A polysilicon thin film transistor, a manufacturing method thereof, an array substrate involve display technology field, and can repair the boundary defect and the defect state in polysilicon, suppress the hot carrier effect and make the characteristics of TFTs more stable. The polysilicon thin film transistor includes a gate electrode, a source electrode, a drain electrode and an active layer, the active layer comprises at least a channel area, first doped regions, second doped regions and heavily doped regions, and the first doped regions are disposed on two sides of the channel area, the second doped regions are disposed on sides of the first doped regions away from the channel area; the heavily doped regions are disposed on sides of the second doped regions opposed to the first doped regions; and dosage of ions in the heavily doped regions lies between that in the first doped regions and that in the second doped regions.

A liquid crystal display with low-temperature polysilicon thin film transistors (LTPS-TFTs) has merits of high resolution, fast response speed, high luminance, high aperture ratio, etc. Due to the characteristics of LTPS, LTPS-TFTs have high electron mobility. In addition, a peripheral drive circuit can also be produced on a glass substrate of the LCD together with a pixel array, so as to achieve goals of system integration, space saving and cost reduction for a drive IC, and this may decrease yield of products as well.
With the development trend toward miniaturization, an LTPS-TFT has become more and more small gradually. However, because the power supply voltage and the working voltage of the LTPS-TFT are not reduced to a great degree correspondingly, the electric field intensity in operation is increased consequently, which leads to increasing of motion rate of electrons. In this case, when the energy of electrons is high enough, the electrons will leave a substrate and tunnel into a gate oxide layer, which phenomenon is called as a hot carrier effect. This effect will cause the threshold voltage of an N-type metal oxide semiconductor (NMOS) to increase, or the threshold voltage of P-type metal oxide semiconductor (PMOS) to decrease, thus affecting characteristic parameters of a MOS, such as threshold voltage (VT), transconductance (gm), sub-threshold slope (St), saturation current (Idsat), etc. This results in degradation of characteristics of an MOS, and brings about a long-teim reliability problem.
In a fabrication process of a traditional LTPS-TFT array substrate, heavy doping on a polysilicon layer is included, namely, an ion implantation is conducted so as to form source and drain regions (SD). Owing to a higher doping concentration, source and drain regions are very close to a gate electrode, and it will produce a strong electric field in the vicinity of source and drain regions and result in the hot carrier effect. When TFTs are turned off, leakage current (off-state current) is overlarge, so that the performance of TFTs is very unstable.
At present, in order to decrease a leakage current, it is usually required that a light doping process be conducted on the drain region, so as to reduce the leakage current by way of decreasing the electric field at the boundary of the drain electrode. For example, one fabrication method comprises the following steps.
Step S101, as illustrated in FIG. 1, a polysilicon layer is formed on a substrate 10, and then it is formed to be an active layer through one patterning process, and the active layer comprises a channel area 200 and first patterns 201 located on two sides of the channel area, as well as third patterns 203 located on the sides of the first patterns 201 away from the channel area 200.
S102, as illustrated in FIG. 2, a gate insulating layer 30 is formed on the substrate 10, and a first photoresist pattern 401 corresponding to the channel area 200 and the first patterns 201 is formed.
S103, as illustrated in FIG. 3, a first ion implantation process is conducted to form heavily doped regions 2031 at the location of the third patterns 203, and then the first photoresist pattern 401 is removed.
S104, as illustrated in FIG. 4, after completion of the above steps, a gate electrode 50 positioned over the channel area 200 is formed, and a second ion implantation process is conducted, so as to form lightly doped regions 2011 at the location of the first patterns 201.
S105, as illustrated in FIG. 5, on the substrate subjected to the above steps, a protection layer 60, a source electrode 701 and a drain electrode 702, and a pixel electrode 801 electrically connected to the drain electrode 702 are formed.
Although the leakage current can be suppressed to a certain extent by the above method, it still has such problems that the effect is not good enough, the boundary defect is high, and so on.

Polysilicon thin film transistor and manufacturing method thereof, array substrate

ORDOS YUANSHENG OPTOELECTRONICS CO., LTD.


The system has a predetermined number of semiconductor memory devices with a commonly shared data input/output bus and a processor which controls operations of the predetermined number of semiconductor memory devices with a clock signal, a read/write control signal and a chip selection control signal, wherein the predetermined number of devices respectively comprise: a predetermined number of groups of data input/output drivers for inputting data from outside and outputting the data to outside in response to an internal output control signal; control means for generating a first state of a first control signal in response to a first state of a clock signal of a following cycle when a clock signal, a read/write control signal and a chip selection control signal is inputted from outside to transmit a read command to a previous cycle and when a write or non-selection command is transmitted to a current cycle, and for generating a second state of a second control signal in response to the first state of the clock signal when a write or non-selection command is transmitted to the previous cycle and when a read command is transmitted to the current cycle; and a predetermined number of repeaters for controlling in groups the predetermined number of groups of data input/output drivers by generating an internal output control signal which shifts to the first state of the second control signal in response to the second state thereof and which shifts to the second state of the first control signal in response to the first state thereof, thereby rapidly transmitting an internal output control signal for controlling data output drivers and preventing data conflict on the data buses.

1. Field of the Invention
The present invention relates to a semiconductor memory device and system, and more particularly to a semiconductor memory device which can make a progress in transmission of an internal control signal which might be delayed due to the load on a data line and which can prevent data conflict on a data bus when data is transmitted to the data bus located between semiconductor memory devices and a processor.
2. Description of the Related Art
A conventional semiconductor memory device generates an internal output control signal by inputting an output control signal from outside, transmits it to data output drivers connected to respective data input/output pins to enable or disable outputting of data. Therefore, the single internal output control signal is used as a control signal for a plurality of data output drivers.
In this case, the time for transmitting the internal output control signal is delayed because of the load on the data transmission line because the internal output control signal is transmitted to a plurality of data output drivers.
Accordingly, in case that the semiconductor memory device is operating at a low speed, a margin is sufficiently secured between the input/output data so that it can be negligible that the transmission of the internal output control signal is delayed. On the other hand, in case that the semiconductor memory device is operating at a high speed, a margin is not so sufficiently provided between the input/output data that it becomes impossible for the device to successfully drive at a high speed.
Furthermore, the system having the conventional semiconductor memory device is constructed with two semiconductor memory devices sharing a data bus and a processor. In the system, data is transmitted via the data bus when the two semiconductor memory devices are enabled or disabled by the processor.
When the system constructed with semiconductor memory devices sharing the data bus is operating at a low speed, the margin is provided between the input/output data transmitting on the data bus so sufficiently that data conflict may be available. However, when the system is operating at a high speed, the margin is not sufficiently secured between the input/output data transmitting on the data bus so that data conflict may happen.
In other words, in the operations to output data from the two semiconductor memory devices commonly connected to a data bus, after the data output driver completes transmitting data to the data output pin of the one semiconductor memory device and is disabled, but before the data inputted at the data bus is completely transmitted to the processor, if the data output driver is enabled to transmit data to the data output pin of the other semiconductor memory device and transmit the data to the commonly shared data bus, data conflict may happen on the data bus.
In order to solve the aforementioned problems, a technique titled "clocked logic circuitry preventing double driving on shared data bus" has been disclosed to add a dummy cycle at every time that the drivers driving the data bus are changed. In other words. That is, after the driver operated at the previous cycle is disabled, a dummy cycle is added to complete disabling the driver and to enable another driver operating at the current cycle. However, there is a disadvantage in the aforementioned method in that the additional dummy cycle lowers the efficiency of the data bus to make it impossible to apply at a system operating at a high speed.
Also, another technique titled "driver for tri-state bus" has been disclosed at U.S. Pat. No. 5,646,553 to solve the aforementioned problem. Data is transmitted to the data bus during the first half cycle of a clock signal, and the data is then kept there during the second half cycle thereof. However, there is also a problem in this method in that an additional consideration should be made in the course of designing the system to provide all the data buses with keepers which include latches to keep the transmitted data on the data buses.
The present invention is disclosed to solve the aforementioned problem as the data conflict on the shared data bus in the prior art is caused because there is only one internal output control signal for controlling the data output drivers of the semiconductor memory devices and because the single control signal simultaneously controls all the data output drivers connected to the data input/output pins, which increases the load on the data line so greatly as to slow down the speed of transmitting the control signal.
The aforementioned problems can also be solved by mismatching the size of transistors located on the path which generates the internal output control signal to thereby speed up the time for enabling or disabling the internal output control signal. However, if the time for enabling the internal output control signal is shortened, data conflict may happen on the system with the shared data bus. On the other hand, if the time for disabling the internal output control signal is shortened, it may be impossible to make the system operate at a high speed because the time for accessing data lags in spite of one advantage of preventing the data conflict on the shared data bus.
On the other hand, the time for enabling and disabling the internal output control signal can be shortened by using an identically big transistors on the path to generate the internal output control signal. However, in this case the size of all the transistors which generate the internal output control signal increases to proportionally influence on the switching current, and the increased current load slows down the speed of transmitting the signal more adversely than when the size of transistors is mismatched.


An improved sled for recreational use. The sled comprises a support member which is formed in the shape of a seat to accommodate a rider in an upright position. The support member has handholds at either edge for the rider to grasp. A block of ice is coupled to the bottom side of the support member. The ice is held in place by an adjustable retention member. The retention member is made up of two support blocks which are rigidly attached to the support member. A compression block is adjustably connected to each of the support blocks by means of a locking screw disposed through the support blocks. As the screw is turned, the compression blocks move inwardly clamping the ice. In alternative embodiments of the retention member, the locking screws are replaced by springs which automatically force the support blocks inward and pieces of flexible foam rubber are used to hold the ice block in place.

During the winter months, a popular recreational activity for children and adults, is riding a sled down snow-covered hillsides. Naturally, this activity can only be practiced in an area where the climate is cold enough to allow for snowfall. Consequently, many people in areas with a warm climate are unable to enjoy this activity unless they travel to colder climates or mountainous areas.
A common form of sled that is used in the prior art typically consists of a flat surface mounted on top of runners. These runners are typically made of metal and have a sharpened edge which rides along the surface of the snow. The edges are sharpened in order to minimize the amount of friction between the sled and the hillside. Since small children often use sleds, the sharpened runners can pose a threat of injury. This injury can occur simply when a child handles the sled in an improper manner. Even more dangerous situations can arise when a person riding the sled allows the sled to get out of control, and collides with another person on the hillside.


The invention relates to a method of controlling the thermal balance of the reaction shaft of a suspension smelting furnace and to a concentrate burner for feeding reaction gas and pulverous solid mater into the reaction shaft of the suspension smelting furnace. In the method, endothermic material (16) is fed by the concentrate burner (4) to constitute part of the mixture formed from the powdery solid matter (6) and reaction gas (5), so that a mixture containing the powdery solid matter (6), reaction gas (5) and endothermic material (6) is formed in the reaction shaft (2). The concentrate burner (4) comprises cooling agent feeding equipment (15) for adding the endothermic material (16) to constitute part of the mixture, which is formed from the pulverous solid matter (6) that discharges from the orifice (8) of the feeder pipe and the reaction gas (5) that discharges through the annular discharge orifice (14).

The object of the invention is a method of controlling the thermal balance of the reaction shaft of a suspension smelting furnace.
Another object of the invention is a concentrate burner for feeding a reaction gas and pulverous solid matter into the reaction shaft of the 10 suspension smelting furnace.
The invention relates to the method that takes place in the suspension smelting furnace, such as a flash smelting furnace, and to the concentrate burner for feeding the reaction gas and pulverous solid matter into the reaction shaft of the suspension smelting furnace, such as flash the smelting furnace.
The flash smelting furnace comprises three main parts: a reaction shaft, a lower furnace and an uptake. In the flash smelting process, the pulverous solid matter that comprises a sulphidic concentrate, slag forming agent and other pulverous components, is mixed with the reaction gas by means of the concentrate burner in the upper part of the reaction shaft. The reaction gas can be air, oxygen or oxygen-enriched air. The concentrate burner comprises normally a feeder pipe for feeding the pulverous solid matter into the reaction shaft, where the orifice of the feeder pipe opens to the reaction shaft. The concentrate burner further comprises normally a dispersing device, which is arranged concentrically inside the feeder pipe and which extends to a distance from the orifices of the feeder pipe inside the reaction shaft and which comprises dispersion gas openings for directing a dispersion gas to the pulverous solid matter that flows around the dispersing device. The concentrate burner further comprises normally a gas supply device for feeding the reaction gas into the reaction shaft, the gas supply device opening to the reaction shaft through an annular discharge orifice that surrounds the feeder pipe concentrically for mixing the said reaction gas that discharges from the annular discharge orifice with the pulverous solid matter, which discharges from the middle of the feeder pipe and which is directed to the side by means of the dispersion gas. The flash smelting process comprises a stage, wherein the pulverous solid matter is fed into the reaction shaft through the orifice of the feeder pipe of the concentrate burner. The flash smelting process further comprises a stage, wherein the dispersion gas is fed into the reaction shaft through the dispersion gas orifices of the dispersing device of the concentrate burner for directing the dispersion gas to the pulverous solid matter that flows around the dispersing device, and a stage, wherein the reaction gas is fed into the reaction shaft through the annular discharge orifice of the gas supply device of the concentrate burner for mixing the reaction gas with the solid matter, which discharges from the middle of the feeder pipe and which is directed to the side by means of the dispersion gas.
In most cases, the energy needed for the melting is obtained from the mixture itself, when the components of the mixture that is fed into the reaction shaft, the powdery solid matter and the reaction gas react with each other. However, there are raw materials, which do not produce enough energy when reacting together and which, for a sufficient melting, require that fuel gas is also fed into the reaction shaft to produce energy for the melting.
At present, there are various known alternatives of correcting upwards the thermal balance of the reaction shaft of the suspension smelting furnace, i.e., raising the temperature of the reaction shaft of the suspension smelting furnace to prevent the reaction shaft of the suspension smelting furnace from cooling. There are not many known ways of correcting downwards the thermal balance of the reaction shaft of the suspension smelting furnace, i.e., lowering the temperature of the reaction shaft of the suspension smelting furnace. One known method is to decrease the feed, i.e., to feed a lesser amount of concentrate and reaction gas into the reaction shaft, for example. For the sake of productivity, it would also be good to succeed in decreasing the thermal balance without decreasing the feed.
The patent specification WO 2009/030808 presents a concentrate burner.

Method of controlling the thermal balance of the reaction shaft of a suspension smelting furnace and a concentrate burner


A device for mounting the headrail of a vertical Venetian blind and for holding a valance to the headrail in which a bracket has the valance mounted on it and carries a rearwardly extending arm which is engageable in a rearwardly extending channel formed in a clip body. The clip can be hooked on to and snap in to elongate recesses in the front and rear flanges of the headrail and the clip carries members which mount the clip, the headrail and the bracket to a support thereabove. The clip also carries detents which engage in holes in the rearward arm of the bracket so that the position of the valance can be adjusted.

The present invention relates to vertical Venetian blinds.
Various forms of vertical Venetian blinds have been proposed and diverse systems for holding these blinds to a support are known. It is very often advantageous with vertical Venetian blinds to have a valance which extends in front of the headrail, the valance having a more pleasing appearance than the headrail itself and covering the headrail and the support arrangement.
One particular form of headrail for a vertical Venetian blind includes a member of generally inverted channel cross-section having an upper web and front and rear flanges. The flanges each have, adjacent the upper web, an elongate recess which extends along the length of the headrail which is conveniently formed by extrusion, for example from aluminium. This structure of headrail while convenient for the purpose for which it is intended, is rather unsightly and a valance is most advantageous, therefore. The arrangements for holding the valance and for holding the Venetian blind are rather cumbersome and do not enable the headrail and valance to be mounted easily.

Valance bracket for vertical venetian blind


A connector is configured to be connected to a syringe assembly provided with at least one syringe having an outer cylinder with a protruding tube-shaped port, and a holder which holds the syringe. The connector includes a connector main body mountable on a container containing a medical solution; a tube-shaped fitting section protruding from the upper section of the connector main body for receiving the syringe to connect the inside of the syringe and the inside of the container when the syringe port is fitted in the fitting section; and fixing means having a lock mechanism that fixes the syringe assembly to the connector main body when the syringe port is fitted in the fitting section, an operating section to release the fixed state provided by the lock mechanism, and a push-out section that pushes out the syringe assembly when the fixing releasing operation is performed.

In medical facilities, to perform drop injection into a patient, or to administer an anti-adhesive material, a living tissue adhesive or the like into a patient, or the like, a medical solution may be used by drawing the solution from a medical solution container in which it is contained through use of a syringe. In such a situation, the medical solution container and the syringe are interconnected through a connector. An example of a connector is disclosed in Japanese Patent Laid-Open No. 2004-97253.
The connector described in this document includes a tube-like fitting section for having a port of a syringe fitted therein, and a needle which communicates with the fitting section and pierces a rubber stopper mounted to a port of the medical solution container. The connector thus configured is used by piercing the rubber stopper of the medical solution container with the needle to connect the connector with the solution container. In this condition, the port of the syringe is fitted into the fitting section so as to load the syringe with the medical solution.
In the connector, however, the connection with the port of the syringe is based on the fitting structure, so that the problem of difficult disconnection of the syringe from the connector can arise when the fitting is unsatisfactory, for example. Besides, in the case where the fitting force is excessively high in magnitude, an attempt to disconnect the syringe from the connector may be followed by a situation in which the disconnection is very difficult or impossible to achieve.

This patent is subject to a terminal disclaimer.

Connector, syringe assembly, and connector for mixing


An image forming method is disclosed, comprising exposing a silver halide photographic material through a transparent, high definition-screening original and developing the photographic material with a developer to form a halftone dot image, wherein:. the photographic material forms a halftone dot image having a dot area of 57% or less when exposed, through the transparent original comprising a halftone dot image having a dot area of 50%, in two times an amount that gives a halftone dot having a dot area of 50%; and the photographic material has a maximum density of 3.0 or more and a contrast of 8.0 or more;. and wherein the photographic material is exposed to light having an emission peak at a wavelength of 360 to 450 nm and developed with a developer having a pH of 10.5 or less.

Recently, there have been actively undertaken research and development of high definition printing in the field of printing arts. Ordinary printed-pictures are comprised of halftone dots having a line-number of 175 lines per inch, which are liable to produce a moire or Roset pattern. To avoid these problems and make a printed image close to a photographic image, there have increased high definition prints having a high screen frequency. (Hereinafter, unless otherwise noted, the high definition printing material indicates one comprised of a screen frequency of 400 lines/inch or more.)
In printing a conventional roomlight-handling photographic material in contact with a film which has been printed by a scanner, for example, at 600 lines/inch, the dot percentage is excessively increased before reaching a required density because contrast thereof is liable to be varied. Accordingly, in printing further on a presensitized plate, if an original dot density is low, no small dot is produced so that an unnatural image was produced. Liability to contrast variation becomes larger with an increase of the line number because variation of dot percentage versus exposure amount becomes larger due to increased total circular length of dots.
In the high definition printing, a small dot area is smaller and a minimum density portion of a large dot becomes smaller, as compared to the case of printing at 175 lines/inch. Accordingly, in a low contrast photographic material, a density of the small dot is lowered and a large dot becomes filled-in so that an exposure latitude becomes narrow. Therefore, in a contact printing process of high definition screening printing, there has been desired a roomlight handling material having a high contrast and little liability to variation thereof.
Processing of a silver halide photographic material is carried out conventionally by use of a automatic processor with replenishing of processing solutions from the view-points of stability, rapidness, easiness and handling. In a developer for processing a black and white photographic material, dihydroxybenzenes have been employed as a developing agent. In practice, the dihydroxybenzenes have been advantageously used for development of most black and white photographic material from the view points of photographic activity, stability, availability, handling and cost. However, the dihydroxybenzenes are undesirable for human body as they are allergic.
Therefore, there has been strongly desired development of a developer free from the dihydroxybenzenes. U.S. Pat. No. 5,236,816, for example, discloses a developer containing ascorbic acid in place of the dihydroxybenzene.
Photographic processing waste liquor is not allowed to be released to a public sewer since it contains an undesirable component; therefore, the waste liquor is collected and subjected to decomposition treatment by a troublesome and expensive combustion technique. In view thereof, there has been desired reduction of photographic processing waste liquor. As a means for solving these problems, there was proposed reduction of a replenishing amount in processing with a processor. However, the reduction of the replenishing amount tends to accumulate unnecessary reaction products resulted from processing in a processing bath of the processor. Particularly, a silver salt dissolved out from a photographic material precipitates on the surface of the photographic material to form metalic silver, which causes stain due to so-called silver sludge.
There has been desired a lower replenishing rate from the view points of low cost and low waste liquor. The processing amount per day of roomlight films is much larger than that of photographic films for camera and scanner so that super-rapid processing has been demanded. However, processing at a low replenishing rate or super-rapid processing has led to deterioration in processing stability.


An ink tank includes a housing and an ink absorbing member accommodated in the housing. The ink absorbing member is constructed using a water jet cutter. The ink absorbing member is a thermosetting foamed block having a porous three-dimensional divergent circuit network; the foamed block is molded of a condensate comprising a compound having an amino group and a formaldehyde. The foamed block is formed for placement in the housing by actuating the water jet cutter and worked by actuating the water jet cutter to provide slits or holes in the ink absorbing member different from pores of the foamed block.

1. Field of the Invention
The present invention relates to an ink tank, a head cartridge including the ink tank and an ink jet head integrated with each other, and an ink jet printing apparatus including the ink tank and the head cartridge for performing a printing operation with them. More particularly, the present invention relates to the structure of the ink tank of the type having an ink absorbing member accommodated therein for the purpose of ink retaining.
Here, the printing operation represents all type of operations each to be performed for a various kind of ink receiving medium such as a cloth, a thread, a paper, a sheet-like material or the like so as to allow ink to be adhesively secured thereto. Therefore, the present invention can be applied to a printing apparatus, i.e., a printer serving as an information outputting apparatus operatively associated with a various kind of information processing apparatus.
2. Description of the Related Art
Many foamed blocks each molded of a polyurethane resin are hitherto used as an ink absorbing member to be accommodated in an ink tank of the foregoing type. In the case that a urethane foamed block is used as an ink absorbing member, films are formed in the foamed block during each molding operation in such a manner as to wrap each of a number of voids (pores) in the foamed block with a film. Thus, since the voids are isolated from each other due to the presence of the film between adjacent voids, the foamed block can not exhibits a function of absorbing ink therein as it is. To cope with this problem, the foamed block is subjected to film removing treatment via heating, cleaning and others. However, it is very difficult to completely remove films in the foamed block with the film removing treatment as mentioned above. In most cases, a considerable amount of residue practically adheres to each void or pore on completion of the film removing treatment.
In the case that the urethane foamed block is used as the ink absorbing member, it is usually accommodated in the ink tank in the compressed state. In addition, to assure that an adequate intensity of negative pressure acts on a communicating portion between the foamed block and a connecting member for an ink outflow portion while maintaining a certain pressure gradient across the foregoing communicating portion, a part of the foamed block is usually compressed at the communicating portion. However, since film residues remaining between adjacent voids or pores are liable to overlap in the foamed block, there arise malfunctions that ink hardly flows in the ink absorbing member, and moreover, ink fails to be fed outside of the ink tank.
On the other hand, in contrast with the urethane foamed block, an ink absorbing member comprising a foamed block molded of a condensate composed of a melamine and a formaldehyde is described in an official gazette of, e.g., International Patent Laid-Open Publication NO. WO 91/02652. The ink absorbing member as described in the above official gazette is molded in the form of a skeleton having no thin film in each gap present in the circuit network of the foamed block while assuming a net-shaped structure. Thus, the ink absorbing member composed of a melamine foamed block has many advantages that any type of film removing treatment is not required, a large quantity of ink can storably be received in the melamine foamed block owing to the presence of a number of fine fibers constituting the circuit network compared with the urethane foamed block, initial ink filling treatment can easily be conducted owing to an excellent hydrophilic property of the melamine foamed block in contrast with the urethane foamed block having a water repelling property, no ink remains in the melamine foamed block having no film formed therein due to the presence of a residue on completion of ink consumption, and the ink in the melamine foamed block can completely be utilized at a high efficiency.
Basically, it is preferable that the ink absorbing member composed of a melamine foamed block which is disclosed in the above-stated gazette is practically used in the compressed state, and ink is fed to an ink outflow portion disposed at the lower part of an ink tank by the function of the gravity force of ink itself. Thus, the ink feeding direction orienting toward the ink outflow portion is firmly determined to coincide with the downward direction. For this reason, there arises a problem that an attitude to be assumed at the time of practical use of the ink tank described in the official gazette is restrictively determined. In addition, in the case that the ink absorbing member is accommodated in the ink tank in the preferably employable uncompressed state, it is difficult that the ink absorbing member is brought in close contact with the inner wall surface of the ink tank. Thus, a gap is liable to appears between the ink absorbing member and the inner wall surface of the ink tank. When the atmospheric air taken through an atmospheric air communication port or an ink ejecting port of an ink jet head stays in the gap, there arises a malfunction that as ink is ejected from the ink jet head, a bubble is involved in the ink fed to the ink jet head, causing a quality of printed image to be remarkably degraded. Especially, with respect to an ink jet recording apparatus of the type including an ink tank and an ink jet head integrated with each other to perform a printing operation by reciprocably scanning the integrated structure composed of the ink tank and the ink jet head relative to a printing medium, there readily arises a problem that the ink tank is vibratively displaced due to the reciprocable scanning of the foregoing integrated structure. In the case that the ink jet printing apparatus is adversely affected by the vibrative displacement of the ink tank or in the case that the ink tank includes a member at the position located in the vicinity of an ink outflow portion, when a part of the ink absorbing member located in the vicinity of the ink outflow portion exhibits deterioration in terms of properties as time elapses, a gap is liable to appear at the above-noted part of the ink absorbing member. At this time, it is anticipated that the adverse influence given to the ink absorbing member due to staying of air at the gap becomes more remarkable. In an extreme case, it is preestimated that the atmospheric air communicating portion and the gap located in the vicinity of the ink outflow portion are communicated with each other. Once such a malfunction as mentioned above has arose, it becomes impossible to perform a desired ink ejecting operation, and moreover, the ink present in an ink feeding path leaks from an ink ejecting port, causing the interior of the ink jet printing apparatus to be contaminated with the leaked ink.
Since feeding of ink to the ink outflow portion is achieved by utilizing the gravity force of the ink itself, when an ink jet head is driven at a high frequency highly desired in recent years, there is a possibility that the ink feeding can not follow the driving of the ink jet head at a high frequency. To improve a property of followability of the ink jet head at the driving of the latter at a high frequency, it is thinkable that a pore size is enlarged to some extent and a magnitude of resistance against flowing of the ink is reduced. In this case, however, there is a possibility that an ink retaining capability of the ink absorbing member is degraded, causing ink to leak from the atmospheric air communicating port.
According to the description of the official gazette of the prior invention, in some case, it is desirable that a certain intensity of compressing force is applied to a foamed structure for the ink absorbing member in a specific application example of the ink jet printing apparatus in order to maintain useful or suitable properties of the ink absorbing member in the uncompressed state, and moreover, adjust a gap space of the foamed structure.
It is considered that the description of the official gazette was made in consideration of the relationship between inner dimensions of the accommodating space and outer dimensions of the ink absorbing member. The inventors of the present invention conducted a variety of examinations and as a result derived from the examinations, they found that it was acceptable that the ink absorbing member was properly compressed in order to assure that ink could smoothly and reliably be fed to the ink absorbing member regardless of an attitude assumed by the ink tank while utilizing advantages of the ink absorbing member molded of a condensate composed of a melamine and a formaldehyde. In addition, the inventors found the following technical problems to be solved. Specifically, one of the problems is that the ink absorbing member should be compressed corresponding to the structure of the ink absorbing member in a certain adequate direction in order to assure that ink can smoothly be fed to the ink absorbing member, other one is that so-called warpage or breakage is liable to occur at a compressible part of the ink absorbing member having a comparative brittle fibrous structure, and another one is that once the warpage has occurred with the ink absorbing member, the compressed state of the latter can not be maintained any more, resulting in the ink absorbing member assuming an uncompressed state.
In addition, a filter is usually disposed at the ink outflow portion for removing foreign materials involved in the ink fed from the ink absorbing member, and an opening area of the ink outflow portion is determined corresponding to a quantity of ink to be fed therefrom. However, since the thermosetting melamine based condensate is brittle in structure, a part of the condensate is peeled away from the ink outflow portion when the ink absorbing member is worked, accommodated in the ink tank or put in later practical use, and the filter is clogged with fractured pieces of the condensate. In this connection, the inventors found another technical problem to be solved at this time, i.e., a problem that a desired quantity of ink to be fed could not be assured with the ink absorbing member. These technical problems mentioned above is not described in the official gazette.

Ink tank with ink absorbing member having particular holes or slits


A mobile object combination detection apparatus includes a plurality of moving image input units, a plurality of mobile object detection units each connected to one of the moving image input units, and a combination determination unit. Each of the plurality of mobile object detection unit detects a mobile object at a predetermined position on a moving image inputted thereto from the moving image input unit, and sends detection information to the combination determination unit. The combination determination unit compares the detection information of the mobile object sent thereto from each of the mobile object detection unit with a predetermined condition to determine that a target mobile object is detected-when the detection information satisfies the predetermined condition.

1. Field of the Invention
The present invention relates generally to an apparatus for detecting mobile objects from a moving image inputted from a camera, and more particularly to an apparatus and method which combine information detected from a plurality of moving images or information detected from a plurality of locations in a single moving image for detection of invaders, measurement of speed or the like.
2. Description of the Related Art
At present, a variety of places such as roads, railroad crossings, service floors in banks, or the like are monitored through video images produced by cameras. These are provided for purposes of eliminating traffic jams and obviating accidents and crimes by monitoring objects (mobile objects) in such particular places. There is extremely high needs for monitoring such mobile objects through video images. However, the current video monitoring still cannot go without resorting to intervention of man power due to technical problems. Thus, automated monitoring processing through a computer or the like is needed in view of the situation mentioned.
As a previously proposed method of detecting a mobile objects, U.S. Pat. No. 5,721,692 describes xe2x80x9cMOVING OBJECT DETECTION APPARATUS.xe2x80x9d This patent realizes detection and extraction of a mobile object and a reduction in video processing time with a complicated background. A method employed in this patent will be explained below with reference to FIG. 2.
In FIG. 2, frame images F1 (241) to F5 (245) represent frame images of a video inputted from time T1 (221) to time T5 (225). A line segment S (231) drawn in each frame image of FIG. 2 specifies a target area to be monitored within the input video as a line segment. Hereinafter, this linear target area is referred to as the slit. Pairs in images 201 to 205 in FIG. 2 each represent an image on the slit S (hereinafter referred to as the slit image) and a background image from time T1 (221) to time T5 (225). In this example, a background image at the beginning of the processing is set to be an image of the target area to be monitored when no mobile object has been imaged by the camera.
This method performs on each frame image the following processing steps of: (1) extracting a slit image and a background image in a particular frame; (2) calculating the amount of image difference between the slit image and the background image by an appropriate method such as that for calculating the sum of squares of differences between pixel values in the images or the like; (3) tracing the amount of image difference in a time sequential manner to determine the existence of a mobile object if the amount of image difference transitions along a V-shaped pattern; and (4) determining that the background image has been updated when the amount of image difference has not varied for a predetermined time period or more and has been flat.
The foregoing step (3) will be explained in detail with reference to a sequence of frame images in FIG. 2. As shown in this example, when an object crosses the slit, the amount of image difference transitions along a V-shaped curve as illustrated in an image changing amount graph (211) of FIG. 2. First, before the object passes the slit (time T1 (221)), the image on the slit S and the background image are substantially the same (201), thus producing a small amount of image difference. Next, as.the object begins crossing the slit (time T2 (222)), the slit image becomes different from the background image (202) to cause an increase in the amount of image difference. Finally, after the object has passed by the slit (time T3 (223)), the amount of image difference again returns to a smaller value. In this way, when an object crosses the slit S, the amount of image difference exhibits a V-shaped curve. It can be seen from the foregoing that a V-shaped portion may be located to find a mobile object, tracing the amount of image difference in a time sequential manner. In this example, the V-shaped portion is recognized to extend from a point at which the amount of image difference exceeds a threshold value a (213) to a point at which the amount of image difference subsequently decreases below the threshold value a (213).
Next, the foregoing step (4) will be explained with reference again to the sequence of frame images in FIG. 2. As shown in this example, when a baggage (252) or the like is left on the slit (time T4 (224)), the amount of image difference increases. However, the amount of image difference remains at a high value and does not vary (from time T4 (224) to time T5 (225)) since the baggage (252) remains stationary. In this method, when the amount of image difference presents a small fluctuating value for a predetermined time period, a slit image at that time is employed as an updated background.
As explained above, since U.S. Pat. No. 5,721,692 can use a line segment as a target area for which the monitoring is conducted, a time required to calculate the amount of image difference can be largely reduced as compared with an earlier method which monitors an entire screen as a target area. Also, since this method can find the timing of updating the background by checking time sequential variations of the amount of image difference, the monitoring processing can be applied even to a place at which the background can frequently change, such as an outdoor video or the like.
However, when the above-mentioned prior art method is simply utilized, the following problems may arise.
A first problem is that only one target area for monitoring can be set on a screen.
A second problem is the inabilities of highly sophisticated detection and determination based on the contents of a monitored mobile object, such as determination on a temporal relationship of detecting times of a mobile object, determination on similarity of images resulting from the detection, and so on.
A mobile object combination detection apparatus according to the present invention comprises a plurality of sets of a unit for inputting a video and a unit for detecting a mobile object from the input video, a mobile object combination determination unit for combining mobile object detection results outputted from the respective sets to determine the mobile object detection results, and a unit for outputting the detected results.
When each of the mobile object detection unit detects an event such as invasion of a mobile object, an background update, and so on, the mobile object detection unit outputs mobile object detection information including an identifier of the mobile object detection unit, detection time, the type of detected event, and an image at a slit used for determining the detection. The mobile object combination determination unit determines final detection of a mobile object through total condition determination from the information outputted from the respective mobile object detection units.

Mobile object combination detection apparatus and method


The present invention provides recombinant polypeptides derived from CMV glycoprotein gB and truncated fragments thereof which contain at least one epitope which is immunologically identifiable with one encoded by the CMV genome. The complete characterization of the gB protein, including the identity of glycoprotein gp55, permits the production of polypeptides which are useful as standards or reagents in diagnostic tests and/or as components of vaccines. This invention provides recombinant polypeptides and recombinant polynucleotides encoding these polypeptides wherein a neutralizing epitope of gB is localized within gp55.

Human cytomegalovirus (CMV) is a ubiquitous agent in human populations. Infections are generally asymptomatic, but there can be serious medical manifestations of the disease in immunocompromised individuals (transplant recipients and AIDS patients) and in congenitally infected newborns. In immunodeficient patients, primary CMV infection and reactivation of latent virus is associated with serious disease including retinitis and pneumonia. CMV infection also predisposes the patient to fungal and bacterial infections. Congenital CMV infection of the fetus occurs in about 1% (36,000) of infants born in the U.S. per year. Of these infants 10-20% will have symptomatic infection at birth or within two years of birth with a mortality rate of 10-15%. Among the survivors, many will have mild to severe neurologic complications including hearing loss, learning disabilities and mental retardation.
Vaccines that prevent or reduce CMV-associated disease are clearly needed. The CMV (Towne) strain has been tested as a vaccine candidate in normal individuals and renal transplant patients (Quinnan, Jr., G. V. et al. (1984) Am Intern Med 101:478-483); (Plotkin, S. A. 1985, CMV Vaccines, In: The Herpes Viruses vol. 4, ed., Roizman and Lopez, Plenum Press, N.Y., p. 297-312). While this vaccine appeared to have no deleterious effects and did reduce symptoms of CMV disease in transplant recipients, there are many objections to the use of experimental live attenuated virus vaccines, including the possibility of immune impairment resulting from virus infection and reports of possible association between CMV and oncogenesis.
In the absence of a complete understanding of the biology of CMV, the most rational approach to a vaccine would involve the development of subunit vaccines based upon the surface glycoproteins of the virus using recombinant viral glycoproteins which elicit neutralizing antibodies.
Like other herpesviruses, CMV specifies multiple glycoproteins (Stinski, M. (1976) J Virol 19:594-609; Pereira, L., et al. (1982) Infect Immun 36:933-942). Characterization of these have involved studies of CMV-infected cells and purified virions using polyclonal and monoclonal antibodies (Pereira, L., et al. (1984) Virology 139:73-86; Britt, W. J. (1984) Virology 135:369-378; Nowak, B., et al. (1984) Virology 132:325-338; Law, K.M., et al. (1985) J Med Virol 17:255-266; Rasmussen, L., et al. (1984) Proc Natl Acad Sci USA 81:876-880; and Britt and Auger (1986) J Virol 58:185-191).
U.S. Pat. No. 4,689,225, issued Aug. 25, 1987 and based upon the work described in the Pereira et al. references, supra, describes a method and vaccine for CMV infections using a polypeptide designated therein as glycoprotein A (gA1-A7) of cytomegalovirus. Two glycoproteins designated p130 (gp130) and p55 (gp55) (based on the molecular weights given in kilodaltons) have been partially purified and shown to elicit a neutralizing response in guinea pigs (Rasmussen, L., et al. (1985) J Virology 55:274-280). The gp130 glycoprotein appears to be a precursor to the gp55 glycoprotein.
The gB gene from CMV strain AD169 (which appears to be similar to the pl30 CMV protein described by Rasmussen et al., supra) has been identified by nucleotide sequencing (Cranage, M. P. et al. (1986) EMBO J 5(11):3057-3063) with a 906 amino acid protein deduced therefrom. The gB gene product was expressed in recombinant vaccinia virus and rabbits immunized with this gene product produced antibodies that immunoprecipitate gB from CMV-infected cells and neutralize CMV infectivity in vitro (See also WO 87/05326).
Although there is much ongoing activity towards both the identification of major gylcoproteins which are the targets for viral neutralization and the development of a subunit CMV vaccine, to date, the origin of the gp55 CMV glycoprotein has not been established nor has gp55 been identified by nucleotide or amino acid sequence and therefore, no vaccine composed of the 55,000 dalton recombinant viral gB protein or any truncated recombinant polypeptide thereof has been reported. Clearly, in light of the absence of a complete understanding of the biology of CMV, it would be desirable to provide a safe, effective and economic vaccine capable of affording protection against cytomegalovirus infections, as well as to provide diagnostic reagents capable of detecting the particular immunogenic stimulus resulting from CMV infections.
Disclosure of the Invention
The present invention provides recombinant polypeptides derived from the 55,000 dalton protein derived from gB and truncated fragments thereof which contain an epitope which is immunologically identifiable with one encoded by the CMV genome. A recombinant polypeptide derived from the gp55 CMV glycoprotein gB is provided in one embodiment of the invention.
The complete characterization of the gp55 protein derived from gB permits the production of polypeptides which are useful as standards or reagents in diagnostic tests and/or as components of vaccines. Since the desired polypeptide can be synthetically made in a relatively pure form or by recombinant DNA technology, the problems with other methods of immunogen and vaccine manufacture, including coproduction of competitive antigens and contaminants, are avoided.
In a preferred embodiment of the invention, the truncated gp55 gB fragment contains an epitope that is immunologically reactive with a CMV neutralizing antibody. The neutralizing antibody can be generated by techniques known in the art such as that described for monoclonal antibodies disclosed in Rasmussen et al., supra and U.S. Pat. No. 4,689,225.
Also provided in another preferred embodiment of the invention is a recombinant polypeptide encoded within CMV glycoprotein gB, which has a modified endoproteolytic cleavage site such that cleavage of the gB protein is effectively inhibited. The modification of the cleavage site is accomplished using site specific mutagenesis on the DNA encoding the polypeptide at or near the proteolytic cleavage site. Related to this aspect of the invention are the polynucleotides encoding the recombinant polypeptides.
Another aspect of the invention is a recombinant gp55 polynucleotide comprising a nucleotide sequence derived from the CMV gB gene. Related to this aspect of the invention are truncated recombinant polynucleotides containing regions encompassing nucleotides 1381 through 2040 of gp55 and nucleotides 1381 through 1938 of gp55, which regions contain an epitope which is immunologically reactive with a CMV neutralizing antibody.
Yet another aspect of the invention provides an expression system comprising host cells transformed with a vector containing the recombinant polynucleotides of the invention.
Another aspect of the invention provides a vaccine or prophylactic agent against human cytomegalovirus infection, said vaccine comprising a recombinant gp55 polypeptide derived from the CMV gB genome or the endoproteolytic cleavage site modified gB polypeptide in amounts effective to elicit viral neutralizing activity against cytomegalovirus when administered to a susceptible individual.
Still another aspect of the invention provides a vaccine against human cytomegalovirus infection, said vaccine comprising a recombinant polypeptide derived from a truncated fragment encoded within CMV glycoprotein gB wherein the truncated fragment contains an epitope which is immunologically reactive with a CMV neutralizing antibody, said recombinant polypeptide being present in an immunologically acceptable carrier in an amount effective to elicit viral neutralizing activity against cytomegalovirus when administered to a susceptible individual.
Another aspect of the invention provides for a DNA hybridization assay for detecting CMV homologous sequences in a biological sample comprising: a) incubating a biological sample with a DNA probe, which probe may be optionally labeled with an enzyme, radioactive tag or a fluorescent tag, under conditions which promote the formation of DNA duplexes, wherein said DNA probe is derived from gp55 nucleotide sequences; and b) detecting the formed DNA duplexes containing the DNA probe.
A further aspect of the invention provides an immunoassay for detecting antibodies directed against a CMV antigen in a biological specimen comprising:
(a) incubating a biological sample with a probe polypeptide under conditions which allow the formation of an antibody-antigen complex, wherein said probe polypeptide consists of the p55 CMV recombinant protein or a truncated fragment thereof and said protein or truncated fragment contains an epitope which is immunologically reactive with a CMV-neutralizing antibody; and
(b) detecting an antibody-antigen complex containing the probe antigen.
Yet another aspect of the invention provides polyclonal antibodies against the recombinant gp55 or truncated polypeptides thereof, for immune prophylaxis.
Other and further aspects of the present invention will be apparent from the following description and claims and other embodiments of the invention employing the same or equivalent principles may be used by those skilled in the art without departing from the present invention and the purview of the appended claims.

Method to detect CMV by hybridization with a gp55 specific DNA probe


A quenching vessel being, in use, vertically elongated and provided with an inlet for gas at its upper end, an outlet for cooled gas at its lower end defining a pathway for a gas flow directed downwardly, the vessel being provided at its upper end with a first internal tubular wall part which wall part has an opening fluidly connected to the inlet for gas and wherein the tubular wall part is connected at its lower end with a divergent conical part having walls which are inclined outwardly in the direction of the pathway for gas, wherein an arrangement of more than one nozzle for atomisation and spraying a liquid quench medium in a downward direction into the pathway for the gas flow are present in the space enclosed by the divergent conical part.

Such a vessel is known from US-A-2006/0260191. In FIG. 4 of this publication a gasification reactor is shown for gasification of a solid carbonaceous feedstock to obtain a synthesis gas mixture having a temperature of between 1200 and 1800° C. The reactor has an outlet for hot synthesis gas at its upper end and an outlet for slag at its lower end. The reactor itself is provided with a quenching means to lower the temperature in a first step to a temperature below the solidification point of the non-gaseous components as present in the synthesis gas. The synthesis gas is further reduced in temperature by injecting a mist of water into the flow of synthesis gas in a separate quenching vessel connected to the gasification reactor by means of a duct. An advantage of the quenching vessel is that the design of such a vessel can be much simpler than a waste heat boiler having multiple heat exchanger banks. A further advantage is that a synthesis gas may be obtained which contains water at a level lower than the saturation content. This makes it possible to obtain a substantially cooled synthesis gas from which ash can be separated using a filter as for example described in EP-B-1178858 or by using a cyclone.
JP-A-53110967 describes a quenching vessel wherein a quenching medium is injected into a downwardly flowing gas under an angle.
Applicants have found however that the design of the vessel as shown in FIG. 4 of US-A-2006/0260191 or the design of JP-A-53110967 has certain disadvantages. A major concern regarding these designs is that ash, as one of the non-gaseous components as present in the synthesis gas, can form deposits on the vessel walls at downstream points relative to the position where water is injected.


A color measurement apparatus includes a color measurement portion, a carriage, and a movement mechanism the color measurement portion starts color measurement after a predetermined initialization process, a moving section between patches from a point P1 to a point P3 overlaps an initialization section where the spot moves at the time of performing the initialization process, and the moving section between the patches is a section between a forward point having a distance as a radius of the spot with respect to the X direction and a backward point having a distance as a radius of the spot with respect to the X direction, based on a boundary of the patches.

1. Technical Field
The present invention relates to a color measurement apparatus and a printing apparatus.
2. Related Art
A technology is known in which a printing apparatus prints a color chart as an aggregation of multiple patches and measures a color of each of the patches in the color chart using a color measurement portion. In this technology, there is a case in which a size of the patch in the color chart affects a result of the measured color. For example, in a case in which the size of patch is small, it is not easy to purely obtain only the color of the patch as a target to be measured. On the other hand, in a case in which the size of the patch is large, printing of the color chart takes a long time, and loss of ink or paper is also increased.
Here, a technology is known in which printing is performed many times by changing a size of a target patch, a color of the printed patch is measured, and the smallest (optimum) size of the target patch is determined based on an obtained value of the measured color, or the like (refer to JP-A-2010-201845).
However, a color measurement portion emits a spot of the light having a certain size, and measures a color of the patch using the reflected light of the spot. As the color measurement portion, there is a type of the color measurement portion which needs a predetermined initialization process before measuring the color of one of the patches.
As seen from the above, when the spot having a certain size is positioned at a boundary of the adjacent patches, the reflected light of the spot includes other colors other than a color of the patch to be a target, whereby the color thereof cannot accurately measured. In addition, the initialization process hinders reduction of a time necessary for measuring the color.

Wavelength variable interference filter and driving method of the wavelength variable interference filter


The invention relates to an ultrahigh contrast photographic material comprising a support bearing a silver halide emulsion layer, containing a combination of two or more hydrazide nucleating agents in the emulsion layer and/or a hydrophilic colloid layer, characterized in that the combination comprises a nucleating agent(s) of formulae (I) and/or (I) with a nucleator of formula (III), in which the nucleating agent of formula (I) comprises (a) two nicotinamide moieties, which may be the same or different, which are linked by a linking group, and (b) a hydrazide moiety linked to only one of those nicotinamide moieties; the nucleating agent of formula (II) comprises a dimeric molecule comprising two monomers linked by a linking group, each monomer of which (a) may be the same or different and (b) comprises a hydrazide moiety and a nicotinamide moiety; and the nucleating agent of formula (III) comprises an aryl sulfonamido aryl hydrazide.

This invention relates to high contrast photographic silver halide materials containing a combination of hydrazide nucleating agents and in particular to those materials of the graphic arts type.
In the field of graphic arts, an ultrahigh contrast photographic material is required for achieving satisfactory halftone dot reproduction of a continuous tone or reproduction of a line image in the process of making a lithographic printing plate. For many years these ultrahigh contrast photographic images were obtained by developing a xe2x80x98lithxe2x80x99 emulsion (usually high in silver chloride content) in a hydroquinone, low sulphite, xe2x80x98lithxe2x80x99 developer by the process known as infectious development. However, such low sulphite developers are inherently unstable and are particularly inappropriate for machine processing.
More recently an image formation system providing ultrahigh contrast where the gamma (contrast) exceeds 10 has been provided conventionally in a material wherein silver halide bearing a surface latent image is developed in the presence of a hydrazine (also known as a nucleating agent), specifically an acylhydrazine, which can be incorporated into the photographic material or into the developer. The pH of the developer solution is usually in the range 10.0 to 12.3, typically about 11.5, and the developer includes conventional amounts of sulphite, hydroquinone and possibly metol or a pyrazolidone. While such a process is better than the low sulphite xe2x80x98lithxe2x80x99 process, the developer still has a high pH requirement for it to function correctly. Such a solution is not as stable as is desirable. Additionally, high pH solutions are environmentally undesirable because of the care needed in handling and disposing of the effluent.
Unfortunately, light sensitive materials whose contrast is enhanced by the presence of a hydrazine nucleating agent show large variations in their photographic properties as the developer is exhausted or through the course of time, for example as the pH of the developer varies and in particular as the pH is lowered. The pH of the developer can vary for a number of reasons: for example, exhaustion and absorption of carbon dioxide causes the pH to drop whilst air oxidation causes the pH to rise, as can concentration through evaporation.
Also during development of silver halide materials, particularly those which use chlorobromide emulsions, there is a release of bromide locally into area of the development as a consequence of the development process to convert silver halide to elemental silver. Both of these effects can influence the development rate of the film and give rise to process unevenness or variability during the processing run. There is an overall effect that shows up as a change to the developer component levels in solution but there is also a local effect that occurs within the developing layer and is exposure dependent. These effects can also depend on the formulation of the developer used and overcoming these problems can increase tolerance to a wider range of developer formulations.
It is also known that a developer solution having a pH below 11 can be employed by using certain hydrazides active at this pH. Hydrazides proposed for such use are described, for example, in U.S. Pat. Nos. 4,278,748; 4,031,127; 4,030,925,4,323,643, 4,988,604 and 4,994,365 and in EP-A-0 333435. A nucleator containing both a hydrazide moiety and a nicotinamide moiety is disclosed in U.S. Pat. No. 5,288,590. However the use of these nucleating agents does not entirely remove sensitivity to both bromide and pH.
A nucleating agent which comprises a dimeric molecule comprising two monomers linked by a linking group, each monomer of which (a) may be the same or different and (b) comprises a hydrazide and a nicotinamide moiety has been disclosed in EP-A-1 008 902. A nucleating agent comprising (a) two nicotinamide moieties, which may be the same or different, which are linked by a linking group, and (b) a hydrazide moiety linked to only one of those nicotinamide moieties, either alone or together with the nucleating agent comprising the dimeric molecule, has been described in EP Patent application No. 01201989.9. U.S. Pat. Nos. 4,988,604 and 4,994,365 describe aryl sulfonamidophenyl hydrazide nucleating agents that are capable of high contrast development.
Developer solutions with these low pHs can also be used by the introduction of a contrast-promoting agent (commonly called a booster) to give adequate activity. The booster can be incorporated into the photographic layer or may be dissolved in the developer solution. The booster may be, for example, one of the boosters as described in U.S. Pat. No. 5,316,889 or an amine booster as described in U.S. Pat. Nos. 4,269,929; 4,668,605, 4,740,452, 4,975,354 or EP-A-0 364166. Compounds bearing different functionalities e.g. phosphonium and pyridinium, have also been shown to be active, as described in U.S. Pat. No. 5,744,279.
The design of nucleators and boosters is continuing to develop by varying their structures to fine tune the performance of the system and to enhance image quality and process stability during the running of a process. U.S. Pat. No. 5,328,801 describes the use of an inhibitor releasing redox compound suitable for nucleated systems. The problems associated with processing unevenness are described in U.S. Pat. No. 5,882,841.
The problem is therefore to provide nucleators for incorporation into a photographic material which has improved processing evenness through a reduced sensitivity to variations in the developer pH and bromide level which occur in the film during development and which exhibits greater tolerance to a wider range of developers.
It has been found that these objectives can be achieved by the use of a combination of nucleating agent(s) of formulae (I) and/or (II) with a nucleating agent of formula (III), in which the nucleating agent of formula (I) comprises (a) two nicotinamide moieties, which may be the same or different, which are linked by a linking group, and (b) a hydrazide moiety linked to only one of those nicotinamide moieties; the nucleating agent of formula (II) comprises a dimeric molecule comprising two monomers linked by a linking group, each monomer of which (a) may be the same or different and (b) comprises a hydrazide moiety and a nicotinamide moiety; and the nucleating agent of formula (III) comprises an aryl sulfonamido aryl hydrazide.
Such a combination of nucleating agents can lead to high contrast nucleation providing excellent processing evenness in a developer whose pH is variable and can give greater tolerance to a wide range of developer solutions.
According to the present invention therefore there is provided an ultrahigh contrast photographic material comprising a support bearing a silver halide emulsion layer, containing a combination of two or more hydrazide nucleating agents in the emulsion layer and/or a hydrophilic colloid layer, characterised in that the combination comprises a nucleating agent(s) of formulae (I) and/or (II) with a nucleator of formula (III), in which the nucleating agent of formula (J) comprises (a) two nicotinamide moieties, which may be the same or different, which are linked by a linking group, and (b) a hydrazide moiety linked to only one of those nicotinamide moieties; the nucleating agent of formula (II) comprises a dimeric molecule comprising two monomers linked by a linking group, each monomer of which (a) may be the same or different and (b) comprises a hydrazide moiety and a nicotinamide moiety; and the nucleating agent of formula (III) comprises an aryl sulfonamido aryl hydrazide.
In another aspect of the invention there is provided an ultrahigh contrast photographic material, as hereinbefore defined, which also contains in the emulsion layer or a hydrophilic colloid layer, a booster compound, as hereinafter defined.
In yet another aspect of the invention there is provided a process of forming a photographic image having ultrahigh contrast which comprises imagewise exposing a photographic material comprising a support bearing a silver halide emulsion layer and processing it with an alkaline developer solution, characterised in that it is developed in the presence of a combination of two or more hydrazide nucleating agents, comprising a nucleating agent of formula (I) and/or (II) with a nucleating agent of formula (III), optionally in the presence of a booster compound, as hereinafter defined.
The combination of nucleating agents for use in the invention show less sensitivity to variation in the development conditions than do the individual nucleating types.
This leads to significant improvements in processing robustness with reduced density variation across the length and width of processed sheets, making the processing more uniform and reducing the variation in the day-to-day running of the film and processor. There is less change in image quality with processing and tolerance to a wider range of developer solutions.
The nucleators of formula (I) for use in photographic materials of the invention preferably have one of the following general formulae:
wherein BG is a blocking group;
one of A1 and A2 is a hydrogen atom and the other is a hydrogen atom, an acyl group or an alkyl- or aryl-sulfonyl group, any of which groups may be substituted,
Z1 and Z2 are the same or different and each is a nicotinamide residue, at least one of which is positively charged;
Y is a substituted aryl or heterocyclic ring;
L is a linking group;
T is an anionic counterion
and n is 1 or 2.
The nucleators of formula (II) preferably have one of the following general formulae:
wherein each monomer linked by linking group L is the same or different;
Z is a positively charged nicotinamide residue; and
Y, A1, A2, BG, L and T are as defined for a compound of formula (I).
The nucleators of formula (III) preferably have the general formula:
wherein V and W are independently a substituted or unsubstituted arylene group;
r is 1 to 6;
R is selected from the class consisting of Sxe2x80x94Rxe2x80x2, wherein Rxe2x80x2 is an unsubstituted or substituted monovalent group comprising at least three ethyleneoxy units, and a positively charged pyridinium residue substituted with from 1 to 3 unsubstituted or substituted alkyl groups, with its associated cation;
and A1, A2 and BG are as defined for a compound of formula (I).
In a preferred embodiment in each of the formulae (I), (II) and (III) d A2 is a hydrogen atom.
More preferably the nucleating agent of formula (I) has one of the following formulae A, B or C, formula A being the most preferred:
More preferably the nucleating agent of formula (II) has one of the following formulae D, E or F, formula D being the most preferred:
More preferably the nucleating agent of formula (III) has one of the following formulae (G) or (H):
In these embodiments (A) to (H),
each R1CO comprises a blocking group and in particular each R1 is independently selected from a hydrogen atom and an unsubstituted or substituted alkyl, aryl, alkoxy, aryloxy, alkoxy- or aryloxy-carbonyl and alkyl- or aryl-aminocarbonyl group; or each R1 independently is or contains an unsubstituted or substituted heterocyclic group, having a 5- or 6-membered ring containing at least one nitrogen, oxygen or sulfur atom, wherein the ring may be linked either directly to the carbonyl group or via an alkyl, alkoxy, carbonyl, amino- or alkylamino-carbonyl group and wherein the ring may be fused to a benzene ring;
each R2 and each R3 is independently selected from hydrogen and an unsubstituted or substituted alkyl or aryl group and each p is independently 0 or 1;
each R4 and each R5 and each R6 is independently selected from hydrogen, halogen, hydroxy, cyano and an unsubstituted or substituted alkyl, aryl, heterocyclyl, alkoxy, acyloxy, aryloxy, carbonamido, sulfonamido, ureido, thioureido, semicarbazido, thiosemicarbazido, urethane, quaternary ammonium, alkyl- or aryl-thio, alkyl- or aryl-sulfonyl, alkyl- or aryl-sulfinyl, carboxyl, alkoxy- or aryloxy-carbonyl, carbamoyl, sulfamoyl, phosphonamido, diacylamino, imido or acylurea group, a group containing a selenium or a tellurium atom, and a group having a tertiary sulfonium structure;
each m is independently an integer from 0 to 4;
each q is independently an integer from 0 to 4;
each R7 is independently selected from hydrogen and an unsubstituted or substituted alkyl or aryl group;
each X is independently selected from C, Sxe2x95x90O and Cxe2x80x94NH;
each (link1) is a linking group independently selected from an unsubstituted or substituted alkylene, polyalkylene, aryl, arylaminocarbonyl or heterocyclyl group and each n is independently 0 or 1;
each (link2) is a linking group independently selected from an unsubstituted or substituted polyalkylene, polyalkylene oxide, polyalkylene containing one or more heteroatoms selected from nitrogen, oxygen and sulfur, separated from each other by alkylene groups, or an unsubstituted or substituted polyalkylene in which the alkylene groups are separated by an unsubstituted or substituted aryl or heterocyclic ring;
V is an unsubstituted or substituted phenylene or naphthalene group;
Rxe2x80x2 is an unsubstituted or substituted monovalent group comprising at least three ethyleneoxy units;
Rxe2x80x3 is an unsubstituted or substituted alkyl group;
r is 1 to 6;
s is 1 to 3
and
Txe2x88x92 is an anionic counterion.
The term xe2x80x98blocking groupxe2x80x99 refers to a group suitable for protecting the (hydrazine) group but which is readily removable when necessary.
It is preferred that R1 is a hydrogen atom or a group selected from unsubstituted or substituted alkyl, for example methyl, trifluoromethyl, 3-methylsulfonamidopropyl, methyl- or phenyl-sulfonylmethyl, carboxy-tetrafluoroethyl; unsubstituted or substituted aryl, for example phenyl, 3,5-di-chlorophenyl, o-methane-sulfonamidophenyl, 4-methanesulfonylphenyl, 2(2xe2x80x2-hydroxyethyl)phenyl, 2-hydroxy-4-methylphenyl, 2-hydroxymethylphenyl, o-hydroxybenzyl, hydroxyalkylbenzyl; a carbonyl-containing group, for example an alkylamino-, alkoxy-, aryloxy- or hydroxyalkylamino-carbonyl; or contains an imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyridyl, pyridinium, piperidinyl, morpholino, quinolinium or a quinolinyl group or R1 may include a group which splits off a photographically useful fragment, such as a phenylmercaptotetrazole or a 5-or 6-nitroindazole group. Examples of some of these are disclosed in U.S. Pat. No. 5,328,801.
More preferably in compounds of formulae (I) and (II) R1 contains a morpholino group and especially has the formula xe2x80x94CONH(CH2)n-morpholino, wherein n is 0-4 and is conveniently 3.
R2 and R3 are preferably hydrogen atoms or alkyl groups with p being preferably 1 and R4, R5 and R6 being preferably hydrogen, alkyl, alkoxy, alkylthio, trifluoromethyl or methylsulfonamido groups, with q being preferably 0 or 1 and m being preferably 0. R7 is preferably hydrogen or an alkyl group, optionally substituted with, for example, a dialkylamino group.
When X is Sxe2x95x90O or Cxe2x80x94NH it is preferred that n is 1 and that (link,) comprises an arylamino group or an arylaminocarbonyl group, preferably a phenylaminocarbonyl group, which may be substituted in the ring, for example, with one or more alkyl, carboxyl groups or halogen atoms. When X is C it is preferred that n is 0 such that no (link1) group is present.
The (link2) group preferably comprises a polyalkylene group comprising alkylene groups, preferably methylene groups, typically four or six, which may be separated by one or more O or S atoms. For example (link2) may be (CH2)4, (CH2)6, (CH2)2S(CH2)2 or (CH2)2O(CH2)2O(CH2)2. Alternatively (link2) may be a polyalkylene oxide chain extending from an even number of methylene groups such as (CH2CH2O)14CH2CH2 or may comprise, for example, a CHU2C6H4CH2 group.
In formula (III), both V and W may be substituted with one or more substituents such as, or example, an alkyl, halo, alkoxy, haloalkyl or alkoxyalkyl group. V and W are preferably each a phenylene group.
In formula (G) there are least three repeating ethyleneoxy units in Rxe2x80x2, more preferably from four to fourteen units and even up to fifty repeating ethyleneoxy units. In formula (H) the sum of the number of carbon atoms represented by Rxe2x80x3 is preferably at least 4, more preferably at least 8, each Rxe2x80x3 group preferably having from 1 to 12 carbon atoms.
The anionic counterion may be selected from any well known in the art and may typically be selected from Clxe2x88x92, Brxe2x88x92, Ixe2x88x92, CF3COOxe2x88x92, CH3SO3xe2x88x92 and TsOxe2x88x92.
As used herein and throughout the specification the term alkyl refers to an unsaturated or saturated straight or branched chain alkyl group (including alkenyl and aralkyl) having 1-20 atoms and includes cycloalkyl having 3-8 carbon atoms. The term aryl specifically includes fused aryl and the term heterocyclic specifically includes fused heterocyclic within its scope. The term polyalkylene is defined as the group (CH2)n wherein n is an integer from 2 to 50.
Unless otherwise specifically stated, substituent groups usable on molecules herein include any groups, whether substituted or unsubstituted, which do not destroy properties necessary for photographic utility.
When the term xe2x80x9cgroupxe2x80x9d is applied to the identification of a substituent containing a substitutable hydrogen, it is intended to encompass not only the substituent""s unsubstituted form, but also its form further substituted with any group or groups as herein mentioned.
Suitably, the group may be halogen or may be bonded to the remainder of the molecule by an atom of carbon, silicon, oxygen, nitrogen, phosphorus, or sulfur. The substituent may be, for example, halogen, such as chlorine, bromine or fluorine; nitro hydroxyl; cyano; carboxyl; or groups which may be further substituted, such as alkyl, including straight or branched chain alkyl, such as methyl, trifluoromethyl, ethyl, t-butyl, 3-(2,4-di-t-pentylphenoxy) propyl, and tetradecyl; alkenyl, such as ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di-t-pentylphenoxy)ethoxy, and 2-dodecyloxyethoxy; aryl such as phenyl, 4-t-butylphenyl, 2,4,6-trimethyl-phenyl, naphthyl; aryloxy, such as phenoxy, 2-methylphenoxy, alpha- or beta-naphthyloxy, and 4-tolyloxy; carbonamido, such as acetamido, benzamido, butyramido, tetradecanamido, alpha-(2,4-di-t-pentylphenoxy)-acetamido, alpha-(2,4-di-t-pentylphenoxy)butyramido, alpha-(3-pentadecylphenoxy)-hexanamido, alpha-(4-hydroxy-3-t-butylphenoxytetradecanamido, 2-oxo-pyirolidin-1-yl, 2-oxo-5-tetradecylpyrrolidin-1-yl, N-methyltetradecanamido, N-succinimido, N-phthalimido, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, and N-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino, 2,5-(di-t-pentylphenyl)carbonylamino,p-dodecyl-phenylcarbonylamino, p-toluylcarbonylamino, N-methylureido, N,N-dimethylureido, N-methyl-N-dodecylureido, N-hexadecylureido, N,N-dioctadecylureido, N,N-di-octyl-Nxe2x80x2-ethylureido, N-phenylureido, N,N-diphenylureido, N-phenyl-N-p-toluyl-ureido, N-(m-hexadecylphenyl)ureido, N,N-(2,5-di-t-pentylphenyl)-Nxe2x80x2-ethylureido, and t-butylcarbonamido; sulfonamido, such as methylsulfonamido, benzene-sulfonamido, p-toluylsulfonamido, p-dodecylbenzenesulfonamido, N-methyltetra-decylsulfonamido, N,N-di-propylsulfamoylamino, and hexadecylsulfonamido; sulfamoyl, such as N-methylsulfamoyl, N-ethylsulfamoyl, N,N-di-propylsulfamoyl, N-hexadecylsulfamoyl, N,N-dimethylsulfamoyl; N-[3-(do-decyloxy)propyl]-sulfamoyl, N-[4-(2,4-di-t-pentylphenoxybutyl]sulfamoyl, N-methyl-N-tetradecyl-sulfamoyl, and N-dodecylsulfamoyl; carbamoyl, such as N-methylcarbamoyl, N,N-dibutylcarbamoyl, N-octadecylcarbamoyl, N-[4-(2,4-di-t-pentylphenoxy)-butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl, and N,N-dioctylcarbamoyl; acyl, such as acetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl, p-dodecyloxy-phenoxycarbonyl, methoxycarbonyl, butoxycarbonyl, tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 3-pentadecyloxycarbonyl, and dodecyloxy-carbonyl; sulfonyl, such as methoxysulfonyl, octyloxysulfonyl, tetradecyloxy-sulfonyl, 2-ethylhexyloxysulfonyl, phenoxysulfonyl, 2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecyl-sulfonyl, phenylsulfonyl, 4-nonylphenylsulfonyl, and p-toluylsulfonyl; sulfonyloxy, such as dodecylsulfonyloxy, and hexadecylsulfonyloxy; sulfinyl, such as methyl-sulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl, 4-nonylphenylsulfinyl, and p-toluylsulfinyl; thio, such as ethylthio, octylthio, benzylthio, tetradecylthio, 2-(2,4-di-t-pentylphenoxy)ethylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, and p-tolylthio; acyloxy, such as acetyloxy, benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy, N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, and cyclohexylcarbonyloxy; amine, such as phenylanilino, 2-chloroanilino, diethylamine, dodecylamine; imido, such as 1 (N-phenylimido)ethyl, N-succinimido or 3-benzylhydantoinyl; phosphate, such as dimethylphosphate and ethylbutylphosphate; phosphite, such as diethyl and dihexylphosphite; a heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group, each of which may be substituted and which contain a 3 to 7-membered heterocyclic ring composed of carbon atoms and at least one hetero atom selected from the group consisting of oxygen, nitrogen and sulfur, such as 2-furyl, 2-thienyl, 2-benzimidazolyloxy or 2-benzothiazolyl; quaternary ammonium, such as triethylammonium; and silyloxy, such as trimethylsilyloxy.
If desired, the substituents may themselves be further substituted one or more times with the described substituent groups. The particular substituents used may be selected by those skilled in the art to attain the desired photographic properties for a specific application and can include, for example, hydrophobic groups, solubilizing groups, blocking groups, releasing or releasable groups and groups which adsorb to silver halide. Generally, the above groups and substituents thereof may include those having up to 48 carbon atoms, typically 1 to 36 carbon atoms and usually less than 24 carbon atoms, but greater numbers are possible depending on the particular substituents selected.
In some embodiments, the nucleators of the invention may be selected from the following:
The photographic material of the invention may also contain a booster compound to enhance the ultrahigh contrast and to promote activity. Alternatively the booster compound can be present in the developer solution.
One class of such boosters are amines which
(1) comprise at least one secondary or tertiary amino group, and
(2) have an n-octanol/water partition coefficient (log P) of at least one, preferably at least three, and most preferably at least four,
log P being defined by the formula:       log              xe2x80x83            P    =      log                      [                  X          octanol                ]                    [                  X          water                ]
wherein X is the concentration of the amino compound.
Preferably such an amine contains within its structure a group comprising at least three repeating ethyleneoxy units as described in U.S. Pat. No. 4,975,354. These units are preferably directly attached to the nitrogen atom of a tertiary amino group.
Included within the scope of the amino compounds that may be utilised in this invention are monoamines, diamines and polyamines. The amines can be aliphatic amines or they can include aromatic or heterocyclic moieties. Aliphatic, aromatic and heterocyclic groups present in the amines can be substituted or unsubstituted groups. Preferably, the amine boosters are compounds having at least 20 carbon atoms.
Preferred amino compounds for inclusion in photographic materials of the invention are bis-tertiary amines which have a partition coefficient of at least three and a structure represented by the formula:
R1R2N(CH2CH2O)nCH2CH2NR3R4
wherein n is an integer from 3 to 50, and more preferably 10 to 50;
R1, R2, R3 and R4 are, independently, alkyl groups of 1 to 8 carbon atoms, or
R1 and R2 taken together represent the atoms necessary to complete a heterocyclic ring, and/or R3 and R4 taken together represent the atoms necessary to complete a heterocyclic ring.
A particularly preferred booster for use in photographic materials of the invention or in the developer therefor is the booster B1 wherein in the above formula R1, R2, R3 and R4 are each n-propyl groups and n is 14, i.e. the structure:
Another preferred group of amino compounds is that of bis-secondary amines which have a partition coefficient of at least three and a structure represented by the formula:
RHN(CH2CH2O)nCH2CH2NHR
wherein n is an integer from 3 to 50, and more preferably 10 to 50, and
each R is, independently, a linear or branched, substituted or unsubstituted, alkyl group of at least 4 carbon atoms.
Particular amines suitable as booster compounds are listed in EP-A-0 364 166.
Other types of boosters are described in U.S. Pat. No. 5,744,279 as having one of the formulae:
(a) Y((X)nxe2x80x94Axe2x80x94B)M
wherein
Y is a group which adsorbs to silver halide,
X is a divalent linking group composed of hydrogen, carbon, nitrogen and sulfur atoms,
A is a divalent linking group,
B is an amino group that may be substituted or an ammonium group of a nitrogen-containing heterocyclic group,
m is 1,2 or 3 and
n is 0 or 1,
(b) R1R2Nxe2x80x94R3xe2x80x94(X)nxe2x80x94SMx
wherein
R1 and R2 are each hydrogen or an aliphatic group, or R1 and R2 may together form a ring,
R3 is a divalent aliphatic group,
X is a divalent heterocyclic ring having at least one nitrogen, oxygen or sulfur atom as heteroatom,
n is 0 or 1,
M is hydrogen or an alkali metal atom, alkaline earth metal atom, a quaternary ammonium, quaternary phosphonium atom or an amidino group, and
x is 1 when M is a divalent atom;
said compound optionally being in the form of an addition salt;
(c) a phosphonium structure as disclosed in col. 8 of U.S. Pat. No. 5,744,279 and as exemplified by the following formula:
or
(d) a pyridinium structure as disclosed in col. 21 of the aforementioned US patent as exemplified by the following formula:
The nucleators and optionally the booster compound can be incorporated in the photographic element, for example in a silver halide emulsion layer. Alternatively they can be present in a hydrophilic colloid layer of the photographic element, preferably a hydrophilic layer which is coated to be adjacent to the emulsion layer in which the effects of the nucleator are desired. They can however be present in the photographic element distributed between or among emulsion and hydrophilic colloid layers, such as undercoating layers, interlayers and overcoating layers.
The total amount of nucleating agent of formula (J) and/or (II) is from about 0.3 xcexcmol/m2 to 70 xcexcmol/m2, preferably 1 xcexcmol/m2 to 10 xcexcmol/m2, more preferably 2 xcexcmol/m2 to 7 xcexcmol/m2. The amount of nucleating agent of formula (III) is from about 0.14 xcexcmol/m2 to 70 xcexcmol/m2, preferably 0.7 xcexcmol/m2 to 14 xcexcmol/m2, more preferably 1.4 xcexcmol/m2 to 7 xcexcmol/m2. Preferably the ratio of the amount of a nucleating agent of formula (I) and/or (II): a nucleating agent of formula (III) is greater than 1.0, preferably greater than 1.5. Corresponding amounts for the booster are from 0 mol/m2 to about 1 mmol/m2, preferably 10 xcexcmol/m2 to 100 xcexcmol/m2, most preferably 30 xcexcmol/m2 to 100 xcexcmol/m2.
When a nucleating agent of formula (I) is in combination with a nucleating agent of formula (II), any relative proportions of the components may achieve the advantages of the invention. However preferably the amount of nucleating agent of formula (I): nucleating agent of formula (II) is in the range from about 10:90 to about 90:10, preferably from about 20:80 to about 80:20. Conveniently however for simplicity of synthesis the nucleating agent of formula (II) is produced in excess and generally the relative amounts of the components are then in the range about 10:90 to about 30:70.
The emulsions employed in photographic materials of the invention and the addenda added thereto, the binders, supports etc. may be as described in Research Disclosure Item 36544, September 1994, published by Kenneth Mason Publications, Emsworth, Hants, PO10 7DQ, United Kingdom, which will be identified hereinafter by the term xe2x80x9cResearch Disclosure.xe2x80x9d
The hydrophilic colloid may be gelatin or a gelatin derivative, polyvinylpyrrolidone or casein and may contain a polymer. Suitable hydrophilic colloids and vinyl polymers and copolymers are described in Section IX of the Research Disclosure. Gelatin is the preferred hydrophilic colloid.
The photographic materials may also contain an overcoat hydrophilic colloid layer which may also contain a vinyl polymer or copolymer located as the last layer of the coating (furthest from the support). It contains one or more surfactants to aid coatability and may also contain some form of matting agent. The vinyl polymer is preferably an acrylic polymer and preferably contains units derived from one or more alkyl or substituted alkyl acrylates or methacrylates, alkyl or substituted alkyl acrylamides, or acrylates or acrylamides containing a sulfonic acid group.
The photographic materials of the invention preferably contain an antihalation layer that may be on either side of the support, preferably on the opposite side of the support from the emulsion layer. In a preferred embodiment an antihalation dye is contained in the hydrophilic colloid underlayer. The dye may also be dissolved in or dispersed in the underlayer. Suitable dyes are listed in the Research Disclosure disclosed above.
The emulsions are preferably chemically sensitised, for example with both sulfur and gold. The latent-image forming grains can be bromoiodide, chlorobromoiodide, bromide, chlorobromide, chloroiodide or chloride, preferably chlorobromide. They should preferably be spectrally sensitised. More than one type of spectrally sensitised silver halide grain may be present and hence grains sensitised to different spectral regions may be present in the emulsion layer.
The coating may be made by blending two or more emulsion melts containing grains of the required spectral sensitivity, allowing the production of multi-wavelength sensitive products and giving rise to manufacturing cost advantages through both material and inventory reduction. Combining the different emulsion grains within one layer can give improvements in process sensitivity over multilayer graphics nucleated systems, as described in EP-A-0 682 288.
The silver halide grains may be doped with rhodium, ruthenium, iridium or other Group VIII metals either alone or in combination, preferably at levels in the range 10xe2x88x929 to 10xe2x88x923, preferably 10xe2x88x926 to 10xe2x88x923 mole metal per mole of silver. The grains may be mono- or poly-disperse. The preferred Group VIII metals are rhodium and/or iridium and ammonium pentachlororhodate may conveniently be used.
The present photographic materials are particularly suitable for exposure by red or infra-red laser diodes, light emitting diodes or gas lasers, e.g. a helium/neon or argon laser.
The light-sensitive silver halide contained in the photographic elements can be processed following exposure to form a visible image by associating the silver halide with an aqueous alkaline medium in the presence of a developing agent contained in the medium or the element. The photographic elements of this invention can be processed in conventional developers as opposed to specialised developers sometimes employed in conjunction with lithographic photographic elements to obtain very high contrast images. When the photographic elements contain incorporated developing agents the elements can be processed in the presence of an activator, which can be identical to the developer in composition, but otherwise lacking a developing agent.
Very high contrast images can be obtained at pH values below 11, preferably in the range of from 10.0 to 10.8, preferably in the range of 10.3 to 10.5 and especially at pH 10.4.
The developers are typically aqueous solutions, although organic solvents, such as diethylene glycol, can also be included to facilitate the solution of organic components. The developers contain one or a combination of conventional developing agents, such as, for example, a polyhydroxybenzene, such as dihydroxybenzene; aminophenol, paraphenylenediamine; ascorbic acid, eiythorbic acid and derivatives thereof, pyrazolidone, pyrazolone, pyrimidine, dithionite and hydroxylamine.
It is preferred to employ hydroquinone and 3-pyrazolidone developing agents in combination or an ascorbic acid-based system. An auxiliary developing agent exhibiting superadditive properties may also be used. The pH of the developers can be adjusted with alkali metal hydroxides and carbonates, borax and other basic salts. It is, as previously mentioned, a particular advantage of the present invention that the use of nucleators as described herein reduces the sensitivity of the photographic material to changes in this developer pH.
To reduce gelatin swelling during development, compounds such as sodium sulfate can be incorporated into the developer. Chelating and sequestering agents, such as ethylenediaminetetraacetic acid or its sodium salt, can be present. Generally any conventional developer can be used in the practice of this invention. Specific illustrative photographic developers are disclosed in the Handbook of Chemistry and Physics, 36th Edition, under the title xe2x80x9cPhotographic Formulaexe2x80x9d at page 30001 et seq. and in xe2x80x9cProcessing Chemicals and Formulasxe2x80x9d 6th Edition, published by Eastman Kodak Company (1963).
The invention will now be described with reference to the following examples that are in no way to be considered as limiting the scope thereof.

High contrast photographic element containing a novel combination of nucleators

Abstract: The combination of nucleating agents show less sensitivity to variation in the development conditions than do the individual nucleating types, leading to significant improvements in processing robustness with less change in image quality with processing and tolerance to a wider range of developer solutions.