, thus causing the agent to target a broad range of factors and biological processes in addition to the intended target. Other areas of concern include drug toxicity and metabolism, such that compounds that elicit toxic responses can disrupt normal cellular and tissue function and lead to cell death. Certain compounds have also been demonstrated to regulate their own metabolism, thereby stimulating the breakdown of the target agent and excretion from the body leading to decreased drug efficacy. [0003] Current high throughput screening assays generally focus on measuring the effectiveness of compounds in regulating the activity of a single factor or target, and rely on extended processes of secondary screening and follow-up analyses in order to determine other characteristics of compound function, such as specificity and toxicity. This increases the amount of time and cost required to develop and optimize compounds into drugs with high therapeutic indices (i.e. high efficacy, high specificity, low toxicity). As a result, many compounds, originally selected because of their activity on the target, are eventually discarded because of subsequently discovered side effects, resulting in wasted effort on evaluating drug leads which ultimately prove unsatisfactory. [0004] In the process of drug discovery and lead optimisation, there is a requirement for faster, more effective, less expensive and especially information-rich screening assays that provide simultaneous information on various compound characteristics and their affects on various cellular pathways (i.e. efficacy, specificity, toxicity and drug metabolism). [0005] One approach that has been previously taken, for example, is described in US 2005/0164321 (Promega Corp) which describes a method using enzyme-mediated reactions for multiplex luminogenic and non-luminogenic assays in the same well to detect the amount (e.g., activity) or presence in a sample of one or more moieties, including cofactors for enzymatic reactions such as ATP, proteins (peptides or polypeptides) that bind to and/or alter the conformation of a molecule, e.g., proteins that modify or cleave a peptide or polypeptide substrate, or a molecule which is bound by and/or altered by a protein. [0006] WO 98/58074 (Allelix Biopharma) describes assay methods and compositions useful for screening chemical compounds to identify ligands for receptors including G-protein coupled receptors. The invention employs cells in which a receptor of interest is coupled through a second messenger system to an ion channel that is gated by cyclic nucleotide. Receptor stimulation causes the second messenger system to produce cyclic nucleotide, which results in a measurable ion influx through the channel. The invention also provides a multiplexed system in which mixed cell cultures expressing different receptor types are loaded with different fluorescent reporters of ion influx. [0007] EP1439384 (Cellomics Inc) provides methods and analytical systems for the determination of the distribution, environment, or activity of fluorescently labelled reporter molecules in cells for the purpose of screening large numbers of compounds for those that specifically affect particular biological functions. [0008] Bertelsen, M., (Methods in Enzymology, (2006), 414, 348-363) describes multiplex analysis of inflammatory signalling with intracellular protein translocation using a high-content imaging system. [0009] Howell, B. J. et al. (Methods in Enzymology, (2006), 414, 284-300, 2006) describe the development and implementation of multiplexed cell-based imaging assays for monitoring cell proliferation, cell cycle stage and apoptosis employing fluorescence microscopy. [0010] Nickischer, D. et al. (Methods in Enzymology, (2006), 414, 389-418) describe the development and implementation of three mitogen-activated protein kinase (MAPK) intracellular signalling pathway imaging assays to provide MAPK module selectivity profiling for kinase inhibitors: MK2-EGFP translocation, c-JUN and ERK activation. [0011] Hanson, B. et al. (J. Biomolecular Screening, (2006), 11, 644-651) describe multiplex intracellular assays through the combination of a fluo-4 calcium mobilisation assay and the beta lactamase reporter system, enabling two G-protein coupled receptor assays drug screens with one cell line. [0012] Jonas, J-C. et al. (Diabetes, (1998), 47, 1266-1273) describe the temporal and quantitative relationship between intracellular Ca 2+ concentration and extracellular insulin secretion from a cellular perfusate of isolated pancreatic islet cells stimulated with glucose. Cultured islets were loaded with the calcium indicator fura-PE3 in a medium containing glucose and one islet transferred to a perfusion chamber. The [Ca 2+ ] was measured by fluorescence microscopy, while insulin was determined by RIA from fractions collected downstream from the perfusate. This publication therefore describes the relationship between [Ca 2+ ] and insulin secretion from a large, mixed (i.e. heterogeneous) population of cells, and thus there is no specific correlation between cell stimulation and associated analyte production at the single cell level. Furthermore, Jonas et al does not describe multiplexed assays or the measurement of cell-associated molecules/analytes. [0013] Marriott et al. (J. Cellular Physiology, 1998, 177, 2, 232-240) describe induction of interleukin-6 mRNA expression and cellular calcium measurements in murine peritoneal macrophages. Both mRNA and cellular calcium measurements are intracellular events as mRNA is not secreted by the cell. [0014] Veronesi et al. (Neurotoxicology, 2003, 24, 463-473) describe intracellular calcium and extracellular IL-6 measurements from broncheal-tracheal epithelial cells. In this paper, IL-6 is not cell associated and is measured downstream by ELISA. [0015] The measurement of intracellular calcium and extracellular IL-6 measurements from human monocytes by downstream radioimmunoassay, which are carried out without a cellular washing step, is described by McMillen et al. (Clinical Care Medicine, 1995, 23, (1) 34-40). [0016] Drucker et al. (Blood, 2002, 100, (11) Abstract number 5025) report intracellular calcium and extracellular IL-6 measurements from multiple myeloma cell lines by downstream ELISA without a cellular washing step. [0017] The measurement of intracellular calcium and neuropeptide Y (NPY) immunochemical staining in the same population of cells is disclosed by Kohno et al. (Diabetes, 2003, 52, (4) 948-956). NPY was detected following cellular fixation with 4% paraformaldehyde on non-living cells. [0018] Lundgren et al. (World Journal of Surgery, 1996, 20, (7) 727-735) describe intracellular calcium and extracellular PTH measurements from human parathyroid cells by downstream radioimmunoassay, without use of a cellular washing step. [0019] None of the above methods give temporal and multiplexed, high content information from stimulated live cells where intracellular and cell-associated signalling factors are measured in a cell from a single homogeneous population of cells. The above methods are therefore unable to correlate specific intracellular events and the downstream production of cell-associated analytes. The present invention addresses these limitations as well as providing numerous advantages over known methods. SUMMARY OF THE INVENTION [0020] The present invention provides methods useful in multiplex cell-based assays for compound screening employing imaging instrumentation, which assays offer high content information relating to the biological potency of test agents, off-target effects and cellular toxicity of potential drug candidates. Thus, according to a first aspect of the present invention, there is provided a method for measuring at least one intracellular event and a cell-associated analyte in a single population of living cells wherein the at least one intracellular event and the cell-associated analyte are each components of a concerted biochemical process operating in the cells, the method comprising the steps of: [0000] a) providing a sample containing a single population of living cells; b) contacting at least one living cell in the single population of cells with a test agent causing or suspected of causing the at least one cell to produce a cell-associated analyte; c) measuring a change in a physical property in the at least one cell as a measure of at least one intracellular event; d) washing the cells to remove extracellular fluids; e) measuring the presence, amount or activity of the cell-associated analyte; and f) correlating the change in the at least one intracellular event in the at least one cell with the presence, amount or activity of the cell-associated analyte. [0021] The present invention therefore provides an integrated high-content, high-throughput cell-based assay method capable of yielding data on biological activity of exogenous agents acting upon cells. Living cells are constantly responding to essential signals in their environment through a complex network of biochemical pathways regulated in time and space, to provide a cell with an integrated exchange of information that is essential for coordinated responses. Hormones, growth factors and neurotransmitters are among the signalling agents that have been the most extensively studied. Moreover, the present invention provides an information-rich method for measuring multiple events taking place in the same cell, which method is capable of assisting with biochemical pathway analysis. This, in turn, will help to elucidate the various pathways associated with such clinical conditions as cancer, atherosclerosis, psoriasis, rheumatoid arthritis, multiple sclerosis, asthma and chronic obstructive pulmonary disease. Suitably, the sample employed in the method herein described, will contain a single population of cells. According to the method, cells are contacted with a test agent to stimulate the cells to trigger a cascade of downstream biochemical processes (or events). Such processes may result in altered levels of intracellular hormones, second messengers, gases, enzymes, transcription factors, response elements and/or products of gene expression. Furthermore, it is possible to correlate changes in observed intracellular events following cell stimulation, as characterised by a change in the levels or amounts of one or more corresponding intracellular effector molecules, with the formation of cell-associated analytes that may be produced in response to such cell stimulation. [0022] In one embodiment, the changes in the intracellular event and changes in the presence, amount or activity of a cell-associated analyte measured in the presence of a test agent may be compared with control values for each of the at least one intracellular event and the presence, amount or activity of said cell-associated analyte in the absence of the test agent. The control value may be conveniently stored electronically in a database or other electronic format. [0023] The test agent may be a chemical entity such as a drug, a food dye, a hormone, a toxin, an alkylating agent, an oxidising agent, or a carcinogen. Alternatively, the test agent is a physical agent such as electromagnetic radiation (e.g. UV, X-ray, microwave), β − radiation, or heat. [0024] It will be understood by the skilled person that washing step d), to remove extracellular fluids, may be carried out after step b) but before step c). [0025] As disclosed herein, the term “multiplex assay” or “multiplex method” relates to or is a method of measurement or communication of information or signals from two or more messages from the same source (an example of a multiplex assay is described by Ugozzoli, et al. (Analytical Biochemistry, 2002, 307, 47-53). [0026] The term, “high-content screening”, as used herein, is a drug discovery method that uses living cells as the test tube for molecular discovery. It describes the use of spatially or temporally resolved methods to discover more from an individual experiment than one single experiment with one output alone. It uses a combination of cell biology, with molecular tools, typically with automated high resolution microscopy and robotic handling (Giuliano et al., J Biomol Screen., 1997, 2, 249-259). The method described herein describes use of an assay method with living cells. [0027] As disclosed herein, the term “intracellular event” is intended to mean a basic cellular process associated with cell signalling and signal transduction, including for example, receptor activation, calcium release, second messenger production, nitric oxide release, phosphorylation, enzyme activation, activation of transcription factors and response elements and gene expression. Thus, in the context of the present invention, detecting a change in a physical property as a measure of the intracellular event is intended to mean the detection of the presence or absence, or the measurement of a change in a level or in the amount of an intracellular effector molecule, or change in the activity of an intracellular enzyme, second messenger, nitric oxide, transcription factor, response element or one or more products of gene expression. Preferably, the intracellular event is an increase in ion concentration (for example intracellular calcium) and/or an increase in gene expression. [0028] As disclosed herein, the term “cellular process” is intended to include the normal processes which living cells undergo and include: biosynthesis, uptake, transport, regulation, receptor binding and internalisation, metabolism, cell physiology, biochemical response, cellular respiration, growth and cell death. Additional cellular processes may include cell adhesion, in which cells become attached to another cell or to an underlying substrate or matrix via cell adhesion molecules, cell signalling, morphogenesis, reproduction and response to stimuli. [0029] As disclosed herein, the term “cell-associated analyte” is intended to refer to a cellular component that is produced upon stimulation of a cell generally by a concerted biochemical process or pathway and which may subsequently be secreted by the cell but which is physically associated with the cell at the time of measuring the presence, amount or activity of the cell-associated analyte. The present invention describes combination or multiplex assays that are designed to measure two or more different analytes present in intracellular and extracellular fluids. For example, intracellular molecules may be present within the cell cytoplasm and nucleus, whereas cell-associated analytes may be present within fluids bathing the immediate surface of the cell. In a preferred embodiment, the assay is designed to measure a cell-associated analyte that is closely associated with the cell, for example bound to the cell membrane, or alternatively present in the immediate environment of the cell, since this gives an accurate measure of the level of expression and temporal nature of the level of generation of the secreted factor or analyte. [0030] The methods of the present invention are applicable in virtually any type of cell. In one embodiment, the population of cells are normal (i.e. un-modified) cells derived from any recognised source with respect to origin including cells of mammalian, bacterial, plant, insect and yeast. In a preferred embodiment, eukaryotic cell types are employed, for example, mammalian cells. Examples include CHO, 3T3, Cos-7, HEK-293, Jurkat, HeLa, Sf-9, HUVEC, HMEC, HL-60, U2OS, J774, BHK, ECV304 and THP-1 cells. Alternative cells include yeast and insect cells. [0031] In another embodiment, cells are modified by transfection with a recombinant expression vector comprising a first reporter gene construct comprising a nucleic acid sequence encoding a first detectable reporter molecule operably linked to and under the control of an expression control element. In this embodiment, suitably, the contacting step b) according to the first aspect is performed under conditions permitting expression of the reporter gene construct. [0032] As disclosed herein, the term “operably linked” indicates that the elements comprising the reporter gene construct are arranged such that they function in concert for their intended purposes, i.e. the reporter gene construct is arranged such that transcription initiates in a promoter and proceeds through the DNA sequence coding for the reporter molecule. [0033] In a further embodiment, the reporter gene construct may additionally encode a protein interest, for example the green fluorescent protein (GFP), a nitroreductase (NTR) reporter or a luciferase gene that catalyzes a reaction with luciferin to produce light. Another common reporter in bacteria is the lacZ gene which encodes the protein β-galactosidase, thereby causing cells expressing the gene to appear blue when grown on a medium containing the substrate analog X-gal. [0034] As described herein, a reporter gene (or reporter) is a gene that is attached to another gene (expressing, for example a luciferase) of interest in cells in culture. Certain genes are chosen as reporters, either because the characteristics they confer on organisms expressing them can be readily identified and measured, or because the genes are selectable markers of an intracellular event or molecule and can therefore be used in techniques such as GFP translocation assays. Reporter genes are used to determine whether the gene of interest has been taken up by the cells or is expressed, or if gene expression is activated or altered in the cell or cell population. In order to introduce a reporter gene into an organism, the reporter gene and the gene of interest are placed in the same nucleic acid construct which is to be inserted or transfected into the cell or cell population. For example, for bacteria or eukaryotic cells in culture, the construct is usually in the form of circular (plasmid) DNA as is well known. [0035] In one embodiment, cells modified by transfection with a first reporter gene construct comprise a nucleic acid sequence encoding a fluorescent protein, for example a Green Fluorescent Protein (GFP) or a functional GFP analogue derived from Aequorea Victoria . Preferred fluorescent proteins for use in the disclosed method include EGFP (Cormack, B. P. et. al., Gene, (1996), 173, 33-38); EYFP and ECFP (U.S. Pat. No. 6,066,476, Tsien, R. et. al.); F64L-GFP (U.S. Pat. No. 6,172,188, Thastrup, O. et. al.); BFP, (U.S. Pat. No. 6,077,707, Tsien, R. et. al.). Other fluorescent proteins include NFP (Clontech) and Renilla GFP (Stratagene). [0036] In another embodiment, the modified cells comprise a first reporter gene construct comprising a nucleic acid sequence encoding an enzyme, for example a luciferase, a β-galactosidase, an alkaline phosphatase and a nitroreductase. In a particularly preferred embodiment, the reporter gene construct encodes a nitroreductase. Suitable enzyme reporters are those which are capable of generating a detectable (e.g. a fluorescent or a luminescent) signal in a substrate for that enzyme. Particularly suitable enzyme/substrates include: luciferase/luciferin; β-galactosidase/DDAO galactoside; β-galactosidase/fluorescein di-β-D-galactopyranoside; alkaline phosphatase/Attophos; nitroreductase/CytoCy5S™ (as disclosed in WO 2005/118839). [0037] Methods for using a variety of enzyme genes as reporter genes are well known (for a review see Naylor L. H., Biochemical Pharmacology, (1999), 58, 749-757). The reporter gene is chosen to allow the product of the gene to be measurable in the presence of other cellular proteins and is introduced into the cell under the control of a chosen regulatory sequence which is responsive to changes in gene expression in the host cell. Typical regulatory sequences include those responsive to hormones and other cellular control and signalling factors. For example, agonist binding to seven transmembrane receptors is known to modulate promoter elements including the cAMP responsive element, NFAT, SRE and AP1; MAP kinase activation leads to modulation of SRE leading to Fos and Jun transcription; DNA damage leads to activation of transcription of DNA repair enzymes and the tumour suppressor gene p53. By selection of an appropriate regulatory sequence, the reporter gene can be used to assay the effect of added agents on cellular processes involving the chosen regulatory sequence under study. [0038] For use as a reporter, a nitroreductase gene may be isolated by well known methods, for example by amplification from a cDNA library by use of the polymerase chain reaction (PCR) (Molecular Cloning, A Laboratory Manual 2 nd Edition, Cold Spring Harbour Laboratory Press 1989 pp 14.5-14.20). Once isolated, the nitroreductase gene may be inserted into a vector suitable for use with mammalian promoters (Molecular Cloning, A Laboratory Manual 2 nd Edition, Cold Spring Harbour Laboratory Press 1989 pp 16.56-16.57) in conjunction with and under the control of the gene regulatory sequence under study. The vector containing the nitroreductase reporter and associated regulatory sequences may then be introduced into the host cell by transfection using well known techniques, for example by use of DEAE-Dextran or Calcium Phosphate (Molecular Cloning, A Laboratory Manual 2 nd Edition, Cold Spring Harbour Laboratory Press 1989 pp 16.30-16.46). Other suitable techniques will be well known to those skilled in the art. Nitroreductase has been shown to be retained in cells when expressed in this manner (see Bridgewater et al, Eur. J. Cancer 31a, 2362-70). [0039] A DNA construct may be prepared by the standard recombinant molecular biology techniques of restriction digestion, ligation, transformation and plasmid purification by methods familiar to those skilled in the art and are as described in Sambrook, J. et al (1989), Molecular Cloning—A Laboratory Manual, Cold Spring Harbor Laboratory Press. Alternatively, the construct can be prepared synthetically by established methods, e.g. the phosphoramidite method described by Beaucage and Caruthers, (Tetrahedron Letters, (1981), 22, 1859-1869) or the method described by Matthes et al (EMBO J., (1984), 3, 801-805). According to the phosphoramidite method, oligonucleotides are synthesised, e.g. in an automatic DNA synthesizer, purified, annealed, ligated and cloned into suitable vectors. The DNA construct may also be prepared by polymerase chain reaction (PCR) using specific primers, for instance, as described in U.S. Pat. No. 4,683,202 or by Saiki et al, (Science, (1988), 239, 487-491). A review of PCR methods may be found in PCR protocols, (1990), Academic Press, San Diego, Calif., U.S.A. [0040] During the preparation of the DNA construct, the gene sequence encoding the reporter must be joined in frame with the cell cycle phase specific destruction control element and optionally the spatial localisation control element. The resultant DNA construct should then be placed under the control of a suitable cell cycle phase specific expression control element. [0041] Measurement of an intracellular event, for example changes upon cell stimulation in the levels of a hormone, a second messenger, or calcium may be suitably accomplished by detecting and quantitating fluorescence emitted by the cell by employing a fluorescent probe specific for such a molecule. The measurement of intracellular hormones, second messengers, transcription factors and the like may be accomplished by known methods. Examples of intracellular events and the associated effector molecules that may be measured include: i) Cellular Calcium Flux or Calcium Transient Assays [0042] Such assays employ a cell permeable fluorescent indicator dye molecule such as Fluo-2 and Fluo-4, such that there is an increase in fluorescence emission as a result of the binding of the probe to the calcium ions. See for example, “Cellular Calcium, A Practical Approach”, Edited by McCormack and Cobbold (1991), IRL Press. ii) GFP-Tagged Translocation Assays [0043] These assays require a nucleic acid construct expressing GFP so that protein translocations occurring between the cytoplasm and either the cell membrane, early endosomes or the nucleus can be identified. See for example, Hancock et al, The Society for Biomolecular Screening, 9 th Annual Conference and Exhibition, Drug Discovery at the Cutting Edge, (2003), Portland, Oreg.) which describes live intracellular GFP-tagged protein translocation assays for the monitoring and quantitation of a variety of signalling events including activation of AKT-1. [0000] iii) Reporter Gene Assays [0044] Reporter gene assays may be used to assay for the expression of a gene of interest, producing a cellular protein that has little obvious or immediate effect on the cultured cells. Here, the reporter is directly tagged to the gene of interest to create a gene fusion. The two genes are under the control of the same promoter and are transcribed into a single messenger RNA molecule, which is translated into protein, e.g. an enzyme reporter. It is important in these examples that both proteins are able to properly fold into their active conformations and interact with their enzyme substrates despite being fused. In forming the DNA construct, a segment of DNA coding for a flexible polypeptide linker region is often included such that interference between the reporter and the gene product is minimised. Examples of such approaches are well known, see for example, Bronstein et al, Chemiluminescent and Bioluminescent Reporter Gene Assays, Analytical Biochemistry, (1994), 219, 169-181. iv) Cellular Lysis Assays [0045] Here, intracellular components are measured in a cell lysis fluid, often coupled with detergents which are used to dissociate the cell membrane. Examples of such cell lysis steps and assays may be found in U.S. Pat. No. 6,900,019 (Horton). [0046] Assays to measure the presence, amount or activity of a cell-associated analyte are well known, and include immunocytochemistry, protein-binding assays and enzyme assays. Components of an assay may typically comprise: [0000] a) a sample of cells containing or suspected of containing the analyte to be measured; b) an unlabelled specific binding partner of the analyte which is, or is capable of being, immobilised onto a solid support; c) a specific binding partner, or an analogue, of the analyte, which is either labelled or unlabelled and capable of being labelled. [0047] In one embodiment, the assay is an enzyme-assay. In this format, components a), b) and c) are contained in the wells of a microwell plate, component c) being an enzyme-labelled specific binding partner of the compound being tested for. The assay measurement is initiated by the addition to the wells of detection reagents suitable for the detection of the enzyme label. See for example, Berg, J., Tymoczko J and Stryer L, Biochemistry, W.H. Freeman and Company, (2002). [0048] In another embodiment, the labelled specific binding partner can include a fluorescence label. Suitable fluorescent labels for use in the measurement of analytes by immunocytochemistry assay method will be well known and will include for example, fluorescein, rhodamine and cyanine dyes. [0049] In another embodiment, an enzyme-linked immunospot (ELISPOT) assay is employed for measurement of the cell-associated analyte. See Czerkinsky, C., et al, J. Immunol. Methods, (1983), 65 (1-2), 109-21). In this embodiment, cell-associated analytes may be measured with a translucent (PVDF) membrane acting as a solid-support for antibodies or other binding reagents, and detecting the cell-associated analyte with an enzyme-labelled probe and fluorescent substrate. [0050] In a still further embodiment, the measurement of cell-associated analyte can be performed using the live cell-ELISA technique, in which a sample of cells possibly containing the analyte to be measured is contained in a vessel, and the cell-associated analyte is detected with suitable probes and luminescent or fluorescent substrates. See for example, Grunow, R. et al, J. Immunological Methods, (1994), 171, 93-102. [0051] The nature of the cell-associated analyte is not material to the invention, except insofar as the presence, activity or amount of the analyte can be correlated with an intracellular event (as measured by a change in an intracellular component, or reporter gene activation, or GFP translocation). Any cell-associated analyte for which a specific binding partner is available can in principle be utilised in the invention. Typical specific-binding partner combinations suitable for use with the invention may be selected from: hapten-antibody, ligand-receptor, DNA-DNA, RNA-RNA, DNA-RNA, biotin-streptavidin, protein-antibody, peptide-antibody, and polypeptide-antibody interactions. Preferably, a specific binding assay is a protein-binding assay or more particularly an immunocytochemistry assay. Typical analytes include proteins, peptides, neurotransmitters, neurotrophins, vitamins, peptide hormones, enzymes, growth factors, steroids, prostaglandins, integrins, matrix components, adhesins, cluster of differentiation molecules, cytokines, chemokines, lymphokines and leukotrienes and the like. [0052] Measurement of certain intracellular components are indicative of a change in an intracellular event and such components include second messengers, ADP, ATP, AMP, cyclic ADP-ribose, cellular calcium, cGMP, cAMP, IP 3 , IP 1 , IP 4 , serine-threonine kinases, PI3-kinase, diacylglycerol, AKT-1, ribosomal protein S6 kinase, SMAD-9, phospholipase C, phospholipase C delta-1, amyloid beta precursor protein, ras homolog gene family, member A.PARAPARA (ARHA), receptor-interacting serine/threonine kinase 2, heat-shock 70-kD protein 1A, (HSPA1A), sphingosine kinase-1 (SPHK1), SPHK2, Forkhead Box O1A (FOXO-1A), glucocorticoid receptor (GCCR), caspases, AKT1 and transcriptional factors. Individually, these intracellular analytes may be measured, for example, using GFP translocation markers, reporter-gene assays, fluorescent or luminescent probes, enzyme-mediated assays, protein-binding techniques, electrophysiology, spectroscopy, nuclear magnetic resonance techniques, flow cytometry, ion transport, microscopy and radiometric assays. [0053] The detection and measurement of changes in fluorescence intensity may be made using an optical imaging method employing instruments incorporating a charge coupled device (CCD) imager (such as a scanning imager or an area imager). For example, the LEADseeker™ Multimodality Imaging System (GE Healthcare) features a CCD camera allowing quantitative fluorescence imaging of high density microwell plates in a single pass. Alternatively, cells may be imaged in “live cell” format using an IN Cell 1000 Analyzer Optical Imaging System (GE Healthcare). In this format, a suitable cell marker should be introduced into the cell, such as a cytosolic, nuclear or membrane fluorescent label having a fluorescence emission wavelength that is different and distinguishable from the fluorescence emission of the compound of interest. [0054] According to the present invention, methodologies are combined which enable intracellular and extracellular, cell-associated events to be monitored in parallel in single cells or single homogeneous populations of cells treated with test agents. The present invention therefore provides an advantageous method for directly determining the effect of a putative drug, or agent on a single cell or single population of cells, thus reducing the amount of time and cost required to develop and optimize a compound with a high therapeutic effect. BRIEF DESCRIPTION OF THE INVENTION [0055] For the purposes of clarity, certain embodiments of the present invention will now be described by way of example with reference to the following figures in which: [0056] FIG. 1 shows results from a combination assay according to Example 1. An increase in cytosolic intracellular calcium resulting from calcium ionophore A23187-stimulated U2OS cells derived from a single population, was detected by binding to a calcium sensitive, cell permeable dye Fluo-4. Fluorescence emission (λ em =535 nm) was measured using an IN Cell 1000 Analyzer Optical Imaging System and imaged using a 10× objective, 505 light pass dichroic 475/535 filter set with 200 ms exposure. [0057] FIG. 2 is an image of an immunocytochemical analysis showing cell-associated, secreted human IL-6 from A23187-stimulated U2OS cells derived from a single population according to Example 4. Fluorescence was measured on an IN Cell 1000 Analyzer. [0058] FIG. 3 shows calcium ionophore-stimulated IL-6 generation from U2OS cells demonstrating cell-associated IL-6 secretion from a single population of A23187-stimulated U2OS cells in culture according to Example 3. Cells were contacted with the test agent (calcium ionophore A23187) for 4 hours and cell-associated IL-6 measured post cell-stimulation with the test agent. After stimulation, the cell supernatant was decanted, the cells were washed thoroughly ×3 with PBS, before incubating with the anti-IL-6 antibody. The cells were washed ×3 with PBS before addition of the chemiluminescent substrate. Results from the calcium transient were obtained prior to the IL-6 results using the same population of cells. Data was obtained in combination with results shown in FIG. 1 . The results ( FIG. 3 ) were obtained using a LEADseeker Multimodality Imaging System, exposing for 20 seconds, using the chemiluminescent substrate and the luminescent signal reporter (anti-IL-6 labelled with the enzyme horseradish peroxidise). [0059] FIG. 4 shows results from a combination assay according to Example 2. An increase in cytosolic intracellular calcium resulting from histamine-stimulated U2OS cells derived from a single population, was detected by binding to a calcium sensitive, cell permeable dye Fluo-4. Fluorescence emission (λ em =535 nm) was measured using an IN Cell 1000 Analyzer and imaged using a 10× objective, 505 light pass dichroic 475/535 filter set with 200 ms exposure. [0060] FIG. 5 shows histamine-stimulated IL-6 generation from human U2OS cells derived from a single population, according to Example 3. Cells were contacted with the histamine test agent overnight and cell-associated IL-6 measured post cell-stimulation. The results were obtained on the LEADseeker Multimodality Imaging System, exposing for 20 seconds, using the chemiluminescent substrate and the luminescent signal reporter (anti-IL-6 labelled with the enzyme horseradish peroxidise). [0061] FIG. 6 shows a calibration curve of known amounts of recombinant IL-6, using known amounts of recombinant IL-6 (0.48-1500 pg/ml) using a chemiluminescent assay (R&D Systems, catalogue code Q6000B) according to Example 3. Results were measured on a LEADseeker Multimodality Imaging System. [0062] FIG. 7 shows a calcium transient from calcium ionophore A23187-stimulated human U2OS cells grown in culture obtained in combination data for IL-6 measurement according to Example 4. Image analysis was performed on an IN Cell 1000 Analyzer and imaged using a 10× objective, 505 light pass dichroic 475/535 filter set 200 ms exposure. Fluorescence measurement shows an increase in intracellular calcium compared with the unstimulated (zero ionophore) control. [0063] FIG. 8 shows the relationship between intracellular calcium and cell-associated IL-6 from A23187-stimulated U2OS cells, both intracellular and cell-associated molecules exhibiting a dose-dependent rise with increasing concentration of the ionophore A23187. Cells were derived from a single population. Results were obtained using an IN Cell 1000 Analyzer according to Example 4. [0064] FIG. 9 shows the relationship between intracellular and cell-associated IL-6 from A23187-stimulated U2OS cells derived from a single population. The data shows an increase in intracellular calcium and cell-associated IL-6 when cells are in contact with the test agent only. No correlation between intracellular and cell-associated IL-6 was exhibited with unstimulated (control) cells. Results were obtained using an IN Cell 1000 Analyzer according to Example 4. [0065] FIG. 10 shows an excellent correlation between intracellular calcium and cell-associated IL-6 from A23187-stimulated human U2OS cells derived from a single population (correlation coefficient >0.99). Results were obtained using an IN Cell 1000 Analyzer according to Example 4. [0066] FIG. 11 shows EGFP-NFAT1c translocation from the combination assay of EGFP translocation and PDGF measurement (cell-associated molecule). [0067] FIG. 12 shows ionomycin-stimulated PDGF release from EGFP-NFAT1c transfected U2OS cells in combination with EGFP-NFAT1c translocation. [0068] FIG. 13 shows a correlation between intracellular NFAT1c translocation and cell-associated PDGF from ionomycin-stimulated EGFP-NFAT1c transfected U2OS cells from a single population. [0069] FIG. 14 shows EGFP-NFAT1c translocation upon stimulation of transfected cells with ionomycin+PMA as measured using an imaging system. [0070] FIG. 15 shows ionomycin+PMA stimulated TNFα release from EGFP-NFAT1c transfected U2OS cells obtained in combination with EGFP-NFAT1c translocation. [0071] FIG. 16 shows a correlation between intracellular NFAT1c translocation and cell-associated human TNFα from ionomycin+PMA-stimulated EGFP-NFAT1c transfected U2OS cells. DETAILED DESCRIPTION OF THE INVENTION Examples 1. Measurement of a Calcium Transient in Ionophore A23187-Stimulated U2OS Cells Materials [0072] Calcium flux buffer (5 mM KCl, containing 1 mM MgSO4, 100 mM HEPES, 10 mM D-glucose, 145 mM NaCl and 1 mM CaCl2 pH 7.4). Fluo-4 (InVitrogen) Hoescht 33342 (InVitrogen) [0073] 7.5% albumin (Sigma) Calcium ionophore A23187 (Sigma) U2OS cells (European Collection of Cell Cultures, Porton Down, UK) 1.2 Method and Results [0074] i) U2OS cells were seeded into 96-well Greiner cluster plates at 6000 cell/well in 100 μl of complete McKoys media and incubated overnight at 37° C., 5% CO 2 . [0075] ii) Loading buffer was prepared with 42.8 ml of calcium flux buffer with 6.65 ml of 7.5% albumin. This buffer was stored at 37° C. [0076] iii) 120 ml of maintenance buffer was prepared with 118.16 ml calcium flux buffer and 1840 μl of 7.5% albumin. [0077] iv) 5 mg of calcium ionophore A23187 was dissolved in 1 ml of DMSO. The ionophore was subsequently diluted in complete maintenance buffer to give final concentration of ionophore over the range of 1.56-100 μM. Fluo-4 dye was prepared by adding 456 μl DMSO to a 50 μg vial, and the vial was mixed well to provide a Fluo-4 stock concentration of 100 μM. 100 μl of 100 μM Fluo-4 dye and 6 μl of 16 mM Hoescht nuclear dye were added to 9.894 ml of loading buffer. The media was removed from the cell culture plate, and 100 μl/well of warmed complete loading buffer was added. The plate was incubated for 40 minutes at 37° C., 5% CO 2 . Following incubation, the loading buffer was removed and 150 μl/well of maintenance buffer was added. The plate was transferred to an IN Cell 1000 Analyzer (Kinetic Module) using a 10× objective, 505 light pass dichroic 475/535 filter set (Fluo-4), 200 ms exposure, 360/460 filter set (Hoescht), 300 ms exposure. Images were acquired every five seconds after the following time: 0, 5-60 seconds. After 20 seconds the ionophore was dispensed and image acquisition was continued. The results were analysed using an object intensity algorithm (INCell Investigator software). [0078] v) FIG. 1 shows the results from a combination assay of intracellular calcium concentration following stimulation by calcium ionophore A23187 (1.56-100 μM) of U2OS cells grown in culture. An increase in cell-associated IL-6, is shown in FIG. 3 . The data shows that upon stimulation with the calcium ionophore, the cells respond with an increase in cytosolic intracellular calcium as shown by an increase in emitted fluorescence from the cell permeable dye Fluo-4 (λ em =535 nm). FIG. 1 shows a rise in intracellular calcium over eight minutes and indicates a temporal change in intracellular calcium levels with a peak and decline. The change in the intracellular event is also dependent on the dose of the calcium ionophore employed in the assay. 2. Measurement of a Calcium Transient in Histamine-Stimulated U2OS Cells 2.1 Materials [0079] Calcium flux buffer (5 mM KCl, containing 1 mM MgSO 4 , 100 mM HEPES, 10 mM D-glucose, 145 mM NaCl and 1 mM CaCl 2 pH 7.4). Fluo-4 calcium fluor (InVitrogen) Hoesch 33342 DNA stain (InVitrogen) 7.5% albumin (Sigma) Histamine (Sigma) [0080] U2OS cells (European Collection of Cell Cultures, Porton Down, UK) 2.2 Method and Results [0081] i) U2OS cells were seeded into 96-well Greiner cluster plates at 6000 cell/well in 100 μl of complete McKoys media and incubated overnight at 37° C., 5% CO 2 . [0082] ii) Loading buffer was prepared with 42.8 ml of calcium flux buffer with 6.65 ml of 7.5% albumin. This buffer was stored at 37° C. [0083] iii) 120 ml of maintenance buffer was prepared with 118.16 ml calcium flux buffer and 1840 μl of 7.5% albumin. [0084] iv) 25.3 mg of histamine was weighed out and dissolved in 1 ml of warmed maintenance buffer. Histamine was subsequently diluted in complete maintenance buffer to give final concentration of histamine over the range of 1.56-100 μM. Fluo-4 dye was prepared by adding 456 μl DMSO to a 50 μg vial, and the vial was mixed well to provide a Fluo-4 stock concentration of 100 μM. 100 μl of 100 μM Fluo-4 dye and 6 μl of 16 mM Hoescht nuclear dye were added to 9.894 ml of loading buffer. The media was removed from the cell culture plate, and 100 μl/well of warmed complete loading buffer was added. The plate was incubated for 40 minutes at 37° C., 5% CO 2 . Following incubation, the loading buffer was removed and 150 μl/well of maintenance buffer was added. The plate was transferred to an IN Cell 1000 Analyzer (Kinetic Module) using a 10× objective, 505 light pass dichroic 475/535 filter set (Fluo-4) 200 ms exposure, 360/460 filter set (Hoescht), 300 ms exposure. Images were acquired every five seconds after the following times: 0, 5-60 seconds. After 20 seconds the histamine was dispensed and image acquisition was continued. The results were analysed using an object intensity algorithm (IN Cell Investigator software). [0085] v) FIG. 4 shows the results from a combination assay of intracellular calcium concentration following histamine stimulation (1.56-100 μM) of U2OS cells grown in culture. An increase in cell-associated IL-6, is shown in FIG. 5 . The data shows that upon stimulation with the histamine test agent, the population of cells respond with an increase in cytosolic intracellular calcium as shown by an increase in emitted fluorescence from the cell permeable dye Fluo-4 (λ em =535 nm). FIG. 4 shows a rise in intracellular calcium over eight minutes and also indicates a temporal change in intracellular calcium levels with a peak and decline. The change intracellular event is also dependent on the dose of the histamine test agent employed in the assay. 3. Combination Assay of Human Interleukin-6 from Histamine or Calcium Ionophore A23187-Stimulated U2OS Cells Following Measurement of the Calcium Transient 3.1 Materials [0086] Anti-human IL-6 antibodies (R&D Systems Q6000B) Luminescent substrate (R&D Systems Q6000B) Calcium ionophore A23187 (Sigma) Histamine (Sigma) [0087] U2OS cells (European Collection of Cell Cultures, Porton Down, UK) 3.2 Method and Results [0088] i) U2OS cells were seeded into 96-well tissue culture plates at 6000 cell/well in 100 μl of complete McKoys media and incubated overnight at 37° C., 5% CO 2 . [0089] ii) Cells were stimulated with A23187 or histamine (see Examples 1 and 2 above) and a calcium transient was measured (see FIGS. 1 and 4 ). After stimulation with ionophore or histamine, the cell supernatant was decanted, the cells were washed thoroughly ×3 with PBS, before incubating with the anti-IL-6 antibody. The cells were washed ×3 with PBS before addition of the chemiluminescent substrate. Results from the calcium transient were obtained prior to the IL-6 results using the same single population of cells. [0090] iii) IL-6 data was obtained in combination with results shown in FIGS. 1 and 4 . The results (Table 1 and FIG. 3 , ionophore stimulation; FIG. 5 histamine stimulation) were obtained on the LEADseeker Multimodality Imaging System, exposing for 20 seconds, using the chemiluminescent substrate and the luminescent signal reporter (anti-IL-6 labelled with the enzyme, horseradish peroxidase). [0091] iv) The results of the calibration curve using known amounts of recombinant IL-6 as a standard are shown in Table 2 and FIG. 6 , allowing accurate measurement of cell-associated IL-6. The results (Table 2 and FIG. 6 ) show an increase in chemiluminescent signal with increasing concentration of IL-6. These data were obtained on the LEADseeker Multimodality Imaging System. [0000] TABLE 1 Interleukin-6 sample measurements from stimulated U2OS in culture Cell sample number for IL6 measurement IOD 1 1151.51 1411.74 2 1698.92 1803.51 3 2370.45 2417.2 4 3006.14 2869.03 5 4554.7 4876.76 6 6204.84 5156.72 7 17974.71 13584.73 8 50076.31 51643.99 9 49946.58 47382.19 10 37931.93 36675.02 11 14217.31 16212.06 12 3176.96 3308.5 13 2687.38 2537.77 14 3193.71 3092.18 15 4323.73 4128.06 16 3429.57 3257.39 17 4793.5 4566.47 18 4962.54 5262.34 19 6455.98 6390.91 20 7017.89 6417.23 21 7796.78 7123.62 22 7454.8 7246.66 23 6511.13 6664.44 24 5146.23 5008.23 [0000] TABLE 2 Interleukin-6 calibration curve from an Imaging System IL-6 pg/ml IOD 0.48 273.47 300.3 2.4 1392.55 1530.24 12 9826.55 10791.35 60 50222.06 51335.14 300 62251.67 61541.55 1500 62551.34 61015.07 4. Combination Assay of Intracellular Calcium and Human Interleukin-6 from Calcium Ionophore A23187-Stimulated U2OS Cells on IN Cell 1000 4.1 Materials Anti-IL-6 (R&D Systems) [0092] Goat anti-human IgG Cy-5 linked (GE Healthcare) Calcium ionophore A23187 (Sigma) U2OS cells (European Collection of Cell Cultures, Porton Down, UK) 4.2 Method and Results [0093] i) U2OS cells were seeded into 96-well tissue culture plates at 6000 cell/well in 100 μl of complete McKoys media and incubated overnight at 37° C., 5% CO 2 . [0094] ii) Cells were stimulated with A23187 for 8 minutes before measurement of a calcium transient on an IN Cell 1000 Analyzer as described in Example 1. FIG. 7 shows a calcium transient from calcium ionophore A23187-stimulated human U2OS cells grown in culture obtained in combination data for IL-6 measurement, data which is shown in FIG. 2 . The results from this assay were measured on an IN Cell 1000 Analyzer using a 10× objective, 505 light pass dichroic 475/535 filter set 200 ms exposure. Fluorescence measurement shows an increase in intracellular calcium (1.56 μM ionophore) compared with the unstimulated (zero ionophore) control. [0095] iii) FIG. 2 shows immunocytochemistry from a combination assay (with intracellular calcium, see FIG. 1 ) showing cell-associated IL-6 (the cell-associated analyte) from a population of A23187-stimulated U2OS cells in culture. Cells were contacted with the test agent (calcium ionophore A23187) for 4 hours and cell-associated IL-6 measured post cell-stimulation with test agent. After stimulation with the ionophore, the supernatant was decanted and the cells were washed thoroughly ×3 with PBS. Cell-associated IL-6 was localised with an anti-human IL-6 antibody (anti-IL-6 monoclonal antibody) and a fluorescent dye-labelled anti-human IgG (anti-human gG, Cy-5 linked, (GE Healthcare). After 60 minutes incubation with the monoclonal anti-IL-6 antibody, the cells were washed ×3 and the dye labelled anti-human IgG added. After 60 minutes incubation with the fluor-labelled second antibody, the cell were washed ×3 with PBS, and fluorescence detected on an IN Cell 1000 Analyzer, using a 10× objective, 51008bs dichroic 620/700 filter set (Cy-5 filter set), 500 ms exposure. The results were analysed using an object intensity algorithm (IN Cell Investigator software). The results, ( FIG. 2 ), clearly demonstrate cell-associated IL-6. [0096] iv) FIG. 8 shows the relationship between intracellular calcium and cell-associated IL-6 from A23187-stimulated U2OS cells, both intracellular and cell-associated molecules exhibiting a dose-dependent rise with increasing concentration of the ionophore A23187. Cells were derived from a single population. Results were obtained in an IN Cell 1000 Analyzer Optical Imaging System as described above. The results were analysed using an object intensity algorithm (IN Cell Investigator software). [0097] v) FIG. 9 shows the relationship between intracellular and cell-associated IL-6 from A23187-stimulated U2OS cells derived from a single population. The data shows a biphasic increase in intracellular calcium and cell-associated IL-6 when cells are in contact with the test agent only. No correlation between intracellular and cell-associated IL-6 was exhibited with unstimulated (control) cells. Results were obtained in the IN Cell 1000 Analyzer Optical Imaging System as described above. The results were analysed using an object intensity algorithm (IN Cell Investigator software). [0098] vi) FIG. 10 shows a correlation between intracellular calcium and cell-associated IL-6 from A23187-stimulated human U2OS cells derived from a single population (correlation coefficient >0.99). Results were obtained in the IN Cell 1000 Analyzer Optical Imaging System as described above. The results were analysed using an object intensity algorithm (IN Cell Investigator software). 5. EGFP NFAT Assay Using Genetically Engineered Cells 5.1 NFAT Proteins [0099] The nuclear factor of activated T cells (NFAT) proteins are transcription factors whose activation is controlled by the Ca 2+ /calmodulin-dependent phosphatase, calcineurin. NFAT signalling is involved in many processes including lymphocyte development and activation, skeletal muscle gene expression, remodelling and development and function of the cardiovascular system. Five different NFAT genes have been identified so far; NFATc (NFATc1 or NFAT2), NFATp (NFATc2 or NFAT1), NFAT4 (NFATc3 or NFATx), NFAT3 (NFATc4) and NFAT5. [0100] The NFATc1 subtype is activated by antigen signalling in T cells resulting in cytokine expression but has also been shown to be involved in morphogenesis of the mammalian heart. [0101] The upstream receptor-ligand interactions that lead to activation of NFATs are not well characterised in most cell types. However, members of the NFATc (cytoplasmic) family of proteins (NFATc1-c4) can be activated by various GPCRs that activate PLC and induce IP 3 -mediated transient release of calcium from intracellular stores. In most cell-types, additional calcium influx through specialised calcium release activated calcium (CRAC) channels is required for activation of NFATc target genes. IP 3 can also spread through GAP junctions and activate CRAC channels and NFATc target genes in neighbouring cells. [0102] A second pathway resulting in the activation of NFATs exist in some cell types such as mast cells. FcεR1 activation of mast cells is mediated by calcineurin controlled signalling pathways acting in synergy with the pathways regulated by GTPases of the Ras superfamily, Ras and Rac-1. [0103] Inactive NFATc resides in the cytosol. It is phosphorylated at serine residues, which masks its nuclear localisation sequence (NLS) and presents its nuclear export sequence (NES). In response to sustained elevated calcium levels, NFATc is dephosphorylated by calcineurin, which exposes its NLS and it rapidly translocates to the nucleus. In the nucleus, it forms transcription complexes with other transcription factors such as AP-1, GATA4, GATA2 and MEF2. If calcium levels drop, NFATc is rephosphorylated, exposes the NES and the protein is exported back to the cytoplasm. [0104] NFATc dephosphorylation and nuclear translocation can be inhibited by both cellular and pharmacological products. Four cellular inhibitors of calcineurin phosphatase complexes have been identified; scaffold protein AKAP79, CAIN or CABIN protein, calcineurin B homologue, CHP and the Down Syndrome Critical Region 1 related genes; MCIP1, 2 and 3. The microbial products, FK506 and Cyclosporine-A binds to the intracellular proteins, FKBP and Cyclophilin, respectively, and, subsequently binds to calcineurin and block phosphatase activity. These agents revolutionised transplant therapy because of their ability to prevent the immune response to transplanted tissue. Various kinases have been implicated in the negative regulation of NFATs including the GSK3, casein kinase 1, MEKK-1 and p38 MAPKs. 5.2 EGFP-NFAT Assay [0105] The present patent specification describes a method for monitoring the NFATC1 signalling pathway with a cell-secreted, cell-associated analyte. The assay method is based on the intracellular translocation of an EGFP-NFATc1 fusion protein in stably transfected mammalian cells. NFATc1 is a transcription factor involved in T-cell signalling and tissue development. Inactive NFATc1 transcription factors reside in the cytoplasm. Following activation with agonists these translocate to the nucleus. [0106] The NFAT assay is optimised for image acquisition and analysis on the INCell Analysis System (GE Healthcare) using the Nuclear Trafficking-Analysis Module, although the assay can be imaged on other systems. The Nuclear Trafficking-Analysis Module measures the degree of EGFP-NFAT translocation from the cytoplasm to the nucleus on the addition of agonists. 5.3 U-2 OS Derived Parental Cell Line [0107] The parental cell line U-2 OS (ATCC HTB-96) was derived from a moderately differentiated sarcoma of the tibia of a 15 year old girl. The U-2 OS cell line is chromosomally highly alerted, with chromosome counts in the hypertriploid range, and expresses the insulin-like growth factor I and II receptors. 5.4 U-2 OS Derived EGFP-NFATc1 Expressing Cell Line [0108] U-2 OS cells were transfected with the pCORON1000 EGFP-NFATc1 vector (GE Healthcare) using the FuGENE 6 transfection method (Roche Applied Science) according to the manufacturers instructions. A stable clone expressing the recombinant fusion protein was selected using 500 μg/ml Geneticin for approximately 2 weeks. The stable cell line was cloned and sorted using a fluorescence activated cell sorter machine to obtain a uniform cell line. The passage number was set to one after FACS. Following sorting, the cells were grown for a further 8 passages before freezing. The cells tested were negative for mycoplasma, bacterial and yeast contamination. 5.5 EGFP-NFATc1 Expressing Vector [0109] The 8.6 kb pCORON1000-EGFP-NFATc1, contains a bacterial ampicillin resistance gene and a mammalian neomycin resistance gene. 5.6 Material and Equipment Required [0110] Microplates. For analysis using InCell, Packard Black 96-well ViewPlates (Perkin Elmer 6005182) were used. [0111] A CASY 1 Cell Counter and Analyser System (Model TT) (Scharfe System GmbH) is recommended to ensure accurate cell counting prior to seeding. Alternatively a haemocytometer may be used. [0112] Environmentally controlled incubator (5% CO 2 , 95% relative humidity, 37° C.). Imager (e.g. INCell 1000 GE Healthcare). [0113] Laminar flow cell culture bench. [0114] Tissue culture flasks (T-flasks) and pipettes. [0115] Controlled freezing rate device providing a controlled freezing rate of 1° C. per min. [0116] Standard tissue culture reagents and facilities. 5.6.1 Software Requirements [0117] INCell Analysis System: The Nuclear Trafficking-Analysis Module is available from GE Healthcare for automated image analysis of the EGFP-NFAT assay. Analysed data are exported as numerical files in an ASCII format. ASCII format data can be imported into Microsoft Excel, Microsoft Access or any similar package for further data analysis. [0118] Culture and maintenance of U-2 OS derived EGFP-NFATc1 expressing cell line. 5.6.2 Tissue Culture Media and Reagents Required [0119] The following media and buffers are required to culture, maintain and prepare the cells, and to perform the assay. [0120] GIBCO Dulbecco's Modified EAGLE MEDIA (DMEM) with Glutamax-1, Invitrogen Life Technologies 31966-021 or equivalent. [0121] Foetal Bovine Serum (FBS), JRH Biosciences 12103 or equivalent. Heat inactivate serum by incubation in a water bath at 56° C. for 30 minutes. GIBCO Penicillin-Streptomycin (P/S), (5000 units/ml penicillin G sodium and 5000 μg/ml streptomycin sulphate) Invitrogen Life Technologies 15140-122 or equivalent. [0122] Geneticin (G418), Sigma G-7034 or equivalent. [0123] GIBCO Trypsin-EDTA in HBSS without calcium or magnesium, Invitrogen Life Technologies 25300-054 or equivalent. [0124] GIBCO HEPES buffer, 1M solution, Invitrogen Life Technologies 15630-056 or equivalent [0125] Bovine serum albumin (BSA), Sigma A-7888 or equivalent. [0126] GIBCO Phosphate Buffered Saline (PBS) Dulbecco's without calcium, magnesium or sodium bicarbonate, Invitrogen Life Technologies 14190-094 or equivalent. [0127] Dimethylsulphoxide (DMSO), Sigma D-5879 or equivalent. [0128] GIBCO Nutrient Mixture F-12 medium with Glutamax, Invitrogen Life Technologies 31765-027 or equivalent. [0129] Ionomycin, calcium salt, Calbiochem, 407952 [0130] Hoechst 33258, Molecular Probes H-3569 5.6.3 Reagent Preparation [0131] Growth-medium: DMEM with Glutamax-1 supplemented with 10% (v/v) FBS, 1% (v/v) Penicillin-Streptomyccin, and 0.5 mg/ml Geneticin. [0132] Freeze-medium: DMEM with Glutamax-1 supplemented with 10% (v/v) FBS, 1% (v/v) Penicillin-Streptomycin and 10% (v/v) DMSO. [0133] Assay-medium: Nutrient Mixture F-12 medium with Glutamax supplemented with 10 mM HEPES, 0.5% (w/v) BSA and 3.0 μM Hoechst Nuclear Stain. [0134] Ionomycin: Prepare a 1 mM stock in 100% DMSO. This can be stored at −20° C. Prepare a 4 μM working dilution with assay-medium (four fold of the final concentration). This results in a final concentration of DMSO in the assay of 0.1% (v/v). 0.4% (v/v) DMSO (four fold of the final concentration) should be prepared in Assay-medium for control wells. 5.6.4 Cell Thawing Procedure [0000] 1. Remove a cryo-vial from storage. 2. Holding the cryo-vial, dip the bottom three-quarters of the cryo-vial into a 37° C. water bath, and swirl gently 1-2 minutes until the contents are thawed. 3. Remove the cryo-vial from the water bath and wipe it with 70% (v/v) ethanol. Transfer the cells immediately to a T-25 flask and add 5 ml pre-warmed Growth-medium drop wise to prevent cell damage. Add a further 2 ml Growth-medium and incubate at 37° C. 5.6.5 Cell Subculturing Procedure [0000] Incubation: 5% CO 2 , 95% humidity, 37° C. The cells should be split at a ratio of 1:10, two or three times a week, when they are 90% confluent. 1. Warm all reagents to 37° C. 2. Aspirate the medium from the cells and discard. 3. Wash the cells with PBS, taking care not to damage the cell layer while washing, but ensure the that the cell surface is washed. 4. Aspirate the PBS from the cells and discard. 5. Add trypsin-EDTA (2 ml for T-75 flasks and 4 ml for T-162 flasks) ensuring that all cells are in contact with the solution. Wait for 3-10 minutes for the cells to round up/loosen. 6. When the cells are loose, tap the flask gently to dislodge the cells. Add Growth-medium (6 ml for T-75 and 8 ml for T-162 flasks) and gently resuspend the cells with a 10 ml pipette until all the clumps have dispersed. 7. Aspirate the cell suspension and dispense 1 ml cells into a new culture vessel. 5.6.6 Cell Seeding Procedure [0000] 1. The following procedure is optimised for cells grown in standard T-75 and T-162 flasks to be seeded into 96-well microplates. 2. Warm all reagents to 37° C. 3. Aspirate the medium from the cells and discard. 4. Wash the cells with PBS. Take care not to damage the cell layer while washing, but ensure that the entire cell surface is washed. 5. Aspirate the PBS from the cells and discard. 6. Add Trypsin-EDTA (2 ml for T-75 and 4 ml for T-162 flasks), ensuring that all cells are in contact with the solution. Wait for 3-10 minutes for the cells to round up/loosen. 7. When the cells are loose, tap the flask gently to dislodge the cells. Add growth-medium (3 ml for T-75 and 6 ml for T-162 flasks) and gently resuspend the cells with a 10 ml pipette until all the clumps have dispersed. 8. Count the cells using an automated cell counter or a haemocytometer. 9. Using fresh Growth-medium, adjust the cell density to deliver the desired number of cells to each well. For example, to add 1.0×10 4 cells per well in a volume of 200 μl, adjust the suspension to 5×10 4 cells per ml. 10. Dispense 200 μl of the cells into each well of the microplate. 11. Incubate the plated cells for 24 h at 37° C. before starting the assay. 5.6.7 Cell Freezing Procedure [0000] 1. Harvest and count the cells. 2. Centrifuge the cells at 300×g for 5 minutes. Aspirate the medium from the cells. 3. Gently resuspend the cells until no clumps remain in freeze medium at a concentration of 1×10 6 cells in 1 ml and transfer into cryo-vials. Each vial should contain 1×10 6 cells in 1 ml of freeze medium. 4. Transfer the vials to a cryo-freezing device and freeze at −80° C. for 16-24 h. 5. Transfer the vials to the vapour phase in a liquid nitrogen storage device. 5.6.8 Growth Characteristics [0163] Under standard growth conditions, the cells should maintain an average size of 18.5 μM as measured using a CASY1 Cell Counter and Analyzer System (Model TT). The doubling time of the cell line in an exponential growth phase is 14 hours under standard conditions. [0000] 5.6.9 Agonist Assay Protocol (96-well format) 1. Incubate the microplate at 37° C., 5% CO 2 and 95% humidity. 2. The day before commencing the assay, seed at 1×10 4 cells per well in 200 μl of growth medium. Incubate for 24 hours at 37° C. If one of the wells on the cell plate is used for flat field correction, it should not contain cells. 3. On the day of the assay, prepare the test compounds, solvent controls (if used) and reference agonist control (Ionomycin). These samples were typically prepared at four fold of the final concentration in assay medium. 4. The growth medium from the cell plate was decanted, removing all excess liquid and add 200 μl. Using cell culture medium, wash the cells. Decant the wash. 5. Add 150 μl assay medium containing test agent. Incubate for 60 minutes. 6. The total volume is 200 μl. After the suitable incubation period, image the plate on the INCell 1000 using appropriate filters and dichroic mirror. 7. Carry out the data analysis using the Nuclear Trafficking Analysis module. 6. CHO-M1 Nitroreductase Gene Reporter Assay Using Genetically Engineered Cells 6.1 Introduction [0171] Reporter gene assay technology is widely used to monitor the cellular events associated with signal transduction and gene expression. The term reporter gene is used to define a gene with a readily measurable phenotype that can be distinguished easily over a background of endogenous proteins. A reporter gene construct is comprised of an inducible transcriptional control element driving the expression of a reporter gene. [0172] Generally, such reporters are selected on the basis of the sensitivity, dynamic range, convenience and reliability of the assay. Nitroreductase (NTR) is an FMN-dependent enzyme isolated from Escherichia coli B. NTR is one member of a structurally homologous family, containing four flavoproteins whose crystal structures have been solved. This family can be divided into two groups, nitroreductases, of which NTR is a member and flavin reductases such as FRase 1. The nitroreductase can be further sub-divided into two classes; oxygen sensitive and insensitive. The NTR described in this system belongs to the oxygen insensitive class of enzymes. The structure of NTR consists of a homodimers of 48 kDa with two molecules of FMN bound which is capable of reducing a number of nitro-containing compounds. Expression of NTR has been demonstrated in a number of mammalian cells without any reported toxicity. The ability of this enzyme to reduce nitro groups, a common mechanism for quenching the fluorescence of molecules has led to the development of a convenient gene reporter assay system based on the expression of NTR and a cell permeable quenched cyanine dye-CytoCy5S. CytoCy5S is membrane permeant and acts as a substrate for the enzyme permitting the use of NTR as a reporter of gene expression in living mammalian cells. The substrate has been optimised to improve the cellular retention of the reaction product. Typically current reporter gene systems available are invasive and require destruction of the cell in order to measure gene reporter expression (firefly luciferase) or have limited sensitivity (GFP) due to the absence of enzymatic amplification. To overcome these limitations the NTR gene reporter system has been developed as a non-invasive live cell reporter system that uses a cell permeable fluorogenic substrate. Analysis of NTR gene reporter assays on the INCell 1000 allows visualisation of gene expression in single living cells. The NTR gene reporter system is simple and convenient to use. 6.2 Transfection Methods [0173] To establish a reporter gene assay, the reporter gene is placed under the transcriptional control of a promoter or an enhancer with a minimal promoter. The promoter plus reporter gene is inserted into a suitable vector such as a plasmid containing a selectable marker that confers resistance to growth suppressing compounds, such as antibiotics e.g. neomycin. The reporter DNA is introduced into cells to provide either a transient assay or stably integrated into the genome of the host cell line to provide a stable reporter cell line. Introduction of the plasmid construct into mammalian cells is termed transfection and there are many commercially available reagents for delivering DNA into cells, such examples include liposomes, calcium phosphate and dendrimer technologies. [0174] Transient transfection with plasmids is a very versatile and easy to carry out technique. Transient transfections are generally performed overnight and allow the researcher to do single “one-off” experiments that will provide information on the functionality of the vector DNA. The vector DNA molecule does not integrate into the host chromatin but exists as an extrachromosomal molecule with a lifetime of typically 24-96 hours after which the DNA and expression of the reporter gene are lost. One major limitation with transient transfections is the variation in transfection efficiency, which can produce a heterogeneous population of cells and poor results if internal controls are not included. [0175] Stable transfection will provide a cell line which contains the reporter gene plus a selection marker integrated into the host genome, i.e. an inheritable genotype. 6.3 Production of Stable and Transiently Transfected Cell Lines 6.3.1 Transient Transfection 6.3.1.1 Method-Plasmid Based Transfection [0000] 1. Seed cells into sterile 60 mm tissue culture treated Petri dishes. Incubate the dishes overnight at 37° C. 2. When the cells attain 50-70% confluence, replace the medium with 3 ml of fresh growth medium. 3. Add reporter DNA/transfection reagent complex to each dish (ratio of DNA to transfection agent prepared and optimised according to suppliers instructions). Incubate overnight at 37° C. 4. After overnight incubation, remove the medium from each dish (ratio of DNA to transfection agent prepared and optimized according to suppliers instructions). Incubate overnight at 37° C. 5. After overnight incubation, remove the medium from each dish and wash cell monolayers with 3 ml phosphate buffered saline (PBS). Trypsinise and pool cells from each dish to produce a suspension of transfected cells. 6.3.2 Stable Transfection [0181] The process of establishing stable cell lines involves a large number of variables, many of which are cell-line dependent. Standard methods and guidelines for the generation of cell lines can be found in: Freshney R. I. Cloning and Selection of Specific Cell Types in Culture of Animal Cells, 3rd edition, Wiley-Liss Inc, Chapter 11, pp 161-178, 1994. Briefly, for stable cell line production, selection with G418 for pCORON-1003NFAT-NTR vector or hygromycin for pCORON5023NFAT-NTR vector is necessary. 24-48 hours post-transfection the cells should be placed under selection with the appropriate concentration of antibiotic. [0182] Once sufficient cells have grown, they should be seeded at a low density into a suitable dish or plate in medium containing selection antibiotic. The optimal concentration of selection antibiotic will vary according to the cell type and growth rate and users should perform a death curve on the host cells prior to transfection. The media containing the selection antibiotic should be changed twice a week, until drug-resistant colonies appear. This may take between 2 and 6 weeks depending on cell type. A negative control of non-transfected cells should be included to determine the effectiveness of the selection procedure. Death of the control cells should be observed between 3-10 days following selection. Single colonies should be selected and expanded to create a library of cell lines. The individual clonal cell lines should be screened for correct biological response and optimal assay performance based on the user criteria. 6.4 Cell Culture of CHO-M1 NFAT-NTR Cell Line 6.4.1 Cell Thawing Procedure [0183] Remove a cryo-vial from storage. [0184] Holding the cryo-vial, dip the bottom three-quarters of the cryo-vial into a 37° C. water bath, and swirl gently for 1-2 minutes until the contents are thawed. Do not thaw the cells for longer than 3 minutes as this decreases viability. [0185] Remove the cryo-vial from the water bath and wipe it with 70% (v/v) ethanol. Transfer the cells immediately to a T-flask containing growth medium at 37° C. CHO-M1 NFAT-NTR cells are routinely passaged 1:10 in Ham's F12 medium supplemented with 10% foetal calf serum, 2 mM L-glutamine, 100 units/ml penicillin and 100 μg/ml streptomycin. Selection is maintained with 0.5 mg/ml Neomycin (G418) and 0.25 mg/ml Hygromycin. The cells are grown as monolayers in 162 cm2 tissue-culture treated flasks and incubated at 37° C. in an atmosphere containing 5% CO 2 . On removal of the cells from cryopreservation, it is recommended that 0.5 mg/ml G-418 and 0.25 mg/ml Hygromycin is omitted until the cells have adhered to the flask, typically overnight. Once cells are established in culture, selection should be maintained with 0.5 mg/ml G-418 and 0.25 mg/ml Hygromycin. 6.4.2 Assay Protocol [0186] A reporter plasmid was constructed containing the 4 repeats of the NFAT response element upstream of the NTR gene. The plasmid was introduced into CHO-M1 cells and maintained under dual selection until clones were obtained. Single clones were isolated using limited dilution, propagated and assessed for biological response. 6.5 Reagent Preparation 6.5.1 Phosphate Buffered Saline Gibco BRL 14190-094 [0187] Alternative formulations and commercially available concentrates etc may be used. 6.5.2 CytoCy5S Solution [0188] Reconstitute with DMSO to a concentration Of 1-5 mM. Further dilutions should be made in assay buffer to give a solution (typically 5-10 μM) which is added to the cells usually as a 10× stock to give final concentrations required. 6.5.3 Carbachol Sigma C4382-1g [0189] Prepare a 100 mM stock solution in PBS. Vortex to resuspend the contents. Dilute the required concentration in assay medium. 6.5.4 Hoechst Reagent [0190] If nuclear staining is required for image analysis, prepare a stock of Hoechst solution in assay buffer. Prepare Hoechst at 25 μM in phenol red/serum free medium and add 10 μl per well. For imaging plates on the INCell 1000 Analyzer, a suitable cell marker should be introduced into the cell. An example is the nuclear marker Hoechst. This label should be bright enough to permit identification of the cell as an object during analysis and spectrally separated from the CytoCy5S so as not to interfere with the signal. Typically concentrations between 2.5-5 μM are used for Hoechst. 6.5.5 Controls for Transient Assays 6.5.5.1 Non-Transfected Control [0191] This should be included in each experiment. The non-transfected control provides information on any background level of fluorescence and is a check to ensure there is no NTR-like activity present in the host cell line. Assays should be carried out with and without agonist. 6.5.5.2 Non-Stimulated Control [0192] The non-stimulated control provides information on the baseline expression of the NTR gene under the control of the NFAT response element in the cell line chosen. The value from this control may vary with different cell lines and with assay set-up conditions. 6.6 Example 96-Well Assay Protocol [0193] Prepare CHO-M1 NFAT-NTR cells at 2.5×10 5 cells per ml in complete Ham's F12 medium containing 2 mM L-glutamine and 10% FCS (without selection agents). Dispense 200 μl (5×10 4 cells) into each well of a 96-well microplate. Incubate plates overnight at 37° C. 1. Following overnight incubation remove medium and wash cell monolayers with 200 μl PBS. 2. Add 90 μl agonist (e.g. carbachol) in assay medium to appropriate wells, and, 90 μl assay medium to control wells. Incubate plates at 37° C. for 16 hours. 3. After the 16 hour incubation, dispense 10 μl 10 μM CytoCy5S in assay medium (final concentration is typically 0.5 μM-1 μM). 4. Incubate at 37° C. for a further 2 hours. 5. Add 10 μl of 25 μM Hoechst nuclear dye in phenol red/serum-free medium. Incubate for 30 minutes at room temperature. 6. Image plates. Use appropriate filters for CytoCy5S (excitation filter 620/60 nm; emission filter 700/75 nm). Assays were imaged on the InCell Analyzer 1000 using the Object Intensity Algorithm. 7. ELISPOT Assays for the Measurement of Secreted/Cell-Associated Analyte 7.1 Introduction [0200] The Elispot (Enzyme Linked Immuno-Spot) assay provides an effective method of measuring antibody or cytokine production from cells at the single cell level or at very low cell numbers. 7.2 Reagents [0000] 1. Anti-TNF antibodies (Sigma) 2. ELISPOT Plate (Millipore HTS cat number MSIPS4510) 3. Ionomycin or carbachol (Sigma) 4. Biotinylated anti-TNF antibodies (R&D Systems) 7.3 Method [0205] Day 1 1. Coat ELISPOT plate (Millipore HTS cat number MSIPS4510) with primary antibody (see below). 2. Pre-wet each well with 15 μl of 35% ethanol for one minute. Rinse with 150 μl sterile PBS three times before the ethanol evaporates. 3. Coat plates with 100 μl (10 μg/ml) (for example) anti-TNF antibodies in sterile PBS. Incubate overnight at 4° C. 4. The following control wells were incorporated into the assay. 5. No cells 6. No primary antibody 7. No test-agent stimulation [0213] Day 2 1. Block membrane 2. Decant primary antibody solution. 3. Wash off unbound antibody with 150 μl sterile PBS per well; decant wash and repeat. 4. Block membrane with 150 μl per well of cell medium (RPMI-1640, 10% foetal calf serum, 1% non-essential amino acids, penicillin, streptomycin, glutamine) for at least 2 hours at 37° C. 5. Prepare cells (e.g. wild-type U-2 OS (ECAAC), or, U-2 OS derived cell line expressing EGFP-NFATc1 fusion protein (GE Healthcare), or, Chinese Hamster Ovary (CHO) NFAT-NTR cells (GE Healthcare). 6. Wash cells in sterile PBS and resuspend cells at a final concentration of 2.5×10 5 cells/ml in cell medium. 7. Stimulate the cells with the test agent (for example ionomycin or carbachol). 8. Plate out cells. 9. Decant blocking medium from the ELISPOT plate. 10. Add cells in 100 μl cell medium per well. 11. Incubate for 18 to 48 hours at 37° C., 5% CO 2 and 95% humidity. [0225] Day 3 1. Decant cells. 2. Wash plate 6 times with PBS/0.01% Tween 20. A squeeze bottle can be utilized to ensure adequate washing. 3. Dilute biotinylated anti-TNF antibodies to 2 μg/ml in PBS/0.5% BSA. Filter through a 0.45 μM filter. Add 100 μl/well. 4. Incubate for 2 hours at 37° C., 5% CO 2 , and 95% humidity. 5. Wash 6 times with PBS/0.01% Tween 20. 6. Prepare streptavidin-alkaline phosphatase enzyme conjugate at 1:1000 in sterile PBS. 7. Add 100 μl per well of streptavidin-alkaline phosphatase. Incubate for 45 minutes at room temperature. 8. Decant streptavidin, wash 3 times with PBS/0.01% Tween 20, followed by 3 washes with PBS. 9. Add 100 μl/well BCIP/NBT plus substrate. Incubate for 5 minutes. 10. Stop spot development under running water and wash extensively. While washing, remove underplate plate seal and continue rinsing. 11. Blot plate to remove excess liquid and dry back of wells with an absorbent wipe. This will ensure that the substrate has been completely removed from the membrane. 12. Capture cellular/spot images immediately, or, alternatively, let the ELISPOT plate dry overnight in the dark. 13. Analyze plate using INCell Imaging System using bright field settings. 8. Combination Assay of Human TNF, IL-8, or PDGF from Ionomycin, Ionomycin+PMA or Calcium Ionophore A23187 Stimulated EGFP-NFATc1, Using EGFP Translocation Assay and Transfected U-2OS Cells on INCell 1000 8.1 Materials [0000] Rabbit anti-human TNF or rabbit anti-human IL-8 antibodies (Sigma) Anti-rabbit anti-PDGF-A (N-30) antibodies (Santa Cruz Biotechnology, sc-128). Anti-rabbit IgG (whole molecule) R-Phycoerythrin conjugate (Sigma; P9537). Anti-rabbit IgG (whole molecule) fluorescein conjugate (GE Healthcare; N1034). Ionomycin (Sigma; 13909). Calcium ionophore A23187 (Sigma) C7522. PMA Sigma (P1585). 8.2 Method [0000] 1. The day before commencing the assay, seed EGFP-NFATc1 transfected U2OS cells at 1×10 4 cells per well in 200 μl of growth medium. 2. On the day of the assay, prepare the test agent (ionomycin, ionomycin+PMA, A23187). These samples are typically prepared in assay medium. 3. Decant the growth medium from the cell plate, removing all excess liquid and add 200 μl. Using the cell culture medium, wash the cells. Decant the wash. 4. Add 150 μl assay medium containing test agent. Incubate for 60 minutes. 5. The total volume is 200 μl. After the suitable incubation period, image the plate on the INCell 1000 using appropriate filters and dichroic mirror. 6. Carry out the data analysis using the Nuclear Trafficking Analysis module. 7. Cells were contacted with test agent for a further 3-18 hours and cell associated TNF, IL-8 or PDGF was measured post stimulation with test agent. 8. After stimulation with the test agent, the supernatant was decanted and the cells were washed ×3 with PBS. Cell-associated TNF, IL-8 or PDGF was localised with an anti-human TNF, IL-8 or PDGF antibody and a fluorescent dye-labelled anti-rabbit IgG (anti-rabbit IgG (whole molecule) R-Phycoerythrin conjugate (Sigma; P9537), or, anti-rabbit IgG (whole molecule) fluorescein conjugate (GE Healthcare; N1034). 9. After 60 minutes incubation with the rabbit antibody, the cells were washed ×3 and the dye labelled anti-rabbit IgG added. After 60 minutes incubation with the fluor-labelled second antibody, the cell were washed ×3 with PBS, and fluorescence detected on an IN Cell 1000 Analyser (GE Healthcare), using a 10× objective, suitable filter set and dichroic, 500 ms exposure. The results were analysed using an object intensity algorithm (IN Cell Investigator software). [0255] FIG. 11 shows EGFP-NFAT1c translocation from the combination assay of EGFP translocation and PDGF measurement (cell-associated molecule). Transfected U2OS cells were stimulated with ionomycin or calcium ionophore A23187 resulting in the EGFP-NFAT1c cell response measured on INCell. [0256] FIG. 12 shows ionomycin-stimulated PDGF release from EGFP-NFAT1c transfected U2OS cells in combination with EGFP-NFAT1c translocation ( FIG. 11 ). [0257] FIG. 13 shows a correlation between intracellular NFAT1c translocation and cell-associated PDGF from ionomycin-stimulated EGFP-NFAT1c transfected U2OS cells from a single population (correlation coefficient 0.9629). Results were obtained on the INCell Analyser Optical Imaging System as described above. [0258] FIG. 14 shows EGFP-NFAT1c translocation upon stimulation of transfected cells with ionomycin+PMA as measured on the INCell 1000 Analyser Optical Imaging System. [0259] FIG. 15 shows ionomycin+PMA stimulated TNFα release from EGFP-NFAT1c transfected U2OS cells obtained in combination with EGFP-NFAT1c translocation ( FIG. 14 ). [0260] FIG. 16 shows a correlation between intracellular NFAT1c translocation and cell-associated human TNFα from ionomycin+PMA-stimulated EGFP-NFAT1c transfected U2OS cells from a single population (correlation coefficient 0.9975). Results were obtained on the INCell Analyser Optical Imaging System as described above. 9. Combination Assay of Human TNF Using ELISPOT Assay for Cell-Associated Analyte and EGFP Translocation, from Ionomycin+PMA Stimulated EGFP-NFATc1 Transfected U2OS Cells on INCell 1000 [0261] 9.1 Reagents [0262] 1. Anti-TNF antibodies (Sigma) [0263] 2. ELISPOT Plate (Millipore HTS cat number MSIPS4510) [0264] 3. Ionomycin or carbachol (Sigma) [0265] 4. Biotinylated anti-TNF antibodies (R&D Systems) [0266] 9.2 Method 1. Coat ELISPOT plate (Millipore HTS cat number MSIPS4510) with primary antibody. 2. Pre-wet each well with 15 μl of 35% ethanol for one minute. Rinse with 150 μl sterile PBS three times before the ethanol evaporates. 3. Coat plates with 100 μl (10 μg/ml) (for example) anti-TNF antibodies in sterile PBS. Incubate overnight at 4° C. 4. The following control wells were incorporated into the assay. 5. No cells 6. No primary antibody 7. No test agent stimulation 8. Decant primary antibody solution. 9. Wash off unbound antibody with 150 μl sterile PBS per well; decant wash and repeat. 10. Block membrane with 150 μl per well of cell medium (RPMI-1640, 10% foetal calf serum, 1% non-essential amino acids, penicillin, streptomycin, glutamine) for at least 2 hours at 37° C. Decant blocking medium from the ELISPOT plate. 11. Prepare cells (a cell line expressing EGFP-NFATc1 fusion protein (GE Healthcare), Wash cells in sterile PBS and resuspend cells at a final concentration of 2.5×10 5 cells/ml in cell medium. 12. Plate out cells in 100 μl cell medium per well. 13. Stimulate the cells with the test agent (e.g. ionomycin+PMA). 14. The total volume is 200 μl. 15. Incubate for 60 minutes. Add Hoescht stain to a final concentration of 1 μM. 16. Wash cells with assay medium. 17. Carry out cellular analysis on InCell 100 using the Nuclear Trafficking Analysis Module. 18. Incubate cell in assay medium for a further 18 to 48 hours at 37° C., 5% CO 2 and 95% humidity. 19. Decant cells. 20. Wash plate 6 times with PBS/0.01% Tween 20. A squeeze bottle can be utilized to ensure adequate washing. 21. Dilute biotinylated anti-TNF antibodies to 2 μg/ml in PBS/0.5% BSA. Filter through a 0.45 μM filter. Add 100 μl/well. 22. Incubate for 2 hours at 37° C., 5% CO 2 , and 95% humidity. 23. Wash 6 times with PBS/0.01% Tween 20. 24. Prepare streptavidin-alkaline phosphatase enzyme conjugate at 1:1000 in sterile PBS. 25. Add 100 μl per well of streptavidin-alkaline phosphatase. Incubate for 45 minutes at room temperature. 26. Decant streptavidin, wash 3 times with PBS/0.01% Tween 20, followed by 3 washes with PBS. 27. Add 100 μl/well BCIP/NBT plus substrate. Incubate for 5 minutes. 28. Stop spot development under running water and wash extensively. While washing, remove underplate plate seal and continue rinsing. 29. Blot plate to remove excess liquid and dry back of wells with an absorbent wipe. This will ensure that the substrate has been completely removed from the membrane. 30. Let the plate dry overnight in the dark. 31. Analyze plate using InCell Analyser 1000 Imaging System using bright field settings. 10. Combination Assay of Carbachol-Stimulated CHO-M1 NFAT-NTR with Measurement of NFAT1c-NTR Intracellular Reporter Gene Assay and Human Integrin 5 Alpha Cell-Associated Analyte 10.1 Reagents [0000] Carbachol (Sigma) CytoCy5S (GE Healthcare) Hoechst nuclear dye (Invitrogen) Rabbit anti-hamster Integrin 5 antibody (Antibodies OnLine ABIN219718) Fluorescein labelled anti-rabbit IgG (GE Healthcare) 10.2 Method [0000] 1. Prepare CHO-M1 NFAT-NTR cells at 2.5×10 5 cells per ml in complete Ham's F12 medium containing 2 mM L-glutamine and 10% FCS (without selection agents). Dispense 200 μl (5×10 4 cells) into each well of a 96-well microplate. Incubate plates overnight at 37° C. 2. Following overnight incubation remove medium and wash cell monolayers with 200 μl PBS. 3. Add 90 μl agonist (e.g. carbachol) in assay medium to appropriate wells, and, 90 μl assay medium to control wells. Incubate plates at 37° C. for 16 hours. 4. After the 16 hour incubation, dispense 10 μl 10 μM CytoCy5S in assay medium (final concentration is typically 0.5 μM-1 μM). 5. Incubate at 37° C. for a further 2 hours. 6. Add 10 μl of 25 μM Hoechst nuclear dye in phenol red/serum-free medium. Incubate for 30 minutes at room temperature. 7. Image plates Use appropriate filters for CytoCy5S (excitation filter 620/60 nm; emission filter 700/75 nm). Assays were imaged on the InCell Analyzer 1000 using the Object Intensity Algorithm. 8. Incubate cells overnight at 37° C., 5% CO 2 . 9. Cells were contacted with test agent for a further 18 hours and cell associated Integrin alpha 5 was measured post-stimulation with test agent. After stimulation with the test agent, the supernatant was decanted and the cells were washed ×3 with PBS. Cell-associated Integrin was localised with a rabbit anti-hamster Integrin 5 antibody and a fluorescent dye-labelled anti-rabbit IgG (whole molecule) fluorescein conjugate (GE Healthcare; N1034). 10. After 60 minutes incubation with the rabbit antibody, the cells were washed ×3 and the dye labelled anti-rabbit IgG added. After 60 minutes incubation with the fluor-labelled second antibody, the cell were washed ×3 with PBS, and fluorescence detected on an INCell 1000 Analyser (GE Healthcare), using a 10× objective, suitable filter set and dichroic, 500 ms exposure. The results were analysed using an object intensity algorithm (INCell Investigator software).
Disclosed are methods useful in multiplex cell-based assays for compound screening employing imaging instrumentation. The methods described herein offer high content information relating to the biological potency of test agents, off-target effects and cellular toxicity of potential drug candidates.
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TECHNICAL FIELD OF THE INVENTION [0001] The present invention relates to the field of medical imaging, and in particular to in vivo imaging of disease states associated with the upregulation of a particular class of chemokine receptor (CCR). Compounds and methods are provided that are useful for imaging such disease states. DESCRIPTION OF RELATED ART [0002] The chemokine system regulates the trafficking of immune cells to tissues and thus plays a central role in inflammation. The system is also involved in many other biological processes such as growth regulation, haematopoiesis and angiogenesis. In addition, chemokines are thought to play a central role in the central nervous system. Chemokines (chemotactic cytokines) are small secreted molecules characterised by 4 conserved cysteine residues forming two essential disulphide bonds (Cys1-Cys3; Cys2-Cys4). They can be briefly classified, based on the relative position of the two cysteine residues, as CC and CXC, which represent the two major classes. Chemokines act as chemical mediators, released either by invading immune cells or by resident cells locally at the site of inflammation. [0003] Chemokines induce their biological effects through interaction with chemokine receptors (CCR). CCR are integral membrane proteins, formed of seven transmembrane α-helix domains linked by intracellular and extracellular loops, an extracellular N-terminus and a cytosolic C-terminus. They all share a common fold of three stranded antiparallel β-sheets covered on one face by a C-terminus α-helix and preceded by a disordered N-terminus. The dimerisation/oligomerisation process, essential for their functional properties, involves the N-terminus. [0004] Expression of chemokine receptors (CCR) has been found to be perturbed in certain disease states where inflammation plays a role. For example, neuroinflammatory diseases such as multiple sclerosis (MS) [Rottman et al 2000 Eur. J. Immunol. 30 p 2372], Alzheimer's disease (AD) and Parkinson's disease (PD), [Xia & Hyman 1999 J. Neurovirology 5 p 32] and also other pathological inflammatory conditions such as atherosclerosis [Greaves & Channon 2002 Trends Immunol. 23(11) p 535], chronic obstructive pulmonary disorder (COPD), rheumatoid arthritis, osteoarthritis, allergic disease, HIV/AIDS, asthma and cancer. [0005] One chemokine receptor that is particularly important in certain disease states is CCR5. It has been the subject of considerable therapeutic development as it is the chemokine receptor which the human immunodeficiency virus (HIV) uses to gain entry into macrophages and CCR5 expression is upregulated in chronic HIV infection. CCR5 has also received attention due to its involvement in the pathophysiology of various neuroinflammatory conditions such as MS, Alzheimer's disease and PD. [0006] Chemokine receptor ligands have been reviewed by Gao and Metz [Chem. Rev., 103, 3733-52 (2003)], and Ribeiro and Horuk [Pharmacol. Ther., 107, 44-58 (2005)]. [0007] Targeting cytokine and chemokine receptors for nuclear medical imaging has been described as a challenge [Signore et al, Eur. J. Nucl. Med. Mol. Imaging, 30(1), 149-165 (2003)]. Signore et al reported that the main approach known to target chemokine receptors was radiolabelled interleukin-8 (IL-8). [0008] WO 02/36581 teaches radiopharmaceuticals that bind to the CCR1 receptor and that are able to pass through the blood-brain barrier (BBB). These radiopharmaceuticals are taught as useful in diagnosing Alzheimer's disease. [0009] WO 2006/102395 teaches targeting of imaging moieties (referred to therein as “imaging agents”) to atherosclerotic plaques. The ligand RANTES, which binds to the CCR5 receptor, is taught as one of a number of targeting moieties suitable for the delivery of an imaging moiety to atherosclerotic lesions when linked thereto. The imaging moieties taught include those suitable for a range of in vivo imaging modalities, e.g. single photon emission tomography (SPECT), magnetic resonance imaging (MRI) and positron emission tomography (PET). [0010] The ability to image conditions where CCR5 is specifically implicated, especially neuroinflammation, may represent an important tool for early diagnosis of different acute and chronic pathological conditions and to support therapeutic approaches and strategies. There is therefore a need for imaging agents which image CCR5, and in particular those that can cross the BBB. SUMMARY OF THE INVENTION [0011] The present invention relates to in vivo imaging and in particular to novel imaging agents suitable for use in in vivo imaging of the chemokine receptor 5 (CCR5). The invention also provides a method for the preparation of the imaging agents of the invention as well as pharmaceutical compositions comprising them. For the facile preparation of the pharmaceutical compounds, kits are provided. In addition, the invention provides methods for the use of the imaging agents and pharmaceutical compositions of the invention. DETAILED DESCRIPTION OF THE INVENTION [0012] In a first aspect, the present invention provides an imaging agent which comprises a synthetic compound having affinity for chemokine receptor 5 (CCR5) and having a molecular weight of 3000 Daltons or less, labelled with at least one imaging moiety, wherein following administration of said compound to the mammalian body in vivo, the imaging moiety can be detected externally in a non-invasive manner and said imaging moiety is chosen from: (i) a gamma-emitting radioactive halogen; or (ii) a positron-emitting radioactive non-metal. [0015] A compound having “affinity for CCR5” is defined in the present invention as that which inhibits binding of MIP-1β CCR5-expressing CHO cells with IC 50 values of between 0.1 nM to 10 nM, where MIP-1β is Macrophage Inflammatory Protein 1β (ligand of CCR5) [Samson et al., J. Biol. Chem., 272, 24934-41 (1997)]. See also Example 4. The CCR5 compounds of the present invention are also preferably selective for CCR5 over other chemokine receptors (such as CCR1 or CCR3). Such selective inhibitors suitably exhibit a greater potency for CCR5 over CCR1, defined by Ki, of a factor of at least 50, preferably at least 100, most preferably at least 500. [0016] The synthetic compound is preferably a non-peptide. By the term “non-peptide” is meant a compound which does not comprise any peptide bonds, i.e. an amide bond between two amino acid residues. The synthetic compound having affinity for chemokine receptor 5 (CCR5) preferably has a molecular weight of 1000 Daltons or less, and most preferably 600 Daltons or less. The synthetic compound preferably comprises 2 to 6, most preferably 2 to 5 nitrogen (N) atoms. Said N atoms are present as part of amide; amine; or 5- or 6-membered nitrogen-containing heteroaryl ring functional groups. The heteroaryl ring can have 1 or 2 N heteroatoms. When an amine is present, it is suitably either open chain or as part of a 5- or 6-membered saturated aliphatic ring. Preferred such cyclic amines are piperidine, piperazine or morpholine. When an amide is present, it is suitably open chain, i.e. does not comprise a lactam. Preferred such amides are benzamides or acyl derivatives of aniline, benzylamine or aminopiperidine residues. The synthetic compound also preferably comprises 1 to 3 phenyl rings, most preferably 1 or 2 phenyl rings. The CCR5 pharmacophore preferably comprises two hydrogen bond acceptors and three hydrophobic interactions; in particular it has a basic amine located 5-7 Å from a phenyl ring. [0017] The term “labelled with” means that either a functional group comprises the imaging moiety, or the imaging moiety is attached as an additional species. When a functional group comprises the imaging moiety, this means that the ‘imaging moiety’ forms part of the chemical structure, and is a radioactive isotope present at a level significantly above the natural abundance level of said isotope. Such elevated or enriched levels of isotope are suitably at least 5 times, preferably at least 10 times, most preferably at least 20 times; and ideally either at least 50 times the natural abundance level of the isotope in question, or present at a level where the level of enrichment of the isotope in question is 90 to 100%. Examples of such functional groups include CH 3 groups with elevated levels of 11 C, and fluoroalkyl groups with elevated levels of 18 F, such that the imaging moiety is the isotopically labelled 11 C or 18 F atom within the chemical structure. The radioisotopes 3 H and 14 C are not suitable imaging moieties. [0018] When the imaging moiety is a gamma-emitting radioactive halogen, the radiohalogen is suitably chosen from 123 I, 131 I or 77 Br. A preferred gamma-emitting radioactive halogen is 123 I. When the imaging moiety is a positron-emitting radioactive non-metal, the imaging agent is suitable for positron emission tomography (PET). Suitable such positron emitters include: 11 C, 13 N, 17 F, 18 F, 75 Br, 76 Br or 124 I. Preferred positron-emitting radioactive non-metals are 11 C, 13 N, 124 I and 18 F, especially 11 C and 18 F, most especially 18 F. [0019] The imaging moiety is preferably a positron-emitting radioactive non-metal. The use of a PET imaging moiety has certain technical advantages, including: (i) the development of PET/CT cameras allowing easy co-registration of functional (PET) and anatomical (CT) images for improved diagnostic information; (ii) the facility to quantify PET images to allow accurate assessment for staging and therapy monitoring; (iii) increased sensitivity to allow visualisation of smaller target tissues. [0023] In one embodiment, the imaging agent comprises a synthetic compound of Formula I: [0000] [0024] wherein: R 1 and R 2 are independently C 1-6 alkyl, or C 1-6 haloalkyl; R 3a and R 3b are independently represent a bond, or a linker group selected from C 1-5 alkylene, —O—[C 1-4 alkylene]- or —[C 1-2 alkylene]-O—[C 1-2 alkylene]-; R 4 is selected from H, C 1-6 alkyl or C 1-6 alkoxy; and, Q a and Q b are independently an A 3 group or -(A 2 ) n -R 5 ; wherein A 2 is selected from —O—, —OCH 2 —, —CH 2 O—, CH 2 , C═O, S═O, SO 2 , —NH(CO)— or —CO(NH)—, R 5 is a phenyl group with 0-3 substituents which are A 3 groups, and n is an integer of value 0 to 3; wherein -A 3 is H, C 1-6 alkyl, OH or Hal. [0031] Preferred compounds of Formula I are as follows: [0032] R 1 and R 2 are independently selected from methyl, ethyl, 1-methylethyl, fluoromethyl, 2-fluoroethyl, 3-fluoropropyl or 1-fluoromethylethyl; [0033] R 3a and R 3b are independently C 1-3 alkylene or C 1-3 alkoxy; [0034] R 4 is H or a C 1-3 alkyl; [0035] Q is 3-phenoxy, 4-phenoxy, 4-(3-hydroxyphenoxy), 4-(4-methylphenyl)sulfonyl, 4-(4-chlorophenyl)sulfonyl, 4-(2,4-dichlorophenyl)sulfonyl, 4-(4-chlorophenoxy), 4-methylphenylamino, 4-phenylamino, 4-phenylthio, 4-phenylsulfonyl, 4-benzoyl, 4-(4-iodophenoxy), 3-(4-iodophenoxy), 4-(4-fluorophenoxy), 3-(4-fluorophenoxy), or 3-(4-fluoroethyl)phenoxy. [0036] Preferred imaging agents which comprise compounds of Formula I are of Formula Ia: [0000] [0037] wherein: IM 1 and IM 3 are independently H or an imaging moiety; IM 2 is C or the imaging moiety 11 C; with the proviso that at least one of IM 1-3 is an imaging moiety. [0041] Preferred compounds of Formula Ia are as follows: [0000] [0042] An alternative preferred compound of Formula I is a compound of Formula Ib: [0000] [0043] wherein IM 1a and IM 2a are independently H, Hal, or an imaging moiety; IM 3a is C or the imaging moiety 11 C; with the proviso that at least one of IM 1-3 is an imaging moiety. [0047] In a further embodiment, the imaging agent comprises a synthetic compound of Formula II: [0000] [0048] wherein: R 6 is acyl, fluoroacyl or methylsulfonyl; R 8 -R 9 are independently selected from H, C 1-3 alkyl, OH or Hal. E is N or CH; when E is N, X 1 is —CH 2 — and when E is CH, X 1 is —CH 2 — or —O—; Ar 1 is a 6-membered aryl ring having 0-2 N heteroatoms, and substituted with 0 to 3 R 7 groups; each R 7 is independently chosen from C 1-3 alkyl, OH, Hal, NO 2 , NH 2 , CO 2 H, C 1-6 alkoxy, C 1-6 amino, C 1-6 amido, —O(CH 2 CH 2 O) x X 2 or —NH(CH 2 CH 2 O) x X 2 where x is an integer of value 0 to 4, and X 2 is H or CH 3 . [0055] In Formula II, R 6 is preferably acetyl; R 8 -R 9 are preferably selected from H, CH 3 , OH, Cl, F and I; and Ar 1 preferably comprises a phenyl or pyridine ring, most preferably a phenyl ring. Preferably, the Ar 1 ring is unsubstituted or substituted with one R 7 group. When present, R 7 is preferably chosen from: —OH, —NHCH 3 , F, —O(CH 2 CH 2 O) x X 2 or —NH(CH 2 CH 2 O) x X 2 . X 2 is preferably H. [0056] Preferred imaging agents which comprise compounds of Formula II are of Formula IIa: [0000] [0057] wherein: IM 4 is independently H, CH 3 or an imaging moiety IM 6 , IM 7 and IM 8 are independently H or an imaging moiety; IM 5 is C or the imaging moiety 11 C; with the proviso that at least one of IM 4-8 is an imaging moiety; and, X 1 is as defined above for Formula II. [0063] Preferred compounds of Formula IIa are: [0000] [0064] wherein X 1 is as defined above for Formula II. [0065] In a further embodiment, the imaging agent comprises a synthetic compound of Formula III: [0000] [0066] wherein: R 10 is H or C 1-3 alkyl; R 10a is CH 2 or a phenylene group with 0-2 substituents selected from C 1-3 alkyl, C 1-3 haloalkyl, or Hal; R 11 is H or a phenyl group with 0-3 substituents independently selected from OH, Hal, C 1-6 alkyl, C 1-6 alkoxyalkyl, C 1-6 fluoroalkyl or nitrile; R 11a is selected from CH, C 1-3 alkylene, and —O—C 1-3 alkylene; R 12 is a phenyl group with 0-3 substituents selected from C 1-3 alkyl, C 1-3 haloalkyl, Hal, C 1-3 alkylsulfonyl, or R 12 is —NHC═O—R x R y wherein: R x is selected from oxygen and (CH 2 ) p wherein p is an integer of value 0 to 3; and, R y is a six-membered ring with 0-3 heteroatoms selected from O, N and S; R 12a is H or OH; R 13 is H, C 1-3 alkyl or a C 1-3 haloalkyl; and, Q c and Q d are independently substituents selected from H, Hal, C 1-3 alkyl, and C 1-3 alkyl sulfonyl. [0077] Preferred compounds of Formula III have: R 10 ═H; R 10a ═CH 2 ; R 11 =3-fluorophenyl, 4-fluorophenyl, 3-chlorophenyl, 3,5-difluorophenyl, 3-fluoro, 4-chloro-phenyl, 3-hydroxy,4-iodophenyl, 4-iodophenyl; R 11a ═CH; R 12 =a phenyl group with 1 or 2 substituents selected from C 1-3 alkyl, C 1-3 haloalkyl, Hal, C 1-3 alkylsulfonyl or R 12 is NHC═O—R x R y wherein: R x is oxygen; and, R y is cyclohexyl, dihydropyran or tetrahydropyran; R 12a ═H; R 13 =ethyl, fluoroethyl, propyl, or fluoropropyl; and, Q c is H and Q d is 4-C 1-3 alkyl or 4-C 1-3 alkyl sulfonyl. [0088] Alternatively preferably, for compounds of Formula III: R 10 ═H or CH 3 ; R 10a =a phenylene group with a Hal substituent; R 11 ═H; R 11a ═C 1-3 alkoxy; R 12 =a phenyl group with 1 or 2 substituents selected from C 1-3 alkyl, C 1-3 haloalkyl, Hal, C 1-3 alkylsulfonyl or R 12 is NHC═O—R x R y wherein: R x is oxygen; and, R y is cyclohexyl, dihydropyran or tetrahydropyran; R 12a ═OH; R 13 =ethyl, fluoroethyl, propyl, or fluoropropyl; and, Q c is H and Q d is 4-C 1-3 alkyl or 4-C 1-3 alkyl sulfonyl. [0099] Preferred imaging agents which comprise compounds of Formula III are of Formulae IIIa-IIIc: [0000] [0100] wherein: IM 9 and IM 10 are independently H or an imaging moiety; with the proviso that at least one of IM 9-10 is an imaging moiety. [0000] [0103] wherein: IM 11 and IM 12 are independently H, CH 3 or an imaging moiety; with the proviso that at least one of IM 11-12 is an imaging moiety. [0000] [0106] wherein: IM 12a -IM 12d are independently H, CH 3 or an imaging moiety; with the proviso that at least one of IM 12a -IM 12d is an imaging moiety. [0109] Preferred imaging agents of Formula IIIa are selected from: [0000] [0110] Preferred imaging agents of Formula IIIb are selected from: [0000] [0111] In a further embodiment, the imaging agent comprises a synthetic compound of Formula IV: [0000] [0112] wherein: [0113] R 14 is H, C 1-6 alkyl, C 1-6 fluoroalkyl, C 1-6 alkoxy, or a phenyl or benzyl group optionally substituted with an A 4 group; wherein A 4 is C 1-6 alkyl, C 1-6 alkoxy or Hal; [0115] R 14a is selected from Hal or C 1-3 haloalkyl; and, [0116] R 14b and R 14c are independently selected from CH 2 or N. [0117] Preferably in Formula IV: [0118] R 14 is C 1-3 fluoroalkyl or halophenyl; [0119] R 14a is C 1-3 haloalkyl; and, [0120] R 14b and R 14c are both N. [0121] Alternatively preferably in Formula IV: [0122] R 14 is C 1-3 alkyl; [0123] R 14a is Hal; and, [0124] R 14b and R 14c are both CH 2 . [0125] Preferred imaging agents which comprise compounds of Formula IV are of Formula IVa or Formula IVb: [0000] [0126] wherein: IM 13 is independently CH 3 or an imaging moiety; IM 14 is independently C or the imaging moiety 11 C; with the proviso that at least one of IM 13-14 is an imaging moiety. [0000] [0130] wherein: IM 14a is independently CH 3 or an imaging moiety; IM 14b is independently C or the imaging moiety 11 C; with the proviso that at least one of IM 14a-14b is an imaging moiety. [0134] Preferred imaging agents of Formula IVa are selected from: [0000] [0135] Preferred imaging agents of Formula IVb are selected from: [0000] [0136] In a further embodiment, the imaging agent comprises a synthetic compound of Formula V: [0000] [0137] wherein: R 15 and R 16 are independently H, OH, C 1-3 alkyl or Hal; and, R 17 is H, C 1-6 alkyl, or C 1-6 haloalkyl. [0140] Preferred compounds of Formula V are those wherein: R 15 and R 16 are independently H or Hal; and, R 17 is C 1-3 fluoroalkyl. [0143] Preferred imaging agents which comprise compounds of Formula V are of Formula Va: [0000] [0144] wherein: IM 15 to IM 17 are independently H or an imaging moiety; with the proviso that at least one of IM 15-17 is an imaging moiety. [0147] Preferred imaging agents of Formula Va are selected from: [0000] [0148] In a further embodiment, the imaging agent comprises a synthetic compound of Formula VI: [0000] [0149] wherein: [0150] R 18 is H or Hal; [0151] R 19 is C 1-6 alkyl or C 1-6 haloalkyl; [0152] R 39 H, OH, or Hal; and, [0153] R 21 is C 1-6 alkyl, C 1-6 cycloalkyl, or C 1-6 haloalkyl. [0154] Examples of preferred imaging agents of Formula VI are as follows: [0000] [0155] The synthetic compound having affinity for chemokine receptor 5 (CCR5) can be obtained as follows: [0156] Formula I—WO 00/06146, Shiraishi et al [J. Med. Chem. 43 pp 2049-63 (2000)]. [0157] Formula II—Piperidine-4-carboxamide derivatives, Imamura et al, [Bioorg. Med. Chem. 13 p. 397-416 (2005), and J. Med. Chem. 49 pp 2784-93 (2006)]. [0158] Formula III—diphenylpropylpiperidine derivatives, Cumming et al [Bioorg. Med. Chem. Lett., 16 p 3533-3536 (2006)], and Shou-Fu Lu et al. Bioorg. Med. Chem. Lett., 2007, 17, 1883-1887. [0159] Formula IV—piperazine-based derivatives, Tagat et al [J. Med. Chem., 47, 2405-8 (2004)]; and Tagat et al [J. Med. Chem 44, 3343-6 (2001)] [0160] Formula V—Wood and Armour [Prog. Med. Chem., 43, 239-271(2005)] [0161] Formula VI—Mitsuya et al [J. Med. Chem. 49 pp 4140-52 (2006), and Bioorg. Med. Chem. Lett. 17 pp 727-31 (2007)] [0162] The imaging agents of the first aspect are suitably prepared by reaction with a precursor, as described in the second aspect below. [0163] In a second aspect, the present invention provides a method for the preparation of the imaging agent of the first aspect, which comprises reaction of: (i) a non-radioactive precursor; and, (ii) a suitable source of the imaging moiety of the first aspect, [0166] wherein said precursor is a derivative of the synthetic compound of the first aspect, and said derivative comprises a substituent Y 1 which is capable of reaction with said suitable source of the imaging moiety to give the desired imaging agent. [0167] The “precursor” suitably comprises a non-radioactive derivative of the synthetic compound, which is designed so that chemical reaction with a convenient chemical form of the desired non-metallic radioisotope can be conducted in the minimum number of steps (ideally a single step), and without the need for significant purification (ideally no further purification) to give the desired radioactive product. Such precursors are synthetic and can conveniently be obtained in good chemical purity. The “precursor” may optionally comprise a protecting group (P GP ) for certain functional groups of the synthetic CCR5 compound. Suitable precursors are described by Bolton, J. Lab. Comp. Radiopharm., 45, 485-528 (2002). [0168] By the term “protecting group” (P GP ) is meant a group which inhibits or suppresses undesirable chemical reactions, but which is designed to be sufficiently reactive that it may be cleaved from the functional group in question under mild enough conditions that do not modify the rest of the molecule. After deprotection the desired product is obtained. Protecting groups are well known to those skilled in the art and are suitably chosen from, for amine groups: Boc (where Boc is tert-butyloxycarbonyl), Fmoc (where Fmoc is fluorenylmethoxycarbonyl), trifluoroacetyl, allyloxycarbonyl, Dde [i.e. 1-(4,4-dimethyl-2,6-dioxocyclohexylidene)ethyl] or Npys (i.e. 3-nitro-2-pyridine sulfenyl); and for carboxyl groups: methyl ester, tert-butyl ester or benzyl ester. For hydroxyl groups, suitable protecting groups are: methyl, ethyl or tert-butyl; alkoxymethyl or alkoxyethyl; benzyl; acetyl; benzoyl; trityl (Trt) or trialkylsilyl such as tert-butyldimethylsilyl. For thiol groups, suitable protecting groups are: trityl and 4-methoxybenzyl. The use of further protecting groups are described in ‘Protective Groups in Organic Synthesis’, Theorodora W. Greene and Peter G. M. Wuts, (Third Edition, John Wiley & Sons, 1999). [0169] Preferred precursors are those wherein Y 1 comprises a derivative which either undergoes direct electrophilic or nucleophilic halogenation; undergoes facile alkylation with a labelled alkylating agent chosen from an alkyl or fluoroalkyl halide, tosylate, triflate (i.e. trifluoromethanesulphonate), mesylate, maleimide or a labelled N-haloacetyl moiety; alkylates thiol moieties to form thioether linkages; or undergoes condensation with a labelled active ester, aldehyde or ketone. Examples of the first category are: (a) organometallic derivatives such as a trialkylstannane (e.g. trimethylstannyl or tributylstannyl), or a trialkylsilane (e.g. trimethylsilyl); (b) a non-radioactive alkyl iodide or alkyl bromide for halogen exchange and alkyl tosylate, mesylate or triflate for nucleophilic halogenation; (c) aromatic rings activated towards electrophilic halogenation (e.g. phenols) and aromatic rings activated towards nucleophilic halogenation (e.g. aryl is iodonium, aryl diazonium, aryl trialkylammonium salts or nitroaryl derivatives). [0173] Preferred derivatives which undergo facile alkylation are alcohols, phenols, amine or thiol groups, especially thiols and sterically-unhindered primary or secondary amines. [0174] Preferred derivatives which alkylate thiol-containing radioisotope reactants are maleimide derivatives or N-haloacety) groups. Preferred examples of the latter are N-chloroacetyl and N-bromoacetyl derivatives. [0175] Preferred derivatives which undergo condensation with a labelled active ester moiety are amines, especially sterically-unhindered primary or secondary amines. [0176] Preferred derivatives which undergo condensation with a labelled aldehyde or ketone are aminooxy and hydrazides groups, especially aminooxy derivatives. [0177] The “precursor” may optionally be supplied covalently attached to a solid support matrix. In that way, the desired imaging agent product forms in solution, whereas starting materials and impurities remain bound to the solid phase. Precursors for solid phase electrophilic fluorination with 18 F-fluoride are described in WO 03/002489. Precursors for solid phase nucleophilic fluorination with 18 F-fluoride are described in WO 03/002157. The solid support-bound precursor may therefore be provided as a kit cartridge which can be plugged into a suitably adapted automated synthesizer. The cartridge may contain, apart from the solid support-bound precursor, a column to remove unwanted fluoride ion, and an appropriate vessel connected so as to allow the reaction mixture to be evaporated and allow the product to be formulated as required. The reagents and solvents and other consumables required for the synthesis may also be included together with a compact disc carrying the software which allows the synthesiser to be operated in a way so as to meet the customer requirements for radioactive concentration, volumes, time of delivery etc. Conveniently, all components of the kit are disposable to minimise the possibility of contamination between runs and will be sterile and quality assured. [0178] When the imaging moiety comprises a radioactive iodine isotope, Y 1 suitably comprises: a non-radioactive precursor halogen atom such as an aryl iodide or bromide (to permit radioiodine exchange); an activated precursor aryl ring (e.g. phenol or aniline groups); an imidazole ring; an indole ring; an organometallic precursor compound (e.g. trialkyltin or trialkylsilyl); or an organic precursor such as triazenes or a good leaving group for nucleophilic substitution such as an iodonium salt. Methods of introducing radioactive halogens (including 123 I and 18 F) are described by Bolton [J. Lab. Comp. Radiopharm., 45, 485-528 (2002)]. Examples of suitable precursor aryl groups to which radioactive halogens, especially iodine can be attached are given below: [0000] [0179] Both contain substituents which permit facile radioiodine substitution onto the aromatic ring. Alternative substituents containing radioactive iodine can be synthesised by direct iodination via radiohalogen exchange, e.g. [0000] [0180] For radioactive isotopes of iodine, the radioiodine atom is preferably attached via a direct covalent bond to an aromatic ring such as a benzene ring, or a vinyl group since it is known that iodine atoms bound to saturated aliphatic systems are prone to in vivo metabolism and hence loss of the radioiodine. An iodine atom bound to an activated aryl ring like phenol has also, under certain circumstances, been observed to have limited in vivo stability. [0181] When the imaging moiety comprises a radioactive isotope of fluorine the radiofluorine atom may form part of a fluoroalkyl or fluoroalkoxy group, since alkyl fluorides are resistant to in vivo metabolism. For radioactive isotopes of fluorine (e.g. 18 F), the radiohalogenation may be carried out via direct labelling using the reaction of 18 F-fluoride with a suitable precursor having a good leaving group, such as an alkyl bromide, alkyl mesylate or alkyl tosylate. Alternatively, the radiofluorine atom may be attached via a direct covalent bond to an aromatic ring such as a benzene ring. For such aryl systems, the precursor suitably comprises an activated nitroaryl ring, an aryl diazonium salt, or an aryl trialkylammonium salt. Direct radiofluorination can, however, be detrimental to sensitive functional groups since these nucleophilic reactions are carried out with anhydrous [ 18 F]fluoride ion in polar aprotic solvents under strong basic conditions. [0182] When the synthetic compound has alkali-sensitive functional groups, or other functionality unsuitable for direct radiohalogenation, an indirect radiohalogenation method is preferred. Thus, when the imaging moiety comprises a radioactive halogen, such as 123 I and 18 F, Y 1 preferably comprises a functional group that will react selectively with a radiolabelled synthon and thus upon conjugation gives the desired imaging agent product. By the term “radiolabelled synthon” is meant a small, synthetic organic molecule which is: (i) already radiolabelled such that the radiolabel is bound to the synthon in a stable manner; (ii) comprises a functional group designed to react selectively and specifically with a corresponding functional group which is part of the desired compound to be radiolabelled. This approach gives better opportunities to generate imaging agents with improved in vivo stability of the radiolabel relative to direct radiolabelling approaches. [0185] A synthon approach also allows greater flexibility in the conditions used for the introduction of the imaging moiety. [0186] 18 F-can also be introduced-by N-alkylation of amine precursors with alkylating agent synthons such as 18 F(CH 2 ) 3 OMs (where Ms is mesylate) to give N—(CH 2 ) 3 18 F, O-alkylation of hydroxyl groups with 18 F(CH 2 ) 3 OMs, 18 F(CH 2 ) 3 OTs or 18 F(CH 2 ) 3 Br or S-alkylation of thiol groups with 18 F(CH 2 ) 3 OMs or 18 F(CH 2 ) 3 Br. 18 F can also be introduced by alkylation of N-haloacetyl groups with a 18 F(CH 2 ) 3 OH reactant, to give —NH(CO)CH 2 O(CH 2 ) 3 18 F derivatives or with a 18 F(CH 2 ) 3 SH reactant, to give —NH(CO)CH 2 S(CH 2 ) 3 18 F derivatives. 18 F can also be introduced by reaction of maleimide-containing precursors with 18 F(CH 2 ) 3 SH. For aryl systems, 18 F-fluoride nucleophilic displacement from an aryl diazonium salt, an aryl nitro compound or an aryl quaternary ammonium salt are suitable routes to aryl- 18 F labelled synthons useful for conjugation to precursors of the imaging agent. [0187] Precursors wherein Y 1 comprises a primary amine group can also be labelled with 18 F by reductive amination using 18 F—C 6 H 4 —CHO as taught by Kahn et al [J. Lab. Comp. Radiopharm. 45, 1045-1053 (2002)] and Borch et al [J. Am. Chem. Soc. 93, 2897 (1971)]. This approach can also usefully be applied to aryl primary amines, such as compounds comprising phenyl-NH 2 or phenyl-CH 2 NH 2 groups. [0188] An especially preferred method for base-sensitive precursors is when Y 1 comprises an aminooxy group of formula —NH(C═O)CH 2 —O—NH 2 which is condensed with 18 F—C 6 H 4 —CHO under acidic conditions (e.g. pH 2 to 4). Further details of synthetic routes to 18 F-labelled derivatives are described by Bolton, J. Lab. Comp. Radiopharm., 45, 485-528 (2002). [0189] The precursor is preferably in sterile, apyrogenic form. Methods for maintaining 3 0 sterility are described in the third aspect below. [0190] Examples of precursors suitable for the generation of imaging agents of the present invention are those where Y 1 comprises an amine group which is condensed with the synthon N-succinimidyl 4-[ 123 I]iodobenzoate at pH 7.5-8.5 to give amide bond linked products. [0191] Preferred precursors comprising the compounds of Formula I to Formula V are of Formula Ip to Vp respectively: [0000] [0192] wherein at least one of E 1 -E 4 and Y a -Y b comprises Y 1 , and the remaining E 1 -E 4 and Y a -Y b groups are R 1 -R 4 and Q a -Q b groups respectively of Formula I. [0000] wherein at least one of E 6 -E 9 comprises Y 1 , and the remaining E 6 -E 9 groups are R 6 -R 9 groups respectively of Formula II. [0000] wherein at least one of E 10 , E 11 , E 12 , or E 13 comprises Y 1 and the remaining E 10 , E 11 , E 12 , or E 13 groups are R 10 -R 13 groups respectively of Formula III; E 11a -E 12a are as defined for E 11a -E 12a of Formula III; and, Y c and Y d are as defined for Q c and Q d of Formula III. [0000] wherein E 14 is an R 14 group of Formula IV which comprises Y 1 ; and, E 14a -E 14c are as defined for R 14a -R 14c of Formula IV. [0000] wherein at least one of E 15 -E 17 comprises Y 1 and the remaining E 15 -E 17 groups are R 15 -R 17 respectively of Formula V. [0000] wherein at least one of E 18 -E 20 comprises Y 1 and the remaining E 18 -E 20 groups are R 18 -R 20 respectively of Formula VI; and, E 21 is R 21 as defined for Formula VI. [0202] In a third aspect, the present invention provides a pharmaceutical composition which comprises the imaging agent of the first aspect together with a biocompatible carrier, in a form suitable for mammalian administration. [0203] The “biocompatible carrier” is a fluid, especially a liquid, in which the imaging agent can be suspended or dissolved, such that the composition is physiologically tolerable, i.e. can be administered to the mammalian body without toxicity or undue discomfort. The biocompatible carrier is suitably On injectable carrier liquid such as sterile, pyrogen-free water for injection; an aqueous solution such as saline (which may advantageously be balanced so that the final product for injection is isotonic); an aqueous solution of one or more tonicity-adjusting substances (e.g. salts of plasma cations with biocompatible counterions), sugars (e.g. glucose or sucrose), sugar alcohols (e.g. sorbitol or mannitol), glycols (e.g. glycerol), or other non-ionic polyol materials (e.g. polyethyleneglycols, propylene glycols and the like). Preferably the biocompatible carrier is pyrogen-free water for injection or isotonic saline. [0204] Such radioactive pharmaceutical compositions (i.e. radiopharmaceutical compositions) are suitably supplied in either a container which is provided with a seal which is suitable for single or multiple puncturing with a hypodermic needle (e.g. a crimped-on septum seal closure) whilst maintaining sterile integrity. Such containers may contain single or multiple patient doses. Preferred multiple dose containers comprise a single bulk vial (e.g. of 10 to 30 cm 3 volume) which contains multiple patient doses, whereby single patient doses can thus be withdrawn into clinical grade syringes at various time intervals during the viable lifetime of the preparation to suit the clinical situation. Pre-filled syringes are designed to contain a single human dose, or “unit dose” and are therefore preferably a disposable or other syringe suitable for clinical use. The pre-filled syringe may optionally be provided with a syringe shield to protect the operator from radioactive dose. Suitable such radiopharmaceutical syringe shields are known in the art and preferably comprise either lead or tungsten. [0205] The radiopharmaceutical compositions may be prepared from kits, as is described in the fourth aspect below. Alternatively, the radiopharmaceuticals may be prepared under aseptic manufacture conditions to give the desired sterile product. The radiopharmaceuticals may also be prepared under non-sterile conditions, followed by terminal sterilisation using e.g. gamma-irradiation, autoclaving, dry heat or chemical treatment (e.g. with ethylene oxide). [0206] In a fourth aspect, the present invention provides a kit for the preparation of the pharmaceutical composition of the third aspect, which kit comprises the precursor of the second aspect: Such kits comprise the “precursor” of the second-aspect, preferably in sterile non-pyrogenic form, so that reaction with a sterile source of the radioisotopic imaging moiety gives the desired radiopharmaceutical with the minimum number of manipulations. Such considerations are particularly important when the radioisotope has a relatively short half-life, and for ease of handling and hence reduced radiation dose for the radiopharmacist. Hence, the reaction medium for reconstitution of such kits is preferably a “biocompatible carrier” as defined above, and is most preferably aqueous. [0207] Suitable kit containers comprise a sealed container which permits maintenance of sterile integrity and/or radioactive safety, plus optionally an inert headspace gas (e.g. nitrogen or argon), whilst permitting addition and withdrawal of solutions by syringe. A preferred such container is a septum-sealed vial, wherein the gas-tight closure is crimped on with an overseal (typically of aluminium). Such containers have the additional advantage that the closure can withstand vacuum if desired e.g. to change the headspace gas or degas solutions. [0208] The non-radioactive kits may optionally further comprise additional components such as a radioprotectant, antimicrobial preservative, pH-adjusting agent or filler. By the term “radioprotectant” is meant a compound which inhibits degradation reactions, such as redox processes, by trapping highly-reactive free radicals, such as oxygen- containing free radicals arising from the radiolysis of water. The radioprotectants of the present invention are suitably chosen from: ascorbic acid, para-aminobenzoic acid (i.e. 4-aminobenzoic acid), gentisic acid (i.e. 2,5-dihydroxybenzoic acid) and salts thereof with a biocompatible cation. By the term “biocompatible cation” is meant a positively charged counterion which forms a salt with an ionised, negatively charged group, where said positively charged counterion is also non-toxic and hence suitable for administration to the mammalian body, especially the human body. Examples of suitable biocompatible cations include: the alkali metals sodium or potassium; the alkaline earth metals calcium and magnesium; and the ammonium ion. Preferred biocompatible cations are sodium and potassium, most preferably sodium. [0209] By the term “antimicrobial preservative” is meant an agent which inhibits the growth of potentially harmful micro-organisms such as bacteria, yeasts or moulds. The antimicrobial preservative may also exhibit some bactericidal properties, depending on the dose. The main role of the antimicrobial preservative(s) of the present invention is to inhibit the growth of any such micro-organism in the radiopharmaceutical composition post-reconstitution, i.e. in the radioactive diagnostic product itself. The antimicrobial preservative may, however, also optionally be used to inhibit the growth of potentially harmful micro-organisms in one or more components of the non-radioactive kit of the present invention prior to reconstitution. Suitable antimicrobial preservative(s) include: the parabens, i.e. methyl, ethyl, propyl or butyl paraben or mixtures thereof; benzyl alcohol; phenol; cresol; cetrimide and thiomersal. Preferred antimicrobial preservative(s) are the parabens. [0210] The term “pH-adjusting agent” means a compound or mixture of compounds useful to ensure that the pH of the reconstituted kit is within acceptable limits (approximately pH 4.0 to 10.5) for human or mammalian administration. Suitable such pH-adjusting agents include pharmaceutically acceptable buffers, such as tricine, phosphate or TRIS [i.e. tris(hydroxymethyl)aminomethane], and pharmaceutically acceptable bases such as sodium carbonate, sodium bicarbonate or mixtures thereof. When the conjugate is employed in acid salt form, the pH adjusting agent may optionally be provided in a separate vial or container, so that the user of the kit can adjust the pH as part of a multi-step procedure. [0211] By the term “filler” is meant a pharmaceutically acceptable bulking agent which may facilitate material handling during production and lyophilisation. Suitable fillers include inorganic salts such as sodium chloride, and water soluble sugars or sugar alcohols such as sucrose, maltose, mannitol or trehalose. [0212] Preferred aspects of the “precursor” when employed in the kit are as described for the second aspect above. The precursors for use in the kit may be employed under aseptic manufacture conditions to give the desired sterile, non-pyrogenic material. The precursors may also be employed under non-sterile conditions, followed by terminal sterilisation using e.g. gamma-irradiation, autoclaving, dry heat or chemical treatment (e.g. with ethylene oxide). Preferably, the precursors are employed in sterile, non-pyrogenic form. Most preferably the sterile, non-pyrogenic precursors are employed in the sealed container as described above. [0213] In a fifth aspect, the present invention provides a method for the in vivo diagnosis or imaging in a subject of a CCR5 condition, comprising administration of the pharmaceutical composition of the third aspect. By the term “CCR5 condition” is meant a disease state of the mammalian, especially human, body where CCR5 expression is upregulated or downregulated. Preferably, the CCR5 expression is upregulated since that should give better signal-to-background in diagnostic imaging in vivo. CCR5 expression is upregulated in chronic HIV infection. CCR5 conditions also include various pathological inflammatory conditions as well as neuroinflammatory conditions. Pathological inflammatory conditions include: atherosclerosis, chronic obstructive pulmonary disorder (COPD), rheumatoid arthritis, osteoarthritis, allergic disease, HIV/AIDS, asthma and cancer. Neuroinflammatory conditions include: multiple sclerosis (MS), Alzheimer's disease (AD) and Parkinson's disease (PD). A preferred method of the fifth aspect is the in vivo diagnosis or imaging of neuroinflammation. Most neurodegenerative diseases have an element of inflammation. [0214] In a sixth aspect, the present invention provides the use of the pharmaceutical composition of the third aspect for imaging in vivo in a subject a CCR5 condition wherein said subject is previously administered with said pharmaceutical composition. The “CCR5 condition” and preferred embodiments thereof are as defined for the fifth aspect, above. By “previously administered” is meant that the step involving the clinician, wherein the imaging agent composition is given to the patient e.g. intravenous injection, has already been carried out. [0215] In a seventh aspect, the present invention provides the use of the imaging agent of any one of the first aspect for the manufacture of a pharmaceutical for use in a method for the diagnosis of a CCR5 condition. The “CCR5 condition” and preferred embodiments thereof are as defined for the fifth aspect, above. [0216] In an eighth aspect, the present invention provides a method of monitoring the effect of treatment of a human or animal body with a drug to combat a CCR5 condition, said method comprising administering to said body the pharmaceutical composition of the third aspect, and detecting the uptake of the imaging agent of said pharmaceutical composition. The “CCR5 condition” and preferred embodiments thereof are as defined for the fifth aspect, above. [0217] In a ninth aspect, the present invention provides the pharmaceutical composition of the invention for use in a method for the diagnosis of a CCR5 condition. The “CCR5 condition” and preferred embodiments thereof are as defined for the fifth aspect, above. [0218] The invention is illustrated by the following Examples. [0219] Example 1 provides the synthesis of a non-radioactive 19 F counterpart compound falling within Formula I of the present invention (“Compound 1”). Since the 18 F version differs only in the fluorine isotope, it is chemically almost identical. [0220] Example 2 provides the synthesis of a non-radioactive 19 F counterpart compound falling within Formula II of the present invention (“Compound 8”). Since the 18 F version differs only in the fluorine isotope, it is chemically almost identical. [0221] Examples 3 and 4 provide prophetic examples of the syntheses of 18 F-labelled Compounds 1 and 8. Example 5 provides a prophetic example of the syntheses of an 18 F-labelled compound of Formula V. [0222] Example 6 provides biological screening data for Compound 8 of Example 2. This shows that compound 8 binds CCR5 with high affinity and is selective for CCR5 as it does not bind CCR1 and CCR2B. [0223] Example 7 provides the screening of Compounds 1 and 8 in a membrane permeability assay (PAMPA assay). Pe (permeability) predict a high CNS (blood brain barrier) permeability for Compound 8 and intermediate permeability for Compound 1. [0224] Abbreviations. [0225] The following abbreviations are used: [0226] DCM=dichloromethane. [0227] DIAD=diisopropyl azodicarboxylate. [0228] DEA=diisopropylethylamine [0229] DMF=N,N′-dimethylformamide. [0230] EDCl=1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. [0231] HOBT=1-hydroxybenzotriazole. [0232] LCMS=liquid chromatography mass spectroscopy. [0233] THF=tetrahydrofuran. EXAMPLES Example 1 Synthesis of Compound 1 [0234] Step (i): Synthesis of Compound A (Scheme 1) [0235] A solution of 5-amino-2-methoxyphenol (2.78 g, 0.020 mol), 4-phenoxybenzoic acid (4.28 g, 0.020 mol), DIEA (3.1 g, 4.2 mL, 0.024 mol) and HOBT (3.2 g, 0.024 mol) in DMF (20 mL) was cooled to 0° C., EDCl (4.6 g, 0.024 mol) was added in one portion under nitrogen. The mixture was stirred at room temperature overnight. The mixture was poured into ice-water (100 mL) and extracted with ethyl acetate (50 mL×3). The combined ethyl acetate layer was washed with water, brine, dried (MgSO 4 ) and concentrated to dryness. The residue solid was triturated with DCM/hexanes, affording a white solid (4.1 g, 62%). 1 H NMR and LCMS analysis indicated > 98% purity. Step (ii): Synthesis of 2-(ethyl-2′-fluoroethylamino)ethanol [0236] The required intermediate 2-(ethyl-2′-fluoroethylamino)ethanol was prepared as shown in Scheme 2 [0000] [0237] A mixture of 2-ethylaminoethanol (6.7 g, 0.075 mol), 2-fluoroethyl bromide (12 g, 0.094 moll, anhydrous potassium carbonate (10.3 g, 0.075 mol) and dry benzene (50 mL) was heated under reflux with stirring for 48 h. After cooling to room temperature, the solid was removed by filtration-and washed with benzene. The benzene was removed in vacuo. 1 H NMR analysis indicated the purity of the product was ˜90% and it was used directly in the next step without any further purification. (9.0 g, 89%). Step (iii): Synthesis of Compound 1 [0238] DIAD (1.36 g, 1.3 mL, 6.71 mmol) was added dropwise to a solution of Compound A from Step (i) (1.50 g, 4.47 mmol), 2-(ethyl-2′-fluoroethylamino)ethanol from Step (ii) (0.91 g, 6.71 mmol) and PPh 3 (1.76 g, 6.71 mmol) in anhydrous DCM (/THF (12 mL, 5:1). An exothermic reaction was immediately observed. The mixture was then stirred at room temperature overnight. The reaction mixture was concentrated to dryness and the residue solid was purified by column chromatography [silica, DCM→DCM/MeOH (98:2)]. The second fraction was the desired product, this fraction was chromatographed again under the same condition stated above. Recrystallisation from DCM/hexanes afforded a colourless solid (0.81 g, 40%). Analytical data indicated >98% purity. LCMS (API-ES+) m/z 453.3 (M+H + ) [0239] Supporting Data: 1 H NMR, 13 C NMR, HPLC, LCMS of Compound 1. Example 2 Synthesis of Compound 8 [0240] Compound 8 was prepared according to Schemes 3 and 4: [0000] Step (i): Synthesis of Compound 5 [0241] Ethylpiperidine-4-carboxylate (10 g, 0.064 mol, 1.1 eq) and triethylamine (15 ml, 2 eq) were dissolved in DCM (30 ml), and cooled on ice water bath with magnetic stirring. 2-Fluoroacetylchloride (5 g, 0.052 mol, 1.0 eq) in DCM (20 ml) was added dropwise (15 min) to the reaction and stirred for 1 h. Water (100 ml) was added and solvent was removed in vacuo. The residue was extracted into ethyl acetate (300 ml), which was washed with water, 2N HCl, saturated NaHCO 3 , brine and dried over Mg 2 SO 4 . The organic solution was filtered, then concentrated. After silica gel column chromatography 6.2 g (yield 55%) of product compound 5 was obtained. Step (ii): Synthesis of Compound 6 [0242] Compound 5 (6.2 g, 0.029 mol, 1 eq) was dissolved in methanol (100 ml) and 2N NaOH (30 ml, 2 eq) was added and stirred overnight. The methanol was then removed in vacuo. The residue was acidified with 2N HCl to pH 3, extracted with ethyl acetate (3×500 ml), dried over MgSO 4 , filtered and concentrated to afford compound 6 (4.3 g, yield 78%). Step (iii): Synthesis of Compound 7 [0243] Compound 6 (4.3 g, 0.023 mol) dissolved in DCM (50 ml), and DMF (one drop) was added, cooled on ice water bath, followed by addition of oxalyl dichloride (2.3 g, 1.5 ml, 2.5 eq) and stirred for 2 h. Solvent was removed and dry toluene (50 ml) was added to chase out possible residual solvent on a 50° C. water bath to give compound 7 (4.2 g, yield 88%). Step (iv): Synthesis of Compound 1 of Scheme 4 [0244] 3-chloro-4-methylbenzenamine (15 g, 0.106 mol, 1 eq), 2-(ethoxycarbonyl)-acetic acid (14 g, 0.106 mol, 1 eq), diisopropylethylamine (16.5 g, 22.3 ml, 1.2 eq), HOBT (17 g, 1.2 eq) and DCM (150 ml) were mixed together. [1-ethyl-(3-dimethyl-amino-propyl)carbodiimide hydrochloride anhydrous] (EDCl, 24.5 g, 1.2 eq) was then added, and the resulting mixture stirred overnight under N 2 . Workup, the reaction mixture washed with water, saturated NaHCO 3 , 1N HCl and brine, dried over MgSO 4 . Filtered off and concentrated to afford compound 1 (18.5 g, yield 70%). Step (v): Synthesis of Compound 2 of Scheme 4 [0245] Compound 1 from step (iv) above (18.5 g, ˜0.072 mol) was dissolved in methanol (100 ml), and cooled on an ice water bath. 2N NaOH (72 ml, 2 eq) was added and the mixture stirred overnight. Then solvent methanol was removed in vacuo. The residue was acidified with 2N HCl to pH 2 and extracted with ethyl acetate (500 ml), dried over MgSO 4 , filtered off and concentrated to give compound 2 (13 g, 80%). Step (vi): Synthesis of Compound 3 of Scheme 4 [0246] Compound 2 from step (v) (4.9 g, ˜0.021 mol), 4-fluorobenzylpiperidine hydrochloride (4.9 g, 0.021 mol), diisopropylethylamine (12 g, 2.2 eq), HOBT (3.5 g, 1.2 eq) and DMF (150 ml) were mixed together. [1-ethyl-(3-dimethyl-aminopropyl)carbodiimide hydrochloride anhydrous] (EDCl, 5 g, 1.2 eq) was then added. The resulting mixture was stirred overnight under N 2 . Workup, the reaction mixture was diluted with water (800 ml), extracted with ethyl acetate (500 ml), washed with water, saturated NaHCO 3 , 1N HCl and brine, dried over MgSO4. Filtered off and concentrated to afford compound 3 (6.8 g, yield 80%). Step (vi): Synthesis of Compound 4 of Scheme 4 [0247] Compound 3 from step (v) (6.8 g, 0.017 mol) was dissolved in THF (100 ml), and BH 3 (1M solution in THF, 170 ml, 10 eq) was added and refluxed for 4 days till reaction complete (checked with LCMS). Solvent THF was then removed and methanol (100 ml) 6N HCl (100 ml) was added and refluxed for 5 days till reaction complete (checked with LCMS). Then methanol was removed and the residue was acidified to pH 11. Extracted with DCM (500 ml), dried over MgSO4, filtered off and concentrated (crude 6.2 g). After silica gel column give Compound 4 (3.7 g, 58%). Step (vii): Synthesis of Compound 8 of Scheme 4 [0248] Compound 4 from step (vi) (2.5 g, 0.0067 mol) and triethylamine(7 g, 10 ml, 0.068 mol, 10 eq) was dissolved in DCM (50 ml), cooled on ice water bath, added Compound 7 (4.2 g, ˜3 eq) in DCM (50 ml). The resulting mixture was stirred overnight. Reaction is messy but LCMS showed the desired product molecular weight. Workup, water was added, solvent DCM was removed in vacuo. Residue was extracted with ethyl acetate (500 ml), washed with water, saturated NaHCO 3 , dried over MgSO 4 , filtered off and concentrated, after silica gel column chromatography give final compound 8 (179 mg, 5%). LCMS (API-ES+) m/z 546.3 (M+H + ). Example 3 Synthesis of 18 F-Labelled Compound 1 (Prophetic Example) [0249] 18 F-labelled Compound 1 is prepared as shown in Scheme 5: [0000] Example 4 Synthesis of 18 F-Labelled Compound 8 (Prophetic Example) [0250] The F-18 analogue of Compound 8 is synthesized from Compound 4 of Example 2 as shown in Scheme 6: [0000] Example 5 Synthesis of 18 F-Labelled Compound of Formula V (Prophetic Example) [0251] An 18 F-labelled Compound of Formula V is prepared as shown in Scheme 7: [0000] Example 6 Screening of Compound 8 [0252] Compound 8 of Example 2 was screened in CCR binding assays as follows: [0253] The CCR1 binding assay was performed under the following conditions, according to a method that was adapted from the literature [Ben-Baruch et al., J. Biol. Chem., 270(38), 22123-8 (1995); Pease et al., J. Biol. Chem., 273(32), 19972-6 (1998)]. [0254] Thus, Compound 8 was incubated for 3 hours at 25° C. in 50 mM HEPES, pH7.4 containing 1 mM CaCl 2 , 0.5% BSA, 5 mM MgCl 2 and 1% DMSO with Human recombinant CHO-K1 cells in the presence of 0.02 nM [ 125 I]-MIP-1α. MIP-1α is Macrophage Inflammatory Protein 1α (ligand of CCR1 and CCR5). [0255] CCR2B binding assay was performed under the following conditions, according to a method that was adapted from the literature [Gong et al., J. Biol. Chem., 272, 11682-5 (1997); Moore et al., J. Leukoc. Biol., 62, 911-5 (1997)]. [0256] Thus, Compound 8 was incubated for 1. hour at 25° C. in 25 mM HEPES, pH7.4 containing 1 mM CaCl 2 , 0.5% BSA, 5 mM MgCl 2 , 0.1% NaN 3 and 1% DMSO with Human recombinant CHO-K1 cells in the presence of 0.1 nM [ 125 I]-MCP-1. MCP-1 is monocyte chemoattractant protein (the ligand of CCR2). [0257] CCR5 binding assay was performed under the following conditions, according to a method that was adapted from the literature [Samson et al., J. Biol. Chem., 272, 24934-41 (1997)]. [0258] Thus, Compound 8 was incubated for 2 hours at 25° C. in 50 mM HEPES, pH7.4 containing 1 mM CaCl 2 , 0.5% BSA, 5 mM MgCl 2 and 1% DMSO with Human recombinant CHO-K1 cells in the presence of 0.1 nM [ 125 I]-MIP-1β, where MIP-1β is Macrophage Inflammatory Protein 1β. [0259] Compound 8 was found to be selective for CCR5 (Ki 0.79 nM) since binding affinity for CCR1 was much lower (32% binding inhibition at 10 μM Compound 8) and Compound 8 at 10 μM concentration did not inhibit the binding of MCP-1 to CCR2B. Example 7 Permeability of Compound 8 [0260] The permeability of the CCR compounds was measured in a Parallel Artificial Membrane Permeability Assay (PAMPA) which gives a prediction of the blood brain barrier penetration by passive diffusion [Di et al, Eur. J. Med. Chem., 38(3), 223-232 (2003)]. [0261] The commonly accepted classification ranges for this PAMPA assay are as follows: High predicted passive BBB permeation: Pe>4.0×10 −06 cm/sec. Low predicted passive BBB permeation: Pe<2.0×10 −06 cm/sec. [0264] Uncertain prediction of BBB permeation: 2.0×10 −06 cm/sec<Pe<4.0×10 −06 cm/sec. [0265] The results were Pe=3.2E-06 cm/sec for Compound 1 and Pe=6.8E-06 cm/sec for Compound 8.
The present invention relates to the field of medical imaging, and in particular to imaging of disease states associated with the upregulation of the chemokine receptor 5 (CCR5). Imaging agents, precursors and methods are provided which are useful in imaging such disease states.
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PRIORITY [0001] This application claims priority from U.S. provisional application 60/233,781 which was filed on Sep. 19, 2001. FIELD OF THE INVENTION [0002] This invention is related to the field of compounds having fungicidal activity and processes to make and use such compounds. BACKGROUND OF THE INVENTION [0003] Our history is riddled with outbreaks of fungal diseases that have caused widespread human suffering. One need look no further than the Irish potato famine of the 1850's, where an estimated 1,000,000 people died, to see the effects of a fungal disease. [0004] Fungicides are compounds, of natural or synthetic origin, which act to protect plants against damage caused by fungi. Current methods of agriculture rely heavily on the use of fungicides. In fact, some crops cannot be grown usefully without the use of fungicides. [0005] Using fungicides allows a grower to increase the yield of the crop and consequently, increase the value of the crop. In most situations, the increase in value of the crop is worth at least three times the cost of the use of the fungicide. However, no one fungicide is useful in all situations. [0006] Consequently, research is being conducted to produce fungicides that are safer, that have better performance, that are easier to use, and that cost less. In light of the above, the inventors provide this invention. SUMMARY OF THE INVENTION [0007] It is an object of this invention to provide compounds that have fungicidal activity. It is an object of this invention to provide processes that produce compounds that have fungicidal activity. [0008] It is an object of this invention to provide processes that use compounds that have fungicidal activity. [0009] In accordance with this invention, processes to make and processes to use compounds having a general formula according to formula one, and said compounds are provided. [0010] While all the compounds of this invention have fungicidal activity, certain classes of compounds may be preferred for reasons such as, for example, greater efficacy or ease of synthesis. DETAILED DESCRIPTION OF THE INVENTION [0011] The compounds have a formula according to formula one. In formula one: [0012] A is selected from the group consisting of oxy (—O—) and amino (—NH—); [0013] A 1 is selected from the group consisting of oxo (O═) and thioxo (S═); [0014] E is selected from the group consisting of aza (—N═) and methine (—CH═); [0015] J 1 , J 2 , J 3 , and J 4 are independently selected from the group consisting of hydro (—H), halo (—F, —Cl, —Br, and —I), C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkyl (mono or multi-halo), and C 1-4 alkylthio; [0016] M 1 , and M 2 are selected from the group consisting of hydro (—H), halo (—F, —Cl, —Br, and —I), C 1-6 alkyl, C 1-6 alkoxy, C 1-4 alkyl (mono or multi-halo), and C 1-4 alkylthio, nitro (—NO 2 ), (mono or multi-halo) C 1-4 alkoxy, aryl (-Aryl), substituted aryl (—SAryl), heteroaryl (—HAryl), and substituted heteroaryl (—SHAryl), where “aryl” or “Ph” refers to a phenyl group and where “heteroaryl” refers to pyridyl, pyridinyl, pyrazinyl or pyridazinyl, and where said SAryl and SHAryl have substituents that are independently selected from the group consisting C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkyl, halo-C 1 -C 6 alkoxy, halo, nitro, carbo-C 1 -C 6 alkoxy, or cyano, arylalkyl, alkanoyl, benzoyl, amino, and substituted amino, preferably, hydro (—H), C 1 -C 6 alkyls, arylalkyl, alkanoyl, benzoyl, amino, and substituted amino where said substituted amino has substituents that are independently selected from the group consisting of hydro (—H), alkyl, arylalkyl, alkanoyl, benzoyl, and amino; [0017] Q is selected from the group consisting of hydro, halo, cyano, (mono or multi halo) C 1-6 alkyl, and C 1-6 alkyl; and [0018] T 1 and T 2 are independently selected from the group consisting of hydro (—H), halo (—F, —Cl, —Br, and —I), C 1-6 alkyl, C 1-6 alkoxy, C 1-4 alkyl (mono or multi-halo), and C 1-4 alkylthio, nitro (—NO 2 ), (mono or multi-halo) C 1-4 alkoxy, aryl (-Aryl), substituted aryl (—SAryl), heteroaryl (—HAryl), and substituted heteroaryl (—SHAryl), where “aryl” or “Ph” refers to a phenyl group and where “heteroaryl” refers to pyridyl, pyridinyl, pyrazinyl or pyridazinyl, and where said SAaryl and SHAryl have substituents that are independently selected from the group consisting C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alky, halo-C 1 -C 6 alkoxy, halo, nitro, carbo-C 1 -C 6 alkoxy, or cyano, arylalkyl, alkanoyl, benzoyl, amino, and substituted amino, preferably, hydro (—H), C 1 -C 6 alkyls, arylalkyl, alkanoyl, benzoyl, amino, and substituted amino where said substituted amino has substituents that are independently selected from the group consisting of hydro (—H), alkyl, arylalkyl, alkanoyl, benzoyl, and amino. C 1-4 alkyl or one of the single bonds can be the connecting bond to the pyridyl. [0019] The term “alkyl”, “alkenyl”, or “alkynyl” refers to an unbranched or branched chain carbon group. The term “alkoxy” refers to an unbranched or branched chain alkoxy group. The term “haloalkyl” refers to an unbranched or branched alkyl group substituted with one or more halo atoms. The term “haloalkoxy” refers to an alkoxy group substituted with one or more halo atoms. Throughout this document, all temperatures are given in degrees Celsius and all percentages are weight percentages, unless otherwise stated. The term “Me” refers to a methyl group. The term “Et” refers to an ethyl group. The term “Pr” refers to a propyl group. The term “Bu” refers to a butyl group. The term “EtOAc” refers to ethyl acetate. The term “DMSO” refers to dimethylsulfoxide. The ten “Ether”, when used in the body of text under “Preparation”, refers to diethyl ether. The term “ppm” refers to parts per million. The term, “psi” refers to pounds per square inch. [0020] In general, these compounds can be used in a variety of ways. These compounds are preferably applied in the form of a formulation comprising one or more of the compounds with a phytologically acceptable carrier. Concentrated formulations can be dispersed in water, or another liquid, for application, or formulations can be dust-like or granular, which can then be applied without further treatment. The formulations are prepared according to procedures which are conventional in the agricultural chemical art, but which are novel and important because of the presence therein of one or more of the compounds. [0021] The formulations that are applied most often are aqueous suspensions or emulsions. Either such water-soluble, water suspendable, or emulsifiable formulations are solids, usually known as wettable powders, or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates. The present invention contemplates all vehicles by which one or more of the compounds can be formulated for delivery and use as a fungicide. [0022] As will be readily appreciated, any material to which these compounds can be added may be used, provided they yield the desired utility without significant interference with the activity of these compounds as antifungal agents. [0023] Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of one or more of the compounds, an inert carrier and surfactants. The concentration of the compound in the wettable powder is usually from about 10% to about 90% w/w, more preferably about 25% to about 75% w/w. In the preparation of wettable powder formulations, the compounds can be compounded with any of the finely divided solids, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgte, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier is ground or mixed with the compounds in a volatile organic solvent. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, include sulfonated lignins, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants, such as ethylene oxide adducts of alkyl phenols. [0024] Emulsifiable concentrates of the compounds comprise a convenient concentration, such as from about 10% to about 50% w/w, in a suitable liquid. The compounds are dissolved in an inert carrier, which is either a water miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers. The concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2-ethoxyethanol. [0025] Emulsifiers which can be advantageously employed herein can be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulphonic acids, oil soluble salts or sulphated polyglycol ethers and appropriate salts of phosphated polyglycol ether. [0026] Representative organic liquids which can be employed in preparing the emulsifiable concentrates of the present invention are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the n-butyl ether, ethyl ether or methyl ether of diethylene glycol, and the methyl ether of triethylene glycol. Mixtures of two or more organic liquids are also often suitably employed in the preparation of the emulsifiable concentrate. The preferred organic liquids are xylene, and propyl benzene fractions, with xylene being most preferred. The surface-active dispersing agents are usually employed in liquid formulations and in the amount of from 0.1 to 20 percent by weight of the combined weight of the dispersing agent with one or more of the compounds. The formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture. [0027] Aqueous suspensions comprise suspensions of one or more water-insoluble compounds, dispersed in an aqueous vehicle at a concentration in the range from about 5% to about 50% w/w. Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above. Other ingredients, such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix at the same time by preparing the aqueous mixture and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer. [0028] The compounds may also be applied as granular formulations, which are particularly useful for applications to the soil. Granular formulations usually contain from about 0.5% to about 10% w/w of the compounds, dispersed in an inert carrier which clay or a similar inexpensive substance. Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. Such formulations may also be prepared by making a dough or paste of the carrier and the compound, and crushing and drying to obtain the desired granular particle. [0029] Dusts containing the compounds are prepared simply by intimately mixing one or more of the compounds in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% w/w of the compounds. [0030] The formulations may contain adjuvant surfactants to enhance deposition, wetting and penetration of the compounds onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will vary from 0.01 percent to 1.0 percent v/v based on a spray-volume of water, preferably 0.05 to 0.5%. Suitable adjuvant surfactants include ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulphosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines and blends of surfactants with mineral or vegetable oils. [0031] The formulations may optionally include combinations that can comprise at least 1% of one or more of the compounds with another pesticidal compound. Such additional pesticidal compounds may be fungicides, insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present invention in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use. The compounds and the pesticidal compound in the combination can generally be present in a weight ratio of from 1:00 to 100:1. [0032] The present invention includes within its scope methods for the control or prevention of fungal attack. These methods comprise applying to the locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungicidal amount of one or more of the compounds. The compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity. The compounds are useful in a protectant or eradicant fashion. The compounds are applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds. For example, the compounds may be applied to the roots, seeds or foliage of plants for the control of various fungi, without damaging the commercial value of the plants. The materials are applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrates, or emulsifiable concentrates. These materials are conveniently applied in various known fashions. [0033] The compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants, or with wood, paint, leather or carpet backing. [0034] In particular, the compounds effectively control a variety of undesirable fungi that infect useful plant crops. Activity has been demonstrated for a variety of fungi, including for example the following representative fungi species: [0035] Downy Mildew of Grape ( Plasmopara viticola —PLASVI); [0036] Late Blight of Tomato ( Phytophthora infestans —PHYTIN); [0037] Apple Scab ( Venturia inaequalis —VENTIN); [0038] Brown Rust of Wheat ( Puccinia recondita —PUCCRT); [0039] Stripe Rust of Wheat ( Puccinia striiformis —PUCCST); [0040] Rice Blast ( Pyricularia oryzae —PYRIOR); [0041] Cercospora Leaf Spot of Beet ( Cercospora beticola —CERCBE); [0042] Powdery Mildew of Wheat ( Erysiphe graminis —ERYSGT); [0043] Leaf Blotch of Wheat ( Septoria tritici —SEPTTR); [0044] Sheath Blight of Rice ( Rhizoctonia solani —RHIZSO); [0045] Eyespot of Wheat ( Pseudocercosporella herpotrichoides —PSDCHE); [0046] Brown Rot of Peach ( Monilinia fructicola —MONIFC); and [0047] Glume Blotch of Wheat ( Septoria nodorum —LEPTNO). [0048] It will be understood by those in the art that the efficacy of the compound for the foregoing fungi establishes the general utility of the compounds as fungicides. The compounds have broad ranges of efficacy as fungicides. The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species. [0049] The compounds are effective in use with plants in a disease inhibiting and phytologically acceptable amount. The term “disease inhibiting and phytologically acceptable amount” refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 1 to about 1000 ppm, with 10 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre. EXAMPLES [0050] These examples are provided to further illustrate the invention. They are not meant to be construed as limiting the invention. [0051] Preparation of 5-bromo-3-methylisothiazole (Compound A) and 4,5-dibromo-3-methyliso-thiazole (Compound B) [0052] 5-Amino-3-methylisothiazole hydrochloride (1.0 g; 6.7 mmol) was dissolved in 9M sulfuric acid (13.4 mL) at RT. Copper(II)sulfate (2.7 g; 16.8 mmol; 2.5 eq) and sodium bromide (2.4 g; 23.5 mmol; 3.5 eq) were added, and the resulting thick mixture was cooled to 0° C. in an ice-salt bath. A solution of sodium nitrite (5.8 mg; 7.4 mmol; 1.1 eq) in water (2.5 mL) was added slowly dropwise keeping the internal temperature <10° C. When the addition was complete, stirring continued at 0° C. for 20 minutes and then at RT for 30 minutes until nitrogen evolution was no longer visible. The reaction mixture was poured into water (exotherm) where it stirred until most of the solids dissolved. It was transferred to a separatory funnel and extracted with diethyl ether (×3). The combined organic layers were washed with brine and dried over sodium sulfate. After careful removal of solvent (no heat) the crude residue was purified by flash chromatography (5% ethyl acetate/hexanes) to give Compound A (confirmed by GCMS, m/e 179) in 28% yield (330 mg) and Compound B (m/e 257) in a smaller amount (yield not measured). [0053] Preparation of 4,5-dibromo-3-methyliso-thiazole (Compound B) Method Two. [0054] 5-Amino-3-methylisothiazole hydrochloride (3.1 g; 20 mmol) was equilibrated between ethyl acetate and 10% sodium carbonate. The organic layer was filtered and evaporated in vacuo to 2.25 g (˜20 mmol) of 5-amino-3-methylisothiazole. It was pulverized and added to 100 mL 48% hydrobromic acid. 1.5 g (22 mmol) sodium nitrite was dissolved in 5 mL water and added to the starting material solution at room temperature. When the resultant exotherm was complete, 5.8 g (40 mmol) of pulverized cuprous bromide was added with stirring and left at room temperature ˜5 hours. The mixture was flooded with 200 mL water, then extracted with 1:1 ether/pentane. The organic layer was filtered and evaporated in vacuo to ˜2 g of a yellow gum. Thin layer chromatography (SiO 2 /ether/hexane) showed a small fast spot and a large, slightly slower spot. Dissolution in pentane with a minimum volume of ether, followed by an extractive wash with conc. hydrochloric acid removed all of the faster spot. Subsequent neutralization of the latter with 10% ammonium hydroxide and ether extraction, followed by evaporation of the extract, yielded 100 mg of Compound A with correct spectral data. The acid-washed ether/pentane layer was filtered and evaporated in vacuo to 1 g of the major spot, a low-melting orange solid. It was confirmed to be Compound B by GCMS (m/e 257) and 1H NMR (singlet at 2.6 ppm), in 39% recovered yield. [0055] Preparation of 3-chloro-2-fluoro-(3-methyl-5-isothiazolyl)pyridine (Compound C) [0056] 5-Bromo-3-methylisothiazole (400 mg; 2.2 mmol; 1.1 eq) (Compound A) was dissolved in toluene (5 mL) and tetrakis(triphenylphosphine)palladium(0) (116 mg; 0.1 mmol; 0.05 eq) was added. This mixture was blanketed with nitrogen and heated to 90° C. for the addition of a solution of 3-chloro-2-fluoro-5-(tributylstannyl)pyridine (838 mg; 2.0 mmol; 1 eq) in toluene (2 mL). This mixture was then heated to reflux overnight. It was cooled to RT, diluted with ether and filtered through Celite to give an orange solution which became a yellow-orange solid when the solvent was removed. GCMS showed 2 major products corresponding to the desired Compound C (m/e 228). [0057] Preparation of 2-fluoro-3-methyl-(4bromo-3-methyl-5-isothiazolyl)pyridine (Compound D) [0058] 4,5-Dibromo-3-methylisothiazole (950 mg; 4 mmol) (Compound B) was dissolved in toluene (75 mL) and tetrakis(triphenylphosphine)palladium(0) (240 mg; 0.2 mmol) was added. This mixture was blanketed with nitrogen and heated to 90° C. for the addition of a solution of 2-fluoro-3-methyl-5-(tributylstannyl)pyridine (1.6 g; 4.0 mmol; 1 eq) in toluene (2 mL). This mixture was then heated to reflux 2.5 hrs. Thin layer chromatography (hexane/ether) showed no Compound B, and the presence of a large mid-Rf product spot. The suspension was filtered and the filtrate stored cold overnight. After evaporating in vacuo to a dark oil it was eluted on a silica column with 1:1 pentane/ether to collect 0.8 g of the major, desired product as a clear oil. GCMS m/e=286/288 (confirming), 70% yield. [0059] Preparation of 2-[[[3-chloro-5-[5-[3-methylisothiazoly]]-2-pyridinyl]-oxy]methyl]-alpha-(methoxyimino)-N-methylbenzeneacetamide (Compound 1). [0060] StOH (0.33 g, 0.0015 mol) was dissolved with stirring in dry THF (10 mL) and 60% sodium hydride (0.07 g, 0.0018 mol) added. The mixture was stirred at room temperature for 30 minutes and a solution of compound C (0.29 g, 0.0014 mol) in dry THF (5 mL) added. The mixture was heated with stirring at 50° C. for 5 hours, cooled, and poured into water. The mixture was extracted with ethyl acetate (40 mL) and the organic extracts washed with water (40 mL) and brine (40 mL), and dried over anhydrous sodium sulphate. Evaporation of the solvent under reduced pressure and purification of the residue by chromatography over silica (10-50% ethyl acetate/hexanes) gave the desired product. [0061] Preparation of 2-[[[3-methyl-5-[5-[4-bromo-3-methylisothiazolyl]]-2-pyridinyl]-oxy]methyl]-alpha-(methoxyimino)-N-methylbenzeneacetamide (Compound 2). [0062] Compound D (0.72 g, 2.5 mmol) was dissolved in 50 mL anh. DMSO. To this was added 0.56 g (2.5 mmol) of the methoximinoamide referred to as StOH, with stirring and nitrogen purging. Upon injection of 3 mL (3 mmol) of 1M t-BuOK/THF the solution turned deep red. After stirring 20 min. thin layer chromatography of an acidified aliquot showed no Compound D, and a large low-mid-Rf product spot. Removed most of the DMSO in vacuo, flooded with 100 mL dilute hydrochloric acid (pH 4-5), and extracted twice with ethyl acetate. Filtered and evaporated extract in vacuo to 1.1 g orange gum. Eluted on silica column with 5:2 ether/pentane to collect 0.75 g of the major product as a clear oil which became a hard white foam on extended high vacuum, mp=48-53° C. GCMS m/e=490 (confirming). Biological Results [0063] Pathogen propagation and host inoculation. Plants were inoculated with various pathogens 1-4 days before compound application (curative tests) and 1-7 days after compound application (protectant tests). For all wheat trials, compounds were applied at growth stage 1.2, when the second leaf was expanded to about ½ of its final size (12 days after seeds were first watered). Information on the growth stages of other plant species at the time compound application and on the propagation and inoculation procedures associated with each pathogen is given below. [0064] ERYSGT: Wheat seedlings were infected with fresh spores from the obligate pathogen ERYSGT by shaking heavily infected wheat plants over them. Plants that had been dusted with ERYSGT spores were incubated in the greenhouse at 22° C. until disease symptoms had fully developed (usually 7 days). [0065] PUCCRT: Spores of the obligate pathogen PUCCRT were collected from infected plants with a vacuum apparatus and stored at 4° C. Approximately 0.1 g of fresh spores (stored at 4° C. for less than 30 days) was mixed with several drops of Tween 20. The thick spore paste was diluted to 100 ml with water and sprayed to run-off on wheat seed seedlings. Plants inoculated with PUCCRT were kept in a 20° C. dew chamber overnight and then transferred to a 20° C. growth chamber where symptoms developed in 8-9 days. [0066] SEPTTR: Fresh inoculum is prepared in a manner similar to that described for LEPTNO. In this case, a brownish layer of spores covers the entire surface of the PDA plate and only a few plates are needed to obtain a large number of spores. After incubation overnight in the 20° C. dew chamber, inoculated plants were continually misted for 3 days in a 20° C. greenhouse, then grown at 20° C. without mist until disease symptoms had fully developed (usually about 10 days). [0067] LEPTNO: Fresh inoculum was prepared by streaking PDA plates with spore exudates from an older plate using a sterile spatula. The plates were incubated at 18° C. under black lights and typically produced large quantities of spores in pink exudate in 6-7 days. A small amount of tap water was poured onto several plates and spores were collected by scraping the exudates off the PDA surface into the water. The spore solutions were combined in a large beaker, diluted with 200-300 ml of water and filtered through a 180 u mesh screen. The spore concentration was determined using a hemacytometer and water was added to obtain a final concentration of 10 7 spores/ml. Approximately 3 large drops of Tween 20 were added for each 100 ml of volume and the spore solution was sprayed to run-off on wheat seedlings. Inoculated plants were placed in a 20° C. dew chamber overnight, then moved to a 20° C. greenhouse where they were continually misted (12 seconds of mist every minute) until disease symptoms were fully developed (8-10 days). TABLE ONE “Biological Data for Compounds 1-2 Rate ERYSGT ERYSGT LEPTNO LEPTNO PUCCRT PUCCRT SEPTTR SEPTTR Compound (g ai/ha) 3DC 7DP 3DC 7DP 3DC 7DP 7DP 3DC 1 125 97 100 71 98 100 100 91 99 62.5 94 88 53 95 100 100 76 85 31.3 92 45 60 50 99 94 88 59 15.5 88 51 58 46 93 80 53 22 2 125 failed failed 67 98 93 100 97 95 62.5 47 84 93 100 96 90 31.3 73 79 63 100 85 83 15.5 65 65 50 100 85 97
The present invention provides 2-methoxyimino-2(pyridinyloxymethyl) phenyl acetamides with a isothiazolyl ring on the pyridine ring according to formula (I) as well as their use as fungicidal compounds.
29,280
BACKGROUND OF INVENTION The present invention relates generally to water run-off collected in sheet flow into a special drain. The invention has particular utility in any construction which requires surface water from roadways, parking lots, swimming pool decks, etc. essentially be completed drained away. The open portion of the drain is placed level with, or slightly below, the ground or paved surface, so that water will flow through the opening and into the attached drainpipe, which is installed below the ground. A variety of drains to carry away water are known. U.S. Pat. No. 3,815,213 to Evans, et al, disclosed, generally, drains which include a lower pipe section which has a longitudinal opening along on the upper side to form a slot in which a slotted grate is attached. The grate is formed by placing a pair of spaced plates, firmly attached, to either side of the longitudinal slot. Spacers, of multiple arrangements, are secured to the inside of each plate. These spacers comprise either solid cross-bars, which extend perpendicularly to the axis of the pipe, or a sinusoidal plate, which goes between the two (2) side plates. The plates and spacers were attached by traditional metallic welding processes. The grate is hot-dipped galvanized after fabrication. The grate is attached to galvanized pipe by metallic welding. The weld scar is repaired by applying a zinc-rich paint. Since the '213 patent to Evans, there has been variations of slotted drains. In U.S. Pat. No. 5,380,121 to Schluter, it was disclosed a grate assembly that could be collapsible or expandable, in which to adjust for specific height requirements. The grate portion is welded, by traditional metallic processes, to a longitudinal slot in the lower pipe assembly. The grate portion comprises an upper grate portion and a lower grate portion, which are moveably fixed to one another. The grate portion is then metallic welded to the lower pipe assembly. The weld scar is covered with zinc-rich paint. In U.S. Pat. No. 4,490,067 to Dahowski, the invention discloses a modular draining system which comprises a single piece of plastic extruded in the shape of a pipe during assembly. This assembly is pre-fabricated with little or no modification at the construction site. Although there have been a number of drain structures disclosed, they suffer from a number of disadvantages. A number of prior drain structures involved welding metal grate portions to metal drain portions. Weather, chemicals and non-galvanizing after fabrication has a corrosive effect on metal, and, in time, may destroy the welded bond between the grate portion and the pipe portion, thus causing the drain system to be unstable. In an attempt to overcome this disadvantage, the '067 patent to Dahowski discloses a single piece drain assembly made of extruded plastic. The disadvantage with this invention is that it does not allow for any modification to the drain assembly for height adjustment. Also, size limitations of extruded full scale finished product would be impractical beyond small diameters. The prior drainage systems either do not adequately address the concerns surrounding the corrosiveness of the welded bond by water and chemicals or, when attempting to address this problem, go to the other extreme, and do not allow flexibility in the assembly and construction of such a drain assembly. It is thus apparent that a need exists for an improved, drain assembly which permits flexibility in the assembly thereof, yet addressing the concerns dealing with the corrosive nature of water, chemicals and the welding bond as well as the durability of the entire system. Additionally, a system adaptable over a wide range of diameters is needed in the market place. This invention will span 4" through 18" and easily modified to go larger. SUMMARY OF INVENTION The present invention provides an improved drain assembly system, whose components is provided totally of chemical and weather resistant plastic. The assembly comprises two (2) extruded plastic sections that are joined together to form one unit by introducing spacers on designated distances. This unit assembly is attached to a plastic carrier pipe which has been prepared with a designated longitudinal section removed to form a longitudinal slot. The extruded assemblies include a vertical portion and a curved portion, referred to as a skirt portion. The assembly is attached to the prepared carrier pipe. A lower part of the vertical portion projects into the plastic carrier pipe to a depth of at least to pipe wall thickness. This insures a transfer of ring compression for the plastic carrier pipe. The skirt width is wide enough to reinforce the carrier pipe, and extends a distance to provide bonding and reinforcement of the plastic carrier pipe. Further, since the assembly is in the form of a single piece of extruded plastic, there is no weld seams or other metal on metal to contend with. Thus, the invention eliminates the concerns surrounding corrosion and long term durability. The unit is attached to the plastic carrier pipe by a chemical welding process. Self-tapping stainless steel screws may be used to draw the skirt into contact with the plastic carrier pipe and to hold the unit in place during the curing time of the weld. The extruded assemblies can be of various lengths but a standard length would be used in standard production. The joining of sections would be done by using standard sleeve couplings that are cut in half, and are chemically welded to permit the drain assembly to be butted together for a tight and continuous grate assembly. The leg heights of the assemblies can be made in a variety of heights. Conversely, the assembly can be made taller, using sheared strips separated by small diameter or heavy wall pipe cut to specific lengths and held in place with stainless steel bolts. The assembly can be either increased in height or the slope of the drain can be adjusted by solvent welding strips of plastic to the inside of the assembly. Where surface traffic would dictate, spacers can be installed in the stacking portion as well. In the event that a guard is needed to be placed over the opening, the drain assembly is capable of different methods of supporting such a guard. The assembly would allow for manipulation of the spacer height coupled with the use of stainless steel bolts in which to support a guard being placed on the top portion of the assembly. The spacers would also be able to support the weight of the guard which could be placed inside the assembly. Further, internal supports can be chemically welded or hot welded to the inside of the vertical portion of the assembly. The guard would then be able to rest upon those supports. A method for inserting spacer units into a prepared groove is available and preferred. This groove allows spacers to be inserted in a uniform manner and can be secured by chemical welding or hot welding. The plastic used as the extrudant is prepared to withstand the exposure to the elements, thus preventing UV degradation. Colorant is possible if desired in certain architectural settings. The advantages of the invention will be more fully appreciated by reference to the figures and drawings, a brief description of which follows, in conjunction with the following detailed description of the preferred embodiments of the invention. BRIEF DESCRIPTION OF DRAWINGS FIG. 1: A perspective view of the present invention. FIG. 2: A side view of the present invention. FIG. 3: A cross sectional view of FIG. 2 taken along Line AA FIG. 4: An expanded view of the extruded plastic sections of the present invention. FIG. 5A: A side view of the second embodiment of the present invention. FIG. 5B: A cross section of FIG. 5A. FIG. 6A: A side view of the third embodiment of the present invention. FIG. 6B: A cross section of FIG. 6A. FIG. 7: A fourth embodiment of the extruded plastic section. FIG. 8: A fifth embodiment of the extruded upper plastic section. DETAILED DESCRIPTION OF THE INVENTION The invention has been illustrated and described in considerable detail, so that the configuration and advantages of the improved slotted drain may be readily appreciated by those skilled in the art. It will be understood, however, that various changes may be made in such details without departing from the spirit or scope of the invention. As shown in FIG. 1, a drainage system (10) of the present invention include a carrier pipe (18) and an upper assembly (11). Plastic carrier pipe (18) has a longitudinal axis (19) and an elongated slot (21) extending lengthwise along the top of its surface. Upper assembly (11) includes two extruded plastic sections (12) connected by multiple spacers (24). Each extruded plastic section (12) consists of a vertical portion (14) and a curved portion (16). Curved portion (16) is positioned in such a manner as to create lower lip (17). Vertical portion (14) also includes multiple spacer grooves (22) as shown in FIG. 2. The vertical portion (14) has a bottom portion. Upper assembly (11) is created by joining two extruded plastic sections (12) by placing multiple spacers (24) within the respective spacer grooves (22) of each extruded plastic section (12). Spacers (24) are secured to the extruded plastic sections (12) by either a chemical or hot welding process. An opening is created between the extruded plastic sections (12) so that water run-off can be collected in sheet flow within plastic carrier pipe (18). Upper assembly (11) is secured to plastic carrier pipe (18) by placing lower lip (17) within the longitudinal slot (21) to the extent that curved portion (16) is in contact with the exterior upper surface of plastic carrier pipe (18). Upper assembly (11) is secured to plastic carrier pipe (18) by a chemical welding process. Self-tapping stainless steel screws may be used to hold upper assembly (11) in place during the curing time of the weld. Drain assembly (10) can be made of various lengths depending upon the needs of the individual project. These individual sections are joined together by using a sleeve coupling (20) wherein two drain assembly (10) with a single sleeve coupling (20) secured to the exterior lower surfaces of both drain assemblies (10). In some instances a guard is needed to be placed over the opening created by the spacers (24) positioned between the extruded plastic sections (12). FIGS. 5A and 5B show an embodiment of this aspect of the present invention wherein the height of spacers (24) are less than the heights of vertical portion (14) of the extended extruded plastic sections (12). Further, a cylindrical spacer (30) is positioned near the top of horizontal portion (15) and secured to the vertical portion (14) by means of bolt (34) and securing nut (32). A guard is then able to rest upon cylindrical spacers (30). Referring now to FIGS. 6A and 6B, shows another embodiment of this portion of the invention wherein spacers (24) are just less than flush with the top of vertical portion (14). A guard is able to be placed on top of spacers (24). Referring now to FIG. 7 which shows an additional embodiment of the present invention which includes internal supports (36) which are connected to the internal walls of vertical portion (14) by means of self-tapping stainless steel screws (38). The internal supports (36) are located near the top of vertical portion (14) that allows for a guard to rest within the opening created by spacers (24). While preferred embodiments of the present invention have been described above, various other modifications will become readily apparent to those of ordinary skill without departing from the scope of the invention. An applicant intends to be bound only by the claims appended hereto.
Below ground drain and conduit member to receive surface water. The member comprises two (2) extruded plastic assemblies that are joined together to form one (1) unit. This unit assembly is attached to a plastic carrier pipe, in a longitudinal fashion. The unit assembly is attached to the carrier pipe by a chemical welding process or other means.
12,011
CROSS-REFERENCE TO RELATED APPLICATIONS The present application is a continuation application of International Application No. PCT/EP2006/007207 filed Jul. 21, 2006 which claims priority to German Application Nos. 102005037564.2 filed Aug. 9, 2005 and 102006000623.2 filed Jan. 2, 2006. Each of the above-identified applications is expressly incorporated herein by reference in their entireties. FIELD The invention relates to an arrangement of sheet-pile wall components such as sheet piles and carrier elements. BACKGROUND An arrangement consisting of sheet-wall components of the type cited above is disclosed in U.S. Pat. No. 6,715,964. There, several adjacent sheet-pile sections which extend in an arc are joined by means of connecting profiles with sheet-pile sections held in the soil which serve as anchorages. The regions, which are called open cells, partly surrounded by the sheet-pile sections extending in an arc are filled with soil at least up to the level of the sheet-pile sections, whereas the outer regions which are isolated from the surrounded regions by the sheet-wall sections are filled with soil to a lower height. In this manner the sides of the sheet-wall sections that point in the outward direction partly protrude from the soil. This so-called open cell structure is used in harbor construction, for example, where the sides of the sheet-wall sections which face out form the harbor wall facing the water. In the arrangement known from U.S. Pat. No. 6,715,964, sheet piles provided with simple locks in the form of header bars with an oval cross-section and C-shaped claw bars are used as the straight sheet-pile wall sections which extend in an arc. A star shaped profile at the end of which header bars with an oval cross-section are formed as locks serves as the connecting profile with which the sheet-pile wall sections are secured to the anchorage. A disadvantage of the sheet-pile wall components used there is that the connecting profile joining the sheet-pile wall sections to the anchorages is under extremely high tensile forces particularly due to the soil pressure of the ground held back from the surrounding area. In view of the above, an object of the present invention is to develop an arrangement in which the connecting profile joining the sheet-pile wall sections and the anchorage can also withstand extremely high tensile forces without the mutually engaged locks failing. SUMMARY The above-object is achieved according to the present invention by an arrangement of sheet-pile wall components such as sheet piles and carrier elements. The arrangement comprises two sheet-pile wall sections which include sheet-pile wall components extending in an arc or polygonal shape, and which are joined by means of locks. The sheet-pile wall components of the two sheet-pile wall sections provide on the ends of the two sheet-pile wall sections, which are arranged immediately adjacent one another, locks hooked into two lock profiles of a connecting profile. The provided connection is hooked via a third lock profile into the lock of an anchorage, and the sheet-pile wall components are provided on the respective other ends of the sheet-pile wall sections being secured in their positions such that each of the two sheet-pile wall sections partially encloses a region which serves as an open cell structure. The design at least one of the lock profiles of the connecting profile along with the lock of the sheet-pile wall components, or the anchoring being engaged with said profile in such a way that the lock profile of the connecting profile and the lock engaged therewith hook into one another and surround each other such that they are adjacent and mutually abutting, at least at three points, in at least one installation position when seen in cross-section. According to the invention, it is disclosed that at least one of the lock profiles of the connecting profile and the lock of the sheet-pile wall components or the anchorage in engagement therewith be designed so that, when seen in cross-section, they form at least one so-called three point connection. The lock profile of the connecting profile and the lock of the sheet-pile wall components or anchorage engaged therewith are designed such that they surround each other and hook into each other in a mutual fashion in such a way that the locks adjoin and abut each another at least at three points when seen in cross-section. When tensile force impinges upon the sheet-pile wall components or the anchorage in the direction of contact, the two locks support each other at these three points in such a way that the tensile force is distributed over all three points of impact. This way the combination of a connecting profile and sheet-pile wall components or an anchorage in engagement therewith is able to withstand relatively high tensile forces which prevent the lock connections from becoming loose. Further advantageous developments of the invention derive from the following description and the drawings. It is particularly beneficial when the three-point connection described is formed between each lock profile of the connecting profile and the lock of the sheet-pile wall components in engagement therewith, respectively. In this manner the combination of connecting profile, sheet-pile wall components and anchorage is able to resist the influence of extremely high tensile forces without one of the lock profiles or one of the locks unintentionally opening. Furthermore, in a particularly preferred embodiment of the arrangement according to the invention, a connecting profile is used wherein the two lock profiles at which the two sheet-pile wall components of the sheet-pile wall sections are hooked on have mirror-symmetrical contours relative to the superficial center of gravity of the connecting profile. This causes the tensile forces impinging upon the lock profiles of the connecting profile, as a result of the sheet-pile wall components, to come to bear on the connecting profile from mirror-symmetrical directions so that normally, when at least approximately equal tensile forces impinge upon the sheet-pile wall sections, the forces cancel each other out in part, and this prevents the connecting profile from being warped or twisted by forces of varying magnitude. It is further proposed that the arrangement according to the invention be lengthened or expanded by hooking at least one of the two sheet-pile wall sections onto an additional connecting profile by means of the lock on the other end of the sheet-pile wall components of the section, and connecting the additional connecting profile to an additional sheet-pile wall section and an additional anchorage. By means of this modular construction, it is possible to build structures with correspondingly large dimensions because it is possible to anchor the free ends of the sheet-pile wall sections directly to carrier elements such as double-T carriers, T carriers, or pipe piles, for example. It is further disclosed that a given number of sheet-pile wall sections be provided, extending in the shape of an arc or polygon, and each consisting of sheet-pile wall components that are each part of the sheet-pile wall sections being joined to an immediately adjacent sheet-pile wall section by means of a connecting profile, and each connecting profile in turn is engaged with an anchorage embedded in the soil. In both applications described above, the connecting profiles that are used are advantageously identically constructed. In a first instance, this makes it easier to set up the arrangement. In addition, when all the connecting profiles have the same dimensions, the arrangement does not contain a weak point at the joint. It is beneficial when the anchorage comprises a carrier element which is secured in the soil, preferably a double-T carrier, a T carrier, or a pipe pile which has been driven into solid ground by ramming or vibration. The connecting profile can then be secured directly to the carrier element which is provided with a corresponding lock bar, for instance a weld-on profile, for this purpose. Alternatively, the connecting profile is coupled or joined to the carrier element indirectly. An additional sheet-pile wall section formed from sheet-pile wall components is suitable for this, which serves as a supporting wall or retaining wall. In order to further increase the anchoring effect, Z-piles or U-piles can be used as sheet-pile wall components for the other sheet-pile wall section. The Z or U shape of the sheet piles causes the tensile forces and shearing forces impinging between the connecting profile and the anchorage to be partly reduced by the additional friction and retention forces impinging between the Z or U shaped sheet piles and the ground, thereby relieving the anchorage. This way, the overall arrangement has a higher resistance to forces impinging from the outside. When the arrangement according to the invention is constructed as a quay wall, for example, it is proposed that the area that is partly surrounded by the sheet-pile wall sections extending in the shape of an arc or polygon be filled with soil, while the side of the sheet-pile wall sections averted from the surrounded area protrude from the soil so that the sheet-pile wall sections hold back the soil contained in the surrounded areas. In a particularly preferred embodiment of the connecting profile for the arrangement according to the invention, the directions of contact, with which the directions of main force impact on the sheet-pile wall components which are joined with the connecting profiles and on the anchorage are aligned, lie at a 120 degree angle to one another. The working point of every lock profile, which bears the impact of the resulting tensile force with the sheet-pile wall components hooked on so as to extend in the direction of contact or with the anchorage hooked on, is the same radial distance from the superficial center of gravity of the connecting profile as the working points of the other two lock profiles. One effect of such a configuration of the connecting profile wherein the working points are the same radial distance from the connecting profile's superficial center of gravity is that the tensile forces impinging upon the connecting profile as a result of the sheet-pile wall sections, and the anchorage that is hooked on, are evenly distributed across the connecting profile so that they at least partly cancel one another out. Secondly, the installation position of the connecting profile is immaterial. The connecting profile can be rammed into the ground with one face side as well as the other. Furthermore, it is also immaterial which lock profile of the connecting profile the respective sheet-pile wall components or anchorage engages with. In the past it has been demonstrated that the use of asymmetrical connecting profiles to join three sheet-pile wall sections always causes problems. Frequently the connecting profiles are rammed into the ground on construction sites without checking if they are in the proper position. But when asymmetrical connecting profiles are in the wrong position, the course of the sheet-pile wall sections relative to each other does not correspond to the optimal flow of forces, so in the worst case there is a danger that the forces impinging upon the sheet-pile wall sections will be insufficiently diverted to the anchorage. In order to achieve the greatest possible flexibility in the construction of the arrangement according to the invention, it is proposed that a connecting profile be used wherein the lock profiles are designed so that the lock of the sheet-pile wall components and the anchorage in which the lock profile of the connecting profile is hooked are slewable at least 15 degrees in the lock profile. The effect of such a connecting profile construction is that the sheet-pile wall components and the anchorage move relatively freely when in the inner lock chambers of the lock profiles of the connecting profile, which all but completely rules out the possibility of the locks tilting in the lock profiles of the connecting profile when the piles are driven into the ground. In addition, imprecision in the course of the sheet-pile wall sections and the anchorage which are joined to the connecting profile can be compensated for. It is particularly beneficial to use a connecting profile for the arrangement according to the invention wherein each lock profile comprises a thumb bar with a middle ridge, at which a thumb is formed which extends transverse to its longitudinal direction and protrudes beyond the middle ridge, along with a curved finger bar, the free end of which points in the direction of the thumb bar, forming an inner lock chamber with an at least approximately elliptical or oval cross section and, together with the end of the thumb pointing in the direction of the finger bar, defining a mouth for the lock of the sheet-pile wall section being hooked on and to the lock of the anchorage. The lock of the sheet-pile wall section is hooked on and the lock of the anchorage consists of a curved finger bar and a thumb bar which have corresponding dimensions. When the lock profiles of the connecting profiles and the locks of the sheet-pile wall components and the anchorage are designed in a complementary fashion accordingly, the cross-section of the engaged lock profiles and locks corresponds to the described three-point connection. Now the thumb of the lock of the sheet-pile wall components or the anchorage is received in the locking chamber of the lock profile of the connecting profile, whereas the thumb of the connecting profile is received in the locking chamber of the lock of the sheet-pile wall components or the lock of the anchorage. When tensile force impinges upon the sheet-pile wall, components or the anchorage in the direction of contact, the two thumbs brace against each other and the finger bars of the other lock, respectively, such that the two locks, when viewed in cross-section, abut at three points respectively, which is to say they mutually support each other. This three-point connection is capable of resisting extremely high tensile forces which may amount to several tens of thousands of kilonewtons due to the fact that the interaction of the thumb bars and finger bars of the locks engaging one another makes it all but impossible for the finger bars to bend or the thumb bars to break off under normal tensile forces. At the same time, the lock configuration guarantees that the engaged locks can pivot relative to one another at least to a limited degree without becoming loose. That simplifies the construction of the arrangement in a first instance. It is also makes it easier to configure the sheet-pile wall components in a circle relative to one another in the area of the connecting profile as required in order to construct the open cell structure. It is further proposed in a particularly preferred embodiment of the connecting profile described above which is used for the arrangement according to the invention that at least one of the lock profiles be designed in such a way that it extends at an angle relative to its given direction of contact, when viewed in cross-section, such that the direction of main force impact on the lock of the sheet-pile wall components which is hooked into the lock profile pivots at least 8 to 12 degrees in either direction about the given direction of contact. It has been shown that with a lock profile formed from a thumb bar and finger bar, if it is aligned precisely at the base relative to the given direction of contact, the pivoting of the sheet-pile wall components out of the given direction of contact is limited in the direction of the thumb bar, while the sheet-pile wall components' pivoting motion out of the given direction of contact in the opposite direction is possible many times over. Designing the lock profile at the base so that it is at an angle to the given direction of contact gives the sheet-pile wall components the ability to be pivoted in both possible directions by at least approximately the same maximum angles relative to the given direction of contact with their lock in the lock profile of the connecting profile according to the invention. It is also beneficial when the lock profile in the connecting profile used for the arrangement extends with the main axis of its inner lock chamber, which has an elliptical or oval cross-section, at an angle of 5 to 10 degrees relative to its given direction of contact, with its thumb bar angled away from the given direction of contact. As long as the lock profile extends at such an angle relative to the base, the sheet-pile wall components can pivot in other directions relative to the given direction of contact by approximately the same angle. It is particularly beneficial when the lock profile comprises an angle of 7 to 8 degrees. It is further provided that, in order for all the sheet-pile wall components to be able to pivot relative to the given directions of contact in opposite directions by at least approximately the same angle, all lock profiles should extend at an angle of 5 to 10 degrees relative to the directions of contact, with the two lock profiles whose thumb bars are formed at the base immediately adjacent one another being angled toward one another. But if installation position is not a problem, it is also possible to use a connecting profile wherein the lock profiles whose thumb bars are formed at the base immediately adjacent one another are farther from the superficial center of gravity of the connecting profile than the other of the three lock profiles. This allows the arrangement's sheet-pile wall components which are hooked into the lock profiles with immediately adjacent thumb bars to have enough room to pivot so that they do not collide with the connecting profile's base. In a particularly preferred development of the connecting profile, the ratio between the opening width of the mouth of each lock profile and the maximum opening width of the inner lock chamber of the respective lock profile is between 1 to 2 and 1 to 2.5 so that the locks of the sheet-pile wall components have enough room to pivot inside the connecting profile's lock profiles. Here, it is also beneficial when the ratio of the length of the thumb bar, as viewed transverse to the longitudinal direction of the middle ridge, and the maximum opening width of the inner lock chamber is between 1 to 1.2 and 1 to 1.4 in every lock profile of the connecting profile. When the thumb is appropriately constructed, the lock of the sheet-pile wall components and the lock of the anchorage are guaranteed to be able to pivot in the inner locking chamber, and at the same time the lock is guaranteed to sufficiently hook into the lock profile which prevents the locks engaged with one another from inadvertently becoming loose. In order to improve the ability of the sheet-pile wall components to pivot, in a development of the connecting profile, it is further provided that the middle ridge of the thumb bar be constructed so that the ratio between the thickness of the middle ridge, observed transverse to its longitudinal direction, and the opening width of the mouth is between 1 to 1.2 and 1 to 1.4. The three design features described above, namely the ratio between the opening width of the mouth and the opening width of the locking chamber, the ratio between the length of the thumb and the opening width of the inner lock chamber, and the ratio between the thickness of the middle ridge and the opening width of the mouth, can each be realized jointly, separately, or partially in at least one of the lock profiles. In order to ensure that the forces impinging upon the lock profiles, which are frequently on the order of several thousand kilonewtons, do not damage the lock profile, it is further proposed that in each lock profile of the connecting profile used, the ratio between the thickness of the middle ridge, observed transverse to the longitudinal direction thereof, and the length of the thumb, observed transverse to the middle ridge's longitudinal direction, is between at least 1 to 2.3 and 1 to 2.5. The length of the thumb is a particularly important determinant of the ability of the lock of the sheet-pile wall components to pivot because the lock is pivoted about the thumb of the thumb bar, and the lock is supposed to engage with the thumb of the thumb bar in particular, partly surrounding it, thereby guaranteeing a secure hold in the inner lock chamber. The result of this is that the thickness of the middle ridge at which the thumb is formed is only allowed to be dimensioned such that the lock is able to be pivoted without impediment in the inner lock chamber, on one hand, and so that, on the other hand, the thumb bar is prevented from becoming deformed or breaking off. In order to give the connecting profile that is used sufficient stability, it is further provided that the wall thickness of the curved finger bar of each lock profile in the area of the maximum opening width of the inner lock chamber be larger by a factor of 1.1 to 1.3 than the thickness of the middle ridge, observed transverse to its longitudinal direction, in the area of the maximum opening width of the inner lock chamber. In a particularly preferred embodiment of the connecting profile, the three directions of contact of the three lock profiles run at a 120° offset relative to one another so that sheet-pile wall sections can be connected which approach the connecting profile at a mutual offset of 120 degrees. The present invention also contemplates designing the connecting profile in such a way that, for example, two of the lock profiles stick out of the base in opposite directions of contact, in other words at a 180 degree offset, while the third lock profile runs at a 90 degree angle relative to the other two. The base body of the utilized connecting profile can be designed in the shape of a cylinder from which the lock profiles stick out radially in the different directions of contact. But in the alternative it is also possible to design the base in the shape of a star; i.e., with ridges sticking out in the three directions of contact in the shape of a star, at the ends of which the lock profiles are formed. A connecting profile with this configuration is particularly well suited to bridging large distances between individual sheet-pile wall components that have to be joined. BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be described in detail with the aid of an exemplifying embodiment and modifications thereof, and with reference to the accompanying drawing in which: FIG. 1 is a plan view of an arrangement according to the invention with multiple open cells whose ends are secured in the ground by pipe piles; FIG. 2 is a sectional view along the line A-A in FIG. 1 showing the construction of one of the open cells in a side view; FIG. 3 is a first enlarged section of the arrangement according to FIG. 1 showing three sheet-pile wall sections and two anchorages, with two sheet-pile wall sections joined to one anchorage in each case by means of a connecting profile; FIG. 4 is a second enlarged section of the arrangement according to FIG. 1 showing one full sheet-pile wall section and another, partial sheet-pile wall section, with the full sheet-pile wall section being joined to one anchorage at one end by means of a connecting profile and being joined to a pipe pile at its other end. FIG. 5 is a section corresponding to the section shown in FIG. 3 but with a modified anchorage of the open cell structure; FIG. 6 is a plan view of the face side of an exemplifying embodiment of a connecting profile used in the arrangement according to FIG. 1 with three lock profiles which are offset 180 degrees to one another; FIG. 7 is a plan view of the connecting profile according to FIG. 6 in which a total of three flat profiles are hooked in as sheet-pile wall components; FIG. 8 is a plan view of the face side of a first modification of the exemplifying embodiment shown in FIGS. 6 and 7 wherein the working points of the lock profiles are the same radial distance from the superficial center of gravity; FIG. 9 is a plan view of a second modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the lock profiles are not angled relative to the directions of contact; FIG. 10 is a plan view of a third modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the base is curved and the two lock profiles whose thumb bars face each other are formed at the ends of the curved base; FIG. 11 is a plan view of a fourth modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein a ridge bar is fashioned on the base at the ends of which one of the lock profiles is formed; FIG. 12 is a plan view of a fifth modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the base comprises three rounded star-shaped ridge bars at the ends of which the lock profiles are formed; FIG. 13 is a plan view of a sixth modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the base comprises three straight star-shaped ridge bars at the ends of which the lock profiles are formed; FIG. 14 is a plan view of a seventh modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the base comprises three reinforced star-shaped ridge bars at the ends of which the lock profiles are formed; and FIG. 15 is a plan view of an eighth modification of the exemplifying embodiment represented in FIGS. 6 and 7 wherein the base comprises three rounded and reinforced star-shaped ridge bars at the ends of which the lock profiles are formed. DETAILED DESCRIPTION FIG. 1 is a plan view of a section of an arrangement 10 configured according to the invention. The arrangement 10 is formed from multiple arc-shaped sheet-pile wall sections 12 which are joined by means of connecting profiles 16 to first anchorages 14 which are secured in the ground. Each arc-shaped sheet-pile wall section 12 forms a so-called open cell 18 with two first anchorages 14 . The end of the sheet-pile section 12 represented in FIG. 1 is connected to a pipe pile 20 that has been driven into the ground, which serves as a closing element for the arrangement 10 , as will be explained further below. FIG. 2 is a view representing a section taken along line A-A in FIG. 1 . As the view shows, the open cell 18 which is partly surrounded by the arc-shaped sheet-pile wall section 12 is filled with soil, whereas the area outside the open cell 18 (left-hand side of FIG. 2 ) is a shoreline area which is secured by means of the arrangement 10 in this example. The sheet-pile wall sections 12 have only been partly driven into the ground, so the water pressure of the impinging water (W) on one side and the ground pressure inside the open cell 18 on the other support the sheet-pile wall sections 12 laterally, while in the downward direction the sheet-pile wall section 12 is only partially driven into the ground. In order to prevent the sheet-pile wall sections 12 from coming out of the ground, they are secured in solid ground by the anchorage 14 and 20 . FIG. 3 is an enlarged plan view representing a section of the arrangement 10 for purposes of laying out the construction of the arrangement 10 in greater detail. The sheet-pile wall section 12 represented in FIG. 3 consists of a total of nine sheet piles 22 , in this case union flat profiles, which are driven into the ground in an arc configuration and hooked into each other. The last two sheet piles 22 of the sheet-pile wall section 12 , disposed at either end, are hooked into the lock profiles of two connecting profiles 16 whose construction will be described in detail further below. As FIG. 1 shows, additional arc-shaped sheet-pile wall sections 12 are hooked into the other lock profiles of the two connecting profiles 16 accordingly. The third lock profile of each connecting profile 16 is engaged with a supporting wall 24 which is formed from sheet piles 22 , in this case as well union flat piles. The supporting wall 24 is joined, by means of a weld-on profile 26 , with a double-T carrier 28 which has been rammed into the ground. The supporting wall 26 and the double-T carrier 28 joined therewith form the first anchorage 14 . As made abundantly clear by the arrangement represented in FIG. 1 , deviations in the course of sheet-pile wall sections 12 can be compensated by means of the connecting profile 16 , which is especially important where multiple sheet-pile wall sections have to be joined at a common point. FIG. 4 represents another section of the arrangement 10 in an enlarged plan view. This section represents the securing of the end of the sheet-pile wall section 12 , for instance in solid ground on the shoreline. Stabilization is facilitated by means of the second anchoring 20 , which in this example consists of a pipe pile 30 that has been driven into the ground. The last sheet piles 22 of the sheet-pile wall section 12 are stabilized by means of a weld-on profile 26 which is welded onto the shell of the pipe pile 30 . Lastly, FIG. 5 represents one possible modification of the first anchorage 14 represented in FIG. 3 . In order to relieve the double-T carrier 28 of extremely high tensile and shearing forces, which could be transferred from the sheet-pile wall sections 12 to the double-T carrier 28 by means of the supporting wall 24 , and in order to increase the resistance of the overall anchorage 14 to any tensile forces and shearing forces that might occur, the supporting wall 24 is made of a total of four sheet piles 22 instead of two. Furthermore, the four sheet piles 22 have been driven into the ground at an angle of 10 degrees out of alignment in an alternating fashion, from a cross-sectional perspective, in order to be able to counteract the tensile and shearing forces impinging in alignment upon the supporting wall 24 by means of greater frictional and holding forces. It would also be possible to use U shaped or Z shaped sheet piles driven into the ground for the supporting wall 24 instead of the angled configuration of the sheet piles 22 . FIGS. 6 and 7 represent a plan view of an exemplifying embodiment of a connecting profile 16 which is used in the arrangement 10 , which has a constant cross-section over its entire length. The connecting profile 16 serves for joining two sheet-pile wall sections 12 with the supporting wall 24 . The connecting profile 16 represented in FIGS. 6 and 7 has three prescribed directions of contact X, Y and Z, which are at a 120 degrees offset relative to one another. Direction of contact X, Y or Z in this sense means the direction in which the sheet piles 22 form a so-called three-point connection with the connecting profile 16 in cross-section when the piles are hooked on. The connecting profile 16 has a base 32 from which three lock profiles 34 , 36 and 38 project in directions of contact X, Y and Z. Since lock profiles 34 , 36 and 38 are identical, the construction of lock profiles 34 , 36 and 38 will be described below with reference to FIG. 6 with the aid of lock profile 34 as represented in FIG. 6 above. The lock profile 34 has a thumb bar 40 which projects from the base 32 and, spaced therefrom, a finger bar 42 , the two of which protrude from base 32 together and partly surround an inner lock chamber 44 . The thumb bar 40 is formed by a middle ridge 46 which emerges from the base 32 , at the free end of which a thumb 48 is formed, extending transverse to the longitudinal direction of the ridge, which extends beyond the ridge 46 in both directions. The finger bar 42 also emerges from the base 32 and extends toward the thumb bar 40 in a curved manner. The finger bar 42 ends together with the exterior surface of the thumb 48 in a tangential plane (not represented) and defines a mouth 50 together with the end of the thumb 48 that points in the direction of the finger bar 42 . The transitions between the base 32 and the middle ridge 46 , between the middle ridge 42 and the thumb 48 , and between the base 32 and the finger bar 42 are rounded and their shape conforms to that of an ellipse so that the inner lock chamber 44 has an inner cross-section that is at least approximately elliptical. In the connecting profile 16 the sheet piles 22 that will be hooked on can be pivoted in a defined fashion with their locks 52 in the inner lock chambers 44 of the lock profiles 34 , 36 , and 38 during which time a secure hold of the lock 52 of the sheet pile 22 in the chamber 44 of the connecting profile 16 is still guaranteed in every pivot position of the sheet pile 22 . In order to simplify pivoting, the following design features are additionally provided for the connecting profile 16 according to the invention. First the ratio between the opening width (a) of the mouth 50 and the maximum opening width (b) of the inner lock chamber 44 is approximately 1 to 2.1. The ratio between the thickness (c) of the middle ridge 46 , as viewed transverse to its longitudinal direction, and the opening width (a) of the mouth 50 is 1 to 1.3 in turn. The ratio between the thickness (c) of the middle ridge 46 , as viewed transverse to the longitudinal direction thereof, and the length (d) of the thumb 48 , as viewed transverse to the longitudinal direction of the middle ridge 46 , is 1 to 2.3. Furthermore, the ratio of the length (d) of the thumb 48 , as viewed transverse to the middle ridge 46 , and the maximum opening width (b) of the inner lock chamber 44 is 1 to 1.25. This design feature guarantees that the lock 52 of the sheet pile 22 retains its ability to pivot some 16 degrees without the lock 52 of the sheet pile 22 jumping out of the locking profile 34 , 36 or 38 of the connecting profile 16 . But in order to guarantee that the locking profile 34 , 36 and 38 is able to resist the arising holding forces and does not break despite the potential ability of the sheet-pile wall components to pivot, the bars 40 and 42 which form the locking profile 34 , 36 and 38 are dimensioned accordingly. The wall thickness (e) of the curved finger bar 42 of each locking profile 34 , 36 and 38 in the area of the maximum opening width b of the inner lock chamber 44 is larger by a factor of 1.2 than the thickness (c) of the middle ridge 46 as viewed transverse to its longitudinal direction in the area of the maximum opening width (b) of the inner lock chamber 44 . Since the tensile force portion impinging on the thumb bar 40 along the longitudinal direction of the middle ridge 46 is greater than the transverse force portion, the middle ridge 46 of the thumb bar 40 can be constructed weaker than the finger bar 42 . In contrast, at the finger bar 42 the impinging transverse force is greater, so a relatively large bending momentum impinges upon the finger bar, which the finger bar must absorb. In order to ensure that the sheet piles 22 to be hooked on can pivot at least approximately over the same angle range relative to the directions of contact X, Y and Z respectively, the three locking profiles 34 , 36 and 38 are constructed on the base 32 such that they tilt relative to the directions of contact X, Y and Z, as explained below. The locking profile 34 represented at the top of FIG. 6 is at an angle α, in this case a 7.5 degree angle, relative to direction of contact X, in which case the thumb bar 42 is angled away from direction of contact X. The two other locking profiles 36 and 38 are also fashioned on the base 32 at a 7.5 degree angle to directions of contact Y and Z respectively, with the thumb bars 32 being angled away from the directions of contact Y and Z again here. Since the two locking profiles 36 and 38 represented at the bottom of FIG. 6 are disposed closer to each other by virtue of being angled, in turn the distance from the two locking profiles 36 and 38 to the superficial center of gravity (S) of the connecting profile 16 is greater than the distance between the top locking profile 34 and the same point. This ensures that the sheet piles 22 that will be hooked into the two locking profiles 36 and 38 do not touch even when moved as close together as possible. FIG. 7 represents the connecting profile 16 according to the invention with the union flat profiles represented in FIGS. 1 to 5 as sheet piles 22 hooked onto thumb bars 40 on its lock profiles 34 , 36 and 38 . The pivoting range within which the sheet pile 22 can be hooked on the connecting profile 16 is represented in FIG. 7 for the lock profile 34 represented at the top of the figure. In this example, the sheet pile 22 can be hooked on the connecting profile 16 in a pivoted position, said pivot comprising an angle of some 8.5 degrees between a first end position and a second end position, proceeding from a starting position in which the direction of main force impact F on the sheet pile 22 is parallel to the direction of contact X, so the pivot range is approximately 8.5 degrees as indicated by the two arrows, and the engaged locks 34 and 52 make contact at three points from a cross-sectional perspective. FIG. 8 shows a first modification of the connecting profile 16 represented in FIGS. 6 and 7 . In this modified connecting profile 16 a the lock profiles 34 a , 36 a and 38 a are also fashioned on the base 32 a at a 120° offset from each other. A unique aspect of this connecting profile 10 a is that the working point A of each lock profile 34 a , 36 a and 38 a upon which the resulting tensile force impinges if the sheet pile 22 has been hooked on so as to extend in direction of contact X, Y or Z is the same radial distance (f) from the superficial center of gravity (S) of the connecting profile 16 a as the working points A of the two other lock profiles 36 a , 38 a and 34 a respectively. This configuration of the connecting profile 16 a whereby the working points (A) are the same radial distance from the superficial center of gravity (S) of the connecting profile 16 a causes the tensile forces impinging upon the connecting profile 16 a as a result of the hooked-on sheet piles 22 to be evenly distributed across the connecting profile 16 a and to at least partly cancel each other out. Another consequence is that the installation position of the connecting profile 16 a is variable, so one can integrate the connecting profile 16 a in any position without having to pay any attention to the course of the lock profiles 34 a , 36 a and 38 a when hooking on the sheet piles 22 . FIGS. 9 to 15 represent additional modifications of the connecting profile 16 wherein the base 32 consists of ridge bars in, for instance, a star configuration, at the free ends of which the lock profiles 34 , 36 and 38 are fashioned. However, it should be noted that in all the modifications shown the design features with respect to the opening width of the mouth 50 , the opening width (b) of the inner lock chamber 44 , the thickness (c) of the middle ridge 46 , the length (d) of the thumb 48 , and the wall thickness (e) of the finger bar 42 are realized in an analogous manner. In the modifications represented in the figure, the lock profiles 34 , 36 and 38 are not at an angle to directions of contact X, Y and Z but configured such that the inner lock chamber 44 at its maximum opening width (b) extends approximately at a right angle to the direction of contact X, Y and Z. It bears noting, however, that in these modifications too it is possible for at least one of the lock profiles 34 , 36 and 38 to extend at an angle relative to the directions of contact X, Y and Z as described above with reference to FIGS. 6 and 7 . FIG. 9 represents a second modification 16 b of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the lock profiles 34 b , 36 b and 38 b do not extend at an angle to the directions of contact X, Y and Z. In contrast, FIG. 10 represents a third modification 16 c of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the base 32 c extends in a curved manner, and the two lock profiles 36 c and 38 c are fashioned at the ends of the curved base 32 c . The third lock profile 34 c , on the other hand, is fashioned in the center of the curved base 32 c. FIG. 11 is a plan view representing a fourth modification 16 d of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein a ridge bar 54 d is fashioned at the base 32 d at the ends of which one of the lock profiles 34 d is formed. FIG. 12 is a plan view representing a fifth modification 16 e of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the base 32 e comprises three rounded ridge bars 54 e extending in a star configuration at the ends of which the lock profiles 34 e , 36 e and 38 e are fashioned. The purpose of the rounded course of the ridge bars 54 e is to better dissipate the stresses impinging upon the lock profiles 34 e , 36 e and 38 e. FIG. 13 is a plan view representing a sixth modification 16 f of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the base 32 f comprises three straight ridge bars 54 f extending in a star configuration at the ends of which the lock profiles 34 f , 36 f and 38 f are fashioned. FIG. 14 is a plan view representing a seventh modification 16 g of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the base 32 g comprises three reinforced ridge bars 54 g extending in a star configuration at the ends of which the lock profiles 34 g , 36 g and 38 g are fashioned. The reinforcement of the ridge bars 54 g prevents the lock profiles 34 g , 36 g and 38 g from breaking under extreme tensile force. Lastly, FIG. 15 is a plan view representing an eighth modification 16 h of the connecting profile 16 utilized for the arrangement 10 according to the invention, wherein the base 32 h comprises three rounded and reinforced ridge bars 54 h extending in a star configuration at the ends of which the lock profiles 34 h , 36 h and 38 h are fashioned. Here too the rounded shape is meant to improve the dissipation of stress. The represented exemplifying embodiments are only some of the possible configurations. For instance, the base 32 can also be fashioned such that the lock profiles 34 , 36 and 38 project in different directions of contact. That makes it possible to arrange the open cells 18 of the arrangement 10 at different angles relative to each other.
An arrangement of sheet-pile wall components includes two sheet-pile wall sections. The ends of the two sheet-pile wall sections are arranged. Their locks are hooked into two lock profiles of a connecting profile which is hooked via a third lock profile into the lock of an anchorage. The respective other ends of the sheet-pile wall sections are secured such that each of the two sheet-pile wall sections partially encloses a region. At least one of the lock profiles and the lock of the sheet-pile wall component of the anchorage in engagement therewith are configured in such a way that the lock profile of the connecting profile and the lock in engagement therewith are hooked one inside the other and grip around one another. As viewed in cross section, they bear on one another and are supported against one another by at least three points in at least one installed position.
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FIELD OF THE INVENTION The present invention is relates to chemical products manufacturing field, more particularly to a method for producing methoxypolyethylene glycols. BACKGROUND OF THE INVENTION Methoxypolyethylene glycols with good water solubility, wettability, lubricity, physiological inertia, no irriation to human body and tenderness are widely used in cosmetics and pharmaceutical industry. The methoxypolyethylene glycols with different molecular scales are used for changing the viscosity, hygroscopicity and structure of product. The methoxypolyethylene glycols with low relative molecular weight (less than 2000) are fit for lubricant and consistency regulator in cream, emulsion, toothpaste, shaving cream, etc. The methoxypolyethylene glycols with high relative molecular weight are fit for lipstick, deodorant stick, toilet soap, shaving soap, foundation make-up, beauty products, etc. Methoxypolyethylene glycols can also be used for suspending agent and thickening agent in detergent. And in pharmaceutical industry, methoxypolyethylene glycols can be the matrix of ointment, emulsion, ointment, lotion and suppository. Methoxypolyethylene glycols are obtained from the reaction between methanol and ethylene oxide, and the by-product PEG can be generated from the reaction between ethylene oxide and water in the reactor during the producing process, so a lot of absolute methanol or absolute ethanol is used for washing the reactor and removing water inside to avoid the production of the by-product and to reduce the consumption of ethylene oxide during the producing process of methoxypolyethylene glycols at the prior art with high production cost. Furthermore, the adding rate of ethylene oxide is low and causes long reaction time at the prior art, so that the synthetic process of methoxypolyethylene glycols is relative long. SUMMARY OF THE INVENTION The object of the present invention is to offer a method for producing methoxypolyethylene glycols which overcomes the defects at the prior art. The technical proposal solving the technical matter in the present invention is: Method for producing methoxypolyethylene glycols, comprises the following steps: (1) after the reactor is washed by water, nitrogen is filled in the reactor to elevate the pressure and then the reactor is vacuumized to completely remove water and reduce the oxygen content in the reactor; (2) nitrogen is filled in the rector and pressure is elevated, and then methanol and sodium methoxide as the catalyst in methanol is added into the reactor, and then warming up; (3) ethylene oxide is added into the reactor at 800˜1200 kg/h to process the pre-reaction; (4) ethylene oxide is added into the reactor at 8000˜12000 kg/h to process the reaction after methanol and ethylene oxide in the reactor are completely reacted; (5) the pressure of reaction product is reduced and pH of reaction product is adjusted to 5˜7 after the reaction is finished, and then the reaction product is transferred to the tank yard. In a preferred embodiment, the step (1) is: after the reactor is washed by water, nitrogen is filled in the reactor to elevate the pressure and then the reactor is vacuumized to −0.954˜−0.950 kg/cm 2 ·g to completely remove water and reduce the oxygen content in the reactor. In a preferred embodiment, the step (2) is: nitrogen is filled in the rector and pressure is elevated to −0.75 kg/cm 2 ·g, and then methanol is added into the reactor below 80° C., and the 30 wt % sodium methoxide as the catalyst in methanol is added into the reactor, and then warming up to 90˜100° C., so that the content of sodium methoxide is less than 140 ppm in total reaction products. In a preferred embodiment, the step (3) is: ethylene oxide is added into the reactor at 800˜1200 kg/h to process the pre-reaction of which the reaction temperature is 110˜120° C. and the reaction pressure is less than 6 kg/cm 2 ·g. In a preferred embodiment, the step (4) is: ethylene oxide is added into the reactor at 8000˜12000 kg/h to process the reaction of which the reaction temperature is 165˜180° C. and the reaction pressure is less than 5 kg/cm 2 ·g after methanol and ethylene oxide in the reactor are completely reacted. In a preferred embodiment, the step (5) is: the pressure of reaction product is reduced, and the temperature and pH of reaction product are chilled to 110° C. and adjusted to 5˜7 after the reaction is finished, and then the reaction product is transferred to the tank yard after chilled to 80° C. Compared with the technical proposal at the prior, the benefits of the present invention are: 1 nitrogen is filled in the reactor before adding methanol to remove water inside, so that the reaction between ethylene oxide and water to generate the by-product PEG is avoid, and the vacuum process can also remove the remaining oxygen in the reactor to enhance the purity of product; 2 nitrogen is filled in the reactor to elevate the pressure and then methanol is added, so that over gasification and too high partial pressure are prevented after methanol is added; 3 the dosage of the catalyst is controlled in the present invention to ensure that the sodium content in the product fulfills the demands; 4 ethylene oxide is added at a relative low rate at the beginning of the reaction to prevent the gasification of methanol and too high pressure in the reactor, so that the reaction can be processed safely; the adding rate of ethylene oxide is enhanced after methanol is completely reacted to enhance the reaction rate, cut down the synthesis reaction time and increase the output of the device; 5 temperature during the reaction process is controlled sectionally to enhance the security of the whole device. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the structure schematic view of the reactor in the method of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS With the following description of the drawings and specific embodiments, the invention shall be further described in details. In FIG. 1 , the reaction device used in the method for producing methoxypolyethylene glycols in the present invention comprises: A reactor 1 ; A main circulation heat exchanger 3 , comprising a first feed inlet 31 and a first feed outlet 32 ; A main circulation pump 2 ; An assistant circulation heat exchanger 5 , comprises a second feed inlet 51 and a second feed outlet 52 ; And an assistant circulation pump 4 with lower starting quantity than the said main circulation pump 2 ; The reactor 1 comprises a main body 100 , a main circulation feed inlet 101 , a main circulation feed outlet 102 , an assistant circulation feed inlet 103 , an assistant circulation feed outlet 104 , a vacuumizing pipe 105 , a evacuation pipe 106 , a nitrogen input pipe, a methanol feed inlet 108 and a ethylene oxide feed inlet 109 ; the main circulation feed outlet 102 and the assistant circulation feed outlet 104 are both arranged at the bottom of the main body 100 of the reactor 1 ; automatic valves 6 are arranged on the vacuumizing pipe 105 , the evacuation pipe 106 , the nitrogen input pipe 107 , the main circulation feed outlet 102 and the assistant circulation feed outlet 104 respectively; The main circulation feed outlet 102 is communicated with the first feed inlet 31 of the main circulation heat exchanger 3 through the main circulation pump 2 , and the first feed outlet 32 of the main circulation heat exchanger 3 is communicated with the main circulation feed inlet 101 of the reactor 1 ; the assistant circulation feed outlet 104 of the reactor 1 is communicated with the second feed inlet 51 of the assistant circulation heat exchanger 5 through the assistant circulation pump 4 , and the second feed outlet 52 of the assistant circulation heat exchanger 5 is communicated with the assistant circulation feed inlet 103 of the reactor 1 . A catalyst inlet pipe 7 is arranged at the pipe between the assistant circulation feed outlet 104 of the reactor 1 and the assistant circulation pump 4 , a neutralizer inlet pipe 8 is arranged at the pipe between the main circulation feed outlet 102 of the reactor 1 and the main circulation pump 2 , a product outlet pipe 9 is arranged at the pipe between the main circulation pump 2 and the first feed inlet 31 of the main circulation heat exchanger, automatic valves 6 are arranged on the catalyst inlet pipe 7 , the neutralizer inlet pipe 8 and the product outlet pipe 9 respectively. The working process of the present reaction device in the method in the present invention is as follow: the material flow direction is shown by the arrow in FIG. 1 , (1) Methanol is added into the reactor through the chain initial dose feed inlet 108 to reach the starting quantity of the assistant circulation pump 4 , and then the assistant circulation pump 4 and the stirring device are started, 30% wt sodium methoxide in methanol is added into the reactor through the catalyst inlet pipe 7 to produce the initial product, and then ethylene oxide is added into the reactor at 800˜1200 kg/h through the ethylene oxide feed inlet 109 to produce the middle product, and then the main circulation pump 2 is started when the amount of the middle product gets to the starting quantity of the main circulation pump 2 ; (2) The adding rate of ethylene oxide is enhanced to 8000˜12000 kg/h and is kept until the reaction is over to get the final product; (3) During the working process of the main circulation pump 2 and the assistant circulation pump 4 , the final product can be transferred to the tank yard through the product outlet pipe 9 after the sample is detected qualified. Embodiment 1 Producing MPEG 400 (1) After the reactor is washed by water, nitrogen is filled in the reactor to elevate the pressure to 2 kg/cm 2 g and then evacuated to 1.1 kg/cm 2 g, and then the reactor is vacuumized to −0.952 kg/cm 2 ·g, the process above is executed for 1˜3 times to completely remove water and reduce the oxygen content in the reactor; (2) Nitrogen is filled in the rector and pressure is elevated to −0.75 kg/cm 2 ·g, and then 1260 kg methanol is added into the reactor below 80° C., and the 5 kg 30 wt % sodium methoxide as the catalyst in methanol is added into the reactor, and then warming up to 90˜100° C.; (3) 1964 kg Ethylene oxide is added into the reactor at 800 kg/h to process the pre-reaction of which the reaction temperature is 110˜120° C. and the reaction pressure is less than 6 kg/cm 2 ·g; (4) 11776 kg Ethylene oxide is added into the reactor at 8000 kg/h to process the reaction of which the reaction temperature is 165˜180° C. and the reaction pressure is less than 5 kg/cm 2 ·g after methanol and ethylene oxide in the reactor are completely reacted; (5) The circulation loop of the reactor is kept circulating for 20˜30 min after ethylene oxide is added until the pressure in the reactor is below 1 kg/cm 2 g; (6) The temperature and pH of reaction product are chilled to 110° C. and adjusted to 5˜7 by acetic acid, and then the reaction product is transferred to the tank yard after chilled to 80° C. After tested, the content of PEG is less than 0.5 wt % and the content of sodium methoxide is less than 140 ppm in the produced MPEG400. Embodiment 2 Producing MPEG 1000 (1) After the reactor is washed by water, nitrogen is filled in the reactor to elevate the pressure to 2 kg/cm 2 g and then evacuated to 1.1 kg/cm 2 g, and then the reactor is vacuumized to ˜0.952 kg/cm 2 ·g, the process above is executed for 1˜3 times to completely remove water and reduce the oxygen content in the reactor; (2) Nitrogen is filled in the rector and pressure is elevated to −0.75 kg/cm 2 ·g, and then 539 kg methanol is added into the reactor below 80° C., and the 5 kg 30 wt % sodium methoxide as the catalyst in methanol is added into the reactor, and then warming up to 90˜100° C.; (3) 774 kg Ethylene oxide is added into the reactor at 1000 kg/h to process the pre-reaction of which the reaction temperature is 110˜120° C. and the reaction pressure is less than 6 kg/cm 2 ·g; (4) 13687 kg Ethylene oxide is added into the reactor at 10000 kg/h to process the reaction of which the reaction temperature is 165˜180° C. and the reaction pressure is less than 5 kg/cm 2 ·g after methanol and ethylene oxide in the reactor are completely reacted; (5) The circulation loop of the reactor is kept circulating for 20˜30 min after ethylene oxide is added until the pressure in the reactor is below 1 kg/cm 2 g; (6) The temperature and pH of reaction product are chilled to 110° C. and adjusted to 5˜7 by acetic acid, and then the reaction product is transferred to the tank yard after chilled to 80° C. After tested, the content of PEG is less than 0.5 wt % and the content of sodium methoxide is less than 140 ppm in the produced MPEG1000. Embodiment 3 Producing MPEG 2000 There are two main steps in this producing process: First of all, MPEG350 is produced from methanol: (1) After the reactor is washed by water, nitrogen is filled in the reactor to elevate the pressure to 2 kg/cm 2 g and then evacuated to 1.1 kg/cm 2 g, and then the reactor is vacuumized to −0.952 kg/cm 2 ·g, the process above is executed for 1˜3 times to completely remove water and reduce the oxygen content in the reactor; (2) Nitrogen is filled in the rector and pressure is elevated to −0.75 kg/cm 2 ·g, and then 1432 kg methanol is added into the reactor below 80° C., and the 50 kg 30 wt % sodium methoxide as the catalyst in methanol is added into the reactor, and then warming up to 90˜100° C.; (3) 2248 kg Ethylene oxide is added into the reactor at 1200 kg/h to process the pre-reaction of which the reaction temperature is 110˜120° C. and the reaction pressure is less than 6 kg/cm 2 ·g; (4) 11320 kg Ethylene oxide is added into the reactor at 12000 kg/h to process the reaction of which the reaction temperature is 165˜180° C. and the reaction pressure is less than 5 kg/cm 2 ·g after methanol and ethylene oxide in the reactor are completely reacted; (5) The circulation loop of the reactor is kept circulating for 20˜30 min after ethylene oxide is added until the pressure in the reactor is below 1 kg/cm 2 g; (6) The temperature and pH of reaction product are chilled to 110° C. and adjusted to 5˜7 by acetic acid, and then the reaction product is transferred out of the reactor after chilled to 80° C. Second, MPEG2000 is Produced from MPEG350: (1) 2625 kg MPEG350 from the steps above and 4.1 kg 30 wt % sodium methoxide as the catalyst in methanol are added into the reactor of which the initial pressure is −0.5 kg/cm 2 g, and then warming up to 150° C.; (2) Ethylene oxide (500 kg at most) is added into the reactor to elevate the pressure inside to 2 kg/cm 2 g, and then the pre-reaction between ethylene oxide and MPEG350 is processed, and then the next step is started after the pressure in the reactor is less than 1.5 kg/cm 2 g; (3) 12375 kg Ethylene oxide is added into the main reactor to process the reaction with circulating catalyzed MPEG350, and the reaction temperature and the reaction pressure in the main reactor are kept at 165˜180° C. and 2˜5 kg/cm 2 ·g through the external recirculation cooler; (4) The temperature and pH of reaction product are chilled to 110° C. and adjusted to 5˜7 by acetic acid, and then the reaction product is transferred out of the reactor after chilled to 80° C. After tested, the content of PEG is less than 0.5 wt % and the content of sodium methoxide is less than 140 ppm in the produced MPEG2000. The invention has been described with reference to the preferred embodiments mentioned above; therefore it cannot limit the reference implementation of the invention. It is obvious to a person skilled in the art that structural modification and changes can be carried out without leaving the scope of the claims hereinafter and the description above.
A method for producing methoxypolyethylene glycols includes the steps of, in the order recited: (1) preparing a reactor by washing the reactor with water; pressurizing the reactor with nitrogen; and evacuating to completely remove water and reduce oxygen content in the reactor; (2) pressurizing the reactor with nitrogen, introducing ingredients including methanol and a catalyst comprised of sodium methoxide in methanol into the reactor, and heating the ingredients; (3) introducing ethylene oxide into the reactor at a rate of 800˜1200 kg/h and reacting the methanol and the ethylene oxide to completely react the methanol; (4) introducing additional ethylene oxide into the reactor at a rate of 8000˜12000 kg/h to continue the reaction and provide final reaction products; (5) reducing the pressure in the reactor and adjusting pH of the reaction products to a ph of 5 to 7; and (6) transferring the reaction products to a tank yard.
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FIELD OF THE INVENTION [0001] The present invention relates to a cosmetic composition and method for making up and/or enhancing the appearance of a keratinous substrate, comprising at least one supramolecular polymer, at least one detackifying ingredient which is a hyperbranched functional polymer, at least one fatty phase ingredient(s) and at least one polyethylene wax. The compositions of the present invention may optionally contain at least one colorant. DISCUSSION OF THE BACKGROUND [0002] In general, when women use a makeup product, especially a foundation or lipstick, they wish this product to have good wear and transfer resistance properties. [0003] With regard to this expectation, one or more polymers are typically employed to improve these properties. Illustrations of these polymers include silicone resins, polyacrylates and lattices. [0004] However, the above-mentioned polymers, which are advantageous in terms of wear and transfer-resistance properties, are often found by consumers to be uncomfortable with regards to their initial application (difficult to spread and tacky feeling) and/or after application (tautness, mask effect). In addition, silicone resins provide no shine and moisture to the lip. [0005] Supramolecular polymers such as those described in patent applications EP 2 189 151 and FR 2 938 758 are known for their good wear properties. There remains, however, a sensation of “tackiness” experienced by the user during and after their application on the skin and/or the lips. [0006] Unexpectedly, the inventors have found that it is possible to overcome this drawback by combining certain supramolecular polymers with a hyperbranched functional polymer and a polyethylene wax. At the same time, the inventive compositions provide high water resistance and a creamy film texture and a comfortable feeling on the lip. SUMMARY OF THE INVENTION [0007] The object of the present invention is to provide a cosmetic composition for making up and/or enhancing the appearance of keratinous substrates containing, in a cosmetically acceptable medium: a) at least one supramolecular polymer, b) at least one detackifying ingredient which is a hyperbranched functional polymer, c) at least one fatty phase; d) at least one polyethylene wax; and e) optionally, at least one colorant, [0013] wherein the supramolecular polymer is based on functionalized polyalkene polymer of formula HO—P—OH in which P represents a homopolymer or a copolymer that may be obtained by polymerization of one or more linear or cyclic polyunsaturated C 2 -C 10 and preferably C 2 -C 4 alkenes, further wherein said one or more linear or cyclic polyunsaturated C 2 -C 10 alkenes may be branched, further wherein said supramolecular polymer may be derived from the reaction, especially the condensation, of said functionalized polyalkene polymer with at least one junction group functionalized with at least one reactive group capable of reacting with the reactive group(s) of the functionalized polyalkene polymer, the said junction group being capable of forming at least 3 hydrogen bonds, preferably at least 4 hydrogen bonds, preferentially 4 hydrogen bonds, and wherein the composition provides a creamy film texture, great comfort and transfer resistance properties in a less tacky manner. [0014] According to another aspect of the present invention, there is provided a method of making up and/or enhancing the appearance of a keratinous substrate involving or comprising applying onto the keratinous substrate the above-disclosed composition, wherein the composition provides a creamy film texture, great comfort and transfer resistance properties in a less tacky manner. DESCRIPTION OF THE INVENTION [0015] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be understood as being modified in all instances by the term “about” which encompasses ±10%. [0016] “Keratinous substrate” may be chosen from, for example, hair, eyelashes, lip, and eyebrows, as well as the stratum corneum of the skin and nails. [0017] “Polymers” as defined herein, include homopolymers and copolymers formed from at least two different types of monomers. [0018] As used herein, the expression “at least one” means one or more and thus includes individual components as well as mixture/combinations. [0019] The “wear” of compositions as used herein, refers to the extent by which the color of the composition remains the same or substantially the same as at the time of application, as viewed by the naked eye, after a certain period or an extended period of time. Wear properties may be evaluated by any method known in the art for evaluating such properties. For example, wear may be evaluated by a test involving the application of a composition to human hair, skin or lips and evaluating the color of the composition after a specified period of time. For example, the color of a composition may be evaluated immediately following application to hair, skin or lips and these characteristics may then be re-evaluated and compared after a certain amount of time. Further, these characteristics may be evaluated with respect to other compositions, such as commercially available compositions. [0020] “Tackiness” as used herein refers to the adhesion between two substances. For example, the more tackiness there is between two substances, the more adhesion there is between the substances. To quantify “tackiness,” it is useful to determine the “work of adhesion” as defined by IUPAC associated with the two substances. Generally speaking, the work of adhesion measures the amount of work necessary to separate two substances. Thus, the greater the work of adhesion associated with two substances, the greater the adhesion there is between the substances, meaning the greater the tackiness is between the two substances. [0021] Work of adhesion and, thus, tackiness, can be quantified using acceptable techniques and methods generally used to measure adhesion, and is typically reported in units of force time (for example, gram seconds (“g s”)). For example, the TA-XT2 from Stable Micro Systems, Ltd. can be used to determine adhesion following the procedures set forth in the TA-XT2 Application Study (ref: MATI/PO.25), revised January 2000, the entire contents of which are hereby incorporated by reference. According to this method, desirable values for work of adhesion for substantially non-tacky substances include less than about 0.5 g s, less than about 0.4 g s, less than about 0.3 g s and less than about 0.2 g s. As known in the art, other similar methods can be used on other similar analytical devices to determine adhesion. [0022] “Substituted” as used herein, means comprising at least one substituent. Non-limiting examples of substituents include atoms, such as oxygen atoms and nitrogen atoms, as well as functional groups, such as hydroxyl groups, ether groups, alkoxy groups, acyloxyalky groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, acylamino groups, amide groups, halogen containing groups, ester groups, thiol groups, sulphonate groups, thiosulphate groups, siloxane groups, and polysiloxane groups. The substituent(s) may be further substituted. Supramolecular Polymer [0023] The composition according to the invention comprises at least one supramolecular polymer comprising a polyalkene-based supramolecular polymer. In particular, the polyalkene-based supramolecular polymer is obtained by a reaction, especially the condensation, of at least one polyalkene polymer functionalized with at least one reactive group, with at least one junction group functionalized with at least one reactive group capable of reacting with the reactive group(s) of the functionalized polyalkene polymer, said junction group being capable of forming at least three hydrogen bonds and preferably at least four hydrogen bonds, preferentially four hydrogen bonds. [0024] The terms “polyalkene” and “polyolefin” mean a polymer derived from the polymerization of at least one monomer of alkene type, comprising an ethylenic unsaturation, the said monomer possibly being pendent or in the main chain of the said polymer. The terms “polyalkene” and “polyolefin” are thus directed towards polymers that may or may not comprise a double bond. Preferably, the supramolecular polymers used according to the invention are prepared from a polymer derived from the polymerization of an alkene comprising at least two ethylenic unsaturations. [0025] The supramolecular polymer according to the invention is capable of forming a supramolecular polymer chain or network, by (self)assembly of said polymer according to the invention with at least one other identical or different polymer according to the invention, each assembly involving at least one pair of paired junction groups, which may be identical or different, borne by each of the polymers according to the invention. [0026] For the purposes of the invention, the term “junction group” means any group comprising groups that donate or accept hydrogen bonds, and capable of forming at least three hydrogen bonds and preferably at least four hydrogen bonds, preferentially four hydrogen bonds, with an identical or different partner junction group. These junction groups may be lateral to the polymer backbone (side branching) and/or borne by the ends of the polymer backbone, and/or in the chain forming the polymer backbone. They may be distributed in a random or controlled manner. Functionalized Polyalkene [0027] The polyalkene polymers are functionalized with at least one reactive group and preferably with at least two reactive groups. The functionalization preferably occurs at the chain ends. They are then referred to as telechelic polymers. [0028] The functionalization groups, or reactive groups, may be attached to the polyalkene polymer via linkers, preferably linear or branched C 1 -C 4 alkylene groups, or directly via a single bond. [0029] Preferably, the functionalized polyalkene polymers have a number-average molecular mass (Mn) of between 1000 and 8000. [0030] Even more preferably, they have a number-average molecular mass of between 1000 and 5000, or even between 1500 and 4500. [0031] Even more preferably, they have a number-average molecular mass of between 2000 and 4000. [0032] Preferably, the functionalized polyalkene polymer, capable of forming all or part of the polymer backbone of the supramolecular polymer according to the invention (preferably, it forms all of the backbone of the polymer), is of formula HO—P—OH in which: [0033] P represents a homo- or copolymer that may be obtained by polymerization of one or more linear, cyclic and/or branched, polyunsaturated (preferably diunsaturated) C 2 -C 10 and preferably C 2 -C 4 alkenes. [0034] P preferably represents a homo- or copolymer that may be obtained by polymerization of one or more linear or branched, C 2 -C 4 diunsaturated alkenes. [0035] More preferably, P represents a polymer chosen from a polybutylene, a polybutadiene (such as a 1,4-polybutadiene or a 1,2-polybutadiene), a polyisoprene, a poly(1,3-pentadiene) and a polyisobutylene, and copolymers thereof. [0036] According to one preferred embodiment, P represents a poly(ethylene/butylene) copolymer. [0037] The preferred poly(ethylene/butylenes) are copolymers of 1-butene and of ethylene. They may be represented schematically by the following sequence of units: [—CH 2 —CH 2 —] and [—CH 2 CH(CH 2 —CH 3 )—]. [0038] According to a second preferred embodiment, P is a polybutadiene homopolymer, preferably chosen from a 1,4-polybutadiene or a 1,2-polybutadiene. The polybutadienes may be 1,4-polybutadienes or 1,2-polybutadienes, which may be represented schematically, respectively, by the following sequences of units: [0039] [—CH 2 —CH═CH—CH 2 —] (1,4-polybutadienes), [—CH 2 —CH(CH═CH 2 )—] (1,2-polybutadienes). [0040] Preferably, they are 1,2-polybutadienes. Preferably, P is a 1,2-polybutadiene homopolymer. According to another embodiment, P is a polyisoprene. Polyisoprenes may be represented schematically by the following sequences of units: [0000] [0041] A mixture of above units may obviously also be used, so as to form copolymers. [0042] The functionalized polyalkene polymers may be totally hydrogenated to avoid the risks of crosslinking. Preferably, the functionalized polyalkene polymers used in the compositions according to the invention are hydrogenated. [0043] Preferably, the polyalkene polymers are hydrogenated and functionalized with at least two OH reactive groups, which are preferably at the ends of the polymers. [0044] Preferably, they have functionality as hydroxyl end groups of from 1.8 to 3 and preferably in the region of 2. [0045] The polydienes containing hydroxyl end groups are especially defined, for example, in FR 2 782 723. They may be chosen from polybutadiene, polyisoprene and poly(1,3-pentadiene) homopolymers and copolymers. Mention will be made in particular of the hydroxylated polybutadienes sold by the company Sartomer, for instance the Krasol® Resins and the Poly bd® Resins. Preferably, they are hydrogenated dihydroxylated 1,2-polybutadiene homopolymers, such as Nisso-PB 1, GI3000, GI2000 and GI1000 sold by the company Nisso, which may be represented schematically by the following formula: [0000] [0046] Preferably, n is between 14 and 105 and preferably between 20 and 85. [0047] These polymers have the following number-average molecular masses: GI3000 of Mn=4700, GI2000 of Mn=3300 and GI1000 of Mn=1500. These values are measured by GPC according to the following protocol. Protocol for Determining the Molecular Masses by GPC [0048] Determination of the number-average molecular mass Mn the weight-average molecular mass Mw and the polydispersity index Mw / Mn in polystyrene equivalents. [0049] Preparation of the Standard Solutions Prepared the polystyrene standards from Varian kits (ref.: PS-H (PL2010-0200) [0051] The calibration masses are the following: PS 6035000-PS 3053000-PS 915000-PS 483000-PS 184900-PS 60450-PS 19720-PS 8450-PS 3370-PS 1260-PS 580 Inject 100 μl of each of the solutions into the calibration column. [0054] Preparation of the Sample: Prepare a solution with a solids content of 0.5% in THF (tetrahydrofuran). Prepare the solution about 24 hours before injection. Filter the solution through a Millex FH filter (0.45 μm). [0057] Inject into the column. [0058] Chromatographic Conditions: Columns: PL Rapid M (batch 5M-Poly-008-15) from Polymer Labs PL-gel HTS-D (batch 5M-MD-72-2) from Polymer Labs PL-gel HTS-F (10M-2-169B-25) from Polymer Labs PL-Rapid-F (6M-0L1-011-6) from Polymer Labs Length: 150 mm—inside diameter: 7.5 mm Pump: isocratic M1515 Waters Eluent: THF [0062] Flow rate: 1 ml/minute [0063] Temperature: ambient Injection: 100 μl at 0.5% AM (active material) in the eluent Detection: RI 64 mV (Waters 2424 refractometer) [0066] Temperature: 45° C. [0067] UV at 254 nm at 0.1 OD (Waters 2487 UV detector) Integrator: Empower option GPC [0069] Determination of the Molar Masses [0070] The average molar masses are determined by plotting the calibration curve: Log molar mass=f (illusion volume at the top of the RI detection peak) and using the Empower option GPC software from Waters. [0071] Among the polyolefins with hydroxyl end groups, mention may be made preferentially of polyolefins, homopolymers or copolymers with α,ω-hydroxyl end groups, such as polyisobutylenes with α,ω-hydroxyl end groups; and the copolymers of formula: [0000] [0000] where (m+n) is from 1 to 100 and 0<n<(m+n), more preferably (m+n) is from 5 to 50 and 0<n<(m+n); most preferably (m+n) is from 9 to 35 and 0<n<(m+n). [0072] In a preferred embodiment, the copolymers of the above formula are those sold by Mitsubishi under the brand name Polytail. Junction Group [0073] The supramolecular polymers according to the invention also have in their structure at least one residue of a junction group capable of forming at least three hydrogen bonds and preferably at least four hydrogen bonds, said junction group being initially functionalized with at least one reactive group. [0074] Unless otherwise mentioned, the term “junction group” means in the present description the group without its reactive function. [0075] The reactive groups are attached to the junction group via linkers L. [0076] L is a single bond or a saturated or unsaturated C 1 -C 20 divalent carbon-based group chosen in particular from a linear or branched C 11 -C 20 alkylene; a C 5 -C 20 (alkyl)cycloalkylene alkylene (preferably cyclohexylene methylene), a C 11 -C 20 alkylene-biscycloalkylene (preferably alkylene-biscyclohexylene), a C 6 -C 20 (alkyl)arylene, and an alkylene-bisarylene (preferably an alkylene-biphenylene); the linker L possibly being substituted with at least one alkyl group and/or possibly comprising 1 to 4 N and/or O heteroatoms, especially in the form of an NO 2 substituent. [0077] Preferably, the linker is a group chosen from phenylene; 1,4-nitrophenylene; 1,2-ethylene; 1,6-hexylene; 1,4-butylene; 1,6-(2,4,4-trimethylhexylene); 1,4-(4-methylpentylene); 1,5-(5-methylhexylene); 1,6-(6-methylheptylene); 1,5-(2,2,5-trimethylhexylene); 1,7-(3,7-dimethyloctylene); -isophorone-; 4,4′-methylene bis(cyclohexylene); tolylene; 2-methyl-1,3-phenylene; 4-methyl-1,3-phenylene; and 4,4-biphenylenemethylene. [0078] Preferably, the linker is chosen from the groups: [0079] C 5 -C 20 (alkyl)cycloalkylene alkylene, such as isophorone, [0080] C 11 -C 25 alkylene-biscycloalkylene, such as 4,4′-methylene biscyclohexene, [0081] C 1 -C 20 alkylene such as —(CH 2 ) 2 —; —(CH 2 ) 6 —; —CH 2 CH(CH 3 )—CH 2 —C(CH 3 ) 2 —CH 2 —CH 2 —, and [0082] C 6 -C 20 (alkyl) phenylene, such as 2-methyl-1,3-phenylene. [0083] Preferably, L is chosen from: -isophorone-; —(CH 2 ) 2 —; —(CH 2 ) 6 —; —CH 2 CH(CH 3 )—CH 2 —C(CH 3 ) 2 —CH 2 —CH 2 —; 4,4′-methylene biscyclohexylene; and 2-methyl-1,3-phenylene. [0084] According to one particularly preferred embodiment, the linker is an alkylcycloalkylene alkylene. [0085] Preferably, according to this embodiment, the linker is an isophorone group. The term “isophorone” means the following group: [0000] [0000] where each * represents a reactive group. [0086] The said reactive groups functionalizing the junction group must be capable of reacting with the —OH reactive group(s) borne by the functionalized polyalkene. [0087] Reactive groups that may be mentioned include isocyanate (—N═C═O) and thioisocyanate (—N═C═S) groups. Preferably, it is a group —N═C═O (isocyanate). [0088] The functionalized junction groups capable of forming at least three H bonds may comprise at least three identical or different functional groups, and preferably at least four functional groups, chosen from: [0000] [0089] These functional groups may be classified into two categories: [0090] functional groups that donate H bonds: [0000] [0091] functional groups that accept H bonds: [0000] [0092] The junction groups capable of forming at least three hydrogen bonds form a basic structural element comprising at least three groups, preferably at least four groups and more preferentially four functional groups capable of establishing hydrogen bonds. Said basic structural elements capable of establishing hydrogen bonds may be represented schematically in the following manner: [0000] [0093] in which each of X 1 to X i is an hydrogen-bond accepting functional group (identical or different) and each of Y 1 to Y i is an hydrogen-bond donating functional group (identical or different). [0094] Thus, each structural element should be able to establish hydrogen bonds with one or more partner structural elements, which are identical (i.e. self-complementary) or different, such that each pairing of two partner structural elements takes place by formation of at least three hydrogen bonds, preferably at least four hydrogen bonds and more preferentially four hydrogen bonds. [0095] A proton acceptor X will pair with a proton donor [0096] Y. Several possibilities are thus offered, for example pairing of: [0097] XXXX with YYYY; [0098] XXXY with YYYX; [0099] XXYX with YYXY; [0100] XYYX with YXXY; [0101] XXYY with YYXX self-complementary or otherwise; [0102] XYXY with YXYX self-complementary or otherwise. [0103] Preferably, the junction groups may establish four hydrogen bonds with an identical (or self-complementary) partner group among which are two donor bonds (for example [0000] [0104] two acceptor bonds [0000] (for example [0000] [0105] Preferably, the junction groups capable of forming at least four hydrogen bonds are chosen from: [0106] ureidopyrimidones of formula (capable of forming at least four hydrogen bonds): [0000] [0000] it being understood that all the tautomeric forms are included. [0107] In this formula, R 1 , R 2 and R 3 have the following meanings: [0108] R 1 (or R 1 and R 2 ) are single bonds constituting the point of attachment of the junction group to the linker capable of forming at least three (preferably four) hydrogen bonds to the rest of the graft. Preferably, the said point of attachment is borne solely by R 1 , which is a single bond. [0109] R 2 represents a single bond or a divalent group chosen from a C 1 -C 6 alkylene or a monovalent group chosen from a hydrogen atom, or a linear or branched, saturated C 1 -C 10 monovalent hydrocarbon-based group, which may contain one or more heteroatoms such as O, S or N, these groups being optionally substituted with a hydroxyl, amino and/or thio group. [0110] Preferably, R 2 may be a single bond or a monovalent group chosen from H, CH 2 OH, (CH 2 ) 2 —OH and CH 3 . [0111] According to one particularly preferred embodiment, R 2 is H. [0112] R 3 represents a monovalent or divalent group, in particular, R 3 is chosen from a hydrogen atom or a linear or branched C 1 -C 10 saturated monovalent hydrocarbon-based group, which may contain one or more heteroatoms such as O, S or N, these groups being optionally substituted with a hydroxyl, amino and/or thio function. [0113] Preferably, R 3 may be a monovalent group chosen from H, CH 2 OH, (CH 2 ) 2 —OH and CH 3 . [0114] According to one particularly preferred embodiment, R 3 is a methyl group. [0115] According to one preferred embodiment, the junction groups are chosen from 2-ureidopyrimidone and 6-methyl-2-ureidopyrimidone. Preferably, the preferred junction group is 6-methyl-2-ureidopyrimidone. [0116] The junction groups, and especially the ureidopyrimidone junction groups, may be added directly or may be formed in situ during the process for preparing the supramolecular polymer. The first and second preparation methods described below illustrate these two alternatives, respectively. [0117] In particular, the functionalized junction groups capable of reacting with the functionalized polyalkene polymer to give the supramolecular polymer according to the invention are preferably of formula: [0000] [0118] in which L is as defined above. [0119] Preferably, L is chosen from the groups: [0120] C 5 -C 20 (alkyl)cycloalkylene alkylene, such as isophorone, [0121] C 11 -C 25 alkylene-biscycloalkylene, such as 4,4′-methylene biscyclohexene, [0122] C 1 -C 20 alkylene such as —(CH 2 ) 2 —; —(CH 2 ) 6 —; —CH 2 CH(CH 2 )—CH 2 —C(CH 2 ) 2 —CH 2 —CH 2 —, and [0123] C 6 -C 20 (alkyl) phenylene, such as 2-methyl-1,3-phenylene. [0124] Preferably, L is chosen from: -isophorone-; —(CH 2 ) 6 —; and 4,4′-methylene biscyclohexylene. [0000] According to one particularly preferred embodiment, the junction group is of formula [0000] [0125] in which L is isophorone. [0126] In one particularly preferred embodiment, the supramolecular polymer of the invention corresponds to the formula: [0000] [0127] in which: [0128] L′ and L″ have, independently of each other, the following meaning: a single bond or a saturated or unsaturated C 1-20 divalent carbon-based group chosen in particular from a linear or branched C 1 -C 20 alkylene; a C 5 -C 20 (alkyl)cycloalkylene alkylene (preferably cyclohexylene methylene); a C 11 -C 20 alkylene-biscycloalkylene (preferably alkylene-biscyclohexylene); a C 6 -C 20 (alkyl)arylene; and an alkylene-bisarylene (preferably an alkylene-biphenylene); wherein one or both of L′ and L″ are possibly substituted with at least one alkyl group and/or possibly comprising 1 to 4 N and/or O heteroatoms, especially in the form of an NO 2 substituent; [0129] X and X′═O; and P has the meaning given above for the functionalized polyalkene polymer. [0000] Preferably, L′ and L″ each independently represent a saturated or unsaturated divalent C 1 -C 20 carbon-based group chosen in particular from a linear or branched C 1 -C 20 alkylene; a C 5 -C 20 (alkyl)cycloalkylene; an alkylene-biscycloalkylene; and a C 6 -C 20 (alkyl)arylene. Preferably, L′ and L″ each independently represent a group chosen from: -isophorone-; —(CH 2 ) 2 —; —(CH 2 ) 6 —; —CH 2 CH(CH 3 )—CH 2 —C(CH 3 ) 2 —CH 2 —CH 2 —; 4,4′-methylene biscyclohexylene; and 2-methyl-1,3-phenylene. [0130] Preferably, L′ and L″ are identical. [0131] Preferably, L′ and L″ are each an isophorone group. [0132] Preferably, P is hydrogenated and represents a polyethylene, a polybutylene, a polybutadiene, a polyisoprene, a poly(1,3-pentadiene), a polyisobutylene, or a copolymer thereof, especially a poly(ethylene/butylene). [0133] Preferably, P is a hydrogenated polybutadiene, preferably a hydrogenated 1,2-polybutadiene. [0134] In one particularly preferred embodiment, the supramolecular polymer of the invention corresponds to the formula (I) below: [0000] [0000] wherein n can be an integer from 20 to 70; most preferably an integer from 30 to 40. Preparation Process [0135] The polymer according to the invention may be prepared via the processes usually used by a person skilled in the art, especially for forming a urethane bond between the free OH functions of a polyalkene, and the isocyanate functions borne by the junction group. [0136] By way of non-limiting illustration, a first general preparation process consists in: [0137] optionally ensuring that the polymer to be functionalized does not comprise any residual water; [0138] heating the said polymer comprising at least two reactive OH functions to a temperature that may be between 60° C. and 140° C.; the hydroxyl number of the polymer possibly serving as a reference in order to measure the degree of progress of the reaction; [0139] adding, preferably directly, the ureidopyrimidone junction group bearing the reactive functions, especially isocyanate such as those described in patent WO 2005/042 641; especially such as the junction groups having the CAS numbers 32093-85-9 and 709028-42-2; [0140] optionally stirring the mixture, under a controlled atmosphere, at a temperature of about 90-130° C.; for 1 to 24 hours; [0141] optionally monitoring by infrared spectroscopy the disappearance of the characteristic isocyanate band (between 2500 and 2800 cm −1 ) so as to stop the reaction on total disappearance of the peak, and then allowing the final product to cool to room temperature. [0142] The reaction may also be monitored by assaying the hydroxyl functions; it is also possible to add ethanol in order to ensure the total disappearance of the residual isocyanate functions. [0143] The reaction may be performed in the presence of a solvent, especially methyltetrahydrofuran, tetrahydrofuran, toluene, propylene carbonate or butyl acetate. It is also possible to add a conventional catalyst for forming a urethane bond. An example that may be mentioned is dibutyltin dilaurate. The polymer may finally be washed and dried, or even purified, according to the general knowledge of a person skilled in the art. [0144] According to the second preferred mode of preparation, the reaction may comprise the following steps: Step (i) [0145] Functionalization of the polymer, which has preferably been dried beforehand, with a diisocyanate according to the reaction scheme: [0000] HO-polymer-OH(1 eq.)+OCN—X—NCO(1 eq.)→OCN—X—NH—(O)CO-polymer-OC(O)—NH—X—NCO. [0146] The diisocyanate may optionally be in excess relative to the polymer. This first step may be performed in the presence of solvent, at a temperature of between 20° C. and 100° C. This first step may be followed by a period of stirring under a controlled atmosphere for 1 to 24 hours. The mixture may optionally be heated. The degree of progress of this first step may be monitored by assaying the hydroxyl functions. Step (ii) [0147] Reaction of the prepolymer obtained above with 6-methylisocytosine of formula: [0000] [0148] This second step may optionally be performed in the presence of a cosolvent such as toluene, butyl acetate or propylene carbonate. The reaction mixture may be heated to between 80° C. and 140° C. for a time ranging between 1 and 24 hours. The presence of a catalyst, especially dibutyltin dilaurate, may promote the production of the desired final product. [0149] The reaction may be monitored by infrared spectroscopy, by monitoring the disappearance of the characteristic peak of isocyanate between 2200 and 2300 cm −1 . At the end of the reaction, ethanol may be added to the reaction medium in order to neutralize any residual isocyanate functions. The reaction mixture may be optionally filtered. The polymer may also be stripped directly in a cosmetic solvent. [0150] According to one particular mode, the said supramolecular polymer is dissolved in a hydrocarbon-based oil, which is preferably volatile, in particular isododecane. [0151] Thus, the composition of the invention will comprise at least one hydrocarbon-based oil, which is preferably volatile, in particular at least isododecane, especially provided by the supramolecular polymer solution. [0152] In particular, the supramolecular polymer(s) may be present in a composition according to the invention in an amount ranging from about 1% to about 60% by weight, preferably from about 3% to about 45% by weight, more preferably from about 5% to about 20% by weight, based on the total weight of the composition. [0153] In another particular embodiment of the invention, a makeup composition is in the form of a lipstick and the supramolecular polymer(s) may be present therein in a content ranging from about 1% to about 40% by weight, preferably from about 3% to about 30% by weight, more preferably from about 5% to about 15% by weight, based on the total weight of the composition. Hyperbranched Polymers [0154] Hyperbranched polymers are molecular constructions having a branched structure, generally around a core. Their structure generally lacks symmetry, the base units or monomers used to construct the hyperbranched polymer can be of diverse nature and their distribution is non-uniform. The branches of the polymer can be of different natures and lengths. The number of base units, or monomers, may be different depending on the different branching. While at the same time being asymmetrical, hyperbranched polymers can have: an extremely branched structure around a core; successive generations or layers of branching; a layer of end chains. [0155] Hyperbranched polymers are polymers that are highly branched and contain large number of end groups. Hyperbranched polymer usually contains a central core and the growth of the polymer emanates from this central core. The growth of the polymer is made possible by repeating units of single monomers or linear chains added onto the central core. The end unit of the single monomer or linear chain can be functionalized which can become junction points (i.e., linkage points) for further growth of the polymer. The final form of the hyperbranched polymer exhibits a tree-like structure without any symmetry or regularity. [0156] The synthesis of hyperbranched polymer can be produced by single monomer methodology (SMM) or double monomer methodology (DMM) (Gao and Yan, 2004). For SMM, polymerization involves an AB x , AB* or a latent AB x monomer through generally four different types of reaction mechanism: polycondensation of AB x monomers, self-condensing vinyl polymerization (SCVP), self-condensation ring opening polymerization (SCROP) and proton transfer polymerization (PTP). For DMM, a direct polymerization is possible with two types of monomers or monomer pairs, the most notable being the polymerization of “A 2 +B n , n≧2”, and the couple-monomer methodology (CMM) has also been used. [0157] There are several ways to characterize the topology of a hyperbranched polymer, such as, by its degree of branching and the Wiener index. The degree of branching is defined as B=2D/(2D+L) where D is the number of fully branched units and L is the number of partially reacted units (Holter et al., 1997). For a completely linear polymer, B=0 and for a fully branched hyperbranched polymer B=1. The Wiener index states the sum of paths or branches between all pairs of non-hydrogen atoms in a molecule (Wiener, 1947). It is defined as [0000]  W = 1 2  ?  ?  ?  d ij ?  indicates text missing or illegible when filed [0000] where N is the degree of polymerization and d ij is the number of bonds separating site i and j of the molecule. For two polymers with equal number of molecular weight, the linear polymer will have a smaller Wiener number than the hyperbranched polymer. [0158] An end group can be reacted with the hyperbranched polymer to obtain a particular functionality on the ends of chains. Hyperbranched Functional Polymers [0159] “Hyperbranched functional polymers” refers to polymers comprising at least two, for example three, polymeric branches, forming either the main branch or a secondary branch, and each comprising at least one at least trifunctional branch point, which may be identical or different, and which is able to form at least two at least trifunctional branch points, different from and independent of one another. Each branch point may be, for example, arranged in the interior of at least one chain. The branches may be, for example, connected to one another by a polyfunctional compound. [0160] As used herein, “trifunctional branch point” means the junction point (i.e., linkage point) between three polymer branches, of which at least two branches may be different in chemical constitution and/or structure. For example, certain branches may be hydrophilic, i.e. may predominantly contain hydrophilic monomers, and other branches may be hydrophobic, i.e., may predominantly contain hydrophobic monomers. Further branches may additionally form a random polymer or a block polymer. [0161] As used herein, “at least trifunctional branch” means the junction points (i.e., linkage points) between at least three polymeric branches, for example n polymeric branches (wherein n=3 or more), of which n−1 branches at least are different in chemical constitution and/or structure. [0162] As used herein, “chain interior” means the atoms situated within the polymeric chain, to the exclusion of the atoms forming the two ends of this chain. [0163] As used herein, “main branch” means the branch or polymeric sequence comprising the greatest percentage by weight of monomer(s). [0164] Branches which are not main branches are called “secondary branches”. [0165] Suitable hyperbranched functional polymers include, but are not limited to, hyperbranched polyols and hyperbranched polyacids. [0166] The at least one hyperbranched functional polymer may be present in the composition of the present invention in an amount ranging from about 0.1 to about 30% by weight, more preferably from about 1 to about 20% by weight, most preferably from about 2 to about 10% by weight, relative to the total weight of the composition. Hyperbranched Polyol Compound [0167] According to the present invention, compositions comprising at least one hyperbranched polyol compound are provided. [0168] The at least one hyperbranched polyol compound of the present invention has at least two hydroxyl groups. Preferably, the hyperbranched polyol has a hydroxyl number of at least 15, more preferably of at least 50, more preferably of at least 100, and more preferably of at least about 150. “Hydroxyl number” or “hydroxyl value” which is sometimes also referred to as “acetyl value” is a number which indicates the extent to which a substance may be acetylated; it is the number of milligrams of potassium hydroxide required for neutralization of the acetic acid liberated on saponifying 1 g of acetylated sample. [0169] According to preferred embodiments, the at least one hyperbranched polyol has a hydroxyl number between 50 and 250, preferably between 75 and 225, preferably between 100 and 200, preferably between 125 and 175, including all ranges and subranges therebetween such as 90 to 150. [0170] In accordance with the present invention, “hyperbranched polyol” refers to dendrimers, hyperbranched macromolecules and other dendron-based architectures. [0171] Hyperbranched polyols can generally be described as three-dimensional highly branched molecules having a tree-like structure. They are characterized by a great number of end groups, at least two of which are hydroxyl groups. The dendritic or “tree-like” structure preferably shows irregular non-symmetric branching from a central multifunctional core molecule leading to a compact globular or quasi-globular structure with a large number of end groups per molecule. Suitable examples of hyperbranched polyols can be found in U.S. Pat. No. 7,423,104, and U.S. patent applications 2008/0207871 and 2008/0286152, the entire contents of all of which are hereby incorporated by reference. [0172] Other suitable examples include alcohol functional olefinic polymers such as those available from New Phase Technologies. For example, olefinic polymers can include a functionalized polyalphaolefin comprising the reaction product of admixing an alpha-olefin monomer having at least 10 carbon atoms and an unsaturated functionalizing compound. Non-functionalized olefins that may be used in accordance with the present invention include, but are not limited to, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, as well as such commercial mixtures sold as alpha-olefins including those having mainly C10-C13, C20-C24 chain lengths, C24-C28 chain lengths and C30 and higher chain lengths. [0173] Unsaturated functionalizing compounds useful with the present invention are chosen from alcohols, including olefinic alcohols such as allyl alcohol, 9-decen-1-ol, 10-undecylenyl alcohol, oleyl alcohol, and erucyl alcohol. The molar ratio of alpha-olefin monomer to unsaturated functionalizing compound can range from about 20:1 to 1:20 such as from about 10:1 to 1:10 or such as from about 8:1 to 1:2. [0174] After the polymerization, the alcohol functional olefinic polymers preferably have molecular weights, determined using gel permeation chromatography procedure and a polystyrene standard, of from about 200 daltons to about 150,000 daltons, such as from about 400 daltons to about 80,000 daltons or such as from about 600 daltons to about 6,000 daltons. [0175] According to certain embodiments, the alcohol functional olefinic polymer has a dynamic viscosity ranging from 0.1 Pa·s to 100 Pa·s, such as from 0.1 Pa·s to 50 Pa·s, or such as from 0.1 Pa·s to 10 Pa·s at room temperature. [0176] According to particularly preferred embodiments of the present invention, the at least one hyperbranched polyol compound comprises a hydrophobic chain interior. Preferably, the chain interior comprises one or more hydrocarbon groups, one or more silicon-based groups, or mixtures thereof. Particularly preferred chain interiors comprise olefinic polymers or copolymers and/or silicone polymers or copolymers. [0177] Suitable olefinic monomers include, but are not limited to, compounds having from about 2 to about 30 carbon atoms per molecule and having at least one olefinic double bond which are, for example, acyclic, cyclic, polycyclic, linear, branched, substituted, unsubstituted, functionalized or non-functionalized. For example, suitable monomers include ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, and isobutylene. [0178] Suitable silicone groups for inclusion into the interior chain include, but are not limited to, M, D, T, and/or Q groups in accordance with commonly used silicon-related terminology (M=monovalent; D=divalent; T=trivalent; and Q=quadvalent). Particularly preferred monomers are “D” groups such as dimethicone or substituted dimethicone groups. Such groups can help form, for example, suitable dimethicone copolyols in accordance with the present invention. [0179] A preferred structure of the at least one hyperbranched polyol of the present invention is as follows: [0000] [0180] Where X corresponds to hydroxyl functionality and R corresponds to a methyl group or an alkyl group preferably containing 2-30 atoms. [0181] According to preferred embodiments, the at least one hyperbranched polyol compound has a molecular weight (Mw) between about 1,000 and about 25,000, preferably between about 2,000 and about 22,000, preferably between about 3,000 and about 20,000, including all ranges and subranges therebetween such as about 4000 to about 5500. [0182] According to preferred embodiments, the at least one hyperbranched polyol compound has a viscosity at 90° F. of between 0.01 Pa·s and 10 Pa·s, such as between 0.02 and 7 Pa·s, and such as between 0.03 and 6 Pa·s, including all ranges and subranges therebetween. The viscosity is determined using Brookfield viscometer at 90° F. by ASTMD-3236MOD method. [0183] A particularly preferred at least one hyperbranched polyol compound for use in the present invention is C20-C24 olefin/oleyl alcohol copolymer, commercially available from New Phase Technologies under the trade name Performa V™-6175. [0184] The at least one hyperbranched polyol compound may be present in the composition of the present invention in an amount ranging from about 1 to about 30% by weight, more preferably from about 5 to about 25% by weight, most preferably from about 10 to about 20% by weight, relative to the total weight of the composition. Hyperbranched Polyacid [0185] According to the present invention, compositions comprising at least one hyperbranched polyacid compound are provided. The aforementioned “hyperbranched polyol” refers to the hyperbranched functional polymer wherein the functional groups are substituted with hydroxyl groups. Similar definition applies to the term “hyperbranched polyacid” wherein the functional groups of the hyperbranched functional polymer are substituted with carboxylic acid groups. [0186] The at least one hyperbranched polyacid compound of the present invention has at least two carboxyl groups. Preferably, the hyperbranched polyacid has a carboxyl number of at least 3, more preferably of at least 10, more preferably of at least 50, and more preferably of at least about 150. [0187] According to preferred embodiments, the at least one hyperbranched polyacid has a carboxyl number between 50 and 250, preferably between 75 and 225, preferably between 100 and 200, preferably between 125 and 175, including all ranges and subranges there between such as 90 to 150. [0188] Suitable examples of hyperbranched polyacids can be found in U.S. Pat. No. 7,582,719, and EP1367080, the entire contents of all of which are hereby incorporated by reference. [0189] Unsaturated functionalizing compounds useful with the present invention include, but are not limited to, carboxylic acids, carboxylic acid esters, amides, ethers, amines, phosphate esters, silanes and alcohols. Examples of such carboxylic acids include, but are not limited to, 5-hexenoic acid, 6-heptenoic acid, 10-undecylenic acid, 9-decenoic acid, oleic acid, and erucic acid. Also useful are esters of these acids with linear or branched-chain alcohols having from about 1 to about 10 carbon atoms, as well as triglycerides containing olefinic unsaturation in the fatty acid portion such as tall oil, fish oils, soybean oil, linseed oil, cottonseed oil and partially hydrogenated products of such oils. Other useful materials include olefinic alcohols such as allyl alcohol, 9-decen-1-ol, 10-undecylenyl alcohol, oleyl alcohol, erucyl alcohol, acetic acid or formic acid esters of these alcohols, C1-C4 alkyl ether derivatives of these alcohols and formamides or acetamides of unsaturated amines such as oleylamine, erucylamine, 10-undecylenylamine and allylamine. [0190] A particularly preferred acid functional olefinic polymer is C30+ olefin/undecylenic acid copolymer available from New Phase Technologies under trade name Performa V™-6112. [0191] According to preferred embodiments, the at least one hyperbranched acid compound has a molecular weight (Mw) between about 500 and about 25,000, preferably between about 800 and about 10000, preferably between about 1000 and about 8000, including all ranges and subranges there between such as about 1000 to about 6000. [0192] According to preferred embodiments, the at least one hyperbranched polyacid compound has a viscosity at 210° F. of between 0.01 Pa·s and 10 Pa·s, such as between 0.02 and 7 Pa·s, and such as between 0.03 and 6 Pa·s, including all ranges and subranges there between. The viscosity is determined using Brookfield viscometer at 210° F. by ASTMD-3236MOD method. [0193] According to preferred embodiments, the at least one hyperbranched acid compound has an acid number between about 20 and about 400 mg/KOH, more preferably between about 30 and about 300 mg/KOH, and even more preferably between about 50 and about 100 mg/KOH. [0194] The at least one hyperbranched polyacid compound is present in the composition of the present invention in an amount ranging from about 0.1 to about 20% by weight, more preferably from about 0.2 to about 10% by weight, most preferably from about 0.5 to about 5% by weight, relative to the total weight of the composition. Fatty Phase [0195] A composition according to the invention further comprises a fatty phase. This fatty phase may comprise oils, waxes and/or pasty compounds and/or silicone compounds as defined below. [0196] The fatty phase ranges from 1% to 97% by weight, especially 5% to 95% by weight or even 10% to 90% by weight, relative to the total weight of the composition. [0197] Thus, a composition according to the invention may advantageously comprise one or more oils, which may be chosen especially from hydrocarbon-based oils and fluoro oils, and mixtures thereof. The oils may be of animal, plant, mineral or synthetic origin. [0198] The term “oil” means a water-immiscible non-aqueous compound that is liquid at room temperature (25° C.) and at atmospheric pressure (760 mmHg). [0199] The oils may be volatile or non-volatile. [0200] For the purposes of the invention, the term “volatile oil” means any oil that is capable of evaporating on contact with keratin materials in less than one hour, at room temperature and atmospheric pressure. Volatile oils preferably have a non-zero vapour pressure, at room temperature and atmospheric pressure, ranging from 0.13 Pa to 40,000 Pa, in particular from 1.3 Pa to 13,000 Pa and more particularly from 1.3 Pa to 1,300 Pa. [0201] The term “fluoro oil” means an oil comprising at least one fluorine atom. [0202] The term “hydrocarbon-based oil” means an oil mainly containing hydrogen and carbon atoms. The oils may optionally comprise oxygen, nitrogen, sulfur and/or phosphorus atoms, for example in the form of hydroxyl or acid radicals. [0203] The volatile oils may be chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially C 8 -C 16 branched alkanes (also known as isoparaffins), for instance isododecane, isodecane and isohexadecane. [0204] The volatile hydrocarbon-based oil may also be a linear volatile alkane containing 7 to 17 carbon atoms, in particular 9 to 15 carbon atoms and more particularly 11 to 13 carbon atoms. Mention may be made especially of n-nonadecane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane and n-hexadecane, and mixtures thereof. [0205] Non-volatile oils that may especially be mentioned include: hydrocarbon-based oils of animal origin, hydrocarbon-based oils of plant origin, such as phytostearyl esters, such as phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutamate; triglycerides formed from fatty acid esters of glycerol, in particular whose fatty acids may have chain lengths ranging from C 4 to C 36 and especially from C 18 to C 36 , these oils possibly being linear or branched, and saturated or unsaturated; these oils may especially be heptanoic or octanoic triglycerides, shea oil, alfalfa oil, poppy oil, pumpkin oil, millet oil, barley oil, quinoa oil, rye oil, candlenut oil, passionflower oil, shea butter oil, aloe oil, sweet almond oil, peach stone oil, groundnut oil, argan oil, avocado oil, baobab oil, borage oil, broccoli oil, calendula oil, camellina oil, carrot oil, safflower oil, hemp oil, rapeseed oil, cottonseed oil, coconut oil, marrow seed oil, wheatgerm oil, jojoba oil, lily oil, macadamia oil, corn oil, meadowfoam oil, St-John's wort oil, monoi oil, hazelnut oil, apricot kernel oil, walnut oil, olive oil, evening primrose oil, palm oil, blackcurrant pip oil, kiwi seed oil, grape seed oil, pistachio oil, pumpkin oil, quinoa oil, musk rose oil, sesame oil, soybean oil, sunflower oil, castor oil and watermelon oil, and mixtures thereof, or alternatively caprylic/capric acid triglycerides, such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel, synthetic ethers containing from 10 to 40 carbon atoms; synthetic esters, for instance the oils of formula R 1 COOR 2 , in which R 1 represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R 2 represents a hydrocarbon-based chain, which is especially branched, containing from 1 to 40 carbon atoms, on condition that R 1 +R 2 ≧10. The esters may be chosen especially from fatty acid esters of alcohols, for instance cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, isopropyl isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate, 2-ethylhexyl palmitate, alkyl benzoates, polyethylene glycol diheptanoate, propylene glycol 2-diethylhexanoate, and mixtures thereof, C 12 -C 15 alcohol benzoates, hexyl laurate, neopentanoic acid esters, for instance isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldodecyl neopentanoate, isononanoic acid esters, for instance isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, hydroxylated esters, for instance isostearyl lactate and diisostearyl malate, polyol esters and pentaerythritol esters, for instance dipentaerythrityl tetrahydroxystearate/tetraisostearate, esters of diol dimers and of diacid dimers, copolymers of diol dimer and of diacid dimer and esters thereof, such as dilinoleyl diol dimer/dilinoleic dimer copolymers, and esters thereof, copolymers of polyols and of diacid dimers, and esters thereof, fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance 2-octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2-undecylpentadecanol, C 12 -C 22 higher fatty acids, such as oleic acid, linoleic acid and linolenic acid, and mixtures thereof; dialkyl carbonates, the two alkyl chains possibly being identical or different, such as dicaprylyl carbonate; oils with a molar mass of between about 400 and about 10,000 g/mol, in particular about 650 to about 10,000 g/mol, in particular from about 750 to about 7,500 g/mol and more particularly ranging from about 1,000 to about 5,000 g/mol; mention may be made especially, alone or as a mixture, of (i) lipophilic polymers such as polybutylenes, polyisobutylenes, for example hydrogenated polydecenes, vinylpyrrolidone copolymers, such as the vinylpyrrolidone/1-hexadecene copolymer, and polyvinylpyrrolidone (PVP) copolymers, such as the copolymers of a C 2 -C 30 alkene, such as C 3 -C 22 , and combinations thereof; (ii) linear fatty acid esters containing a total carbon number ranging from 35 to 70, for instance pentaerythrityl tetrapelargonate; (iii) hydroxylated esters such as polyglyceryl-2 triisostearate; (iv) aromatic esters such as tridecyl trimellitate; (v) esters of fatty alcohols or of branched C 24 -C 28 fatty acids, such as those described in U.S. Pat. No. 6,491,927 and pentaerythritol esters, and especially triisoarachidyl citrate, pentaerythrityl tetraisononanoate, glyceryl triisostearate, glyceryl 2-tridecyltetradecanoate, pentaerythrityl tetraisostearate, poly(2-glyceryl)tetraisostearate or pentaerythrityl 2-tetradecyltetradecanoate; (vi) diol dimer esters and polyesters, such as esters of diol dimer and of fatty acid, and esters of diol dimer and of diacid. [0218] In particular, one or more oils according to the invention may be present in a composition according to the invention in a content ranging from 1% to 90% by weight, preferably ranging from 2% to 75% by weight or even from 3% to 60% by weight relative to the total weight of the composition. [0219] It is understood that the above-described weight percentage of oil takes into account the weight of oil used for the formulation of the associated supramolecular polymer, if present. Silicone Oils [0220] For the purposes of the present invention, the term “silicone oil” means an oil comprising at least one silicon atom, and especially at least one Si—O group. [0221] In particular, the volatile or non-volatile silicone oils that may be used in the invention preferably have a viscosity at 25° C. of less than 800,000 cSt, preferably less than or equal to 600,000 cSt and preferably less than or equal to 500,000 cSt. The viscosity of these silicone oils may be measured according to standard ASTM D-445. [0222] The silicone oils that may be used according to the invention may be volatile or non-volatile or mixtures of volatile and non-volatile silicone oils. [0223] Thus, a composition according to the invention or under consideration according to a process of the invention may contain a mixture of volatile and non-volatile silicone oils. [0224] In a preferred embodiment, the term “volatile silicone oil” means an oil that can evaporate on contact with the skin in less than one hour, at room temperature (25° C.) and atmospheric pressure. The volatile silicone oil is a volatile cosmetic oil, which is liquid at room temperature, especially having a non-zero vapour pressure, at room temperature and atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40,000 Pa (10 −3 to 300 mmHg), preferably ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1,300 Pa (0.1 to 10 mmHg). [0225] The term “non-volatile silicone oil” means an oil whose vapour pressure at room temperature and atmospheric pressure is non-zero and less than 0.02 mmHg (2.66 Pa) and better still less than 10 −3 mmHg (0.13 Pa). Volatile Silicone Oils [0226] In one embodiment of the present invention, compositions according to the invention comprise at least one volatile silicone oil. [0227] The volatile silicone oils that may be used in the invention may be chosen from silicone oils especially having a viscosity ≦8 centistokes (cSt) (8×10 −6 m 2 /s). [0228] Furthermore, the volatile silicone oil that may be used in the invention may preferably be chosen from silicone oils with a flash point ranging from 40° C. to 102° C., preferably with a flash point of greater than 55° C. and less than or equal to 95° C., and preferentially ranging from 65° C. to 95° C. Volatile silicone oils that may be mentioned include: volatile linear or cyclic silicone oils, especially those with a viscosity ≦8 centistokes (cSt) (8×10 −6 m 2 /s at 25° C.), and especially containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. [0229] More particularly, the volatile silicone oils are non-cyclic and are chosen in particular from: [0230] (a) the non-cyclic linear silicones of formula (D): [0000] R 3 SiO—(R 2 SiO) n —SiR 3   (D) [0231] in which R, which may be identical or different, denotes: a saturated or unsaturated hydrocarbon-based radical, containing from 1 to 10 carbon atoms and preferably from 1 to 6 carbon atoms, optionally substituted with one or more fluorine atoms or with one or more hydroxyl groups, or a hydroxyl group, one of the radicals R possibly being a phenyl group, n is an integer ranging from 0 to 8, preferably ranging from 2 to 6 and better still ranging from 3 to 5, further wherein none of the R groups in the silicone compound of formula (D) contain more than 15 carbon atoms; [0234] (b) the branched silicones of formula (E) or (F) below: [0000] R 3 SiO—[(R 3 SiO)RSiO]—(R 2 SiO) x —SiR 3   (E) [0000] [R 3 SiO]4Si  (F) [0235] in which R, which may be identical or different, denotes: a saturated or unsaturated hydrocarbon-based radical, containing from 1 to 10 carbon atoms, optionally substituted with one or more fluorine atoms or with one or more hydroxyl groups, or a hydroxyl group, one of the radicals R possibly being a phenyl group, x is an integer ranging from 0 to 8, further wherein none of the R groups in the silicone compound of formula (E) or (F) contain more than 15 carbon atoms. [0238] Preferably, for the compounds of formulae (D), (E) and (F), the ratio between the number of carbon atoms and the number of silicon atoms is between 2.25 and 4.33. [0239] The silicones of formulae (D) to (F) may be prepared according to the known processes for synthesizing silicone compounds. [0240] Among the silicones of formula (D) that may be mentioned are: the following disiloxanes: hexamethyldisiloxane (surface tension=15.9 mN/m), sold especially under the name DC 200 Fluid 0. 65 cSt by the company Dow Corning, 1,3-di-tert-butyl-1,1,3,3-tetramethyldisiloxane; 1,3-dipropyl-1,1,3,3-tetramethyldisiloxane; heptylpentamethyldisiloxane; 1,1,1-triethyl-3,3,3-trimethyldisiloxane; hexaethyldisiloxane; 1,1,3,3-tetramethyl-1,3-bis(2-methylpropyl)disiloxane; pentamethyloctyldisiloxane; 1,1,1-trimethyl-3,3,3-tris(1-methylethyl)disiloxane; 1-butyl-3-ethyl-1,1,3-trimethyl-3-propyldisiloxane; pentamethylpentyldisiloxane; 1-butyl-1,1,3,3-tetramethyl-3-(1-methylethyl)disiloxane; 1,1,3,3-tetramethyl-1,3-bis(1-methylpropyl)disiloxane; 1,1,3-triethyl-1,3,3-tripropyldisiloxane; 3,3-dimethylbutyl)pentamethyldisiloxane; (3-methylbutyl)pentamethyldisiloxane; (3-methylpentyl)pentamethyldisiloxane; 1,1,1-triethyl-3,3-dimethyl-3-propyldisiloxane; 1-(1,1-dimethylethyl)-1,1,3,3,3-pentamethyldisiloxane; 1,1,1-trimethyl-3,3,3-tripropyldisiloxane; 1,3-dimethyl-1,1,3,3-tetrakis(1-methylethyl)disiloxane; 1,1-dibutyl-1,3,3,3-tetramethyldisiloxane; 1,1,3,3-tetramethyl-1,3-bis(1-methylethyl)disiloxane; 1,1,1,3-tetramethyl-3,3-bis(1-methylethyl)disiloxane; 1,1,1,3-tetramethyl-3,3-dipropyldisiloxane; 1,1,3,3-tetramethyl-1,3-bis(3-methylbutyl)disiloxane; butylpentamethyldisiloxane; pentaethylmethyldisiloxane; 1,1,3,3-tetramethyl-1,3-dipentyldisiloxane; 1,3-dimethyl-1,1,3,3-tetrapropyldisiloxane; 1,1,1,3-tetraethyl-3,3-dimethyldisiloxane; 1,1,1-triethyl-3,3,3-tripropyldisiloxane; 1,3-dibutyl-1,1,3,3-tetramethyldisiloxane and hexylpentamethyldisiloxane; the following trisiloxanes: octamethyltrisiloxane (surface tension=17.4 mN/m), sold especially under the name DC 200 Fluid 1 cSt by the company Dow Corning, 3-pentyl-1,1,1,3,5,5,5-heptamethyltrisiloxane; 1-hexyl-1,1,3,3,5,5,5-heptamethyltrisiloxane; 1,1,1,3,3,5,5-heptamethyl-5-octyltrisiloxane; 1,1,1,3,5,5,5-heptamethyl-3-octyltrisiloxane, sold especially under the name Silsoft 034 by the company OSI; 1,1,1,3,5,5,5-heptamethyl-3-hexyltrisiloxane (surface tension=20.5 mN/m), sold especially under the name DC 2-1731 by the company Dow Corning; 1,1,3,3,5,5-hexamethyl-1,5-dipropyltrisiloxane; 3-(1-ethylbutyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane; 1,1,1,3,5,5,5-heptamethyl-3-(1-methylpentyl)trisiloxane; 1,5-diethyl-1,1,3,3,5,5-hexamethyltrisiloxane; 1,1,1,3,5,5,5-heptamethyl-3-(1-methylpropyl)trisiloxane; 3-(1,1-dimethylethyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane; 1,1,1,5,5,5-hexamethyl-3,3-bis(1-methylethyl)trisiloxane; 1,1,1,3,3,5,5-hexamethyl-1,5-bis(1-methylpropyl)trisiloxane; 1,5-bis(1,1-dimethylethyl)-1,1,3,3,5,5-hexamethyltrisiloxane; 3-(3,3-dimethylbutyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane; 1,1,1,3,5,5,5-heptamethyl-3-(3-methylbutyl)trisiloxane; 1,1,1,3,5,5,5-heptamethyl-3-(3-methylpentyl)trisiloxane; 1,1,1,3,5,5,5-heptamethyl-3-(2-methylpropyl)trisiloxane; 1-butyl-1,1,3,3,5,5,5-heptamethyltrisiloxane; 1,1,1,3,5,5,5-heptamethyl-3-propyltrisiloxane; 3-isohexyl-1,1,1,3,5,5,5-heptamethyltrisiloxane; 1,3,5-triethyl-1,1,3,5,5-pentamethyltrisiloxane; 3-butyl-1,1,1,3,5,5,5-heptamethyltrisiloxane; 3-tert-pentyl-1,1,1,3,5,5,5-heptamethyltrisiloxane; 1,1,1,5,5,5-hexamethyl-3,3-dipropyltrisiloxane; 3,3-diethyl-1,1,1,5,5,5-hexamethyltrisiloxane; 1,5-dibutyl-1,1,3,3,5,5-hexamethyltrisiloxane; 1,1,1,5,5,5-hexaethyl-3,3-dimethyltrisiloxane; 3,3-dibutyl-1,1,1,5,5,5-hexamethyltrisiloxane; 3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane; 3-heptyl-1,1,1,3,5,5,5-heptamethyltrisiloxane and 1-ethyl-1,1,3,3,5,5,5-heptamethyltrisiloxane; the following tetrasiloxanes: decamethyltetrasiloxane (surface tension=18 mN/m), sold especially under the name DC 200 Fluid 1.5 cSt by the company Dow Corning; 1,1,3,3,5,5,7,7-octamethyl-1,7-dipropyltetrasiloxane; 1,1,1,3,3,5,7,7,7-nonamethyl-5-(1-methylethyl)tetrasiloxane; 1-butyl-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane; 3,5-diethyl-1,1,1,3,5,7,7,7-octamethyltetrasiloxane; 1,3,5,7-tetraethyl-1,1,3,5,7,7-hexamethyltetrasiloxane; 3,3,5,5-tetraethyl-1,1,1,7,7,7-hexamethyltetrasiloxane; 1,1,1,3,3,5,5,7,7-nonamethyl-7-phenyltetrasiloxane; 3,3-diethyl-1,1,1,5,5,7,7,7-octamethyltetrasiloxane; and 1,1,1,3,3,5,7,7,7-nonamethyl-5-phenyltetrasiloxane; the following pentasiloxanes: dodecamethylpentasiloxane (surface tension=18.7 mN/m), sold especially under the name DC 200 Fluid 2 cSt by the company Dow Corning; 1,1,3,3,5,5,7,7,9,9-decamethyl-1,9-dipropylpentasiloxane; 3,3,5,5,7,7-hexaethyl-1,1,1,9,9,9-hexamethylpentasiloxane; 1,1,1,3,3,5,7,7,9,9,9-undecamethyl-5-phenylpentasiloxane; 1-butyl-1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane; 3,3-diethyl-1,1,1,5,5,7,7,9,9,9-decamethylpentasiloxane; 1,3,5,7,9-pentaethyl-1,1,3,5,7,9,9-heptamethylpentasiloxane; 3,5,7-triethyl-1,1,1,3,5,7,9,9,9-nonamethylpentasiloxane and 1,1,1-triethyl-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane; the following hexasiloxanes: 1-butyl-1,1,3,3,5,5,7,7,9,9,11,11,11-tridecamethylhexasiloxane; 3,5,7,9-tetraethyl-1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane and tetradecamethylhexasiloxane. hexadecamethylheptasiloxane; octadecamethyloctasiloxane; eicosamethylnonasiloxane. [0249] Among the silicones of formula (E) that may be mentioned are: [0250] the following tetrasiloxanes: 2-[3,3,3-trimethyl-1,1-bis[(trimethylsilyl)oxy]disiloxanyl]ethyl; 1,1,1,5,5,5-hexamethyl-3-(2-methylpropyl)-3-[(trimethylsilyl)oxy]trisiloxane; 3-(1,1-dimethylethyl)-1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]trisiloxane; 3-butyl-1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]trisiloxane; 1,1,1,5,5,5-hexamethyl-3-propyl-3-[(trimethylsilyl)oxy]trisiloxane; 3-ethyl-1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]trisiloxane; 1,1,1-triethyl-3,5,5,5-tetramethyl-3-(trimethylsiloxy)trisiloxane; 3-methyl-1,1,1,5,5,5-hexamethyl-3-[trimethylsilyl)oxy]trisiloxane; 3-[(dimethylphenylsilyl)oxy]-1,1,1,3,5,5,5-heptamethyltrisiloxane; 1,1,1,5,5,5-hexamethyl-3-(2-methylpentyl)-3-[(trimethylsilyl)oxy]trisiloxane; 1,1,1,5,5,5-hexamethyl-3-(4-methylpentyl)-3-[(trimethylsilyl)oxy]trisiloxane; 3-hexyl-1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]trisiloxane and 1,1,1,3,5,5,5-heptamethyl-3-[(trimethylsilyl)oxy]trisiloxane; [0251] the following pentasiloxanes: 1,1,1,3,5,5,7,7,7-nonamethyl-3-(trimethylsiloxy)tetrasiloxane and 1,1,1,3,3,7,7,7-octamethyl-5-phenyl-5-[(trimethylsilyl)oxy]tetrasiloxane; the following hexasiloxane: 1,1,1,3,5,5,7,7,9,9,11,11,11-tridecamethyl-3-[(trimethylsilyl)oxy]hexasiloxane. [0253] Among the silicones of formula (F), mention may be made of: 1,1,1,5,5,5-hexamethyl-3,3-bis(trimethylsiloxy)trisiloxane. Use may also be made of other volatile silicone oils chosen from: the following tetrasiloxanes: 2,2,8,8-tetramethyl-5-[(pentamethyldisiloxanyl)methyl]-3,7-dioxa-2,8-disilanonane; 2,2,5,8,8-pentamethyl-5-[(trimethylsilyl)methoxy]-4,6-dioxa-2,5,8-trisilanonane; 1,3-dimethyl-1,3-bis[(trimethylsilyl)methyl]-1,3-disiloxanediol; 3-ethyl-1,1,1,5,5,5-hexamethyl-3-[3-(trimethylsiloxy)propyl]trisiloxane and 1,1,1,5,5,5-hexamethyl-3-phenyl-3-[(trimethylsilyl)oxy]trisiloxane (Dow 556 Fluid); the following pentasiloxanes: 2,2,7,7,9,9,11,11,16,16-decamethyl-3,8,10,15-tetraoxa-2,7,9,11,16-pentasilaheptadecane and the tetrakis[(trimethylsilyl)methyl]ester of silicic acid; the following hexasiloxanes: 3,5-diethyl-1,1,1,7,7,7-hexamethyl-3,5-bis[(trimethylsilyl)oxy]tetrasiloxane and 1,1,1,3,5,7,7,7-octamethyl-3,5-bis[(trimethylsilyl)oxy]tetrasiloxane; the heptasiloxane: 1,1,1,3,7,7,7-heptamethyl-3,5,5-tris[(trimethylsilyl)oxy]tetrasiloxane; the following octasiloxanes: 1,1,1,3,5,5,9,9,9-nonamethyl-3,7,7-tris[(trimethylsilyl)oxy]pentasiloxane; 1,1,1,3,5,7,9,9,9-nonamethyl-3,5,7-tris[(trimethylsilyl)oxy]pentasiloxane and 1,1,1,7,7,7-hexamethyl-3,3,5,5-tetrakis[(trimethylsilyl)oxy]tetrasiloxane. [0261] Volatile silicone oils that may more particularly be mentioned include decamethylcyclopentasiloxane sold especially under the name DC-245 by the company Dow Corning, dodecamethylcyclohexasiloxane sold especially under the name DC-246 by the company Dow Corning, octamethyltrisiloxane sold especially under the name DC-200 Fluid 1 cSt by the company Dow Corning, decamethyltetrasiloxane sold especially under the name DC-200 Fluid 1.5 cSt by the company Dow Corning and DC-200 Fluid 5 cSt sold by the company Dow Corning, octamethylcyclotetrasiloxane, heptamethylhexyltrisiloxane, heptamethylethyltrisiloxane, heptamethyloctyltrisiloxane and dodecamethylpentasiloxane, and mixtures thereof. [0262] It should be noted that, among the above-mentioned oils, the linear oils prove to be particularly advantageous. Non-Volatile Silicone Oils [0263] The non-volatile silicone oils that may be used in the invention may be chosen from silicone oils with a viscosity at 25° C. of greater than or equal to 9 centistokes (cSt) (9×10 −6 m 2 /s) and less than 800,000 cSt, preferably between 50 and 600,000 cSt and preferably between 100 and 500,000 cSt. The viscosity of this silicone oil may be measured according to standard ASTM D-445. [0264] Among these silicone oils, two types of oil may be distinguished, according to whether or not they contain phenyl. [0265] Representative examples of these non-volatile linear silicone oils that may be mentioned include polydimethylsiloxanes (i.e., PDMS); alkyl dimethicones; vinyl methyl methicones; and also silicones modified with optionally fluorinated aliphatic groups, or with functional groups such as hydroxyl, thiol and/or amine groups. [0266] Thus, non-phenyl non-volatile silicone oils that may be mentioned include: PDMSs comprising alkyl or alkoxy groups, which are pendent and/or at the end of the silicone chain, these groups each containing from 2 to 24 carbon atoms, PDMSs comprising aliphatic groups, or functional groups such as hydroxyl, thiol and/or amine groups, polyalkylmethylsiloxanes optionally substituted with a fluorinated group, such as polymethyltrifluoropropyldimethylsiloxanes, polyalkylmethylsiloxanes substituted with functional groups such as hydroxyl, thiol and/or amine groups, polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, and mixtures thereof. [0272] According to one embodiment, a composition according to the invention contains at least one non-phenyl linear silicone oil. [0273] The non-phenyl linear silicone oil may be chosen especially from the silicones of formula: [0000] [0274] in which: [0275] R 1 , R 2 , R 5 and R 6 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms, [0276] R 3 and R 4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms, a vinyl radical, an amine radical or a hydroxyl radical, [0277] X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or an amine radical, [0278] n and p are integers chosen so as to have a fluid compound. [0279] As non-volatile silicone oils that may be used according to the invention, mention may be made of those for which: the substituents R 1 to R 6 and X represent a methyl group, and p and n are such that the viscosity is about 500,000 cSt (measured by Brookfield viscometer using ASTMD-445 method), such as the product sold under the name SE30 by the company General Electric, the product sold under the name AK 500,000 by the company Wacker, the product sold under the name Mirasil DM 500,000 by the company Bluestar, and the product sold under the name Dow Corning 200 Fluid 500,000 cSt by the company Dow Corning (viscosity determined by Brookfield viscometer using ASTMD-445 method), the substituents R 1 to R 6 and X represent a methyl group, and p and n are such that the viscosity is about 60,000 cSt (measured by Brookfield viscometer using ASTMD-445 method), such as the product sold under the name Dow Corning 200 Fluid 60,000 CS by the company Dow Corning, and the product sold under the name Wacker Belsil DM 60,000 by the company Wacker, the substituents R 1 to R 6 and X represent a methyl group, and p and n are such that the viscosity is about 350 cSt (measured by Brookfield viscometer using ASTMD-445 method), such as the product sold under the name Dow Corning 200 Fluid 350 CS by the company Dow Corning, the substituents R 1 to R 6 represent a methyl group, the group X represents a hydroxyl group, and n and p are such that the viscosity is about 700 cSt (measured by Brookfield viscometer using ASTMD-445 method), such as the product sold under the name Baysilone Fluid T0.7 by the company Momentive. [0284] According to one embodiment variant, a composition according to the invention contains at least one phenyl silicone oil. [0285] Representative examples of these non-volatile phenyl silicone oils that may be mentioned include those oils of Formulae II to VII described below. [0286] The phenyl silicone oils corresponding to the formula (II): [0000] [0287] in which the groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl. Preferably, in this formula, the phenyl silicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six. [0288] The phenyl silicone oils corresponding to the formula (III): [0000] [0289] in which the groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl. Preferably, in this formula, the phenyl silicone oil comprises at least three phenyl groups, for example at least four or at least five. Mixtures of these phenyl silicone oils may be used. Examples that may be mentioned include mixtures of triphenyl, tetraphenyl or pentaphenyl organopolysiloxanes. [0290] The phenyl silicone oil corresponding to the formula (IV): [0000] [0291] in which Me represents methyl, Ph represents phenyl. Such a phenyl silicone oil is especially manufactured by Dow Corning under the reference PH-1555 HRI or Dow Corning 555 Cosmetic Fluid (chemical name: 1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane; INCI name: trimethyl pentaphenyl trisiloxane). The reference Dow Corning 554 Cosmetic Fluid may also be used. [0292] The phenyl silicone oils corresponding to the formula (V): [0000] [0293] in which Me represents methyl, y is between 1 and 1,000 and X represents —CH 2 —CH(CH 3 ) (Ph). [0294] The phenyl silicone oils corresponding to formula (VI) below: [0000] [0295] in which Me is methyl and Ph is phenyl, OR′ represents a group —OSiMe 3 and y is 0 or ranges between 1 and 1000, and z ranges between 1 and 1000, such that compound (VI) is a non-volatile oil. [0296] According to a first embodiment, y ranges between 1 and 1000. Use may be made, for example, of trimethyl siloxyphenyl dimethicone, sold especially under the reference Belsil PDM 1000 sold by the company Wacker. [0297] According to a second embodiment, y is equal to 0. Use may be made, for example, of phenyl trimethylsiloxy trisiloxane, sold especially under the reference Dow Corning 556 Cosmetic Grade Fluid. [0298] The phenyl silicone oils corresponding to the formula (VII): [0000] [0299] in which: [0300] R 1 , R 2 , R 5 and R 6 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms, [0301] R 3 and R 4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms or an aryl radical, [0302] X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical, [0303] n and p being chosen so as to give the oil a weight-average molecular mass of less than 200,000 g/mol, preferably less than 150,000 g/mol and more preferably less than 100,000 g/mol. [0304] Mixtures of the phenyl silicone oils corresponding to Formulae (II) to (VII) are also useful. [0305] The phenyl silicone oils that are most particularly suitable for use in the invention are those corresponding to formulae (III), (IV) and (VI), especially to formula (IV) and (VI) hereinabove. [0306] More particularly, the phenyl silicone oils are chosen from phenyl trimethicones, phenyl dimethicones, phenyl-trimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates, and mixtures thereof. Preferably, the weight-average molecular weight of the non-volatile phenyl silicone oil according to the invention ranges from 500 to 10,000 g/mol. Waxes [0307] The composition of the present invention contains at least one polyethylene wax. [0308] The polyethylene wax may be present in the composition of the present invention in an amount ranging from about 1 to about 25% by weight, more preferably from about 2 to about 20% by weight, most preferably from about 4 to about 15% by weight, relative to the total weight of the composition. Colorant(s) [0309] The cosmetic compositions of the present invention may also contain at least one cosmetically acceptable colorant such as a pigment or dyestuff. Examples of suitable pigments include, but are not limited to, inorganic pigments, organic pigments, lakes, pearlescent pigments, iridescent or optically variable pigments, and mixtures thereof. A pigment should be understood to mean inorganic or organic, white or colored particles. Said pigments may optionally be surface-treated within the scope of the present invention, including but not limited to, surface treatments with compounds such as silicones, perfluorinated compounds, lecithin, and amino acids. [0310] Representative examples of inorganic pigments useful in the present invention include those selected from the group consisting of rutile or anatase titanium dioxide, coded in the Color Index under the reference CI 77,891; black, yellow, red and brown iron oxides, coded under references CI 77,499, 77,492 and 77,491; manganese violet (CI 77,742); ultramarine blue (CI 77,007); chromium oxide (CI 77,288); chromium hydrate (CI 77,289); and ferric blue (CI 77,510) and mixtures thereof. [0311] Representative examples of organic pigments and lakes useful in the present invention include, but are not limited to, D&C Red No. 19 (CI 45,170), D&C Red No. 9 (CI 15,585), D&C Red No. 21 (CI 45,380), D&C Orange No. 4 (CI 15,510), D&C Orange No. 5 (CI 45,370), D&C Red No. 27 (CI 45,410), D&C Red No. 13 (CI 15,630), D&C Red No. 7 (CI 15,850), D&C Red No. 6 (CI 15,850), D&C Yellow No. 5 (CI 19,140), D&C Red No. 36 (CI 12,085), D&C Orange No. 10 (CI 45,425), D&C Yellow No. 6 (CI 15,985), D&C Red No. 30 (CI 73,360), D&C Red No. 3 (CI 45,430) and the dye or lakes based on cochineal carmine (CI 75,570) and mixtures thereof. [0312] Representative examples of pearlescent pigments useful in the present invention include those selected from the group consisting of the white pearlescent pigments such as mica coated with titanium oxide, mica coated with titanium dioxide, bismuth oxychloride, titanium oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue, chromium oxide and the like, titanium mica with an organic pigment of the above-mentioned type as well as those based on bismuth oxychloride and mixtures thereof. [0313] The precise amount and type of colorant employed in the compositions of the present invention will depend on the color, intensity and use of the cosmetic composition and, as a result, will be determined by those skilled in the art of cosmetic formulation. Surfactant(s) [0314] A composition according to the invention may also comprise at least one surfactant, which may be present in a proportion of from about 0.1% to about 10% by weight, especially from about 0.5% to about 8% by weight, or even from about 1% to about 6% by weight relative to the total weight of the composition. The surfactant may be chosen from amphoteric, anionic, cationic and nonionic, preferably nonionic, surfactants. Mention may especially be made, alone or as a mixture, of: [0315] a) nonionic surfactants with an HLB (i.e., hydrophilic-lipophilic balance) of less than 8 at 25° C., optionally combined with one or more nonionic surfactants with an HLB of greater than 8 at 25° C., as mentioned below, for instance: saccharide esters and ethers such as sucrose stearates, sucrose cocoate and sorbitan stearate, and mixtures thereof; fatty acid esters, especially of C 8 -C 24 and preferably of C 16 -C 22 fatty acids, and of polyol, especially of glycerol or sorbitol, such as glyceryl stearate, glyceryl laurate, polyglyceryl-2 stearate, sorbitan tristearate and glyceryl ricinoleate; lecithins, such as soybean lecithins; oxyethylenated and/or oxypropylenated ethers (which may comprise 1 to 150 oxyethylene and/or oxypropylene groups) of fatty alcohols (especially of C 8 -C 24 and preferably C 12 -C 18 fatty alcohols) such as stearyl alcohol oxyethylene ether containing two oxyethylene units (CTFA name: Steareth-2); silicone surfactants, for instance dimethicone copolyols and alkyldimethicone copolyols, for example the mixture of cyclomethicone/dimethicone copolyol sold under the name Q2-3225C® by the company Dow Corning; [0321] b) nonionic surfactants with an HLB of greater than or equal to 8 at 25° C., for instance: saccharide esters and ethers such as the mixture of cetylstearyl glucoside and of cetyl and stearyl alcohols, for instance Montanov 68 from SEPPIC; oxyethylenated and/or oxypropylenated glycerol ethers, which may comprise 1 to 150 oxyethylene and/or oxypropylene units; oxyethylenated and/or oxypropylenated ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene units) of fatty alcohols, especially of C 8 -C 24 and preferably of C 12 -C 18 fatty alcohols, such as stearyl alcohol oxyethylene ether containing 20 oxyethylene units (CTFA name: Steareth-20), cetearyl alcohol oxyethylene ether containing 30 oxyethylene units (Ceteareth-30) and the oxyethylene ether of the mixture of C 12 -C 15 fatty alcohols comprising seven oxyethylene units (C 12-15 Pareth-7); esters of a fatty acid, especially of C 8 -C 24 and preferably of C 16 -C 22 fatty acids, and of polyethylene glycol (or PEG) (which may comprise 1 to 150 oxyethylene units), such as PEG-50 stearate and PEG-40 monostearate; esters of a fatty acid, especially of C 8 -C 24 and preferably of C 16 -C 22 fatty acids, and of oxyethylenated and/or oxypropylenated glycerol ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene units), for instance glyceryl monostearate polyoxyethylenated with 200 oxyethylene units; glyceryl stearate polyoxyethylenated with 30 oxyethylene units, glyceryl oleate polyoxyethylenated with 30 oxyethylene units, glyceryl cocoate polyoxyethylenated with 30 oxyethylene units, glyceryl isostearate polyoxyethylenated with 30 oxyethylene units and glyceryl laurate polyoxyethylenated with 30 oxyethylene units; esters of a fatty acid, especially of C 8 -C 24 and preferably of C 16 -C 22 fatty acids, and of oxyethylenated and/or oxypropylenated sorbitol ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene units), for instance polysorbate 20 and polysorbate 60; dimethicone copolyol, especially the product sold under the name Q2-5220® from Dow Corning; dimethicone copolyol benzoate, such as the products sold under the names Finsolv SLB 101® and 201® from Finetex; copolymers of propylene oxide and of ethylene oxide, also known as EO/PO polycondensates, which are copolymers formed from polyethylene glycol and polypropylene glycol blocks, for instance polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates. [0331] c) anionic surfactants such as: salts of C 16 -C 30 fatty acids, especially amine salts, such as triethanolamine stearate or 2-amino-2-methylpropane-1,3-diol stearate; polyoxyethylenated fatty acid salts, especially animated salts or salts of alkali metals, and mixtures thereof; phosphoric esters and salts thereof, such as DEA oleth-10 phosphate (Crodafos N 10N from the company Croda) or monopotassium monocetyl phosphate; sulfosuccinates such as disodium PEG-5 citrate lauryl sulfosuccinate and disodium ricinoleamido MEA sulfosuccinate; alkyl ether sulfates such as sodium lauryl ether sulfate; isethionates; acylglutamates such as disodium hydrogenated tallow glutamate (Amisoft HS21 R® from Ajinomoto) and sodium stearoyl glutamate (Amisoft HS11 PF® from Ajinomoto); soybean derivatives, for instance potassium soyate; citrates, for instance glyceryl stearate citrate; proline derivatives, for instance sodium palmitoyl proline or the mixture of sodium palmitoyl sarcosinate, magnesium palmitoyl glutamate, palmitic acid and palmitoyl proline (Sepifeel One from SEPPIC); lactylates, for instance sodium stearoyl lactylate; sarcosinates, for instance sodium palmitoyl sarcosinate or the 75/25 mixture of stearoyl sarcosine and myristoyl sarcosine; sulfonates, for instance sodium C 14-17 alkyl-sec-sulfonate; glycinates, for instance sodium cocoyl glycinate. [0346] d) cationic surfactants such as: alkylimidazolidiniums such as isostearylethylimidonium ethosulfate, [0348] ammonium salts such as (C 12-30 alkyl)tri(C 1-4 alkyl)ammonium halides, for instance N,N,N-trimethyl-1-docosanaminium chloride (or behentrimonium chloride); [0349] e) amphoteric surfactants, for instance N-acylamino acids, such as N-alkylaminoacetates and disodium cocoamphodiacetate, and amine oxides such as stearamine oxide. Additive(s) [0350] A makeup and/or care composition according to the invention may also comprise at least one agent usually used in cosmetics, chosen, for example, from: reducing agents; thickeners; film-forming agents that are especially hydrophobic, or are softeners, antifoams, moisturizers, or UV-screening agents; ceramides; cosmetic active agents; peptizers; fragrances; proteins; vitamins; propellants; hydrophilic or lipophilic, film-forming or non-film-forming polymers; and lipophilic or hydrophilic gelling agents. The above additives are generally present in an amount for each of them of between 0.01% and 10% by weight relative to the total weight of the composition. A person skilled in the art will take care to select the constituents of the composition such that the advantageous properties associated with the invention are not, or are not substantially, adversely affected. Cosmetically Acceptable Medium [0351] The ready-to-use composition according to the disclosure can be in various forms, such as in the form of liquids, creams, gels, lotions or paste. [0352] The ready-to-use composition can comprise other compounds constituting the cosmetically acceptable medium. This cosmetically acceptable medium comprises water or a mixture of water and at least one cosmetically acceptable organic solvent. [0353] As examples of cosmetically acceptable organic solvents, non-limiting mentions can be made of alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, or glycols or glycol ethers such as, for example, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol or dipropylene glycol, or ethers thereof such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol or propylene glycol, such as, for example, monomethyl ethers of propylene glycol, butylene glycol, hexylene glycol or dipropylene glycol, as well as alkyl ethers of diethylene glycol, for example monoethyl ether or monobutyl ether of diethylene glycol. [0354] The composition of the present invention may be in any form, either liquid or non-liquid (semi-solid, soft solid, solid, etc.). For example, it may be a paste, a solid, a gel, or a cream. It may be an emulsion, such as an oil-in-water or water-in-oil emulsion, a multiple emulsion, such as an oil-in-water-in-oil emulsion or a water-in-oil-in-water emulsion, or a solid, rigid or supple gel. The composition of the invention may, for example, comprise an external or continuous fatty phase. The composition can also be a molded composition or cast as a stick or a dish. EXAMPLES [0355] [0000] Lip Compositions Control Control INCI US Example 1 Example 2 Example 1 C30 + Olefin/Undecylenic 17 0 4.25 Acid Copolymer (Performa V ™-6112) Supramolecular Polymer of 8.75 8.75 8.75 Formula (I) (n = 30-40) RED 7 PIGMENT 6 6 6 Isododecane QS QS QS POLYETHYLENE 500 0 9.71 7.29 POLYETHYLENE 400 0 7.29 5.46 TiO2 4.3 4.3 4.3 All numerical values in the above Table are weight percent active. Procedures: [0356] All materials were mixed with moderate agitation at 80 degrees Celsius until all waxes have melted and contents looked uniform. The mixture was then cooled to room temperature while mixing before pouring to suitable size containers for future testing. [0357] The formulations of the examples above were tested on forearm for rub test. They were also subjected to a texture test upon application on the lips. Rub Test on Forearm [0358] Three subjects evaluated the formulations of Control Examples 1 and 2 and Example 1 on the inner forearm on the same day. Each formulation was applied with a lip gloss applicator for 5 strokes and allowed to dry for 10 minutes on forearm and then a drop of olive oil was added to each patch of test area and allowed to rest for 5 minutes before rubbing with Kimwipe 5 times to measure color transfer. Then a visual evaluation score was given to each Kimwipe with a range between 1 and 5 where 5 represents high transfer of color and is undesirable and 1 represents no transfer of color and is highly desirable. Application Texture Test [0359] Three subjects evaluated the formulations of Control Examples 1 and 2 and Example 1 on their lips on the same day. Each formulation was applied with a lip gloss applicator for 5 strokes and allowed to dry for 10 minutes. Sensorial evaluation was recorded based on the application of the product on the lips. [0000] Evaluation Control Control Test Method Example 1 Example 2 Example 1 Rub Test on 2 2 1 Forearm Application Pasty Creamy creamy and Texture Test shiny [0360] The results above show that, the inventive formulation provided a creamy film texture and a comfortable feeling on the lip with the addition of two polyethylene waxes. At the same time, they provided high oil resistance. [0361] It is to be understood that the foregoing describes preferred embodiments of the invention and that modifications may be made therein without departing from the spirit or scope of the invention as set forth in the claims.
The present invention relates to a cosmetic composition and method for making up and/or enhancing the appearance of a keratinous substrate, comprising at least one supramolecular polymer, at least one detackifying ingredient which is a hyperbranched functional polymer, at least one fatty phase ingredient(s) and at least one polyethylene wax. The compositions of the present invention may optionally contain at least one colorant.
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BACKGROUND OF THE INVENTION Theories regarding the pathophysiology of migraine have been dominated since 1938 by the work of Graham and Wolff (Arch. Neurol. Psychiatry, 39, 737-63 (1938)). They proposed that the cause of migraine headache was vasodilatation of extracranial vessels. This view was supported by knowledge that ergot alkaloids and sumatriptan, a hydrophilic 5-HT 1 agonist which does not cross the blood-brain barrier, contract cephalic vascular smooth muscle and are effective in the treatment of migraine. (Humphrey, et al., Ann. NY Acad. Sci., 600, 587-600 (1990)). Recent work by Moskowitz has shown, however, that the occurrence of migraine headaches is independent of changes in vessel diameter (Cephalalgia, 12, 5-7, (1992)). Moskowitz has proposed that currently unknown triggers for pain stimulate trigeminal ganglia which innervate vasculature within the cephalic tissue, giving rise to release of vasoactive neuropeptides from axons on the vasculature. These released neuropeptides then activate a series of events, a consequence of which is pain. This neurogenic inflammation is blocked by sumatriptan and ergot alkaloids by mechanisms involving 5-HT receptors, believed to be closely related to the 5-HT 1D subtype, located on the trigeminovascular fibers (Neurology, 43(suppl. 3), S16-S20 (1993)). Serotonin (5-HT) exhibits diverse physiological activity mediated by at least four receptor classes, the most heterogeneous of which appears to be 5-HT 1 . A human gene which expresses a fifth 5-HT 1 subtype, named 5-HT 1F , was isolated by Kao and coworkers (Proc. Natl. Acad. Sci. USA, 90, 408-412 (1993)). This 5-HT 1F receptor exhibits a pharmacological profile distinct from any serotonergic receptor yet described. The high affinity of sumatriptan at this subtype, K i =23 nM, suggests a role of the 5-HT 1F receptor in migraine. This invention provides novel 5-HT 1F agonists which inhibit peptide extravasation due to stimulation of the trigeminal ganglia, and are therefore useful for the treatment of migraine and associated disorders. SUMMARY OF THE INVENTION The present invention provides novel optionally substituted 3-<1-alkylenearyl>-4-<1,2,3,6-tetrahydropyridinyl>-1H-indoles and 3-<1-alkylenearyl>-4-piperidinyl-1H-indoles of Formula I: ##STR2## in which A-B is --CH--CH 2 -- or --C═CH--; X is H, halo, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkyl, benzyloxy, hydroxy or carboxamido; Y is O, S or a bond; n is 1-4; Ar is 1-naphthyl, 2-naphthyl, phenyl or phenyl monosubstituted with a substituent selected from the group consisting of halo, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkyl, benzyloxy, hydroxy or trifluoromethyl; and pharmaceutically acceptable acid addition salts thereof providing that: a) when A-B is --C═CH-- and Ar is phenyl, X is other than hydrogen, fluoro, chloro or methoxy; and b) when A-B is --CH--CH 2 -- and Ar is phenyl, X is other than fluoro or chloro. A further embodiment of this invention is a method for increasing activation of the 5-HT 1F receptor for treating a variety of disorders which have been linked to decreased neurotransmission of serotonin in mammals. Included among these disorders are depression, migraine pain, bulimia, premenstrual syndrome or late luteal phase syndrome, alcoholism, tobacco abuse, panic disorder, anxiety, post-traumatic syndrome, memory loss, dementia of aging, social phobia, attention deficit hyperactivity disorder, disruptive behavior disorders, impulse control disorders, borderline personality disorder, obsessive compulsive disorder, chronic fatigue syndrome, premature ejaculation, erectile difficulty, anorexia nervosa, disorders of sleep, autism, mutism or trichotillomania. Any of these methods employ a compound of Formula II: ##STR3## in which A-B is --CH--CH 2 -- or --C═CH--; X is H, halo, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkyl, benzyloxy, hydroxy or carboxamido; Y is O, S or a bond; n is 1-4; Ar is 1-naphthyl, 2-naphthyl, phenyl or phenyl monosubstituted with a substituent selected from the group consisting of halo, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkyl, benzyloxy, hydroxy or trifluoromethyl; and pharmaceutically acceptable acid addition salts thereof. This invention also provides a pharmaceutical formulation which comprises, in association with a pharmaceutically acceptable carrier, diluent or excipient, a compound of Formula II. DETAILED DESCRIPTION OF THE INVENTION The general chemical terms used in the formulae above have their usual meanings. For example, the terms C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, include such groups as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and s-butyl. The term halo includes fluoro, chloro, bromo and iodo. While all of the compounds of this invention are useful as 5-HT 1F agonists, certain of the compounds are preferred. The following paragraphs describe such preferred classes. a) n is 2-4; b) n is 2 or 4; c) Y is a bond; d) X is H; e) X is halo; f) X is carboxamido; g) X is benzyloxy; h) X is hydroxy; i) Ar is phenyl; j) Ar is C 1 -C 4 alkoxyphenyl; k) Ar is 3-methoxyphenyl; l) Ar is halophenyl; m) Ar is 3-chlorophenyl; n) Ar is 3-fluorophenyl; o) Ar is C 1 -C 4 alkylphenyl; p) Ar is 3-methylphenyl; q) Ar is trifluoromethylphenyl; r) Ar is 3-trifluoromethylphenyl; s) the compound is a free base; t) the compound is a salt u) A-B is --CH═CH--; v) A-B is --CH 2 --CH 2 --. It will be understood that the above classes may be combined to form additional preferred classes. The compounds of this invention are useful in a method for increasing activation of the 5-HT 1F receptor for treating a variety of disorders which have been linked to decreased neurotransmission of serotonin in mammals. It is preferred that the mammal to be treated by the administration of compounds of this invention is human. Since the compounds of this invention are amines, they are basic in nature and accordingly react with any of a number of inorganic and organic acids to form pharmaceutically acceptable acid addition salts. Since some of the free amines of the compounds of this invention are frequently oils at room temperature, it is preferable to convert the free amines to their pharmaceutically acceptable acid addition salts for ease of handling and administration, since the latter are routinely solid at room temperature. Acids commonly employed to form such salts are inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, and the like, and organic acids, such as p-toluene-sulfonic acid, methanesulfonic acid, oxalic acid, p-bromo-phenylsulfonic acid, carbonic acid, succinic acid, citric acid, benzoic acid, acetic acid and the like. Examples of such pharmaceutically acceptable salts thus are the sulfate, pyrosulfate, bisulfate, sulfite, bisulfite, phosphate, monohydrogenphosphate, dihydrogenphosphate, metaphosphate, pyrophosphate, chloride, bromide, iodide, acetate, propionate, decanoate, caprylate, acrylate, formate, isobutyrate, caproate, heptanoate, propiolate, oxalate, malonate, succinate, suberate, sebacate, fumarate, maleate, butyne-1,4-dioate, hexyne-1,6-dioate, benzoate, chlorobenzoate, methylbenzoate, dinitrobenzoate, hydroxybenzoate, methoxybenzoate, phthalate, sulfonate, xylenesulfonate, phenylacetate, phenylpropionate, phenylbutyrate, citrate, lactate, b-hydroxybutyrate, glycollate, tartrate, methanesulfonate, propanesulfonate, naphthalene-1-sulfonate, naphthalene-2-sulfonate, mandelate and the like. Preferred pharmaceutically acceptable salts are those formed with hydrochloric acid or oxalic acid. The following group is illustrative of compounds contemplated within the scope of Formula I of this invention: 3-<1-<2-phenylethyl>-4-piperidinyl>-1H-indole hydrochloride 5-methoxy-3-<1-<3-phenylpropyl>-4-piperidinyl>-1H-indole hydrochloride 5-chloro-3-<1-<2-<1-naphthyl>-ethyl>-4-piperidinyl>-1-H-indole oxalate 5-bromo-3-<1-<3-<4-trifluoromethylphenyl>propyl>-4-piperidinyl>-1H-indole mandelate 5-carboxamido-3-<1-<2-phenylethyl>-4-piperidinyl>-1H-indole hydrobromide 5-chloro-3-<1-<2-<2-naphthyl>ethyl>-4-piperidinyl>-1H-indole p-toluenesulfonate 5-hydroxy-3-<1-<2-<3-thiomethylphenyl>ethyl>-4-piperidinyl>-1H-indole 5-propyl-3-<1-<3-<4-methoxyphenyl>ethyl>-4-piperidinyl>-1H-indole 5-iodo-3-<1-<4-<2-chlorophenyl>butyl>-4-piperidinyl>-1H-indole benzoate 5-butoxy-3-<1-<2-<4-ethoxyphenyl>ethyl>-4-piperidinyl>-1H-indole methanesulfonate 5-ethyl-3-<1-<4-thioethylphenylmethyl>-4-piperidinyl>-1H-indole 5-isobutyl-3-<1-<3-<2-trifluoromethylphenyl>propyl>-4-piperidinyl>-1H-indole 5-butyl-3-<1-<2-<3-fluorophenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride 5-ethyl-3-<1-<2-<4-isopropylphenyl>-ethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole 5-methyl-3-<1-<2-naphthylmethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole 5-isopropoxy-3-<1-<2-<2-methylphenyl>ethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrobromide 5-isopropyl-3-<1-<2-<4-benzyloxyphenyl>ethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole maleate 5-ethoxy-3-<1-<2-<4-isopropylphenyl>ethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole 5-(sec-butoxy)-3-<1-<2-<3-bromophenyl>ethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole 5-iodo-3-<1-<4-<2-chlorophenyl>butyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole benzoate Compounds illustrative of the scope contemplated within Formula II of the present invention include all of Formula I and the following group: 5-fluoro-3-<1-<2-phenylethyl>-4-piperidinyl>-1H-indole hydrochloride 5-chloro-3-<1-<3-phenylpropyl>-4-piperidinyl>-1H-indole hydrochloride 3-<1-<3-<4-trifluoromethylphenyl>propyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole mandelate 5-fluoro-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrobromide 5-chloro-3-<1-<2-<3-thiomethylphenyl>ethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole p-toluenesulfonate 5-methoxy-3-<1-<4-<2-chlorophenyl>butyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole benzoate The compounds of this invention are prepared by methods well known to one of ordinary skill in the art. While all of the starting indoles may be prepared by the Fischer indole synthesis (Robinson, The Fischer Indole Synthesis, Wiley, New York, 1983), a majority are commercially available. The indoles are condensed with 4-piperidone.HCl.H 2 O or an appropriately N-substituted 4-piperidone, in the presence of a suitable base to give the corresponding 3-(1,2,3,6-tetrahydro-4-pyridinyl)-1H-indoles as illustrated in the following scheme. ##STR4## The reaction is performed by first dissolving an excess of the base, typically sodium or potassium hydroxide, in a lower alkanol, typically methanol or ethanol. The indole and two equivalents of the 4-piperidone are then added and the reaction refluxed for 8-72 hours. The resulting 3-(1,2,3,6-tetrahydro-4-pyridinyl)-1H-indoles may be isolated from the reaction mixture by the addition of water. Compounds which precipitate may be isolated directly by filtration while others may be extracted with a water immiscible solvent such as ethyl acetate or dichloromethane. The compounds recovered may be used directly in subsequent: steps or first purified by silica gel chromatography or recrystallization from a suitable solvent. The 3-(1,2,3,6-tetrahydro-4-pyridinyl)-1H-indoles may next be hydrogenated to give the corresponding 3-(piperidin-4-yl)-1H-indoles as shown below. ##STR5## The catalyst may be a precious metal catalyst such as platinum oxide, or palladium or platinum on a suitable support such as carbon. When X is a functional group that is labile to hydrogenolysis, such as halo or benzyloxy, a deactivated catalyst such as sulfided platinum on carbon or a mixed catalyst system of sulfided platinum on carbon with platinum oxide may be used to prevent hydrogenolysis. The solvent may consist of a lower alkanol, such as methanol or ethanol, tetrahydrofuran or a mixed solvent system of tetrahydrofuran and ethyl acetate. The hydrogenation may be performed at an initial hydrogen pressure of 20-80 p.s.i., preferably from 50-60 p.s.i., at 0°-60° C., preferably at ambient temperature to 40° C., for 1 hour to 3 days. Additional charges of hydrogen may be required to drive the reaction to completion depending on the specific substrate. The 3-(piperidin-4-yl)-1H-indoles prepared in this manner are isolated by removal of the catalyst by filtration followed by concentration of the reaction solvent under reduced pressure. The product recovered may be used directly in a subsequent step or further purified by chromatography or recrystallization from a suitable solvent. When R is H, either the 3-(1,2,3,6-tetrahydro-4-pyridinyl)-1H-indoles or the 3-(piperidin-4-yl)-1H-indoles prepared as described above are suitable substrates for N-alkylation with an appropriate alklating agent as described below. ##STR6## The starting indole and the base are combined in the reaction solvent followed by the addition of the alkylating agent. The reaction solvent may be any non-reactive solvent typically used for alkylations of this type such as acetonitrile, dimethylformamide or N-methyl-2-pyrrolidinone, limited by the solubility of the substrates and a sufficiently high boiling point. The base must be sufficiently basic to neutralize the acid generated during the progress of the reaction but not so basic as to deprotonate other sites in the substrate giving rise to other products. Additionally, the base must not compete to any great extent with the substrate for the alkylating agent and must have sufficient solubility in the reaction solvent. Bases typically used for these reactions are sodium carbonate and potassium carbonate. The reaction mixture is typically stirred at 80° to 140° C., preferably at about 100° C., for 8 hours to 3 days. The alkylated products are isolated by concentration of the reaction mixture under reduced pressure followed by partitioning of the resultant residue between water and a suitable organic solvent such as ethyl acetate, diethyl ether, dichloromethane, ethylene chloride, chloroform or carbon tetrachloride. The isolated product may be purified by chromatography, crystallization from a suitable solvent, salt formation or a combination of these techniques. The leaving group (LG) of the alkylating agents may be chloro, bromo, iodo, methanesulfonyloxy, trifluoromethanesulfonyloxy, 2,2,2-trifluoroethanesulfonyloxy, benzenesulfonyloxy, p-bromobenzenesulfonyloxy, p-nitrobenzenesulfonyloxy or p-toluenesulfonyloxy, all of which are useful for the preparation of compounds of this invention. The specific alkylating agent employed is determined by its commercial availability or a convenient synthesis from commercially available starting materials. The preferred alkylating agents for synthesis of compounds of this invention are those where the leaving group is chloro, bromo or methanesulfonyloxy. Alkylating agents where the leaving group is chloro, if not commercially available, are prepared from the corresponding alcohol by standard methods, preferably by treating the alcohol with neat thionyl chloride at ambient temperature. Alkylating agents where the leaving group is methanesulfonyloxy are prepared from the corresponding alcohols as described below. ##STR7## The alcohol is dissolved in a suitable anhydrous solvent such as tetrahydrofuran, diethyl ether, p-dioxane or acetonitrile which contains the base. The base must be sufficiently basic to neutralize the acid generated during the progress of the reaction but not so basic as to deprotonate other sites in the substrate giving rise to other products. Additionally, the base must not compete to any great extent with the substrate for the sulfonating reagent and must have sufficient solubility in the reaction solvent. Bases typically used in these reactions are tertiary amines such as pyridine, triethylamine or N-methylmorpholine. To the reaction mixture is then added the sulfonating reagent with cooling. The sulfonating reagent may be a methanesulfonyl halide such as the fluoride or chloride, or methanesulfonic anhydride. The reaction mixture is allowed to react from 1 hour to 24 hours at ambient temperature. The product is isolated by concentrating the reaction mixture under reduced pressure followed by partitioning the residue between water and an appropriate organic solvent such as dichloromethane, ethylene chloride, chloroform or carbon tetrachloride. The isolated product is used directly in the alkylation step. The starting alcohols required for the synthesis of compounds of this invention are either commercially available or may be prepared by employing well established synthetic methodology. A general scheme for the synthesis of the required alcohols when Y is a bond is described below. ##STR8## An appropriate carboxylic acid is reduced to the corresponding alcohol in diethyl ether or, preferably, tetrahydrofuran. The solution is added to a suspension of an appropriate hydride reducing agent, preferably lithium aluminum hydride, in the same solvent at reduced temperature, typically about 0° C. Once the addition is complete the mixture is allowed to warm to ambient and is stirred at ambient to reflux until the reduction is complete. The alcohol recovered may typically be used without further purification. Required alcohols where Y=O or S and n=2-4 are available by the following scheme: ##STR9## The starting phenol or thiophenol and the base, typically sodium or potassium carbonate, are dissolved in the reaction solvent followed by the appropriate w-bromo carboxylic acid ethyl ester. The reaction solvent may be any non-reactive solvent typically used for alkylations of this type such as acetonitrile, dimethylformamide or N-methyl-Z-pyrrolidinone. The reaction is typically performed at 0° to 80° C. for 8 hours to 3 days. The alkylation products are isolated by concentration of the reaction mixture under reduced pressure followed by partitioning the resultant residue between water and a suitable organic solvent such as ethyl acetate, diethyl ether, dichloromethane, ethylene chloride, chloroform or carbon tetrachloride. The isolated product may be purified by chromatography or reduced directly with an appropriate hydride reducing agent, preferably lithium aluminum hydride, in a suitable solvent, preferably tetrahydrofuran. The alcohol recovered may be purified by chromatography or used without further purification. The required alkylating agents where Y is O or S and n is 1 are available by chloromethylation of the corresponding phenol or thiophenol. (March, Advanced Organic Chemistry, 807, Wiley, New York (1985)) Compounds of this invention may alternatively be prepared by N-acylation of the 3-(1,2,3,6-tetrahydro-4-pyridinyl)-1H-indoles or the 3-(piperidin-4-yl)-1H-indoles with an appropriate acylating agent followed by reduction of the resulting amide as described in the following scheme. ##STR10## The 3-(1,2,3,6-tetrahydro-4-pyridinyl)-1H-indoles or the 3-(piperidin-4-yl)-1H-indoles are acylated in a suitable solvent such as dimethylformamide or N-methyl-2-pyrrolidinone with an appropriate acyl halide, preferably an acyl chloride, or an activated ester well known in the synthesis of peptides such as the esters of pentafluorophenol or 2,4,5-trichlorophenol. The acyl halides or activated esters are available from the corresponding carboxylic acids by well established methods. When an acyl halide is used a suitable base, preferably potassium carbonate, is also required in the reaction mixture to neutralize the acid that is formed as the reaction progresses. The reactions are typically performed at ambient to 80° C. for from one hour to three days. The amide prepared in this reaction is then reduced to a compound of this invention with a suitable hydride reducing agent, such as lithium aluminum hydride, aluminum hydride, sodium aluminum hydride, borane tetrahydrofuran complex or borane dimethylsulfide complex, in an anhydrous ethereal solvent such as tetrahydrofuran or diethyl ether. The reaction is typically run at reflux for from 1 to 24 hours. The desired products are recovered by decomposition of the intermediate complexes by the addition of water followed by extraction into a suitable solvent such as ethyl acetate, diethyl ether or dichloromethane. When a hydroxy substituted compound of this invention is desired, it is easily prepared by catalytic O-debenzylation of the corresponding benzyloxy compound. These hydrogenolyses may be performed by dissolution of the substrate in a lower alkanol, such as methanol or ethanol, tetrahydrofuran or a mixed solvent system of tetrahydrofuran and ethyl acetate. The hydrogenation may be performed at an initial hydrogen pressure of 20-80 p.s.i., preferably from 50-60 p.s.i., at 0°-60° C., preferably at ambient temperature to 40° C., for 1 hour to 3 days. Additional charges of hydrogen may be required to drive the reaction to completion depending on the specific substrate. Compounds prepared in this manner are isolated by removal of the catalyst by filtration followed by concentration of the reaction solvent under reduced pressure. The product recovered may be purified by chromatography or recrystallization from a suitable solvent if necessary. It is evident to the skilled artisan that the conditions for hydrogenolysis of an O-benzyl group may be identical to those employed for the reduction of the 4,5-double bond of the tetrahydropyridines described supra. The hydrogenolysis and double-bond reduction steps, therefore, may be combined if desired. Additionally, the skilled artisan would understand that, where substituents allow, the order of N-alkylation and double-bond reduction is not important. The following preparations and examples further illustrate the synthesis of the compounds of this invention and are not intended to limit the scope of the invention in any way. The compounds described below were identified by various standard analytical techniques as stated in the individual preparations and examples. All of the 3-[1,2,3,6-tetrahydro-4-pyridinyl]-1H-indoles useful as intermediates for compounds of this invention may be prepared as described in the following procedure. PREPARATION I 5-bromo-3-<1,2,3,6-tetrahydro-4-pyridinyl>-1H-indole To a solution of 4.29 gm (77 mMol) potassium hydroxide in 50 mL methanol were added 5.0 gm (26 mMol) 5-bromoindole and 7.84 gm (51 mMol) 4-piperidone.HCl.H 2 O and the reaction mixture was stirred for 18 hours at reflux under a nitrogen atmosphere. The reaction mixture was cooled to ambient temperature, diluted with 500 mL water and the mixture extracted well with dichloromethane. The combined organic extracts were washed with water followed by saturated aqueous sodium chloride and dried over sodium sulfate. The remaining organics were concentrated under reduced pressure to give 6.23 gm (86.5%) of the title compound as a yellow oil. 1 H-NMR(DMSO-d 6 ): δ8.00 (s, 1H); 7.40 (s, 1H); 7.30 (d, 1H); 7.20 (d, 1H); 6.10 (s, 1H); 3.35 (br s, 2H); 2.85 (m, 2H); 2.35 (br s, 2H). All of the 3-[piperidin-4-yl]-1H-indoles useful as intermediates for compounds of this invention may be prepared as described in the following procedure. PREPARATION II 5-bromo-3-[piperidin-4-yl]-1H-indole To a solution of 13.61 gm (49 mMol) 5-bromo-3-<1,2,3,6-tetrahydro-4-pyridinyl>-1H-indole in 75 mL 2:1 tetrahydrofuran:ethyl acetate were added 8.0 gm 3% sulfided platinum on carbon and 4.0 gm platinum oxide. The reaction mixture was hydrogenated with an initial hydrogen pressure of 60 p.s.i. at 40° C. for 18 hours and then at ambient temperature for 30 hours. The reaction mixture was filtered and the filtrate concentrated under reduced pressure to give 10.33 gm (75.6%) of the title compound as a light yellow solid. MS (m/e): 278 (M + ). 1 H-NMR(DMSO-d 6 ): δ10.6 (s, 1H); 7.2 (d, 1H); 7.05 (s, 2H); 6.7 (d, 1H); 3.15 (s, 1H); 3.05 (s, 1H); 2.8 (m, 3H), 1.95 (s, 1H); 1.85 (s, 1H); 1.6 (m, 2H). PREPARATION III 5-carboxamidoindole To a solution of 8.06 gm (50 mMol) indole-5-carboxylic acid in 150 mL dimethylformamide were added 8.11 gm (50 mMol) carbonyldiimidazole and the reaction mixture stirred at ambient temperature for 3 hours. The reaction mixture was then added dropwise to 150 mL concentrated ammonium hydroxide and the reaction mixture was stirred for 18 hours at ambient temperature. The reaction mixture was concentrated under reduced pressure to give a viscous oil which was subjected to silica gel chromatography, eluting with a gradient of dichloromethane containing 0-10% methanol. Fractions shown to contain product were combined and concentrated under reduced pressure to give the title compound as an oil which crystallizes upon standing. 1 H-NMR(CDCl 3 ): δ8.18 (s, 1H); 7.74 (d, 1H); 7.45 (d, 1H); 7.35 (s, 1H); 6.65 (s, 1H). The following procedure is typical of the preparation of the alcohols useful for preparation of compounds of the present invention. PREPARATION IV 2-(3-fluorophenyl)ethanol To a suspension of 3.07 gm (81 mMol) lithium aluminum hydride in 115 mL diethyl ether at 0° C. were added dropwise a solution of 7.0 gm (45 mMol) 3-fluorophenylacetic acid in 26 mL tetrahydrofuran dropwise. The reaction was allowed to warm to ambient and then stirred 18 hours. The reaction mixture was quenched by the addition of 3.0 mL 2N NaOH dropwise with cooling. To this mixture was then added 9.0 mL water and the resulting suspension stirred for 1 hour at ambient. The suspension was filtered and the filter cake rinsed well with diethyl ether, The filtrate was concentrated under reduced pressure to give 6.26 gm (100%) of the title compound as a clear oil. The product was used without further purification. The aralkanols were converted to their corresponding mesylates by the method described below. PREPARATION V 1-(2-methanesulfonyloxyethyl)-2-chlorobenzene To a solution of 5.26 mL (40 mMol) 2-(2-chlorophenyl)ethanol and 8.36 mL (60 mMol) triethylamine in 100 mL tetrahydrofuran were added dropwise 3.25 mL (42 mMol) methanesulfonyl chloride with cooling. The reaction mixture was stirred 4 hours at ambient and was then concentrated under reduced pressure. The residue was partitioned between dichloromethane and water. The organic phase was separated and washed sequentially with water and saturated aqueous sodium chloride. The remaining organics were dried over sodium sulfate and concentrated under reduced pressure to give 9.22 gm (98.3%) of the title compound as a yellow oil. The product was used without further purification. EXAMPLE 1 3-<1-<2-<2-fluorophenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride To a solution of 2.10 gm (10.0 mMol) 3-(4-piperidinyl)-1H-indole in 40 mL dimethylformamide were added 2.65 gm sodium carbonate followed by the dropwise addition of a solution of 2.18 gm (10.0 mMol) 1-(2-methanesulfonyloxyethyl)-2-fluorobenzene in 8.0 mL dimethylformamide. The reaction mixture was stirred at 100° C. for 18 hours under a nitrogen atmosphere. The reaction mixture was then cooled to ambient and the solvent removed under reduced pressure. The residue was partitioned between water and dichloromethane. The organic phase was separated and washed twice with water and once with saturated aqueous sodium chloride. The remaining organics were dried over sodium sulfate and concentrated under reduced pressure to give 3.62 gm of a yellow oil. The oil was purified by flash chromatography, eluting with a gradient system consisting of dichloromethane containing 0-5% methanol. Fractions shown to contain product were combined and concentrated under reduced pressure to give a yellow oil. The hydrochloride salt was formed to give 1.53 gm (42.7%) of the title compound as yellow crystals from methanol, m.p.>250° C. (dec). MS(m/e): 322(M + ) Calculated for C 21 H 23 N 2 F.HCl: Theory: C, 70.28; H, 6.74; N, 7.81. Found: C, 70.42; H, 6.82; N, 7.93. The compounds of Examples 2-17 were prepared employing the method described in detail in Example 1. EXAMPLE 2 3-<1-<2-<3-fluorophenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 1.0 gm (5.0 mMol) 3-(4-piperidinyl)-1H-indole and 1.09 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-3-fluorobenzene, 0.87 gm (48.5%) of the title compound were recovered from methanol as colorless crystals, m.p.=297° C. MS (m/e): 322 (M + ) Calculated for C 21 H 23 N 2 F.HCl: Theory: C, 70.28; H, 6.74; N, 7.81. Found: C, 70.52; H, 6.72; N, 7.77. EXAMPLE 3 3-<1-<2-<4-fluorophenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 1.0 gm (5.0 mMol) 3-(4-piperidinyl)-1H-indole and 1.09 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-4-fluorobenzene, 0.87 gm (48.5%) of the title compound were recovered from methanol as pink crystals, m.p.>250° C. MS(m/e): 322 (M + ) Calculated for C 21 H 23 N 2 F.HCl: Theory: C, 70.28; H, 6.74; N, 7.81. Found: C, 70.07; H, 6.92; N, 7.79. EXAMPLE 4 5-methoxy-3-<1-<2-<4-fluorophenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 2.0 gm (8.7 mMol) 5-methoxy-3-(4-piperidinyl)-1H-indole and 1.90 gm (8.7 mMol) 1-(2-methanesulfonyloxyethyl)-4-fluorobenzene, 1.76 gm (52.1%) of the title compound were recovered from methanol/ethyl acetate as brown crystals, m.p. =215° C. MS(m/e): 352 (M + ) Calculated for C 21 H 25 N 2 OF.HCl: Theory: C, 67.94; H, 6.74; N, 7.20. Found: C, 67.89; H, 6.80; N, 7.29. EXAMPLE 5 3-<1-<2-<2-chlorophenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 1.0 gm (5.0 mMol) 3-(4-piperidinyl)-1H-indole and 1.17 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-2-chlorobenzene, 1.00 gm (53.3%) of the title compound were recovered from methanol as light pink crystals, m.p.>250° C. MS (m/e): 338 (M + ) Calculated for C 21 H 23 N 2 Cl.HCl: Theory: C, 67.20; H, 6.44; N, 7.46. Found: C, 66.96; H, 6.46; N, 7.42. EXAMPLE 6 3-<1-<2-<3-chlorophenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 1.0 gm (5.0 mMol ) 3-(4-piperidinyl)-1H-indole and 1.17 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-3-chlorobenzene, 0.76 gm (40.5%) of the title compound were recovered from methanol as pink crystals, m.p.>250° C. MS (m/e): 338 (M + ) Calculated for C 21 H 23 N 2 Cl.HCl: Theory: C, 67.20; H, 6.44; N, 7.46. Found: C, 66.92; H, 6.50; N, 7.60. EXAMPLE 7 3-<1-<2-<4-bromophenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 1.0 gm (5.0 mMol ) 3-(4-piperidinyl)-1H-indole and 1.40 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-4-bromobenzene, 1.10 gm (53.3%) of the title compound were recovered from methanol as off-white crystals, m.p.>250° C. MS (m/e): 382 (M + ) Calculated. for C 21 H 23 N 2 Br.HCl: Theory: C, 60.08; H, 5.76; N, 6.67. Found: C, 59.80; H, 5.79; N, 6.64. EXAMPLE 8 3-<1-<2-<2-methylphenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 1.0 gm (5.0 mMol) 3-(4-piperidinyl)-1H-indole and 1.07 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-2-methylbenzene, 0.63 gm (35.5%) of the title compound were recovered from methanol as tan crystals, m.p.>250° C. MS(m/e): 318(M + ) Calculated for C 22 H 26 N 2 .HCl: Theory: C, 74.45; H, 7.67; N, 7.89. Found: C, 74.18; H, 7.56; N, 7.77. EXAMPLE 9 3-<1-<2-<3-methylphenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 1.0 gm (5.0 mMol) 3-(4-piperidinyl)-1H-indole and 1.07 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-3-methylbenzene, 0.76 gm (42.8%) of the title compound were recovered from methanol as off-white crystals, m.p.>250° C. MS (m/e): 318 (M + ) Calculated for C 22 H 26 N 2 .HCl: Theory: C, 74.45; H, 7.67; N, 7.89. Found: C, 74.23; H, 7.72; N, 7.95. EXAMPLE 10 3-<1-<2-<4-methylphenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 1.0 gm (5.0 mMol) 3-(4-piperidinyl)-1H-indole and 1.07 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-4-methylbenzene, 0.71 gm (40.0%) of the title compound were recovered from methanol as yellow crystals, m.p.>250° C. MS(m/e): 318(M + ) Calculated for C 22 H 26 N 2 .HCl: Theory: C, 74.45; H, 7.67; N, 7.89. Found: C, 74.51; H, 7.77; N, 7.88. EXAMPLE 11 3-<1-<2-<2-methoxyphenyl>ethyl>-4-piperidinyl>-1H -indole hydrochloride Using 1.0 gm (5.0 mMol ) 3-(4-piperidinyl)-1H-indole and 1.15 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-2-methoxybenzene, 0.79 gm (42.6%) of the title compound were recovered from methanol as pink crystals, m.p.=290°-292° C. MS (m/e): 334 (M + ) Calculated for C 22 H 26 N 2 O.HCl: Theory: C, 71.24; H, 7.34; N, 7.55. Found: C, 71.26; H, 7.33; N, 7.66. EXAMPLE 12 3-<1-<2-<3-methoxyphenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 1.0 gm (5.0 mMol ) 3-(4-piperidinyl)-1H-indole and 1.15 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-3-methoxybenzene, 0.95 gm (51.2%) of the title compound were recovered from methanol as pink crystals, m.p.>250° C. MS (m/e): 334 (M + ) Calculated for C 22 H 26 N 2 O.HCl: Theory: C, 71.24; H, 7.34; N, 7.55. Found: C, 71.15; H, 7.30; N, 7.48. EXAMPLE 13 5-methoxy-3-<1-<2-<4-methoxyphenyl>ethyl>-4-piperidinyl>-1H-indole oxalate Using 2.0 gm (8.7 mMol) 5-methoxy-3-(4-piperidinyl)-1H-indole and 2.0 gm (8.7 mMol) 1-(2-methanesulfonyloxyethyl)-4-methoxybenzene, 1.17 gm (29.6%) of the title compound were recovered from methanol as yellow crystals, m.p.=127° C. (dec). MS(m/e): 364(M + ) Calculated for C 23 H 28 N 2 O 2 .C 2 H 2 O 4 : Theory: C, 66.06; H, 6.65; N, 6.16. Found: C, 65.77; H, 6.73; N, 6.42. EXAMPLE 14 3-<1-<2-<4-ethoxyphenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 1.0 gm (5.0 mMol) 3-(4-piperidinyl)-1H-indole and 1.14 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-4-ethoxybenzene, 0.47 gm (24.4%) of the title compound were recovered from methanol as a colorless solid, m.p.=263° C. MS(m/e): 348(M + ) Calculated for C 23 H 28 N 2 O.HCl: Theory: C, 71.76; H, 7.59; N, 7.28. Found: C, 71.50; H, 7.58; N, 7.36. EXAMPLE 15 3-<1-<2-<4-benzyloxyphenyl>ethyl>-4-piperidinyl>-1H-indole Using 2.0 gm (10.0 mMol) 3-(4-piperidinyl)-1H-indole and 3.19 gm (10.0 mMol) 1-(2-methanesulfonyloxyethyl)-4-benzyloxybenzene, 1.09 gm (26.5%) of the title compound were recovered from methanol as colorless crystals, m.p.=180° C. MS(m/e): 410(M + ) Calculated for C 28 H 30 N 2 O: Theory: C, 81.91; H, 7.36; N, 6.82. Found: C, 81.53; H, 7.33; N, 7.04. EXAMPLE 16 3-<1-<2-<2-trifluoromethylphenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Using 1.0 gm (5.0 mMol) 3-(4-piperidinyl)-1H-indole and 1.34 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-2-trifluoromethylbenzene, 0.89 gm (43.5%) of the title compound were recovered as a tan solid, m.p.=228°-230° C. MS (m/e): 372 (M + ) Calculated for C 22 H 23 N 2 F 3 .HCl: Theory: C, 64.62; H, 5.92; N, 6.85. Found: C, 64.83; H, 6.17; N, 6.99. EXAMPLE 17 3-<1-<2-<3-trifluoromethylphenyl>ethyl>-4-piperidinyl>-1H -indole Using 1.0 gm (5.0 mMol ) 3-(4-piperidinyl)-1H-indole and 1.34 gm (5.0 mMol) 1-(2-methanesulfonyloxyethyl)-3-trifluoromethylbenzene, 1.43 gm (76.8%) of the title compound were recovered from cyclohexane, m.p.=126° C. MS(m/e): 372 (M + ) Calculated for C 22 H 23 N 2 F 3 : Theory: C, 70.95; H, 6.23; N, 7.52. Found: C, 71.23; H, 6.34; N, 7.51. EXAMPLE 18 5-fluoro-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrochloride To a solution of 11.0 gm (196 mMol) potassium hydroxide in 100 mL methanol were added 1.49 gm (11.0 mMol) 5-fluoro-1H-indole followed by 4.57 gm (22.5 mMol) N-phenethyl-4-piperidone. The reaction mixture is stirred at reflux under a nitrogen atmosphere for 18 hours. The reaction mixture is cooled to room temperature and then diluted with 200 mL water. The precipitate is filtered and dried overnight in a vacuum dessicator to give 4.44 gm of a crude orange solid. To a solution of 2.44 gm of this orange solid in methanol were added 1.0 equivalents 1.0N HCl and the solution is concentrated to dryness under reduced pressure. The residue was crystallized from ethyl acetate/methanol to give 1.54 gm of the title compound as a light yellow solid, m.p.>220° C.(dec). MS(m/e): 320(M + ) Calculated for C 21 H 21 FN 2 .HCl: Theory: C, 70.68; H, 6.21; N, 7.85. Found: C, 70.51; H, 6.18; N, 7.68. The compounds of Examples 19-24 were prepared employing the method described in detail in Example 18. EXAMPLE 19 3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole Using 3.6 gm (30.7 mMol) of 1H-indole and 12.5 gm (61.5 mMol) N-phenethyl-4-piperidone, 16.2 gm crude product were recovered as an orange solid. The solid was subjected to silica gel chromatography, eluting with a gradient consisting of dichloromethane containing 0-10% methanol. Fractions shown to contain product were combined and concentrated under reduced pressure to give 4.94 gm of the free base of the title compound which was then crystallized from ethyl acetate to give 3.61 gm (38.9%) of the title compound as yellow crystals, m.p.=199°-201° C. (dec). Calculated for C 21 H 22 N 2 : Theory: C, 83.40; H, 7.33; N, 9.26. Found: C, 83.59; H, 7.43; N, 9.38. EXAMPLE 20 5-chloro-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrochloride Using 1.67 gm (11 mMol) 5-chloro-1H-indole and 4.57 gm (22.5 mMol) N-phenethyl-4-piperidone, 4.54 gm of crude product were recovered as an orange solid. 2.55 gm of this crude solid were converted to the hydrochloride salt to give 1.05 gm of the title compound as an off-white solid. m.p.>220° C. (ethyl acetate/methanol) MS(m/e): 336(M + ) Calculated for C 21 H 21 ClN 2 .HCl: Theory: C, 67.56; H, 5.94; N, 7.50. Found: C, 67.61; H, 6.13; N, 7.39. EXAMPLE 21 5-methoxy-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrochloride Using 1.62 gm (11 mMol) 5-methoxy-1H-indole and 4.57 gm (22.5 mMol) N-phenethyl-4-piperidone, 4.71 gm of crude product were recovered as a yellow solid. The solid was subjected to silica gel chromatography, eluting with dichloromethane containing 5% methanol. Fractions shown to contain product were combined and concentrated under reduced pressure to give 3.44 gm of the free base of the title compound. 2.00 gm of this solid were converted to the hydrochloride salt to give 1.26 gm of the title compound as light yellow crystals. m.p.>220° C. (dec)(ethyl acetate/methanol) MS(m/e): 332(M + ) Calculated for C 22 H 24 N 2 O.HCl: Theory: C, 71.63; H, 6.83; N, 7.59. Found: C, 71.88; H, 6.89; N, 7.60. EXAMPLE 22 5-benzyloxy-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrochloride Using 2.46 gm (11 mMol) 5-benzyloxy-1H-indole and 4.57 gm (22.5 mMol) N-phenethyl-4-piperidone, 9.92 gm of crude product were recovered as an orange solid. The solid was subjected to silica gel chromatography, eluting with dichloromethane containing 5% methanol and a trace of ammonium hydroxide. Fractions shown to contain product were combined and concentrated under reduced pressure to give 3.87 gm of the free base of the title compound. 2.47 gm of this solid were converted to the hydrochloride salt to give 1.16 gm of the title compound as light yellow crystals. m.p.>220° C. (dec)(ethyl acetate/methanol) MS(m/e): 409(M + ) Calculated for C 28 H 28 N 2 O.HCl: Theory: C, 75.57; H, 6.57; N, 6.30. Found: C, 75.51; H, 6.68; N, 6.52. EXAMPLE 23 5-methyl-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole maleate Using 3.0 gm (23 mMol) 5-methyl-1H-indole and 9.30 gm (46 mMol) N-phenethyl-4-piperidone, 11.64 gm of crude product were recovered as a brown oil. The oil was subjected to silica gel chromatography, eluting with dichloromethane containing 5% methanol. Fractions shown to contain product were combined and concentrated under reduced pressure to give 2.20 gm of the free base of the title compound. This solid was converted to the maleate salt to give 1.14 gm (11.5%) of the title compound as a light brown solid. m.p.=184°-187° C. (ethyl acetate/methanol) MS(m/e): 316(M + ) Calculated for C 22 H 24 N 2 .C 4 H 4 O 4 : Theory: C, 72.20; H, 6.53; N, 6.48. Found: C, 71.96; H, 6.41; N, 6.33. EXAMPLE 24 5-carboxamido-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole maleate Using 2.0 gm (12.5 mMol) 5-carboxamido-1H-indole and 5.1 gm (25 mMol) N-phenethyl-4-piperidone, 6.5 gm of crude product were recovered as a yellow solid. The solid was subjected to silica gel chromatography, eluting with dichloromethane containing 1-10% methanol. Fractions shown to contain product were combined and concentrated under reduced pressure to give 3.20 gm of the free base of the title compound. 2.20 gm of this solid was converted to the maleate salt to give 2.00 gm of the title compound as a yellow powder. m.p.=188°-189° C. (ethyl acetate/methanol) Calculated for C 22 H 23 N 3 O.C 4 H 4 O 4 : Theory: C, 67.66; H, 5.90; N, 9.10. Found: C, 67.75; H, 5.99; N, 9.11. EXAMPLE 25 5-fluoro-3-<1-<2-phenylethyl>-4-piperidinyl>-1H-indole hydrochloride To a solution of 2.0 gm (6.24 mMol) 5-fluoro-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole (Example 18) in 50 mL ethanol were added 1.0 gm 5% palladium on carbon and the reaction mixture was hydrogenated at room temperature with an initial hydrogen pressure of 60 p.s.i. for 18 hours. The reaction mixture was concentrated under reduced pressure to give a yellow oil which crystallized while standing. The residue was dissolved in methanol to which was added 0.44 mL 1N HCl and the volatiles were then removed under reduced pressure. The residue was recrystallized from methanol/ethyl acetate to give 1.02 gm (45.5%) of the title compound as a colorless solid, m.p.>210° C. (dec). Calculated for C 21 H 23 N 2 F.HCl: Theory: C, 70.28; H, 6.74; N, 7.81. Found: C, 70.03; H, 6.79; N, 7.75. The compounds of Examples 26-31 were prepared by the procedure described in detail in Example 25. EXAMPLE 26 3-<1-<2-phenylethyl>-4-piperidinyl>-1H-indole Beginning with 1.8 gm (6 mMol) 3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole (Example 19), 1.7 gm (93.9%) of the title compound were recovered as an off-white solid. m.p.=122°-124° C. (methanol) Calculated for C 21 H 24 N 2 : Theory: C, 82.85; H, 7.95; N, 9.20. Found: C, 82.85; H, 8.12; N, 9.14. EXAMPLE 27 5-chloro-3-<1-<2-phenylethyl>-4-piperidinyl>-1H-indole hydrochloride Beginning with 1.986 gm (5.9 mMol) 5-chloro-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole (Example 20) and using 1.0 gm 5% sulfided platinum on carbon, 0.65 gm (32.5%) of the title compound were recovered as off-white crystals. m.p>250° C. (methanol/ethyl acetate) MS (m/e): 338 (M + ) Calculated for C 21 H 23 ClN 2 .HCl: Theory: C, 67.20; H, 6.44; N, 7.46. Found: C, 67.50; H, 6.56; N, 7.51. EXAMPLE 28 5-methoxy-3-<1-<2-phenylethyl>-4-piperidinyl>-1H-indole hydrochloride Beginning with 1.45 gm (4.4 mMol) 5-methoxy-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole (Example 21), 0.95 gm (58.2%) of the title compound were recovered as off-white crystals. m.p.>210° C. (methanol/ethyl acetate) MS(m/e): 334(M + ) Calculated for C 22 H 26 N 2 O.HCl: Theory: C, 71.24; H, 7.34; N, 7.55. Found: C, 70.97; H, 7.36; N, 7.70. EXAMPLE 29 5-benzyloxy-3-<1-<2-phenylethyl>-4-piperidinyl>-1H-indole hydrochloride Beginning with 1.40 gm (3.4 mMol) 5-benzyloxy-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole (Example 22) and using 0.7 gm 5% sulfided platinum on carbon, 0.55 gm (36.2%) of the title compound were recovered as off-white crystals. m.p>220° C. (dec)(methanol/ethyl acetate) MS(m/e): 411(M + ) Calculated for C 28 H 30 N 2 O.HCl: Theory: C, 75.23; H, 6.99; N, 6.27. Found: C, 75.50; H, 7.24; N, 6.24. EXAMPLE 30 5-methyl -3-<1-<2-phenylethyl>-4-piperidinyl>-1H -indole hydrochloride Beginning with 1.50 gm (4.7 mMol) 5-methyl-3-<1-<2-phenylethyl>-4-<1, 2,3,6-tetrahydropyridinyl>>-1H-indole (Example 23), 0.52 gm (31.2%) of the title compound were recovered as white crystals. m.p.>225° C. (methanol/ethyl acetate) Calculated for C 22 H 26 N 2 .HCl: Theory: C, 74.45; H, 7.67; N, 7.89. Found: C, 74.40; H, 7.82; N, 7.80. EXAMPLE 31 5-carboxamido-3-<1-<2-phenylethyl>-4-piperidinyl>-1H-indole hydrochloride Beginning with 1.00 gm (2.9 mMol) 5-carboxamido-3-<1-<2-phenylethyl>-4-<1, 2,3,6-tetrahydropyridinyl>>-1H-indole (Example 24), 0.56 gm (50.3%) of the title compound were recovered as a tan powder in two crops. m.p.>300° C. (methanol/ethyl acetate) Calculated for C 22 H 25 N 3 O.HCl: Theory: C, 68.83; H, 6.83; N, 10.94. Found: C, 68.59; H, 7.00; N, 10.71. EXAMPLE 32 3-<1-<2-<4-chlorophenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride To a solution of 4.0 gm (20 mMol) 3-(4-piperidinyl)-1H-indole in 80 mL dimethylformamide were added 5.3 gm (50 mMol) sodium carbonate followed by the dropwise addition of a solution of 3.5 gm (20 mMol) 2-(4-chlorophenyl)ethyl chloride in 16 mL dimethylformamide. Once the addition was complete the reaction mixture was heated at 100° C. under nitrogen for 18 hours. The reaction mixture was then cooled to ambient and the dimethylformamide removed under reduced pressure. The residue was dissolved in dichloromethane then washed twice with water and once with saturated aqueous sodium chloride. The remaining organics were dried over sodium sulfate and then concentrated under reduced pressure to give a yellow oil. The oil was subjected to silica gel chromatography, eluting with 20:1:0.1 dichloromethane:methanol:ammonium hydroxide. Fractions shown to contain product were combined and concentrated under reduced pressure. The residue was dissolved in a minimal volume of methanol and treated with one equivalent of 1N HCl. The solution was concentrated under reduced pressure and the residue crystallized from methanol to give 1.95 gm (26.0%) of the title compound as off-white crystals, m.p.>250° C. MS(m/e): 338(M + ) Calculated for C 21 H 23 N 2 Cl.HCl: Theory: C, 67.20; H, 6.45; N, 7.46. Found: C, 67.16; H, 7.42; N, 7.50. EXAMPLE 33 3-<1-<2-<4-methoxyphenyl>ethyl>-4-piperidinyl>-1H-indole hydrochloride Following the procedure described in detail in Example 32, 2.0 gm (10 mMol) 3-(4-piperidinyl)-1H-indole and 1.0 gm (10 mMol) 2-(4-methoxyphenyl)ethyl chloride were converted to 0.87 gm (23.4%) of the title compound which was recovered as colorless crystals from methanol/ethyl acetate, m.p.>250° C. MS(m/e): 334(M + ) Calculated for C 22 H 26 N 2 O.HCl: Theory: C, 71.24; H, 7.34; N, 7.55. Found: C, 71.05; H, 7.16; N, 7.52. EXAMPLE 34 3-<1-<2-<1-naphthyl>ethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole Following the procedure described in detail in Example 32, 3.97 gm (20 mMol) 3-<1-<1,2,3,6-tetrahydro>-4-pyridinyl>-1H-indole and 4.7 gm (20 mMol) 2-(1-naphthyl)ethyl chloride were converted to 2.0 gm (28.3%) of the title compound which was recovered as yellow crystals from methanol, m.p.=180°-182° C. MS(m/e): 352(M + ) Calculated for C 25 H 24 N 2 : Theory: C, 85.19; H, 6.86; N, 7.95. Found: C, 85.39; H, 6.82; N, 8.09. EXAMPLE 35 3-<1-<2-<1-naphthyl>ethyl>-4-piperidinyl>-1H-indole Following the procedure described in detail in Example 25, 0.77 gm (2.19 mMol) 3-<1-<2-<1-naphthyl>ethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole (Example 34) were converted to 0.25 gm of the title compound which was isolated as a yellow oil. MS(m/e): 354(M + ) EXAMPLE 36 5-hydroxy-3-<1-<2-phenylethyl>-4-piperidinyl>-1H-indole hydrochloride Following the procedure described in detail in Example 25, 3.0 gm (2.19 mMol) 5-benzyloxy-3-<1-<2-phenylethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrochloride (Example 22) were converted to 1.50 gm (62%) of the title compound which was isolated as a yellow granular solid. m.p.=260° C. (dec). MS(m/e): 320(M + ) Calculated for C 21 H 24 N 2 O.HCl: Theory: C, 70.67; H, 7.06; N, 7.85. Found: C, 70.43; H, 6.92; N, 7.95. EXAMPLE 37 3-<1-<2-phenoxyethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrochloride Following the procedure described in detail in Example 32, 3.97 gm (20 mMol) 3-<1-<1,2,3,6-tetrahydro>-4-pyridinyl>-1H-indole and 4.02 gm (20 mMol) 2-bromoethyl phenyl ether were converted to 4.63 gm (65.2%) of the title compound which was recovered as a yellow solid. m.p.=182°-184° C. (methanol/ethyl acetate). MS(m/e): 318(M + ) Calculated for C 21 H 22 N 2 O.HCl: Theory: C, 71.07; H, 6.53; N, 7.89. Found: C, 70.86; H, 6.55; N, 7.84. EXAMPLE 38 3-<1-<3-phenoxypropyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrochloride Following the procedure described in detail in Example 32, 3.97 gm (20 mMol) 3-<1-<1,2,3,6-tetrahydro>-4-pyridinyl>-1H-indole and 4.30 gm (20 mMol) 3-bromopropyl phenyl ether were converted to 3.33 gm (45.1%) of the title compound which was recovered as orange crystals. m.p.=234°-235° C. (methanol/ethyl acetate). MS(m/e): 333(M + ) Calculated for C 22 H 24 N 2 O.HCl: Theory: C, 71.63; H, 6.83; N, 7.59. Found: C, 71.69; H, 6.89; N, 7.35. EXAMPLE 39 3-<1-<2-<phenylthio>ethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole Following the procedure described in detail in Example 32, 3.97 gm (20 mMol) 3-<1-<1,2,3,6-tetrahydro>-4-pyridinyl>-1H-indole and 3.45 gm (20 mMol) 2-chloroethyl phenyl sulfide were converted to 1.29 gm (19.3%) of the title compound which was recovered as yellow crystals. m.p.=121°-122° C. (methanol). MS(m/e): 334(M + ) Calculated for C 21 H 22 N 2 S: Theory: C, 75.41; H, 6.65; N, 8.38. Found: C, 75.14; H, 6.44; N, 8.21. EXAMPLE 40 3-<1-<2-phenoxyethyl>-4-piperidinyl>-1H-indole hydrochloride Following the procedure described in detail in Example 25, 2.0 gm (5.6 mMol) 3-<1-<2-phenoxyethyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole (Example 37) were converted to 0.92 gm (46.0%) of the title compound as an off-white solid. m.p.=231°-233° C. (methanol/ethyl acetate) MS(m/e): 320(M + ) Calculated for C 21 H 24 N 2 O.HCl: Theory: C, 70.67; H, 7.06; N, 7.83. Found: C, 69.88; H, 7.07; N, 7.79. EXAMPLE 41 3-<1-<3-phenoxypropyl>-4-piperidinyl>-1H-indole hydrochloride Following the procedure described in detail in Example 25, 1.51 gm (4.1 mMol) 3-<1-<3-phenoxypropyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole (Example 38) were converted to 0.13 gm (8.5%) of the title compound as a gray solid. m.p.>250° C. (dec)(methanol/ethyl acetate) Calculated for C 22 H 26 N 2 O.HCl: Theory: C, 71.24; H, 7.34; N, 7.55. Found: C, 71.49; H, 7.42; N, 7.76. EXAMPLE 42 3-<1-<2-<phenylthio>ethyl>-4-piperidinyl>-1H-indole Following the procedure described in detail in Example 32, 2.0 gm (10 mMol) 3-<4-piperidinyl>-1H-indole and 1.73 gm (10 mMol) 2-chloroethyl phenyl sulfide were converted to 1.28 gm (38.0%) of the title compound which was recovered as a yellow oil. MS (m/e): 336 (M + ) Calculated for C 21 H 24 N 2 S: Theory: C, 74.96; H, 7.19; N, 8.33. Found: C, 74.95; H, 7.17; N, 8.43. EXAMPLE 43 3-<1-<4-phenylbutyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrochloride Following the procedure described in detail in Example 32, 3.97 gm (20 mMol) 3-<1-<1,2,3,6-tetrahydro>-4-pyridinyl>1H-indole and 3.37 gm (20 mMol) 1-chloro-4-phenylbutane were converted to 3.68 gm (50.1%) of the title compound which was recovered as yellow crystals. m.p.>220° C. (dec) (ethanol). MS (m/e): 330 (M + ) Calculated for C 23 H 26 N 2 .HCl: Theory: C, 75.29; H, 7.42; N 7.63. Found: C, 75.49; H, 7.55; N, 7.86. EXAMPLE 44 3-<1-benzyl-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrochloride Following the procedure described in detail in Example 32, 3.97 gm (20 mMol) 3-<1-<1,2,3,6-tetrahydro>-4-pyridinyl>1H-indole and 2.4 mL (20 mMol) benzyl bromide were converted to 3.93 gm (60.5%) of the title compound which was recovered as a brown solid. m.p.=159° C. (dec)(methanol/ethyl acetate). MS(m/e): 288(M + ) Calculated for C 20 H 20 N 2 .HCl: Theory: C, 73.95; H, 6.52; N, 8.62. Found: C, 74.06; H, 6.49; N, 8.68. EXAMPLE 45 3-<1-benzyl -4-piperidinyl>-1H -indole Following the procedure described in detail in Example 32, 0.94 gm (4.7 mMol) 3-<4-piperidinyl>-1H-indole and 0.803 gm (4.7 mMol) benzyl bromide were converted to 0.41 gm (30.0%) of the title compound which was recovered as a yellow oil. MS(m/e): 290(M + ) Calculated for C 20 H 22 N 2 : Theory: C, 82.72; H, 7.64; N, 9.65. Found: C, 82.44; H, 7.53; N, 9.76. EXAMPLE 46 3-<1-<4-phenylbutyl>-4-piperidinyl>-1H-indole hydrochloride Following the procedure described in detail in Example 25, 1.89 gm (5.2 mMol) 3-<1-<4-phenylbutyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrochloride (Example 43) were converted to 1.19 gm (62.0%) of the title compound as a yellow solid. m.p.=233°-234° C. (methanol/ethyl acetate) Calculated for C 23 H 28 N 2 .HCl: Theory: C, 74.88; H, 7.92; N, 7.59. Found: C, 74.61; H, 7.91; N, 7.59. EXAMPLE 47 3-<1-<3-phenylpropyl>-4-<1,2,3,6-tetrahydropyridinyl>>-1H-indole hydrochloride Following the procedure described in detail in Example 32, 1.98 gm (10 mMol) 3-<1-<1,2,3,6-tetrahydro>-4-pyridinyl>1H-indole and 1.99 gm (10 mMol) 1-bromo-3-phenylpropane were converted to 1.51 gm (42.8%) of the title compound which was recovered as orange crystals. m.p.=215°-217° C. (ethanol). MS (m/e): 316 (M + ) Calculated for C 22 H 24 N 2 .HCl: Theory: C, 74.88; H, 7.14; N, 7.94. Found: C, 74.79; H, 7.34; N, 7.87. EXAMPLE 48 3-<1-<3-phenylpropyl>-4-piperidinyl>-1H-indole hydrochloride Following the procedure described in detail in Example 32, 1.20 gm (6.0 mMol) 3-<4-piperidinyl>-1H-indole and 1.19 gm (6.0 mMol ) 1-bromo-3-phenylpropane were converted to 0.83 gm (39.0%) of the title compound which was recovered as off-white crystals. m.p.=239°-241° C. (methanol) MS(m/e): 318(M + ) Calculated for C 22 H 26 N 2 .HCl: Theory: C, 74.45; H, 7.67; N, 7.89. Found: C, 74.17; H, 7.70; N, 8.16. To demonstrate the use of the compounds of this invention in the treatment of migraine, their ability to bind to the 5-HT 1F receptor subtype was determined. The ability of the compounds of this invention to bind to the 5-HT 1F receptor subtype was measured essentially as described in N. Adham, et al., Proceedings of the National Academy of Sciences (USA), 90, 408-412 (1993). Membrane Preparation: Membranes were prepared from transfected Ltk- cells which were grown to 100% confluency. The cells were washed twice with phosphate-buffered saline, scraped from the culture dishes into 5 mL of ice-cold phosphate-buffered saline, and centrifuged at 200×g for 5 minutes at 4° C. The pellet was resuspended in 2.5 mL of ice-cold Tris buffer (20 mM Tris HCl, pH=7.4 at 23° C., 5 mM EDTA) and homogenized with a Wheaton tissue grinder. The lysate was subsequently centrifuged at 200×g for 5 minutes at 4° C. to pellet large fragments which were discarded. The supernatant was collected and centrifuged at 40,000×g for 20 minutes at 4° C. The pellet resulting from this centrifugation was washed once in ice-cold Tris wash buffer and resuspended in a final buffer containing 50 mM Tris HCl and 0.5 mM EDTA, pH=7.4 at 23° C. Membrane preparations were kept on ice and utilized within two hours for the radioligand binding assays. Protein concentrations were determined by the method of Bradford (Anal. Biochem., 72, 248-254 (1976)). Radioligand Binding: [ 3 H-5-HT] binding was performed using slight modifications of the 5-HT 1D assay conditions reported by Herrick-Davis and Titeler (J. Neurochem., 50, 1624-1631 (1988)) with the omission of masking ligands. Radioligand binding studies were achieved at 37° C. in a total volume of 250 μL of buffer (50 mM Tris, 10 mM MgCl 2 , 0.2 mM EDTA, 10 μM pargyline, 0.1% ascorbate, pH=7.4 at 37° C.) in 96 well microtiter plates. Saturation studies were conducted using [ 3 H]5-HT at 12 different concentrations ranging from 0.5 nM to 100 nM. Displacement studies were performed using 4.5-5.5 nM [ 3 H]5-HT. The binding profile of drugs in competition experiments was accomplished using 10-12 concentrations of compound. Incubation times were 30 minutes for both saturation and displacement studies based upon initial investigations which determined equilibrium binding conditions. Nonspecific binding was defined in the presence of 10 μM 5-HT. Binding was initiated by the addition of 50 μL membrane homogenates (10-20 μg). The reaction was terminated by rapid filtration through presoaked (0.5% polyethyleneimine) filters using 48R Cell Brandel Harvester (Gaithersburg, Md.). Subsequently, filters were washed for 5 seconds with ice cold buffer (50 mM Tris HCl, pH=7.4 at 4° C.), dried and placed into vials containing 2.5 mL Readi-Safe (Beckman, Fullerton, Calif.) and radioactivity was measured using a Beckman LS 5000TA liquid scintillation counter. The efficiency of counting of [ 3 H]5-HT averaged between 45-50%. Binding data was analyzed by computer-assisted nonlinear regression analysis (Accufit and Accucomp, Lunden Software, Chagrin Falls, Ohio). IC 50 values were converted to K i values using the Cheng-Prusoff equation (Biochem. Pharmacol., 22, 3099-3108 (1973). All experiments were performed in triplicate. The results of these binding experiments are summarized in Table I. TABLE I______________________________________COMPOUND COMPOUNDOF 5-HT.sub.1F OF 5-HT.sub.1FEXAMPLE BINDING EXAMPLE BINDINGNUMBER K.sub.i (nM) NUMBER K.sub.i (nM)______________________________________1 29.5 24 23.62 55.5 25 29.63 31.0 26 52.14 35.8 27 45.55 35.2 28 39.26 11.7 29 17.27 73.3 30 37.88 45.0 31 36.99 29.7 32 52.110 67.6 33 127.411 34.0 34 38%*12 21.1 35 76.713 128.0 36 2.514 184.7 37 413.015 843.6 38 136.016 64.3 39 34%*17 16.1 40 191.318 48.3 41 91.419 81.1 42 342.320 38.8 43 546.621 33.9 44 396.022 62%* 45 240.423 28.3 46 20.447 62%* 48 50%*______________________________________ * = % displacement at 1000 nM As was reported by R. L. Weinshank, et al., WO93/14201, the 5-HT 1F receptor is functionally coupled to a G-protein as measured by the ability of serotonin and serotonergic drugs to inhibit forskolin stimulated cAMP production in NIH3T3 cells transfected with the 5-HT 1F receptor. Adenylate cyclase activity was determined using standard techniques. A maximal effect is achieved by serotonin. An E max is determined by dividing the inhibition of a test compound by the maximal effect and determining a percent inhibition. (N. Adham, et al., supra,; R. L. Weinshank, et al., Proceedings of the National Academy of Sciences (USA), 89,3630-3634 (1992)), and the references cited therein. Measurement of cAMP formation Transfected NIH3T3 cells (estimated Bmax from one point competition studies=488 fmol/mg of protein) were incubated in DMEM, 5 mM theophylline, 10 mM HEPES (4-[2-hydroxyethyl]-1-piperazineethanesulfonic acid) and 10 μM pargyline for 20 minutes at 37° C., 5% CO 2 . Drug dose-effect curves were then conducted by adding 6 different final concentrations of drug, followed immediately by the addition of forskolin (10 μM). Subsequently, the cells were incubated for an additional 10 minutes at 37° C., 5% CO 2 . The medium was aspirated and the reaction was stopped by the addition of 100 mM HCl. To demonstrate competitive antagonism, a dose-response curve for 5-HT was measured in parallel, using a fixed dose of methiothepin (0.32 μM). The plates were stored at 4° C. for 15 minutes and then centrifuged for 5 minutes at 500×g to pellet cellular debris, and the supernatant was aliquoted and stored at -20° C. before assessment of cAMP formation by radioimmunoassay (cAMP radioimmunoassay kit; Advanced Magnetics, Cambridge, Mass.). Radioactivity was quantified using a Packard COBRA Auto Gamma counter, equipped with data reduction software. All of the compounds exemplified were tested and found to be agonists at the 5-HT 1F receptor in the cAMP assay. The discovery that the pain associated with migraine and associated disorders is inhibited by agonists of the 5-HT 1F receptor required the analysis of data from diverse assays of pharmacological activity. To establish that the 5-HT 1F receptor subtype is responsible for mediating neurogenic meningeal extravasation which leads to the pain of migraine, the binding affinity of a panel of compounds to serotonin receptors was measured first, using standard procedures. For example, the ability of a compound to bind to the 5-HT 1F receptor subtype was performed as described supra. For comparison purposes, the binding affinities of compounds to the 5-HT 1D α, 5-HT 1D β, 5-HT 1E and 5-HT 1F receptors were also determined as described supra, except that different cloned receptors were employed in place of the 5-HT 1F receptor clone employed therein. The same panel was then tested in the cAMP assay to determine their agonist or antagonist character. Finally, the ability of these compounds to inhibit neuronal protein extravasation, a functional assay for migraine pain, was measured. The panel of compounds used in this study represents distinct structural classes of compounds which were shown to exhibit a wide range of affinities for the serotonin receptors assayed. Additionally, the panel compounds were shown to have a wide efficacy range in the neuronal protein extravasation assay as well. The panel of compounds selected for this study are described below. Compound I 3-[2-(dimethylamino)ethyl]-N-methyl-1H-indole-5-methanesulfonamide butane-1,4-dioate (1:1) (Sumatriptan succinate) ##STR11## Sumatriptan succinate is commercially available as Imitrex™ or may be prepared as described in U.S. Pat. No. 5,037,845, issued Aug. 6, 1991, which is herein incorporated by reference. Compound II 5-fluoro-3-<1-<2-<1-methyl-1H-pyrazol-4-yl>ethyl>-4-piperidinyl>-1H-indole hydrochloride ##STR12## Compound II is available by the following procedure. 2-(1-methyl-3-pyrazolo)-1-ethanol To a mixture of 200 gm (2.85 mole) 2,3-dihydrofuran and 800 mL (4.81 mole) triethylorthoformate were added 0.8 mL (6.5 mMol) boron trifluoride diethyl etherate dropwise. After an initial exotherm the reaction mixture was allowed to stir at ambient temperature for four days. To the reaction mixture was then added 4.0 gm potassium carbonate and the reaction mixture was distilled under 6.0 mm Hg. Fractions distilling between 60° C. and 130° C. were collected to give 261.64 gm (42.1%) of a light yellow oil. MS (m/e): 219 (M + ) To a solution of 87.2 gm (0.40 mole) of the previously prepared yellow oil in 787 mL 1N HCl were added 21.3 mL (0.40 mole) methyl hydrazine and the reaction mixture was stirred at reflux for four hours. The reaction mixture was cooled to ambient temperature and the volatiles were removed under reduced pressure. The residual oil was treated with 2N NaOH until basic and the aqueous extracted well with dichloromethane. The combined organic extracts were dried over sodium sulfate and concentrated under reduced pressure to give 32.15 gm (64.5%) of the title compound as a brown oil. MS(m/e): 126(M + ) 1 H-NMR(DMSO-d 6 ): δ7.45 (s, 1H); 7.25 (s, 1H); 4.65 (t, 1H); 3.75 (s, 3H); 3.55 (m, 2H); 2.55 (t, 2H). 1-methyl-4-(2-methanesulfonyloxyethyl)pyrazole To a solution of 16.0 gm (127 mMol) 2-(1-methyl-3-pyrazolo)-1-ethanol and 27 mL (193 mMol) triethylamine in 550 mL tetrahydrofuran were added 10.8 mL (140 mMol) methanesulfonyl chloride with icebath cooling. Once the addition was complete, the reaction mixture was stirred at ambient for 4 hours. The volatiles were then removed under reduced pressure and the residue partitioned between water and dichloromethane. The organic phase was washed with water followed by saturated aqueous sodium chloride and the remaining organics dried over sodium sulfate. The solvent was removed under reduced pressure to give a crude yield of 28.4 gm of the title compound as a brown oil. The product was used without further purification. 5-fluoro-3-[1,2,3,6-tetrahydro-4-pyridyl]-1H-indole To a solution of 74 gm potassium hydroxide in 673 mL methanol were added 10.0 gm (74 mMol) 5-fluoroindole and 23.3 gm (151 mMol) 4-piperidone.HCl.H 2 O. The reaction mixture was stirred at reflux for 18 hours. The reaction mixture was diluted with 1.3 L of water and the resulting precipitate recovered by filtration and dried under reduced pressure to give 10.75 gm (67.2%) of 5-fluoro-3-[1,2,5,6-tetrahydro-4-pyridyl]-1H-indole as a yellow solid. 5-fluoro-3-(4-piperidinyl)-1H-indole To a solution of 10.75 gm (50 mMol) 5-fluoro-3-[1,2,5,6-tetrahydro-4-pyridyl]-1H-indole in 500 mL ethanol were added 2.0 gm 5% palladium on carbon and the reaction mixture hydrogenated at ambient temperature for 18 hours at an initial hydrogen pressure of 60 p.s.i. The reaction mixture was then filtered through a pad of celite and the filtrate concentrated under reduced pressure to give all off-white solid. The solid was recrystallized from methanol to give 8.31 gm (76.2%) of the title compound as a colorless solid. m.p.=229°-230° C. MS(m/e): 218(M + ) Calculated for C 13 H 15 N 2 F: Theory: C, 71.53; H, 6.93; N, 12.83. Found: C, 71.81; H, 7.02; N, 12.80. Alkylation To a solution of 2.0 gm (9.2 mMol) 5-fluoro-3-(4-piperidinyl)-1H-indole and 2.4 gm (23 mMol) sodium carbonate in 50 mL dimethylformamide were added 1.87 gm (9.2 mMol) 1-methyl-4-(2-methanesulfonyloxyethyl)pyrazole in 5 mL dimethylformamide. The reaction mixture was stirred at 100° C. for 18 hours. The reaction mixture was cooled to ambient and the solvent removed under reduced pressure. The residue was partitioned between dichloromethane and water and the phases separated. The organic phase was washed well with water followed by saturated aqueous sodium chloride. The remaining organic phase was dried over sodium sulfate and concentrated under reduced pressure. The residual oil was subjected to silica gel chromatography, eluting with 20:1 dichloromethane:methanol. Fractions shown to contain the desired compound were combined and concentrated under reduced pressure to give a yellow oil. The oil was converted to the hydrochloride salt and was crystallized from ethyl acetate/methanol. 1.61 gm (51.1%) of Compound II were recovered as colorless crystals. m.p.=239° C. MS(m/e): 326(M + ) Calculated for C 19 H 23 N 4 F.HCl: Theory: C, 62.89; H, 6.67; N, 15.44. Found: C, 62.80; H, 6.85; N, 15.40. Compound III 5-hydroxy-3-(4-piperidinyl)-1H-indole oxalate ##STR13## Compound III is available by the following procedure. 5-benzyloxy-3-[1,2,5,6-tetrahydro-4-pyridinyl]-1H-indole Starting with 5.0 gm (22 mMol) 5-benzyloxyindole and 6.88 gm (45 mMol) 4-piperidone.HCl.H 2 O, 6.53 gm (97.6%) of 5-benzyloxy-3-[1,2,5,6-tetrahydro-4-pyridinyl]-1H-indole were recovered as a light yellow solid by the procedure described in Preparation I. The material was used in the subsequent step without further purification. Hydrogenation/Hydrogenolysis To a solution of 1.23 gm (4 mMol) 5-benzyloxy-3-[1,2,5,6-tetrahydro-4-pyridinyl]-1H-indole in 50 mL 1:1 tetrahydrofuran:ethanol were added 0.3 gm 5% palladium on carbon and the reaction mixture hydrogenated at ambient temperature for 18 hours with an initial hydrogen pressure of 60 p.s.i. The reaction mixture was then filtered through a celite pad and the filtrate concentrated under reduced pressure. The residue was converted to the oxalate salt and 0.98 gm (80.0%) of Compound III were recovered as a brown foam. m.p.=67° C. MS(m/e): 216(M + ) Calculated for C 13 H 16 N 2 O.C 2 H 2 O 4 : Theory: C, 58.81; H, 5.92; N, 9.14. Found: C, 58.70; H, 5.95; N, 9.39. Compound IV 8-chloro-2-diethylamino-1,2,3,4-tetrahydronaphthalene hydrochloride ##STR14## Compound IV is available by the following procedure. 8-chloro-2-tetralone A mixture of 30.0 gm (0.176 mole) of o-chlorophenylacetic acid and 40.0 mL of thionyl chloride was stirred at ambient temperature for 18 hours. The volatiles were then removed in vacuo to give 32.76 gm (99.0%) of o-chlorophenylacetyl chloride as a transparent, pale yellow, mobile liquid. NMR(CDCl 3 ): 7.5-7.1 (m, 4H), 4.2 (s, 2H). To a slurry of 46.5 gm (0.348 mole) AlCl 3 in 400 mL dichloromethane at -78° C. was added a solution of 32.76 gm (0.174 mole) of the previously prepared o-chlorophenylacetyl chloride in 100 mL dichloromethane dropwise over 1 hour. The dry ice/acetone bath then was replaced with an ice/water bath and ethylene was bubbled into the reaction mixture during which time the temperature rose to 15° C. The ethylene addition was discontinued at the end of the exotherm and the reaction mixture was stirred at about 5° C. for 4 hours. Ice was then added to the reaction mixture to destroy aluminum complexes. Upon termination of the exotherm, the reaction mixture was diluted with 500 mL of water and stirred vigorously until all solids had dissolved. The phases were separated and the organic phase was washed with 3×400 mL 1N hydrochloric acid and 2×400 mL saturated aqueous sodium bicarbonate. The remaining organic phase was then dried over sodium sulfate and concentrated in vacuo to give a pale orange residue. The residue was dissolved in 1:1 hexane:diethyl ether and was poured over a flash silica column which was then eluted with 1:1 hexane:diethyl ether to give a light yellow residue which was crystallized from 4:1 hexane:diethyl ether to give 10.55 gm of the title compound. NMR(CDCl 3 ): 7.5-7.2 (m, 3H), 3.7 (s, 2H), 3.3-3.0 (t, J=7 Hz, 2H), 2.8-2.4 (t, J=7 Hz, 2H). MS: 180 (60), 165 (9), 138 (100), 117 (52), 115 (50), 103 (48), 89(20), 76(25), 74(18), 63(30), 57(9), 52(28), 51(20), 42(6), 39(32). IR(nujol mull): 2950 cm -1 , 2927 cm -1 , 1708 cm -1 , 1464 cm -1 , 1450 cm -1 , 1169 cm -1 , 1141 cm -1 . Reductive Amination To a solution of 0.5 gm (2.78 mMol) 8-chloro-2-tetralone in 25 mL cyclohexane were added 1.4 mL (13.9 mMol) diethylamine followed by 0.1 gm p-toluenesulfonic acid monohydrate. The reaction mixture was then heated at reflux with constant water removal (Dean-Stark Trap) for 18 hours. The reaction mixture was then cooled to ambient and the volatiles removed under reduced pressure. The residue was then dissolved in 15 mL methanol to which were then added 1.5 mL acetic acid followed by the portionwise addition of 0.5 gm sodium borohydride. The reaction mixture was then stirred for 1 hour at ambient. The reaction mixture was then diluted with 20 mL 10% HCl and stirred for an additional hour. The mixture was then extracted with diethyl ether and the remaining aqueous phase was poured over ice, made basic with ammonium hydroxide and extracted well with dichloromethane. These extracts were combined, dried over sodium sulfate and concentrated under reduced pressure. The residue was redissolved in dichloromethane and subjected to chromatography over basic alumina, eluting with dichloromethane. Fractions shown to contain product were combined and concentrated under reduced pressure. The residual oil was dissolved in diethyl ether and the solution saturated with hydrogen chloride. The viscous residue was crystallized from acetone/diethyl ether to give 0.20 gm (23.2%) of Compound IV as colorless crystals. m.p.=158°-159° C. MS(m/e): 273 Calculated for C 14 H 21 NCl.HCl: Theory: C, 61.32; H, 7.72; N, 5.11. Found: C, 61.62; H, 7.94; N, 5.03. Compound V 6-hydroxy-3-dimethylamino-1,2,3,4-tetrahydrocarbazole ##STR15## Compound V is available by the following procedure. 4-dimethylamino-1-cyclohexanone ethylene ketal To a solution of 5.0 gm (32 mMol) 1,4-cyclohexanedione mono-ethylene ketal and 10.80 gm (240 mMol) dimethylamine were added 2.0 mL acetic acid and the mixture was stirred at 0° C. for 1.5 hours. To this solution were then added 3.62 gm (58 mMol) sodium cyanoborohydride and the reaction stirred for an additional hour at ambient. The pH of the reaction mixture was adjusted to ˜7 with 16 mL acetic acid and stirred 18 hours at ambient. The volatiles were removed under reduced pressure and the residue dissolved in cold 5% tartaric acid solution and then the aqueous phase was made basic with 5N sodium hydroxide. This aqueous phase was extracted well with dichloromethane. These organic extracts were combined and concentrated under reduced pressure to give 5.04 gm (85%) of the title compound as an oil. 4-dimethylamino-1-cyclohexanone 4.96 gm (26.8 mMol) 4-dimethylamino-1-cyclohexanone ethylene ketal were dissolved in 50 mL formic acid and the solution stirred at reflux for 18 hours. The reaction mixture was then cooled to ambient and the volatiles removed under reduced pressure to give 3.78 gm (100%) of the title compound. 6-benzyloxy-3-dimethlamino-1,2,3,4-tetrahydrocarbazole To a solution of 3.78 gm (26.8 mMol) 4-dimethylamino-1-cyclohexanone and 6.69 gm (26.8 mMol) 4-benzyloxyphenylhydrazine hydrochloride in 50 mL ethanol were added 2.17 mL (26.8 mMol) pyridine. To this solution were added 5×10 mL portions of water and the reaction mixture then stored at 0° C. for 18 hours. The reaction mixture was then diluted with an additional 50 mL of water and the mixture extracted well with dichloromethane. The combined organic extracts were dried over sodium sulfate and the volatiles removed under reduced pressure. The residual oil was subjected to flash silica gel chromatography, eluting with 9:1 chloroform:methanol. Fractions shown to contain the desired product were combined and concentrated under reduced pressure to give 2.14 gm (24.9%) of the title compound. Hydrogenolysis To a solution of 2.14 gm (6.7 mMol) 6-benzyloxy-3-dimethylamino-1,2,3,4-tetrahydrocarbazole in 50 mL ethanol were added 0.20 gm 10% palladium on carbon and the reaction mixture was hydrogenated at ambient temperature with an initial hydrogen pressure of 40 p.s.i. After 5 hours an additional charge of 0.20 gm 10% palladium on carbon were added and the reaction mixture repressurized with hydrogen to 40 p.s.i. for 4 hours. The reaction mixture was then filtered through a pad of celite and the filtrate concentrated under reduced pressure. The residue was subjected to Florisil chromatography, eluting with 9:1 chloroform:methanol. Fractions shown to contain the desired compound were combined and concentrated under reduced pressure. The residue was again subjected to Florisil chromatography, eluting with a gradient consisting of chloroform containing 2-10% methanol. Fractions shown to contain product were combined and concetnrated under reduced pressure to give Compound V as a crystalline solid. MS(m/e): 230(M + ) Calculated for C 14 H 18 N 2 O: Theory: C, 73.01; H, 7.88; N, 12.16. Found: C, 72.75; H, 7.83; N, 11.97. Binding Assays The binding affinities of compounds for various serotonin receptors were determined essentially as described above except that different cloned receptors are employed in place of the 5-HT 1F receptor clone employed therein. The results of these binding experiments are summarized in Table II. TABLE II______________________________________BINDING TO SEROTONIN (5-HT.sub.1) RECEPTOR SUBTYPES(K.sub.i nM)Compound 5-HT.sub.1Dα 5-HT.sub.1Dβ 5-HT.sub.1E 5-HT.sub.1F______________________________________I 4.8 9.6 2520.0 25.7II 21.7 53.6 50.3 2.5III 163.2 196.5 3.9 22.0IV 13.5 145.3 813.0 129.2V 791.0 1683.0 73.6 10.3______________________________________ cAMP Formation All of the compounds of the panel were tested in the cAMP formation assay described supra and all were found to be agonists of the 5-HT 1F receptor. Protein Extravasation Harlan Sprague-Dawley rats (225-325 g) or guinea pigs from Charles River Laboratories (225-325 g) were anesthetized with sodium pentobarbital intraperitoneally (65 mg/kg or 45 mg/kg respectively) and placed in a stereotaxic frame (David Kopf Instruments) with the incisor bar set at -3.5 mm for rats or -4.0 mm for guinea pigs. Following a midline sagital scalp incision, two pairs of bilateral holes were drilled through the skull (6 mm posteriorly, 2.0 and 4.0 mm laterally in rats; 4 mm posteriorly and 3.2 and 5.2 mm laterally in guinea pigs, all coordinates referenced to bregma). Pairs of stainless steel stimulating electrodes (Rhodes Medical Systems, Inc.) were lowered through the holes in both hemispheres to a depth of 9 mm (rats) or 10.5 mm (guinea pigs) from dura. The femoral vein was exposed and a dose of the test compound was injected intravenously (1 mL/kg). Approximately 7 minutes later, a 50 mg/kg dose of Evans Blue, a fluorescent dye, was also injected intravenously. The Evans Blue complexed with proteins in the blood and functioned as a marker for protein extravasation. Exactly 10 minutes post-injection of the test compound, the left trigeminal ganglion was stimulated for 3 minutes at a current intensity of 1.0 mA (5 Hz, 4 msec duration) with a Model 273 potentiostat/galvanostat (EG&G Princeton Applied Research). Fifteen minutes following stimulation, the animals were killed and exsanguinated with 20 mL of saline. The top of the skull was removed to facilitate the collection of the dural membranes. The membrane samples were removed from both hemispheres, rinsed with water, and spread flat on microscopic slides. Once dried, the tissues were coverslipped with a 70% glycerol/water solution. A fluorescence microscope (Zeiss) equipped with a grating monochromator and a spectrophotometer was used to quantify the amount of Evans Blue dye in each sample. An excitation wavelength of approximately 535 nm was utilized and the emission intensity at 600 nm was determined. The microscope was equipped with a motorized stage and also interfaced with a personal computer. This facilitated the computer-controlled movement of the stage with fluorescence measurements at 25 points (500 μm steps) on each dural sample. The mean and standard deviation of the measurements was determined by the computer. The extravasation induced by the electrical stimulation of the trigeminal ganglion was an ipsilateral effect (i.e. occurs only on the side of the dura in which the trigeminal ganglion was stimulated). This allows the other (unstimulated) half of the dura to be used as a control. The ratio of the amount of extravasation in the dura from the stimulated side compared to the unstimulated side dura was calculated. Saline controls yielded a ratio of approximately 2.0 in rats and 1.8 in guinea pigs. In contrast, a compound which effectively prevented the extravasation in the dura from the stimulated side would have a ratio of approximately 1.0. A dose-response curve was generated and the dose that inhibited the extravasation by 50% (ID 50 ) was approximated. This data is presented in Table III. TABLE III______________________________________Inhibition of Protein Extravasation (ID.sub.50 (mMol/kg)Compound i.v. ID.sub.50 (mMol/kg)______________________________________I 2.6 × 10.sup.-8II .sup. 8.6 × 10.sup.-10III 8.9 × 10.sup.-9IV 1.2 × 10.sup.-7V 8.7 × 10.sup.-9______________________________________ To determine the relationship of binding at various serotonin receptors to inhibition of neuronal protein extravasation, the binding affinity of all of the compounds to each of the 5-HT 1D α, 5-HT 1D β, 5-HT 1E and 5-HT 1F receptors was plotted against their ID 50 in the protein extravasation model. A linear regression analysis was performed on each set of data and a correlation factor, R 2 , calculated. The results of this analysis are summarized in Table IV. TABLE IV______________________________________Correlation Factor (R.sup.2) for Specific 5-HT.sub.1 Subtype BindingAffinity vs Inhibition of Protein Extravasation5-HT.sub.1 Subtype Correlation Factor (R.sup.2)______________________________________5-HT.sub.1Dα 0.075-HT.sub.1Dβ 0.0015-HT.sub.1E 0.315-HT.sub.1F 0.94______________________________________ An ideally linear relationship would generate a correlation factor of 1.0, indicating a cause and effect relationship between the two variables. The experimentally determined correlation factor between inhibition of neuronal protein extravasation and 5-HT 1F binding affinity is 0.94. This nearly ideal dependence of the ID 50 in the protein extravasation model on binding affinity to the 5-HT 1F receptor clearly demonstrates that the 5-HT 1F receptor mediates the inhibition of protein extravasation resulting from stimulation of the trigeminal ganglia. While it is possible to administer a compound employed in the methods of this invention directly without any formulation, the compounds are usually administered in the form of pharmaceutical compositions comprising a pharmaceutically acceptable excipient and at least one active ingredient. These compositions can be administered by a variety of routes including oral, rectal, transdermal, subcutaneous, intravenous, intramuscular, and intranasal. Many of the compounds employed in the methods of this invention are effective as both injectable and oral compositions. Such compositions are prepared in a manner well known in the pharmaceutical art and comprise at least one active compound. See, e.g., REMINGTON'S PHARMACEUTICAL SCIENCES, (16th ed. 1980). In making the compositions employed in the present invention the active ingredient is usually mixed with an excipient, diluted by an excipient or enclosed within such a carrier which can be in the form of a capsule, sachet, paper or other container. When the excipient serves as a diluent, it can be a solid, semi-solid, or liquid material, which acts as a vehicle, carrier or medium for the active ingredient. Thus, the compositions can be in the form of tablets, pills, powders, lozenges, sachets, cachets, elixirs, suspensions, emulsions, solutions, syrups, aerosols (as a solid or in a liquid medium), ointments containing for example up to 10% by weight of the active compound, soft and hard gelatin capsules, suppositories, sterile injectable solutions, and sterile packaged powders. In preparing a formulation, it may be necessary to mill the active compound to provide the appropriate particle size prior to combining with the other ingredients. If the active compound is substantially insoluble, it ordinarily is milled to a particle size of less than 200 mesh. If the active compound is substantially water soluble, the particle size is normally adjusted by milling to provide a substantially uniform distribution in the formulation, e.g. about 40 mesh. Some examples of suitable excipients include lactose, dextrose, sucrose, sorbitol, mannitol, starches, gum acacia, calcium phosphate, alginates, tragacanth, gelatin, calcium silicate, microcrystalline cellulose, polyvinylpyrrolidone, cellulose, water, syrup, and methyl cellulose. The formulations can additionally include: lubricating agents such as talc, magnesium stearate, and mineral oil; wetting agents; emulsifying and suspending agents; preserving agents such as methyl- and propylhydroxybenzoates; sweetening agents; and flavoring agents. The compositions of the invention can be formulated so as to provide quick, sustained or delayed release of the active ingredient after administration to the patient by employing procedures known in the art. The compositions are preferably formulated in a unit dosage form, each dosage containing from about 0.05 to about 100 mg, more usually about 1.0 to about 30 mg, of the active ingredient. The term "unit dosage form" refers to physically discrete units suitable as unitary dosages for human subjects and other mammals, each unit containing a predetermined quantity of active material calculated to produce the desired therapeutic effect, in association with a suitable pharmaceutical excipient. The active compounds are generally effective over a wide dosage range. For examples, dosages per day normally fall within the range of about 0.01 to about 30 mg/kg of body weight. In the treatment of adult humans, the range of about 0.1 to about 15 mg/kg/day, in single or divided dose, is especially preferred. However, it will be understood that the amount of the compound actually administered will be determined by a physician, in the light of the relevant circumstances, including the condition to be treated, the chosen route of administration, the actual compound or compounds administered, the age, weight, and response of the individual patient, and the severity of the patient's symptoms, and therefore the above dosage ranges are not intended to limit the scope of the invention in any way. In some instances dosage levels below the lower limit of the aforesaid range may be more than adequate, while in other cases still larger doses may be employed without causing any harmful side effect, provided that such larger doses are first divided into several smaller doses for administration throughout the day. Formulation Example 1 Hard gelatin capsules containing the following ingredients are prepared: ______________________________________ QuantityIngredient (mg/capsule)______________________________________Compound of Example 24 30.0Starch 305.0Magnesium stearate 5.0______________________________________ The above ingredients are mixed and filled into hard gelatin capsules in 340 mg quantities. Formulation Example 2 A tablet formula is prepared using the ingredients below: ______________________________________ QuantityIngredient (mg/tablet)______________________________________Compound of Example 29 25.0Cellulose, microcrystalline 200.0Colloidal silicon dioxide 10.0Stearic acid 5.0______________________________________ The components are blended and compressed to form tablets, each weighing 240 mg. Formulation Example 3 A dry powder inhaler formulation is prepared containing the following components: ______________________________________Ingredient Weight %______________________________________Compound of Example 6 5Lactose 95______________________________________ The active mixture is mixed with the lactose and the mixture is added to a dry powder inhaling appliance. Formulation Example 4 Tablets, each containing 30 mg of active ingredient, are prepared as follows: ______________________________________ QuantityIngredient (mg/tablet)______________________________________Compound of Example 17 30.0 mgStarch 45.0 mgMicrocrystalline cellulose 35.0 mgPolyvinylpyrrolidone(as 10% solution in water) 4.0 mgSodium carboxymethyl starch 4.5 mgMagnesium stearate 0.5 mgTalc 1.0 mgTotal 120 mg______________________________________ The active ingredient, starch and cellulose are passed through a No. 20 mesh U.S. sieve and mixed thoroughly. The solution of polyvinylpyrrolidone is mixed with the resultant powders, which are then passed through a 16 mesh U.S. sieve. The granules so produced are dried at 50°-60° C. and passed through a 16 mesh U.S. sieve. The sodium carboxymethyl starch, magnesium stearate, and talc, previously passed through a No. 30 mesh U.S. sieve, are then added to the granules which, after mixing, are compressed on a tablet machine to yield tablets each weighing 120 mg. Formulation Example 5 Capsules, each containing 40 mg of medicament are made as follows: ______________________________________ QuantityIngredient (mg/capsule)______________________________________Compound of Example 12 40.0 mgStarch 109.0 mgMagnesium stearate 1.0 mgTotal 150.0 mg______________________________________ The active ingredient, cellulose, starch, and magnesium stearate are blended, passed through a No. 20 mesh U.S. sieve, and filled into hard gelatin capsules in 150 mg quantities. Formulation Example 6 Suppositories, each containing 25 mg of active ingredient are made as follows: ______________________________________Ingredient Amount______________________________________Compound of Example 36 25 mgSaturated fatty acid glycerides to 2,000 mg______________________________________ The active ingredient is passed through a No. 60 mesh U.S. sieve and suspended in the saturated fatty acid glycerides previously melted using the minimum heat necessary. The mixture is then poured into a suppository mold of nominal 2.0 g capacity and allowed to cool. Formulation Example 7 Suspensions, each containing 50 mg of medicament per 5.0 ml dose are made as follows: ______________________________________Ingredient Amount______________________________________Compound of Example 9 50.0 mgXanthan gum 4.0 mgSodium carboxymethyl cellulose (11%) 50.0 mgMicrocrystalline cellulose (89%)Sucrose 1.75 gSodium benzoate 10.0 mgFlavor and Color q.v.Purified water to 5.0 ml______________________________________ The medicament, sucrose and xanthan gum are blended, passed through a No. 10 mesh U.S. sieve, and then mixed with a previously made solution of the microcrystalline cellulose and sodium carboxymethyl cellulose in water. The sodium benzoate, flavor, and color are diluted with some of the water and added with stirring. Sufficient water is then added to produce the required volume. Formulation Example 8 Capsules, each containing 15 mg of medicament, are made as follows: ______________________________________ QuantityIngredient (mg/capsule)______________________________________Compound of Example 46 15.0 mgStarch 407.0 mgMagnesium stearate 3.0 mgTotal 425.0 mg______________________________________ The active ingredient, cellulose, starch, and magnesium stearate are blended, passed through a No. 20 mesh U.S. sieve, and filled into hard gelatin capsules in 425 mg quantities. Formulation Example 9 An intravenous formulation may be prepared as follows: ______________________________________Ingredient Quantity______________________________________Compound of Example 1 250.0 mgIsotonic saline 1000 ml______________________________________ Formulation Example 10 A topical formulation may be prepared as follows: ______________________________________Ingredient Quantity______________________________________Compound of Example 1 1-10 gEmulsifying Wax 30 gLiquid Paraffin 20 gWhite Soft Paraffin to 100 g______________________________________ The white soft paraffin is heated until molten. The liquid paraffin and emulsifying wax are incorporated and stirred until dissolved. The active ingredient is added and stirring is continued until dispersed. The mixture is then cooled until solid. Formulation Example 11 Sublingual or buccal tablets, each containing 10 mg of active ingredient, may be prepared as follows: ______________________________________ QuantityIngredient Per Tablet______________________________________Compound of Example 21 10.0 mgGlycerol 210.5 mgWater 143.0 mgSodium Citrate 4.5 mgPolyvinyl Alcohol 26.5 mgPolyvinylpyrrolidone 15.5 mgTotal 410.0 mg______________________________________ The glycerol, water, sodium citrate, polyvinyl alcohol, and polyvinylpyrrolidone are admixed together by continuous stirring and maintaining the temperature at about 90° C. When the polymers have gone into solution, the solution is cooled to about 50°-55° C. and the medicament is slowly admixed. The homogenous mixture is poured into forms made of an inert material to produce a drug-containing diffusion matrix having a thickness of about 2-4 mm. This diffusion matrix is then cut to form individual tablets having the appropriate size. Another preferred formulation employed in the methods of the present invention employs transdermal delivery devices ("patches"). Such transdermal patches may be used to provide continuous or discontinuous infusion of the compounds of the present invention in controlled amounts. The construction and use of transdermal patches for the delivery of pharmaceutical agents is well known in the art. See, e.g., U.S. Pat. No. 5,023,252, issued Jun. 11, 1991, herein incorporated by reference. Such patches may be constructed for continuous, pulsatile, or on demand delivery of pharmaceutical agents. Frequently, it will be desirable or necessary to introduce the pharmaceutical composition to the brain, either directly or indirectly. Direct techniques usually involve placement of a drug delivery catheter into the host's ventricular system to bypass the blood-brain barrier. One such implantable delivery system, used for the transport of biological factors to specific anatomical regions of the body, is described in U.S. Pat. No. 5,011,472, issued Apr. 30, 1991, which is herein incorporated by reference. Indirect techniques, which are generally preferred, usually involve formulating the compositions to provide for drug latentiation by the conversion of hydrophilic drugs into lipid-soluble drugs or prodrugs. Latentiation is generally achieved through blocking of the hydroxy, carbonyl, sulfate, and primary amine groups present on the drug to render the drug more lipid soluble and amenable to transportation across the blood-brain barrier. Alternatively, the delivery of hydrophilic drugs may be enhanced by intra-arterial infusion of hypertonic solutions which can transiently open the blood-brain barrier. The type of formulation employed for the administration of the compounds employed in the methods of the present invention may be dictated by the particular compounds employed, the type of pharmacokinetic profile desired from the route of administration and the compound(s), and the state of the patient.
This invention provides novel 5-HT 1F agonists which are useful for the treatment of migraine and associated disorders having the following formula: ##STR1## wherein A, B, X, Y, Ar and n are defined in the specification.
98,836
RELATED APPLICATION DATA This application claims priority to Japanese Patent Application JP 2002-107463 filed on Apr. 10, 2002 and 2002-107464 filed on Apr. 10, 2002, and the disclosures of these applications are incorporated herein by reference to the extent permitted by law. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a partially-fluorinated-alkyl compound, a lubricant for recording medium including the partially-fluorinated-alkyl compound, and a recording medium having formed a lubricant layer comprising the lubricant. 2. Description of Related Art As conventional recording media, for example, magnetic recording media, there have been known so-called metal thin film type magnetic recording media including a magnetic layer which is formed by depositing a ferromagnetic metal material on a nonmagnetic support by using, for example, a vapor deposition process, and so-called coating type magnetic recording media including a magnetic layer which is formed by applying to a nonmagnetic support a magnetic coating composition including very fine magnetic particles and a resin binder. In these conventional magnetic recording media, the magnetic layer has extremely excellent surface smoothness and hence, the substantial contact area of the magnetic layer with a sliding member, such as a magnetic head or a guide roller, is large, namely, the coefficient of friction is large, leading to problems in that a so-called sticking phenomenon due to cohesion is likely to occur and the transport properties and durability of the magnetic recording media are poor. For solving the problems, various lubricants are studied and, conventionally, it has been attempted to incorporate or apply, as a topcoat, a higher fatty acid or an ester thereof to the magnetic layer in the magnetic recording medium to lower the coefficient of friction. The magnetic recording medium is used under severe conditions, and therefore the lubricant used in the magnetic recording medium is required to have extremely excellent properties. However, the lubricants conventionally used are currently difficult to meet the requirements. Specifically, the lubricant used in the magnetic recording medium must meet such requirements: (1) for securing a predetermined lubricating effect when used in cold places, that the lubricant have excellent properties at low temperatures; (2) for removing a problem of the spacing between a magnetic head and the recording medium, that the lubricant applied to the recording medium have an extremely small thickness and exhibit satisfactory lubricating properties; and (3) that the lubricant endure long-time or long-term use and maintain the lubricating effect. As a lubricant for metal thin film type magnetic recording medium, Japanese Patent Application Laid-Open Specification No. 6-41561 discloses a fluorine-containing alkyl diester of succinic acid represented by the following formula (i): R 1 —CH(COOR 2 )CH 2 COOR 3   (i) wherein R 1 represents an aliphatic alkyl group or an aliphatic alkenyl group; and one of R 2 and R 3 represents a fluoroalkyl ether group, and another represents a fluoroalkyl group, a fluoroalkenyl group, a fluorophenyl group, an aliphatic alkyl group, or an aliphatic alkenyl group. SUMMARY OF THE INVENTION However, the fluorine-containing alkyl diester of succinic acid described above has a problem in that the coefficient of friction is large. Thus, in the field of recording media, there are problems of the practicalities due to the lack of the ability of the lubricant used, for example, a problem that an output level during the replay is lowered in the shuttle transport test. In view of the above, the present invention is conceived. It is desirable to provide a compound which is advantageous not only in that it maintains excellent lubricity under various conditions for use and excellent lubricating effect over a long time, but also in that it can impart excellent transport properties and excellent abrasion resistance as well as excellent durability, a lubricant including the compound, and a recording medium using the lubricant. Specifically, in one aspect of the present invention, there is provided a partially-fluorinated-alkyl compound which is represented by the following formula (1): wherein R represents a saturated or unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms; Rf represents a saturated or unsaturated fluoroalkyl group or hydrocarbon group; and X represents an aromatic ring or heterocyclic group, an aromatic ring or heterocyclic group substituted with a hydroxyl group, an amino group, a carboxyl group, a halogen atom, a hydrocarbon group, or an aromatic ring, or a hydrocarbon group substituted with an aromatic ring or heterocyclic group. In another aspect of the present invention, there is provided a lubricant for recording medium, wherein the lubricant includes a partially-fluorinated-alkyl compound represented by the following formula (1): wherein R represents a saturated or unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms; Rf represents a saturated or unsaturated fluoroalkyl group or hydrocarbon group; and X represents an aromatic ring or heterocyclic group, an aromatic ring or heterocyclic group substituted with a hydroxyl group, an amino group, a carboxyl group, a halogen atom, a hydrocarbon group, or an aromatic ring, or a hydrocarbon group substituted with an aromatic ring or heterocyclic group. In still another aspect of the present invention, there is provided a recording medium which includes a support, a recording layer, and a lubricant layer including a lubricant, wherein the recording layer and the lubricant layer are successively formed on the support, wherein the lubricant includes a partially-fluorinated-alkyl compound represented by the following formula (1): wherein R represents a saturated or unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms; Rf represents a saturated or unsaturated fluoroalkyl group or hydrocarbon group; and X represents an aromatic ring or heterocyclic group, an aromatic ring or heterocyclic group substituted with a hydroxyl group, an amino group, a carboxyl group, a halogen atom, a hydrocarbon group, or an aromatic ring, or a hydrocarbon group substituted with an aromatic ring or heterocyclic group. In another aspect of the present invention, there is provided a partially-fluorinated-alkyl compound which is represented by the following formula (2): RCH(CH 2 COORf)COOX  (2) wherein R represents a saturated or unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms; Rf represents a saturated or unsaturated fluoroalkyl group or hydrocarbon group; and X represents an aromatic ring or heterocyclic group, an aromatic ring or heterocyclic group substituted with a hydroxyl group, an amino group, a carboxyl group, a halogen atom, a hydrocarbon group, or an aromatic ring, or a hydrocarbon group substituted with an aromatic ring or heterocyclic group. In still another aspect of the present invention, there is provided a lubricant for recording medium, wherein the lubricant includes a partially-fluorinated-alkyl compound represented by the following formula (2): RCH(CH 2 COORf)COOX  (2) wherein R represents a saturated or unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms; Rf represents a saturated or unsaturated fluoroalkyl group or hydrocarbon group; and X represents an aromatic ring or heterocyclic group, an aromatic ring or heterocyclic group substituted with a hydroxyl group, an amino group, a carboxyl group, a halogen atom, a hydrocarbon group, or an aromatic ring, or a hydrocarbon group substituted with an aromatic ring or heterocyclic group. In still another aspect of the present invention, there is provided a recording medium which includes a support, a recording layer, and a lubricant layer including a lubricant, wherein the recording layer and the lubricant layer are successively formed on the support, wherein the lubricant includes a partially-fluorinated-alkyl compound represented by the following formula (2): RCH(CH 2 COORf)COOX  (2) wherein R represents a saturated or unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms; Rf represents a saturated or unsaturated fluoroalkyl group or hydrocarbon group; and X represents an aromatic ring or heterocyclic group, an aromatic ring or heterocyclic group substituted with a hydroxyl group, an amino group, a carboxyl group, a halogen atom, a hydrocarbon group, or an aromatic ring, or a hydrocarbon group substituted with an aromatic ring or heterocyclic group. The partially-fluorinated-alkyl compound of the present invention is a novel substance, and, when the compound is used as a lubricant for recording medium, especially for magnetic recording medium, the compound is advantageous not only in that it maintains excellent lubricity under various conditions for use and excellent lubricating effect over a long time, but also in that it can impart to the recording medium excellent transport properties and excellent abrasion resistance as well as excellent durability. DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinbelow, the compound of the present invention will be described, taking as an example the case where the compound is used as a lubricant for magnetic recording medium. In the partially-fluorinated-alkyl compound of the present invention, R represents a saturated or unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms, preferably 8 to 20 carbon atoms. When the carbon atom number of R is less than 6 or more than 30, the solubility of the compound in an organic solvent is too low, making it impossible to form a film of a lubricant layer using an organic solvent on, for example, a carbon film layer. First Embodiment The partially-fluorinated-alkyl compound according to a first embodiment of the present invention may be synthesized, for example, as follows. First, a succinic acid derivative having the substituent R in formula (1) and an alcohol compound having the fluoroalkyl group (Rf) in formula (1) are mixed together and heated to 120° C. to effect a reaction, and then, impurities and the remaining unnecessary substances are removed from the resultant reaction mixture by washing with an organic solvent or an inorganic solvent, extraction using a separatory funnel, or purification by column chromatography to obtain a partially-fluorinated-alkyl monoester monocarboxylic acid compound purified. Then, the obtained partially-fluorinated-alkyl monoester monocarboxylic acid compound and a hydroxyl compound having the substituent X in formula (1) are subjected to esterification so that one hydroxyl group in the hydroxyl compound having the substituent X is reacted with one carboxyl group in the partially-fluorinated-alkyl monoester monocarboxylic acid compound to form an ester linkage, followed by purification, thus obtaining a partially-fluorinated-alkyl compound. In the esterification, a method can be employed in which the carboxyl group in the partially-fluorinated-alkyl monoester monocarboxylic acid compound is preliminarily treated with, e.g., thionyl chloride to form an acid chloride, and then reacted with the hydroxyl group in the hydroxyl compound having the substituent X. As mentioned above, the partially-fluorinated-alkyl compound of the present invention can be advantageously used as a lubricant for recording medium, especially for magnetic recording medium. If desired, various additives, for example, a rust preventing agent can be added to the lubricant. As a rust preventing agent, one which has conventionally been used for magnetic recording medium can be used, and examples include phenols, naphthols, quinones, heterocyclic compounds containing a nitrogen atom, heterocyclic compounds containing an oxygen atom, and heterocyclic compounds containing a sulfur atom. The recording medium of the present invention includes a lubricant layer including the above lubricant. For example, when the recording medium of the present invention is a magnetic recording medium, it can be specifically a so-called metal thin film type magnetic recording medium in which a magnetic layer consisting of a metallic, magnetic thin film formed by, e.g., a vapor deposition process, a carbon film layer, and a lubricant layer including the partially-fluorinated-alkyl compound of the present invention are at least successively formed on a nonmagnetic support. If desired, an undercoat layer may be formed between the nonmagnetic support and the magnetic layer. With respect to the nonmagnetic support, there is no particular limitation, and one which is conventionally known can be used. For example, when a substrate having stiffness, such as an Al alloy plate or a glass plate, used as a nonmagnetic support, an oxide film may be formed by an adonized aluminum treatment or a Ni—P film may be formed on the surface of the substrate so that the surface is hardened. With respect to the metallic, magnetic thin film constituting the magnetic layer, there is no particular limitation, and one which is conventionally known can be used. Examples include metallic, magnetic thin films in the form of a continuous film formed by an electroplating, sputtering, or vacuum vapor deposition process, specifically include in-plane magnetized recording metallic, magnetic thin films consisting of a metal, such as Fe, Co, or Ni, a Co—Ni alloy, a Co—Pt alloy, a Co—Pt—Ni alloy, an Fe—Co alloy, an Fe—Ni alloy, an Fe—Co—Ni alloy, an Fe—Ni—B alloy, an Fe—Co—B alloy, or an Fe—Co—Ni—B alloy, and Co—Cr alloy magnetic thin films. Especially when an in-plane magnetized recording metallic, magnetic thin film is used, an undercoat layer consisting of a low melting-point nonmagnetic material, such as Bi, Sb, Pb, Sn, Ga, In, Ge, Si, or Tl, may be preliminarily formed on the nonmagnetic support, and the above metal may be deposited on the undercoat layer in the direction perpendicular to the undercoat layer by a vapor deposition or sputtering process to diffuse the low melting-point nonmagnetic material to the metallic, magnetic thin film so that the orientation of the metallic, magnetic thin film is cancelled to secure the in-plane isotropy and the coercive properties are improved. As a method for forming the carbon film layer, a sputtering process is generally used, but there is no particular limitation and any known methods can be employed. The carbon film preferably has a thickness of 2 to 100 nm, further preferably 5 to 30 nm. The lubricant layer can be formed by applying, as a topcoat, a lubricant including the partially-fluorinated-alkyl compound of the present invention onto the carbon film layer by a general method. The coating weight of the lubricant is preferably, for example, 0.5 to 100 mg/m 2 , further preferably 1 to 20 mg/m 2 . In formation of the lubricant layer by application, a solution obtained by dissolving a lubricant in an organic solvent, such as hexane, can be used. When a rust preventing agent is used, it may be used in the form of a mixture with a lubricant, but, when a rust preventing agent is first applied to the carbon film layer and then a lubricant is applied onto the rust preventing agent so that they constitute two or more different layers, the rust preventing effect is advantageously increased. It is preferred that the partially-fluorinated-alkyl compound of the present invention is used as a lubricant for recording medium, especially for magnetic recording medium. However, the lubricant of the present invention can be applied not only to magnetic recording media but also to optical recording media. In addition, the support is not limited to a tape but can be used in recording media, such as disc media, e.g., magnetic discs and optical discs. In conventional lubricants, a compound having a relatively high polarity, such as a carboxylic acid, an amine, or a carboxylic acid amine salt, has a small coefficient of friction, but it is poor in the still durability, and a compound having a relatively low polarity, such as an ester compound, has excellent still durability, but it has a large coefficient of friction. The partially-fluorinated-alkyl compound of the present invention has an aromatic ring or a heterocyclic group and two ester groups as terminal polar groups, and hence the compound has such excellent properties that the coefficient of friction is small and the still durability is excellent. Especially when the partially-fluorinated-alkyl compound of the present invention is applied as a lubricant to the carbon film layer, the aromatic ring or heterocyclic group and two ester groups in formula (1), which constitute the polar group portion of the lubricant molecule, adsorb onto the carbon film layer, thus making it possible to form a lubricant layer having more excellent durability due to the cohesion between the hydrophobic groups. Further, the application of a conventional fluorine-containing lubricant needs a fluorine solvent, but, in contrast, the partially-fluorinated-alkyl compound of the present invention advantageously enables application using a hydrocarbon solvent, such as toluene or acetone, thus lowering the load on the environment. EXAMPLES OF THE FIRST EMBODIMENT Hereinbelow, the present invention will be described in more detail with reference to the following Examples and Comparative Examples, which should not be construed as limiting the scope of the present invention. Synthesis Example 1 Synthesis of C 18 H 37 —CH(CH 2 COOC 10 H 6 OH)COO(CH 2 ) 2 (CF 2 ) 8 F Using octadecylsuccinic anhydride as a succinic acid derivative having the substituent R in formula (1), a fluoroalcohol {F(CF 2 ) 8 CH 2 CH 2 OH} as an alcohol compound having the partially-fluorinated-alkyl group (Rf) in formula (1), and 2,3-naphthalenediol {C 10 H 6 (OH) 2 } as a hydroxyl compound having the substituent X in formula (1), a partially-fluorinated-alkyl compound of the present invention was synthesized. The procedure for the synthesis is shown below. 17.7 g of octadecylsuccinic anhydride (C 18 H 37 C 4 H 3 O 3 ) and 23.2 g of fluoroalcohol {F(CF 2 ) 8 CH 2 CH 2 OH} were mixed together and heated under reflux at 120° C. to effect a reaction for 3 hours. After completion of the reaction, the resultant reaction mixture was dissolved in 200 ml of toluene, and 300 ml of a 10% aqueous NaOH solution was added to the resultant solution and vigorously shaken. The resultant white solid matter (Na salt which is a desired product) was taken out by suction filtration using a glass filter. Then, the white solid matter on the glass filter was washed with 240 ml of water twice and then with 200 ml of toluene once. By this operation, the octadecylsuccinic anhydride remaining unreacted could be removed from the white solid matter. Then, the resultant white solid matter was placed in a separatory funnel, and 300 ml of toluene and 300 ml of 7.2% HCl were added to the separatory funnel to wash the solid matter for desalination. Further, the solid matter was washed with 300 ml of 7.2% HCl twice and then with an aqueous solution of sodium chloride twice, and the toluene phase was recovered and dried using magnesium sulfate. After one hour, the magnesium sulfate was removed by filtration and the toluene phase was concentrated. Then, the recovered substance was purified by column chromatography. Conditions for the column are as follows: column packing material: silica gel; column temperature: room temperature; and eluent: mixed solvent including 30% of ethyl acetate and 70% of toluene. The desired product is eluted through the column when using a mixed solvent including 30% of ethyl acetate and 70% of toluene as an eluent. An IR analysis shows that the product recovered has a formula of C 18 H 37 —CH(CH 2 COOH)COO(CH 2 ) 2 (CF 2 ) 8 F. 5.0 g of thionyl chloride was added to 33 g of purified C 18 H 37 —CH(CH 2 COOH)COO(CH 2 ) 2 (CF 2 ) 8 F and heated under reflux at 50° C. to effect a reaction for 2 hours. After completion of the reaction, the resultant reaction mixture was concentrated to recover a desired product. An IR analysis shows that the product recovered has a formula of C 18 H 37 —CH(CH 2 COCl)COO(CH 2 ) 2 (CF 2 ) 8 F. Next, 6.5 g of 2,3-naphthalenediol {C 10 H 6 (OH) 2 } was added to purified C 18 H 37 —CH(CH 2 COCl)COO(CH 2 ) 2 (CF 2 ) 8 F and heated under reflux at 100° C. to effect a reaction for 2 hours. After completion of the reaction, the resultant reaction mixture was dissolved in 200 ml of toluene, and placed in a separatory funnel and-washed with 300 ml of a 10% aqueous NaOH solution twice and then with an aqueous solution of sodium chloride twice, and the toluene phase was recovered and dried using magnesium sulfate. After one hour, the magnesium sulfate was removed by filtration, and the toluene phase was concentrated. Then, the substance recovered was purified by column chromatography. Conditions for the column are as follows: column packing material: silica gel; column temperature: room temperature; and eluent: toluene. The desired product is eluted through the column when using toluene as an eluent. The weight of the product recovered was 34 g, and the recovery rate was about 70%. An IR analysis shows that the product recovered has a formula of (synthesis of C 18 H 37 —CH(CH 2 COOC 10 H 6 OH)COO(CH 2 ) 2 (CF 2 ) 8 F. Synthesis Example 2 Synthesis of C 18 H 37 —CH(CH 2 COOC 10 H 7 )COO(CH 2 ) 2 (CF 2 ) 8 F An acid chloride having a formula of C 18 H 37 —CH(CH 2 COCl)COO(CH 2 ) 2 (CF 2 ) 8 F was synthesized in the same manner as in Synthesis Example 1. Next, 5.9 g of 1-naphthol (C 10 H 7 OH) was added to purified C 18 H 37 —CH(CH 2 COCl)COO(CH 2 ) 2 (CF 2 ) 8 F and heated under reflux at 100° C. to effect a reaction for 2 hours. After completion of the reaction, the resultant reaction mixture was dissolved in 200 ml of toluene, and placed in a separatory funnel and washed with 300 ml of a 10% aqueous NaOH solution twice and then with an aqueous solution of sodium chloride twice, and the toluene phase was recovered and dried using magnesium sulfate. After one hour, the magnesium sulfate was removed by filtration and the toluene phase was concentrated. Then, the substance recovered was purified by column chromatography. Conditions for the column are as follows: column packing material: silica gel; column temperature: room temperature; and eluent: toluene. The desired product is eluted through the column when using toluene as an eluent. The weight of the product recovered was 34 g, and the recovery rate was about 70%. An IR analysis shows that the product recovered has a formula of C 18 H 37 —CH(CH 2 COOC 10 H 7 )COO(CH 2 ) 2 (CF 2 ) 8 F. By employing the above-described procedure, the substituent R, partially-fluorinated-alkyl group (Rf), and substituent X in formula (1) can be arbitrarily selected to synthesize a partially-fluorinated-alkyl compound of the present invention. Specific examples of the partially-fluorinated-alkyl compounds synthesized are shown in Table 1 below. TABLE 1 Succinic acid derivative Compound having Rf Compound having X Weight Yield Desired product C8H17C4H3O3 F(CF2)8CH2CH2OH 1-Naphthol 28 g 70% C8H17—CH(CH2COOC10H7)COO(CH2)2(CF2)8F 10.5 g 23.2 g 5.9 g C12H25C4H3O3 F(CF2)8CH2CH2OH 1-Naphthol 31 g 70% C12H25—CH(CH2COOC10H7)COO(CH2)2(CF2)8F 13.5 g 23.2 g 5.9 g C18H35C4H3O3 F(CF2)8CH2CH2OH 1-Naphthol 34 g 70% C18H35—CH(CH2COOC10H7)COO(CH2)2(CF2)8F 17.5 g 23.2 g 5.9 g C18H37C4H3O3 F(CF2)8CH2CH2OH 2,3-Naphthalenediol 34 g 70% C18H37—CH(CH2COOC10H6OH)COO(CH2)2(CF2)8F 17.7 g 23.2 g 6.5 g C18H37C4H3O3 F(CF2)8(CH2)6OH 2,3-Naphthalenediol 35 g 70% C18H37—CH(CH2COOC10H6OH)COO(CH2)6(CF2)8F 17.7 g 26.0 g 6.5 g C18H37C4H3O3 F(CF2)8(CH2)11OH 2,3-Naphthalenediol 31 g 60% C18H37—CH(CH2COOC10H6OH)COO(CH2)11(CF2)8F 17.7 g 29.5 g 6.5 g C18H37C4H3O3 C18H37OH 2,3-Naphthalenediol 29 g 75% C18H37—CH(CH2COOC10H6OH)COOC18H37 17.7 g 13.5 g 6.5 g C18H37C4H3O3 C18H35OH 2,3-Naphthalenediol 29 g 75% C18H37—CH(CH2COOC10H6OH)COOC18H35 17.7 g 13.4 g 6.5 g C18H37C4H3O3 F(CF2)8CH2CH2OH Phenol 32 g 70% C18H37—CH(CH2COOC6H5)COOCH2CH2(CF2)8 17.7 g 23.2 g 4.3 g C18H37C4H3O3 F(CF2)8CH2CH2OH 9-Anthracenemethanol 30 g 60% C18H37—CH(CH2COOCH2C14H29)COOCH2CH2(CF2)8 17.7 g 23.2 g 6.5 g C18H37C4H3O3 F(CF2)8CH2CH2OH 4-Hydroxypyridine 26 g 55% C18H37—CH(CH2COOC5H4N)COOCH2CH2(CF2)8 17.7 g 23.2 g 5.0 g C18H37C4H3O3 F(CF2)8CH2CH2OH o-Cresol 25 g 50% C18H37—CH(CH2COOC6H4CH3)COOCH2CH2(CF2)8 17.7 g 23.2 g 5.0 g C18H37C4H3O3 F(CF2)8CH2CH2OH 4-Aminophenol 25 g 50% C18H37—CH(CH2COOC6H4NH)COOCH2CH2(CF2)8 17.7 g 23.2 g 6.0 g C18H37C4H3O3 F(CF2)8CH2CH2OH 4-Fluorophenol 25 g 50% C18H37—CH(CH2COOC6H4F)COOCH2CH2(CF2)8 17.7 g 23.2 g 6.0 g C18H37C4H3O3 F(CF2)8CH2CH2OH 4-Hydroxybenzoic 25 g 50% C18H37—CH(CH2COOC6H4COOH)COOCH2CH2(CF2)8 17.7 g 23.2 g acid 5.5 g C18H37C4H3O3 F(CF2)8CH2CH2OH 4-Phenylphenol 33 g 70% C18H37—CH(CH2COOC6H4C6H5)COOCH2CH2(CF2)8 17.7 g 23.2 g 6.0 g Examples 1 to 27 Partially-fluorinated-alkyl compounds of the present invention having the structures shown in Table 2 below were individually synthesized in accordance with the same procedure as in the above Synthesis Examples, and, with respect to each of the compounds synthesized, the tests shown below in respect of lubricant were conducted. TABLE 2 Succinic acid Compound having Example derivative Rf Compound having X 1 C 8 H 17 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 2 C 10 H 21 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 3 C 12 H 25 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 4 C 14 H 29 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 5 C 16 H 33 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 6 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 7 C 18 H 35 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 8 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 (CH 2 ) 6 OH 2,3-Naphthalenediol 9 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 (CH 2 ) 11 OH 2,3-Naphthalenediol 10 C 18 H 37 C 4 H 3 O 3 C 18 H 37 OH 2,3-Naphthalenediol 11 C 18 H 37 C 4 H 3 O 3 C 18 H 35 OH 2,3-Naphthalenediol 12 C 18 H 17 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 13 C 10 H 21 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 14 C 12 H 25 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 15 C 14 H 29 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 16 C 18 H 33 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 17 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 18 C 9 H 19 CH(C 7 H 15 )C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 19 C 18 H 35 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 20 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH Phenol 21 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 9-Anthracenemethanol 22 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 4-Hydroxypyridine 23 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH o-Cresol 24 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 4-Aminophenol 25 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 4-Fluorophenol 26 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 4-Hydroxybenzoic acid 27 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 4-Phenylphenol Comparative Examples 1 to 5 With respect to each of the compounds having the structures in Table 3 below, the tests shown below in respect of ant were conducted. TABLE 3 Comp. Exp. Compound 1 C 18 H 37 NH 2 2 C 8 F 17 (CF 2 ) 10 COOCH 3 3 C 18 H 37 CH(COOC 12 H 25 )C 2 H 4 COOCH 2 CF 2 (OCF 2 ) p [OCF(CF 3 )CF 2 ] q OCF 3 (average molecular weight: 2,140) 4 C 18 H 37 CH(COOH)CH 2 COOCH 2 CF(CF 3 )[CF(CF 3 )CF 2 O] 3 F 5 C 11 H 23 COORfOCOC 11 H 23 (Rf represents a perfluoropolyether chain having an average molecular weight of 2,000) Preparation of Sample Tape Co was deposited on a polyethylene terephthalate film having a thickness of 7.0 μm by a vapor deposition process to form a magnetic layer having a thickness of 180 nm consisting of a metallic, magnetic thin film. Then, a carbon film, layer having a thickness of about 8 nm was formed on the magnetic layer using a magnetron sputtering apparatus. Next, on another surface of the polyethylene terephthalate film that is not the surface on which the magnetic layer was formed, a back coat layer having a thickness of 0.5 μm consisting of carbon and a polyurethane resin was formed. Then, the compounds shown in Tables 2 and 3 were individually dissolved in toluene, and the resultant solutions were individually applied to the surface of the carbon film layer previously formed so that the coating weight of each compound became 5 mg/m 2 . The magnetic recording media obtained were individually cut into 6.35 mm-width tapes to obtain sample tapes. Evaluation of Durability and Transport Properties With respect to each of the thus prepared sample tapes, a coefficient of friction, still durability, and shuttle durability were measured under, respectively, conditions at a temperature of 40° C. at a relative humidity of 80%, conditions at a temperature of 5° C., and conditions at a temperature of 40° C. at a relative humidity of 20%. The results are shown in Table 4. It is considered that the conditions for measurements used in the Examples are most severe conditions for use with respect to each tape. In the measurements of the still durability and shuttle durability, a commercially available digital video camcorder (manufactured and sold by Sony Corporation; trade name: VX1000) was used. (1) Method for Measurement of Coefficient of Friction The coefficient of friction was measured as follows. In a thermostatic chamber controlled at a temperature of 40° C. at a relative humidity of 80%, each sample tape was subjected to 100-cycle transport by means of an apparatus for measuring a coefficient of friction. The measurement values after the 100th-cycle transport are shown as coefficient of friction in the Table below. (2) Method for Measurement of Still Durability The still durability was measured as follows. In a thermostatic chamber at 5° C., a period of time until the replay output was lowered by 3 dB was measured. (3) Method for Measurement of Shuttle Durability The shuttle durability was measured as follows In a thermostatic chamber controlled at a temperature of 40° C. at a relative humidity of 20%, each sample tape having a length corresponding to 60 minutes was subjected to 100-cycle transport in a Play mode, and a value (dB) was determined by subtracting the replay output after the 100th-cycle transport from the initial output. Evaluation of Solubility in Solvent With respect to each of the lubricants used in Examples 1 to 27 and Comparative Example 3, the solubility in solvents, i.e., ethanol, acetone, and toluene was examined. The solubility was evaluated in accordance with the following criteria: a lubricant easily dissolved in the solvent was rated symbol ∘; and a lubricant insoluble in the solvent was rated symbol ×. The results of the evaluation of solubility of the lubricants are shown in Table 5 below. As is apparent from the above results, when the partially-fluorinated-alkyl compound of the first embodiment is used as a lubricant for magnetic recording medium, very excellent results are obtained such that the coefficient of friction and deterioration of the still durability and shuttle durability are extremely small under various conditions for use, e.g., at a high temperature at a high humidity, at a high temperature at a low humidity, or at a low temperature. Second Embodiment A partially-fluorinated-alkyl compound according to a second embodiment of the present invention may be synthesized, for example, as follows. First, a succinic acid derivative having the substituent R in formula (2) and an alcohol compound having the fluoroalkyl group (Rf) in formula (2) are mixed together and heated to 150° C. to effect a reaction, and then, impurities and the remaining unnecessary substances are removed from the resultant reaction mixture by washing with an organic solvent or an inorganic solvent, extraction using a separatory funnel, or purification by column chromatography to obtain a partially-fluorinated-alkyl monoester monocarboxylic acid compound purified. Then, the obtained partially-fluorinated-alkyl monoester monocarboxylic acid compound and a hydroxyl compound having the substituent X in formula (2) are subjected to esterification so that one hydroxyl group in the hydroxyl compound having the substituent X is reacted with one carboxyl group in the partially-fluorinated-alkyl monoester monocarboxylic acid compound to form an ester linkage, followed by purification, thus obtaining a partially-fluorinated-alkyl compound. In the esterification, a method can be employed in which the carboxyl group in the partially-fluorinated-alkyl monoester monocarboxylic acid compound is preliminarily treated with, e.g., thionyl chloride to form an acid chloride, and then reacted with the hydroxyl group in the hydroxyl compound having the substituent X. As mentioned above, the partially-fluorinated-alkyl compound of the present invention can be advantageously used as a lubricant for recording medium, especially for magnetic recording medium. If desired, various additives, for example, a rust preventing agent can be added to the lubricant. As a rust preventing agent, one which has conventionally been used for magnetic recording medium can be used, and examples include phenols, naphthols, quinones, heterocyclic compounds containing a nitrogen atom, heterocyclic compounds containing an oxygen atom, and heterocyclic compounds containing a sulfur atom. The recording medium of the present invention includes a lubricant layer including the above lubricant. For example, when the recording medium of the present invention is a magnetic recording medium, it can be specifically a so-called metal thin film type magnetic recording medium in which a magnetic layer consisting of a metallic, magnetic thin film formed by, e.g., a vapor deposition process, a carbon film layer, and a lubricant layer including the partially-fluorinated-alkyl compound of the present invention are at least successively formed on a nonmagnetic support. If desired, an undercoat layer may be formed between the nonmagnetic support and the magnetic layer. With respect to the nonmagnetic support, there is no particular limitation, and one which is conventionally known can be used. For example, when a substrate having stiffness, such as an Al alloy plate or a glass plate, used as a nonmagnetic support, an oxide film may be formed by an adonized aluminum treatment or a Ni—P film may be formed on the surface of the substrate so that the surface is hardened. With respect to the metallic, magnetic thin film constituting the magnetic layer, there is no particular limitation, and one which is conventionally known can be used. Examples include metallic, magnetic thin films in the form of a continuous film formed by an electroplating, sputtering, or vacuum vapor deposition process, specifically include in-plane magnetized recording metallic, magnetic thin films consisting of a metal, such as Fe, Co, or Ni, a Co—Ni alloy, a Co—Pt alloy, a Co—Pt—Ni alloy, an Fe—Co alloy, an Fe—Ni alloy, an Fe—Co—Ni alloy, an Fe—Ni—B alloy, an Fe—Co—B alloy, or an Fe—Co—Ni—B alloy, and Co—Cr alloy magnetic thin films. Especially when an in-plane magnetized recording metallic, magnetic thin film is used, an undercoat layer consisting of a low melting-point nonmagnetic material, such as Bi, Sb, Pb, Sn, Ga, In, Ge, Si, or Tl, may be preliminarily formed on the nonmagnetic support, and the above metal may be deposited on the undercoat layer in the direction perpendicular to the undercoat layer by a vapor deposition or sputtering process to diffuse the low melting-point nonmagnetic material to the metallic, magnetic thin film so that the orientation of the metallic, magnetic thin film is cancelled to secure the in-plane isotropy and the coercive properties are improved. As a method for forming the carbon film layer, a sputtering process is generally used, but there is no particular limitation and any known methods can be employed. The carbon film preferably has a thickness of 2 to 100 nm, further preferably 5 to 30 nm. The lubricant layer can be formed by applying, as a topcoat, a lubricant including the partially-fluorinated-alkyl compound of the present invention onto the carbon film layer by a general method. The coating weight of the lubricant is preferably, for example, 0.5 to 100 mg/m 2 , further preferably 1 to 20 mg/m 2 . In formation of the lubricant layer by application, a solution obtained by dissolving a lubricant in an organic solvent, such as hexane, can be used. When a rust preventing agent is used, it may be used in the form of a mixture with a lubricant, but, when a rust preventing agent is first applied to the carbon film layer and then a lubricant is applied onto the rust preventing agent so that they constitute two or more different layers, the rust preventing effect is advantageously increased. It is preferred that the partially-fluorinated-alkyl compound of the present invention is used as a lubricant for recording medium, especially for magnetic recording medium. However, the lubricant of the present invention can be applied not only to magnetic recording media but also to optical recording media. In addition, the support is not limited to a tape but can be used in recording media, such as disc media, e.g., magnetic discs and optical discs. In conventional lubricants, a compound having a relatively high polarity, such as a carboxylic acid, an amine, or a carboxylic acid amine salt, has a small coefficient of friction, but it is poor in the still durability, and a compound having a relatively low polarity, such as an ester compound, has excellent still durability, but it has a large coefficient of friction. The partially-fluorinated-alkyl compound of the present invention has an aromatic ring or a heterocyclic group and two ester groups as terminal polar groups, and hence the compound has such excellent properties that the coefficient of friction is small and the still durability is excellent. Especially when the partially-fluorinated-alkyl compound of the present invention is applied as a lubricant to the carbon film layer, the aromatic ring or heterocyclic group and two ester groups in formula (2), which constitute the polar group portion of the lubricant molecule, adsorb onto the carbon film layer, thus making it possible to form a lubricant layer having more excellent durability due to the cohesion between the hydrophobic groups. Further, the application of a conventional fluorine-containing lubricant needs a fluorine solvent, but, in contrast, the partially-fluorinated-alkyl compound of the present invention advantageously enables application using a hydrocarbon solvent, such as toluene or acetone, thus lowering the load on the environment. EXAMPLES OF THE SECOND EMBODIMENT Hereinbelow, the present invention will be described in more detail with reference to the following Examples and Comparative Examples, which should not be construed as limiting the scope of the present invention. Synthesis Example 1 Synthesis of C 18 H 37 —CH(CH 2 COO(CH 2 ) 2 (CF 2 ) 8 F)COOC 10 H 6 OH Using octadecylsuccinic anhydride as a succinic acid derivative having the substituent R in formula (2), a fluoroalcohol {F(CF 2 ) 8 CH 2 CH 2 OH} as an alcohol compound having the partially-fluorinated-alkyl group (Rf) in formula (2), and 2,3-naphthalenediol {C 10 H 6 (OH) 2 } as a hydroxyl compound having the substituent X in formula (2), a partially-fluorinated-alkyl compound of the present invention was synthesized. The procedure for the synthesis is shown below. 17.7 g of octadecylsuccinic anhydride (C 18 H 37 C 4 H 3 O 3 ) and 23.2 g of fluoroalcohol {F(CF 2 ) 8 CH 2 CH 2 OH} were mixed together and heated under reflux at 120° C. to effect a reaction for 3 hours. After completion of the reaction, the resultant reaction mixture was dissolved in 200 ml of toluene, and 300 ml of a 10% aqueous NaOH solution was added to the resultant solution and vigorously shaken. The resultant white solid matter (Na salt which is a desired product) was taken out by suction filtration using a glass filter. Then, the white solid matter on the glass filter was washed with 240 ml of water twice and then with 200 ml of toluene once. By this operation, the octadecylsuccinic anhydride remaining unreacted could be removed from the white solid matter. Then, the resultant white solid matter was placed in a separatory funnel, and 300 ml of toluene and 300 ml of 7.2% HCl were added to the separatory funnel to wash the solid matter for desalination. Further, the solid matter was washed with 300 ml of 7.2% HCl twice and then with an aqueous solution of sodium chloride twice, and the toluene phase was recovered and dried using magnesium sulfate. After one hour, the magnesium sulfate was removed by filtration and the toluene phase was concentrated. Then, the recovered substance was purified by column chromatography. Conditions for the column are as follows: column packing material: silica gel; column temperature: room temperature; and eluent: mixed solvent including 30% of ethyl acetate and 70% of toluene. The desired product is eluted through the column when using a mixed solvent including 30% of ethyl acetate and 70% of toluene as an eluent. An IR analysis shows that the product recovered has a formula of C 18 H 37 —CH(CH 2 COO(CH 2 ) 2 (CF 2 ) 8 F)COOH. 5.0 g of thionyl chloride was added to 33 g of purified C 18 H 37 —CH(CH 2 COO(CH 2 ) 2 (CF 2 ) 8 F)COOH and heated under reflux at 50° C. to effect a reaction for 2 hours. After completion of the reaction, the resultant reaction mixture was concentrated to recover a desired product. An IR analysis shows that the product recovered has a formula of C 18 H 37 —CH(CH 2 COO(CH 2 ) 2 (CF 2 ) 8 F)COCl. Next, 6.5 g of 2,3-naphthalenediol {C 10 H 6 (OH) 2 } was added to purified C 18 H 37 —CH(CH 2 COO(CH 2 ) 2 (CF 2 ) 8 F)COCl and heated under reflux at 100° C. to effect a reaction for 2 hours. After completion of the reaction, the resultant reaction mixture was dissolved in 200 ml of toluene, and placed in a separatory funnel and washed with 300 ml of a 10% aqueous NaOH solution twice and then with an aqueous solution of sodium chloride twice, and the toluene phase was recovered and dried using magnesium sulfate. After one hour, the magnesium sulfate was removed by filtration, and the toluene phase was concentrated. Then, the substance recovered was purified by column chromatography. Conditions for the column are as follows: column packing material: silica gel; column temperature: room temperature; and eluent: toluene. The desired product is eluted through the column when using toluene as an eluent. The weight of the product recovered was 34 g, and the recovery rate was about 70%. An IR analysis shows that the product recovered has a formula of C 18 H 37 —CH(CH 2 COO(CH 2 ) 2 (CF 2 ) 8 F)COOC 10 H 6 OH. Synthesis Example 2 Synthesis of C 18 H 37 —CH(CH 2 COO(CH 2 ) 2 (CF 2 ) 8 F)COOC 10 H 7 An acid chloride having a formula of C 18 H 37 —CH(CH 2 COO(CH 2 ) 2 (CF 2 ) 8 F)COCl was synthesized in the same manner as in Synthesis Example 1. Next, 5.9 g of 1-naphthol (C 10 H 7 OH) was added to purified C 18 H 37 —CH(CH 2 COO(CH 2 ) 2 (CF 2 ))COCl 8 and heated under reflux at 100° C. to effect a reaction for 2 hours. After completion of the reaction, the resultant reaction mixture was dissolved in 200 ml of toluene, and placed in a separatory funnel and washed with 300 ml of a 10% aqueous NaOH solution twice and then with an aqueous solution of sodium chloride twice, and the toluene phase was recovered and dried using magnesium sulfate. After one hour, the magnesium sulfate was removed by filtration and the toluene phase was concentrated. Then, the substance recovered was purified by column chromatography. Conditions for the column are as follows: column packing material: silica gel; column temperature: room temperature; and eluent: toluene. The desired product is eluted through the column when using toluene as an eluent. The weight of the product recovered was 34 g, and the recovery rate was about 70%. An IR analysis shows that the product recovered has a formula of C 18 H 37 —CH(CH 2 COO(CH 2 ) 2 (CF 2 ) 8 F)COOC 10 H 7 . By employing the above-described procedure, the substituent R, partially-fluorinated-alkyl group (Rf), and substituent X in formula (2) can be arbitrarily selected to synthesize a partially-fluorinated-alkyl compound of the present invention. Specific examples of the partially-fluorinated-alkyl compounds synthesized are shown in Table 6 below. TABLE 6 Succinic acid derivative Compound having Rf Compound having X Weight Yield Desired product C8H17C4H3O3 F(CF2)8CH2CH2OH 1-Naphthol 28 g 70% C8H17—CH(CH2COO(CH2)2 10.5 g 23.2 g 5.9 g (CF2)8F)7COOC10H7 C12H25C4H3O3 F(CF2)8CH2CH2OH 1-Naphthol 31 g 70% C12H25—CH(CH2COO(CH2)2 13.5 g 23.2 g 5.9 g (CF2)8F)7COO C10H7 C18H35C4H3O3 F(CF2)8CH2CH2OH 1-Naphthol 34 g 70% C18H35—CH(CH2COO(CH2)2 17.5 g 23.2 g 5.9 g (CF2)8F)7COOC10H7 C18H37C4H3O3 F(CF2)8CH2CH2OH 2,3-Naphthalenediol 34 g 70% C18H37—CH(CH2COO(CH2)2 17.7 g 23.2 g 6.5 g (CF2)8F)COOC10H6 OH C18H37C4H3O3 F(CF2)8(CH2)6OH 2,3-Naphthalenediol 35 g 70% C18H37—CH(CH2COO(CH2)2 17.7 g 26.0 g 6.5 g (CF2)8F)COO C10H6OH C18H37C4H3O3 F(CF2)8(CH2)11OH 2,3-Naphthalenediol 31 g 60% C18H37—CH(CH2COO(CH2)2 17.7 g 29.5 g 6.5 g (CF2)8F)COO C10H6OH C18H37C4H3O3 C18H37OH 2,3-Naphthalenediol 29 g 75% C18H37—CH(CH2COOC18 17.7 g 13.5 g 6.5 g H37)COO C10H6OH C18H37C4H3O3 C18H35OH 2,3-Naphthalenediol 29 g 75% C18H37—CH(CH2COOC18 17.7 g 13.4 g 6.5 g H37)COO C10H6OH C18H37C4H3O3 F(CF2)8CH2CH2OH Phenol 32 g 70% C18H37—CH(CH2COOCH2 17.7 g 23.2 g 4.3 g CH2(CF2)8)COO C6H5 C18H37C4H3O3 F(CF2)8CH2CH2OH 9-Anthracenemethanol 30 g 60% C18H37—CH(CH2COOCH2 17.7 g 23.2 g 6.5 g CH2(CF2)8) COO CH2C14H9 C18H37C4H3O3 F(CF2)8CH2CH2OH 4-Hydroxypyridine 26 g 55% C18H37—CH(CH2COOCH2 17.7 g 23.2 g 5.0 g CH2(CF2)8) COO C5H4N C18H37C4H3O3 F(CF2)8CH2CH2OH o-Cresol 25 g 50% C18H37—CH(CH2COOCH2 17.7 g 23.2 g 5.0 g CH2(CF2)8) COOC6H4CH3 C18H37C4H3O3 F(CF2)8CH2CH2OH 4-Aminophenol 25 g 50% C18H37—CH(CH2COOCH2 17.7 g 23.2 g 6.0 g CH2(CF2)8) COO C6H4NH C18H37C4H3O3 F(CF2)8CH2CH2OH 4-Fluorophenol 25 g 50% C18H37—CH(CH2COOCH2 17.7 g 23.2 g 6.0 g CH2(CF2)8) COO C6H4F C18H37C4H3O3 F(CF2)8CH2CH2OH 4-Hydroxybenzoic 25 g 50% C18H37—CH(CH2COOCH2 17.7 g 23.2 g acid CH2(CF2)8) COO 5.5 g C6H4COOH C18H37C4H3O3 F(CF2)8CH2CH2OH 4-Phenylphenol 33 g 70% C18H37—CH(CH2COOCH2 17.7 g 23.2 g 6.0 g CH2(CF2)8) COO C6H4C6H5 Examples 1 to 2–7 Partially-fluorinated-alkyl compounds of the present invention having the structures shown in Table 7 below were individually synthesized in accordance with the same procedure as in the above Synthesis Examples, and, with respect to each of the compounds synthesized, the tests shown below in respect of lubricant were conducted. TABLE 7 Succinic acid Compound having Example derivative Rf Compound having X 1 C 8 H 17 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 2 C 10 H 21 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 3 C 12 H 25 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 4 C 14 H 29 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 5 C 16 H 33 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 6 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 7 C 18 H 35 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 1-Naphthol 8 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 (CH 2 ) 6 OH 2,3-Naphthalenediol 9 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 (CH 2 ) 11 OH 2,3-Naphthalenediol 10 C 18 H 37 C 4 H 3 O 3 C 18 H 37 OH 2,3-Naphthalenediol 11 C 18 H 37 C 4 H 3 O 3 C 18 H 35 OH 2,3-Naphthalenediol 12 C 18 H 17 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 13 C 10 H 21 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 14 C 12 H 25 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 15 C 14 H 29 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 16 C 18 H 33 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 17 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 18 C 9 H 19 CH(C 7 H 15 )C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 19 C 18 H 35 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 2,3-Naphthalenediol 20 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH Phenol 21 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 9-Anthracenemethanol 22 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 4-Hydroxypyridine 23 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH o-Cresol 24 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 4-Aminophenol 25 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 4-Fluorophenol 26 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 4-Hydroxybenzoic acid 27 C 18 H 37 C 4 H 3 O 3 F(CF 2 ) 8 CH 2 CH 2 OH 4-Phenylphenol Comparative Examples 1 to 5 With respect to each of the compounds having the structures shown in Table 8 below, the tests shown below in respect of lubricant were conducted. TABLE 8 Comp. Exp. Compound 1 C 18 H 37 NH 2 2 C 8 F 17 (CF 2 ) 10 COOCH 3 3 C 18 H 37 CH(COOC 12 H 25 )C 2 H 4 COOCH 2 CF 2 (OCF 2 ) p [OCF(CF 3 )CF 2 ] q OCF 3 (average molecular weight: 2,140) 4 C 18 H 37 CH(COOH)CH 2 COOCH 2 CF(CF 3 )[CF(CF 3 )CF 2 O] 3 F 5 C 11 H 23 COORfOCOC 11 H 23 (Rf represents a perfluoropolyether chain having an average molecular weight of 2,000) Preparation of Sample Tape Co was deposited on a polyethylene terephthalate film having a thickness of 7.0 μm by a vapor deposition process to form a magnetic layer having a thickness of 180 nm consisting of a metallic, magnetic thin film. Then, a carbon film layer having a thickness of about 8 nm was formed on the magnetic layer using a magnetron sputtering apparatus. Next, on another surface of the polyethylene terephthalate film that is not the surface on which the magnetic layer was formed, a back coat layer having a thickness of 0.5 μm consisting of carbon and a polyurethane resin was formed. Then, the compounds shown in Tables 7 and 8 were individually dissolved in toluene, and the resultant solutions were individually applied to the surface of the carbon film layer previously formed so that the coating weight of each compound became5 mg/m 2 . The magnetic recording media obtained were individually cut into 6.35 mm-width tapes to obtain sample tapes. Evaluation of Durability and Transport Properties With respect to each of the thus prepared sample tapes, a coefficient of friction, still durability, and shuttle durability were measured under, respectively, conditions at a temperature of 40° C. at a relative humidity of 80%, conditions at a temperature of −5° C., and conditions at a temperature of 40° C. at a relative humidity of 20%. The results are shown in Table 9. It is considered that the conditions for measurements used in the Examples are most severe conditions for use with respect to each tape. In the measurements of the still durability and shuttle durability, a commercially available digital video camcorder (manufactured and sold by Sony Corporation; trade name: VX1000) was used. (1) Method for Measurement of Coefficient of Friction The coefficient of friction was measured as follows. In a thermostatic chamber controlled at a temperature of 40° C. at a relative humidity of 80%, each sample tape was subjected to 100-cycle transport by means of an apparatus for measuring a coefficient of friction. The measurement values after the 100th-cycle transport are shown as coefficient of friction in the Table below. (2) Method for Measurement of Still Durability The still durability was measured as follows. In a thermostatic chamber at −5° C., a period of time until the replay output was lowered by 3 dB was measured. (3) Method for Measurement of Shuttle Durability The shuttle durability was measured as follows. In a thermostatic chamber controlled at a temperature of 40° C. at a relative humidity of 20%, each sample tape having a length corresponding to 60 minutes was subjected to 100-cycle transport in a Play mode, and a value (dB) was determined by subtracting the replay output after the 100th-cycle transport from the initial output. Evaluation of Solubility in Solvent With respect to each of the lubricants used in Examples 1 to 27 and Comparative Example 3, the solubility in solvents, i.e., ethanol, acetone, and toluene was examined. The solubility was evaluated in accordance with the following criteria: a lubricant easily dissolved in the solvent was rated symbol ∘; and a lubricant insoluble in the solvent was rated symbol ×. The results of the evaluation of solubility of the lubricants are shown in Table 10 below. TABLE 9 Coefficient Still durability Shuttle of friction (min) durability (dB) (40° C., 80% RH) (−5° C.) (40° C., 20% RH) Exp. 1 0.25 >120 −2.0 Exp. 2 0.25 >120 −1.9 Exp. 3 0.25 >120 −2.0 Exp. 4 0.23 >120 −1.8 Exp. 5 0.21 >120 −1.7 Exp. 6 0.21 >120 −1.7 Exp. 7 0.21 >120 −1.5 Exp. 8 0.21 >120 −1.5 Exp. 9 0.21 >120 −1.5 Exp. 10 0.21 >120 −2.1 Exp. 11 0.21 >120 −2.2 Exp. 12 0.25 >120 −2.0 Exp. 13 0.25 >120 −1.9 Exp. 14 0.23 >120 −1.8 Exp. 15 0.20 >120 −1.7 Exp. 16 0.20 >120 −1.6 Exp. 17 0.20 >120 −1.5 Exp. 18 0.20 >120 −2.2 Exp. 19 0.20 >120 −2.0 Exp. 20 0.20 >120 −1.8 Exp. 21 0.20 >120 −1.8 Exp. 22 0.20 >120 −1.8 Exp. 23 0.20 >120 −1.9 Exp. 24 0.20 >120 −1.8 Exp. 25 0.22 >120 −1.6 Exp. 26 0.22 >120 −1.6 Exp. 27 0.20 >120 −1.7 Comp. Exp. 1 0.20 3 −6.0 Comp. Exp. 2 0.35 50 −5.0 Comp. Exp. 3 0.32 >120 −5.0 Comp. Exp. 4 0.25 10 −2.3 Comp. Exp. 5 0.45 100 −2.5 TABLE 10 Compound Ethanol Acetone Toluene Exps. 1 to 27 ∘ ∘ ∘ Comp. Exp. 3 x x x As is apparent from the above results, when the partially-fluorinated-alkyl compound of the present invention is used as a lubricant for magnetic recording medium, very excellent results are obtained such that the coefficient of friction and deterioration of the still durability and shuttle durability are extremely small under various conditions for use, e.g., at a high temperature at a high humidity, at a high temperature at a low humidity, or at a low temperature. While the present invention has been particularly shown and described with reference to preferred embodiments according to the present invention, it will be understood by those skilled in the art that any combinations or sub-combinations of the embodiments and/or other changes in form and details can be made therein without departing from the scope of the invention.
To provide a lubricant for recording medium, which is advantageous not only in that it maintains excellent lubricity under various conditions for use and excellent lubricating effect over a long time, but also in that it can impart excellent transport properties and excellent abrasion resistance as well as excellent durability. For example, when C 18 H 37 —CH(CH 2 COOC 10 H 6 OH)COORf (wherein Rf represents a saturated or unsaturated partially-fluorinated-alkyl group) is used as a lubricant for magnetic recording medium, there can be obtained a magnetic recording medium having excellent transport properties and excellent abrasion resistance as well as excellent durability.
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