JP2000075448A - Vessel for photographic processing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the vessel of the photographic processing agent composition capable of being regenerated and reused and superior in stability of the processing agent composition and superior in handlability of the vessel and capable of being used by installing a developing machine with the processing agent in the form of the cartridge of the processing agent and having a function adapted to the automatic developing machine capable of automatically washing the used vessel. SOLUTION: The inside of the vessel is washed after discharging the content of the vessel by a washing device having a hydraulic pressure of 0.5-3.0 kg/cm2. The vessel is made of a single resin of a high-density polyethylene(HDPE) having a density of 0.951-0.960 g/cm3 and a melt index of 0.3-7.0 g/10 min (ASTM D 1238 a condition of 2.16 kg load), and it is adapted to the automatic developing machine provided with a washing function for washing vacant vessels.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a container for a photographic developer composition used for processing a silver halide color photographic light-sensitive material. The present invention relates to a container for a photographic developer composition having excellent properties such as suitability and storage stability and suitable for development processing by an automatic developing machine.

[0002]

BACKGROUND OF THE INVENTION Generally, processing of silver halide photographic light-sensitive materials, for example, processing of silver halide color photographic light-sensitive materials,
It comprises an image stabilization step such as a color development step, a silver removal step and a water washing step. In each step, an aqueous solution containing one or more processing chemicals (called a processing liquid) is used except for the water washing. . Since each processing solution has a relatively low concentration, it is generally economical, storage space, or work-related to manufacture a processing solution ready for use by a processing chemical manufacturer, transport it to a lab, and store it. And is generally supplied in a concentrated state, that is, as a concentrated liquid treating agent.

[0003] However, liquid processing agents are aqueous solutions of chemicals and are inherently unstable. In particular, developers are susceptible to air oxidation. Therefore, the container must ensure the stability of the processing agent over a long period of time from the production of the processing agent to its use in a laboratory. For this reason, glass containers that do not allow oxygen to pass through have been used before, but there is a risk of breakage and handling is inconvenient. For this reason, composite containers made by laminating a plastic material with low oxygen permeability and a plastic material that is stable with respect to the developing agent have been replaced.However, composite material containers are not only expensive but also used containers. The inability to recycle was disadvantageous from the viewpoint of environmental load.

In order to be recyclable, it is necessary to be made of a single resin material, but many of the single recyclable plastic materials have high oxygen permeability. Insufficient protection against air oxidation, chemically inadequate stability against strong alkaline developing agents and oxidizing bleaching agents, or both .

[0005] For many plastic materials,
A further disadvantage is that colored stains are caused by the developing agents. The color developing agent in the color developer for color light-sensitive materials causes strong coloring that cannot be washed in plastic material containers, which also makes it difficult to recycle plastic containers.

[0006] On the other hand, with the spread of color photography, in addition to independent specialized laboratories, photoshops and small retail laboratories called minilabs or microlabs among large retail stores have increased in the market. are doing. In over-the-counter development,
Unlike specialized laboratories, there are no skilled professionals, so it is necessary to save labor as much as possible. Therefore, it is desired to improve the safety, automation and simplification of the overall work, especially for equipment such as automatic processors and photographic printers. It is desired that the liquid does not adhere to the hand, does not spill on the floor and becomes dirty, and that clean handling can be performed. For this purpose, there has been proposed an automatic developing machine having a function of mounting a processing agent and automatically preparing the processing agent. Therefore, it is necessary to develop a processing agent having a function that can be incorporated into an automatic developing machine. In particular, cleaning of empty containers generally requires high water pressure, but cleaning in a developing machine requires the pressure of the cleaning water to be a level that can be reasonably obtained in a point-of-sale developer. .

As described above, a container for a photographic processing agent composition, especially for a photographic developer composition, is used to stabilize the processing agent to be filled, to simplify the developing operation, to transport and to handle other materials. There has been a demand for improvements in the reusability of containers, and efforts have been made in the past, but they have not been able to sufficiently respond to market demands, and further improvements have been demanded. .

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to meet the above-mentioned demands for improvement of the developer composition, and specifically, it is possible to recycle a container, An object of the present invention is to provide a developer composition container which is excellent in stable preservability and handleability of a developer composition and has a function suitable for an automatic developing machine in which a developing operation is simple. Among them, a particularly specific problem is a means for enabling the recycling of the above-described container.After the container is mounted on an automatic developing machine, the mouth portion is broken by a nozzle to discharge the developer composition, It is an object of the present invention to provide a container for a photographic developer composition which is suitable for developing and container collecting means in which washing water is sprayed into a container at a low pressure to wash the inside of the container and to send the container to a recycling step without coloring the container.

[0009]

With respect to the above-mentioned object of developing a processing agent container, the present inventors have developed a processing agent composition which is made of a plastic material which can be reused and which is compatible with being incorporated in an automatic developing machine. As a result of intensive studies on the material requirements necessary for the product container, the present invention has been achieved. That is, the present invention is achieved by the following configurations.

[0010] 1. A container for a photographic processing agent composition which is used by being attached to an automatic developing machine having a function of washing the inside of the container. After the processing agent composition in the container is attached and discharged, it is sent to a washing nozzle. Water pressure is 0.5-3.0kg / c
m ² of washing water, and the density is 0.951 to 0.969 g / cm ³ , and the melt index is 0.3 to 7.0 g / 10 min (ASTM D12
38. A container for a photographic developer composition, wherein high density polyethylene (HDPE) having a temperature of 90 ° C. and a load of 2.16 kg) is made as a single resin material.

2. 2. The container for a photographic developer composition as described in 1 above, which is produced by an injection blow molding method.

The present invention relates to the material requirements required for a container for a processing agent composition having a function to be mounted on an automatic developing machine suitable for simplifying and automating a developing operation in a storefront developing station or the like. In a specific embodiment using the container, the opening is attached to the automatic developing machine with the opening downward, the opening of each container is automatically opened, the processing agent is discharged to each replenishing tank, and then each Cleaning water is sprayed from a nozzle inserted into the container to wash the inside of the container, and washing wastewater also flows into the replenishing tank and is used for preparing a replenishing solution. , And sent to a recycling process for recycling. The term "reuse" in the present specification means that used containers are recycled into new containers through a recycling process and used, and "reuse" in which the same containers are repeatedly used. Note that this is not the case.

[0013] In order to solve the above-mentioned problems of the present invention, it is necessary to provide a means for thoroughly washing the inside of the container with water sprayed from the nozzles throughout the inside of the container. For this purpose, it is generally considered that high-pressure washing water is sprayed from a spray nozzle. However, a large-sized washing pump, spray nozzle and piping thereof, which are not preferable for over-the-counter developers, are required. In the present invention, as the container, polyethylene is selected from the viewpoint of reusability, cost, handleability, and the like.However, if a material such as the density and melt index of the polyethylene is selected, washing water from an inexpensive small pump can be used. It has been found that cleaning is possible and further defines the container material. That is, when a container made of high-density polyethylene (HDPE) having a density of 0.951 to 0.969 g / cm ³ as a single resin material is selected, a small amount of dirt component adheres to the inside of the container, and the dirt component adheres. However, since it is easy to remove by washing, washing by the above-mentioned small pump of the water pressure, that is, the water pressure is 0.5 to 3.0 k
The inside of the container after the contents have been discharged can be sufficiently washed off by the g / cm ² washing device. Presumably, the molecular orientation of HDPE at this density affects air permeability and molded surface properties, and suppresses air oxidation, reduces insoluble matter, reduces container fouling, and increases insoluble matter even when insoluble matter occurs. It is considered that a favorable effect was obtained on each surface such as non-adhesion. Even if the material has high air permeability, it is naturally conceivable to reduce the permeability by increasing the thickness of the container.However, in that case, the weight of the container and the unit cost of the material must be increased. In addition to this, the dirt reduction effect provided by the flexibility of the vessel wall described below cannot be obtained.

The unexpected effect of the choice of HDPE density, which is that it is easy to wash away any deposits on the vessel wall, is due to the fact that the vessel wall has an appropriate range of thicknesses to maintain adequate flexibility. Further improve. Such an appropriate thickness preferably has an average weight per unit surface area of the container of 0.04 to 0.09 g / cm ² . It is considered that the container wall within this thickness range has a certain degree of oxygen barrier properties as described above, and because the flexibility of the container wall is maintained, even if there is an adhering substance, it easily falls off. Can be The above-mentioned average weight per unit surface area means a weight averaged over the entire surface of the columnar portion of the container, and the columnar portion has a bottom surface and a narrowed inclined surface (shoulder) as described in the perspective view of FIG. Part) and the main part of the container.

In other plastic containers such as low-density polyethylene (LDPE), polypropylene, and polyethylene terephthalate, even if the shape is the same, the above-mentioned cleaning effect is not recognized by the above-mentioned low-pressure water jet. . In addition, in order to recycle the container, the polyethylene container has the advantage that the route for collecting and reusing the waste plastic is most developed, and the cost required for the recycling is small.

The container for the processing agent composition, particularly the container for the developer composition, requires high dimensional accuracy, and if the container is made of HDPE in the above-mentioned density range, it can be manufactured by blow molding. Accuracy is maintained. In particular, high dimensional accuracy and smoothness of the wall surface are ensured by the injection blow molding method. Containers manufactured by the injection blow molding method also have improved removability. Probably, the smoothness of the wall surface and the orientation of the polymer molecules are affecting. 0.5 to 0.5 suitable for the present invention by the injection blow molding method
In order to produce a polyethylene container having a size of about 5.0 liters, the melt index is 0.3 to 7.0 g /.
The value is preferably in the range of 10 min. In addition, the melt index value in this specification may not particularly indicate the measurement conditions and units in each case.
It is the number of grams for 10 minutes obtained at a temperature of 190 ° C. and a load of 2.16 kg in accordance with STM D1238.

[0017]

Embodiments of the present invention will be described below in detail. In the following description, the terms developing agent, bleaching agent and fixing agent are the same as developer, bleaching agent and fixing agent, respectively.

[Material of Container] The container of the concentrated liquid developer of the present invention will be further described. HD used in the present invention
PE is a polymer composed mainly of ethylene as a monomer, and examples thereof include a homopolymer of ethylene, an ethylene / α-olefin copolymer, a blend of an ethylene homopolymer and an ethylene / α-olefin copolymer, and the like. .

As the ethylene homopolymer, there can be used a high-density polyethylene having a density of 0.951 to 0.969 g / cm ³ obtained by a low-pressure method using a Ziegler-Natta catalyst, a medium pressure method such as a Phillips method, or the like. When blended, high pressure polyethylene having a density of 0.925 g / cm ³ or less can be blended as one component as long as the density after blending falls within the above range.

The ethylene / α-olefin copolymer used in the present invention is composed of ethylene and C 3-20, preferably C 3-20.
And α-olefins of propylene, butene-1, pentene-
1, hexene-1,4-methylpentene-1,4-methylhexene-1,4,4-dimethylpentene-1, heptene-1, octene-1, nonene-1, decene-1 and the like. Can be copolymerized alone or in combination of two or more. The α-olefin content in the ethylene / α-olefin copolymer is 0.1 to
The content is 20% by weight, preferably 0.1 to 10% by weight, and the density is preferably 0.951 to 0.969 g / cm ³ .

[0021] The HDPE container of the present invention may be manufactured by injection stretch blow molding in which the injection blow molding is further extended, and a suitable HDPE has a density of 0.951 to 0.951.
0.969 g / cm ³ , preferably 0.951 to 0.96
0 g / cm ³ , and the melt index is 0.3 to 7.0, preferably 0.5 to 3.0 under the above-mentioned measurement conditions. When one type of resin is used for injection blow molding, these characteristic values are values that are satisfied by the resin used alone. It is only necessary to satisfy the characteristic values,
The individual components may be outside the above range.

As the raw material composition for the container for the photographic processing agent composition, a heat stabilizer, a weather stabilizer, a modifier, a lubricant, a colorant, a filler and the like can be used as long as the object of the present invention is not impaired in HDPE. Can be blended.

These components include pigments such as carbon black, titanium white, calcium silicate and silica which do not adversely affect the alkaline developing composition, calcium carbonate, 2,6-di-tert-butyl-4-methylphenol (BHT). Additives such as dicetyl sulfide, tris (laurylthio) phosphite, and other amines,
Known antioxidants such as thioethers and phenols; sliding agents such as stearic acid or metal salts thereof;
Examples include a known ultraviolet absorber compatible with polyethylene, such as hydroxy-4-n-octyloxybenzophenone, and a known plasticizer compatible with polyethylene. The total amount of these components is desirably 50% or less of the total amount of the mixture of the container materials. Preferably, the ratio of polyethylene is 85% or more and no plasticizer is contained, and more preferably, the ratio of polyethylene is 95% or more and no plasticizer is contained.

In the HDPE resin composition of the present invention,
When mixing is necessary, each component can be mixed by dry blending or melt blending using a Banbury mixer, Henschel mixer, extruder or the like.

The blow molding HD thus obtained
PE resin compositions are suitable for blow molding, but are especially suitable for injection blow molding, especially injection stretch blow molding.In addition to polyethylene properties such as impact strength, rigidity, etc., surface gloss and surface smoothness Excellent bottles and other blow molded articles can be produced. In this case, a bottomed barison is injection-molded using the resin of the present invention, the bottomed barison is released at a high temperature and biaxially stretch blow-molded as it is, or the bottomed barison is temperature-controlled in the middle and biaxially stretched. Blow molding can be performed, but no drawdown or melt fracture occurs in any case. Then, a blow-molded product having no surface abnormality such as flow mark and shark skin and excellent in surface gloss and surface smoothness can be obtained.

The cap of the container does not necessarily need to be HDPE, and may be, for example, LDPE, but is preferably HDPE. But HDPE
However, it is not necessary that the HDPE has the same density and melt index as the container body, and an appropriate grade of HDPE is selected depending on the ease of molding as a cap and the confidentiality of the fitting part with the mouth of the container body. be able to. Also, only the sealing portion of the cap of HDPE, that is, the fitting portion with the mouth portion of the container body, is used for the LD having a density of 0.91 to 0.94.
It can also be PE. The use of such a small amount of LDPE does not affect the recycled use of polyethylene.

According to another aspect of the present invention, a container which does not necessarily have a cap, which is not provided with a cap to be fitted to the mouth and which is sealed with a perforated polyethylene sheet, may be used. Further, the aluminum foil and the polyethylene may be hermetically sealed with a sealing member.

[Usage Form of Container] When filling the developer composition into the container, a suitable upper space considering the safety against air oxidation and the buffering against impact rather than filling the developer composition up to the mouth of the container. A portion (called a head space) is provided, and the head space is preferably replaced with nitrogen to fill the space so as to eliminate contact with oxygen in the air. The method is not limited.

The developer composition in container form of the present invention is suitable for use in an automatic processor as described above. In particular, the container filled with the developer composition is attached to the developing machine with the mouth down, and the composition inside the container is poured into a storage tank such as a development replenishment tank, and then the inside of the container is washed with a certain amount of water. In addition, a developing operation method in which water used for washing is introduced into a replenishing tank and used as a part or all of water for preparing a replenishing solution, and development is performed using the replenishing solution thus obtained,
This is a system in which the advantages of the container of the present invention are particularly effectively utilized. In order to wash the inside of the container with a certain amount of water, spray-type washing in which washing water is sprayed from a nozzle hole is particularly preferable. Can lose weight. However, in order to collect and recycle the used container in such a manner, it is assumed that the container has no coloring and no attached matter.

In a preferred embodiment of the present invention in which the washing nozzle is inserted into the container to spray water, the spray direction of the nozzle is obliquely upward, and the angle between the nozzle and the vertical line is 60 degrees.
The cleaning effect is great when the angle is within 15 °, preferably within 15 to 40 °.

With the container made of the HDPE of the present invention, the developer composition is stable, there is no coloring of the container and there is no deposit on the container wall, the contents are easy to flow out, and the container is subsequently washed with water. Since only a small amount of water is required, it is advantageous to combine the developer in a container of the present invention with an automatic developing machine equipped with a container washing mechanism from the viewpoint of recycling of the container and also from the viewpoint of saving water and reducing the amount of wastewater. .

The HDPE container of the same material of the present invention comprises:
As described above, the present invention is particularly preferably applied to a development processing system in which each processing agent container is integrally mounted on an automatic developing machine having a washing mechanism, and a processing agent in the container can be automatically charged into a replenishing tank. This automatic developing machine and developer system
Specifically, after the processing agent in the container is mounted with the mouth down on the processing agent container mounting portion provided at the top of the replenishing tank of the developing machine, and the processing agent in the container is automatically charged into the replenishing tank, Since the inside of the container is washed with a certain amount of water, the water used for washing is introduced into the replenishing tank and used as water for adjusting the replenishing solution, and processing is performed using the obtained replenishing solution. It meets various requirements such as wastewater, simple operation, automatic operation, stability of treating agent composition, and recyclability of containers.

In a particularly preferred embodiment, when the container filled with the processing agent composition is mounted on the developing machine, the seal portion of the cap is pierced at the tip of the nozzle by a mechanism for automatically breaking the cap seal of the container, and the processing in the bottle is performed. A mechanism for smoothly discharging the agent composition into the replenishing tank is provided. Subsequently, the inside of the container is automatically spray-cleaned to wash away the chemical components adhering to the vessel wall, and the water used for the cleaning can be used for preparing a replenisher.

A system for loading a container of such a processing agent composition into an automatic developing machine is disclosed in JP-A-6-82988, JP-A-8-220722, and the like. It is clean without human intervention, can be handled cleanly, and recycling of waste containers is easy. In addition, since the washing water is used as a part of the water for dissolving the treating agent, it does not become a waste liquid. The concept of such a system is a highly enriched small volume, embodied in the present invention.
In addition, it can be realized for the first time by the container for the treating agent composition described above, which has sufficient fluidity for easy handling and is maintained for a long period of time. Containers for the treatment composition of the present invention are described in Japanese Patent Nos. 2613796 and 261.
Nos. 3797 and 2640504 may have a slit treatment tank, which is particularly preferable from the viewpoint of improving the durability of the deserted treatment and the downsizing of the processor.

[Embodiment of Development Processing Using Container of Processing Agent Composition of the Present Invention] (Embodiment of Automatic Developing Machine) As a specific example of the present invention, a storage case containing a container filled with each processing agent composition will be described below. Is attached to an automatic developing machine, and a developing processing system for automatically opening and automatically replenishing a replenisher will be described, but the application of the present invention is not limited to this. FIG. 1 shows a printer processor 10 in which an automatic developing machine to which the present invention is applied is integrated with a printer.
FIG. 2 schematically shows the printer processor 1.
0 is shown.

The printing paper P, which has been subjected to print exposure from the negative in the printer section occupying the left half of the printer processor 10, is transferred to the processor section 7 on the right side of the printer processor.
The developer is sent to a developing tank 74 inside the developing tank 2 for development, and then conveyed to an adjacent bleach-fixing tank 76, where a bleach-fixing process is performed. The photographic paper P that has been subjected to the bleach-fixing process is transported to a plurality of rinsing tanks 79 in which rinsing water is stored. After the rinsing process, the photographic paper P is transported to a drying unit 80 located above the rinsing tank 79 and dried. You. The printing paper P discharged from the drying unit 80 is discharged to the outside of the printer processor 10 while being sandwiched by a plurality of pairs of rollers, and is stacked.

On the other hand, the processor section 72 is provided with a supplement section. In the replenishment section, a processing agent kit (described later)
There is a mounting part (300 in FIG. 2) in which is mounted, and a replenishing tank part in which a replenishing solution is managed. In the mounting part 300, processing agent kit management, automatic opening of processing agent kit, automatic cleaning, Drying is performed, and in the replenishment tank section, the replenishment tanks (347, 349,
351), a replenishment pump operation, and a circulating stirring pump (described later) are managed. In addition, a replenishment tank (347, 349,
351) is supplied. The bleach-fix tank 76 is replenished with a bleach replenisher and a fixing replenisher. The water used for the washing tank, the automatic washing after discharging the contents of the container, and the dilution water for replenisher preparation is a water tank 426.
Supplied from

(Mounting Portion) FIG. 3 is a front view showing the internal structure of the processing agent mounting portion 300 shown in FIG. 2 and the arrangement of the processing agent, and FIG. 4 is a side view thereof and a replenishing tank at the lower portion of the mounting portion. FIG. 3 is a side view of the inside of a processor unit including a dissolution tank. As shown in FIGS. 2 and 3, the mounting section 300 is covered with a mounting section cover 302 that can be opened and closed. Further, the holder 31 on which the processing agent cartridge 202 is mounted is mounted on the mounting section 300.
6 are provided.

As shown in FIG. 3, the processing agent cartridge 202 of this embodiment has a storage case (made of cardboard) 204.
And a container 203 storing the developer, a container 205 storing the bleaching agent, and a container 207 storing the fixing agent. Since the containers 203, 205, and 207 have the same structure, the structure will be described below with the container 203 as a representative.

As shown in FIG. 3, the container 203 is
08 is outside the case from the top of the storage case 204, the center of the screw lid 208 is sealed by a seal member, and is sealed by the cleaning nozzle 346 (130 in FIG. 5).
8). As shown in FIG. 3, below the holder 316, containers 203, 20
Cleaning nozzles 346, 348, and 350 are provided at positions corresponding to the openings 5 and 207, respectively.
When the containers 203, 205, and 207 move downward, the cleaning nozzle 346 seals the container 203 (1308 in FIG. 5), and the cleaning nozzle 348
The cleaning nozzle 350 pushes through the seal of the container 207 and enters the container to open the seal.

As shown in FIGS. 3 and 4, the cleaning nozzle 3
A funnel 352 whose lower end is inserted into a development replenishment tank (PIR) 347 is disposed below 46, and a cleaning nozzle 348 is provided.
Below the bottom is a bleach replenisher tank (3 in FIG. 1) whose lower end is not shown.
49), a funnel 354 having a lower end inserted into a fixing replenisher (351 in FIG. 1) whose lower end is not shown in FIG.

(Structure of Processing Agent Kit and Container Thereof) Next, a photographic processing agent cartridge 20 according to an embodiment of the present invention is described.
Bottle 13 as containers 203, 205, 207 for 2
00 will be described with reference to FIG.

FIG. 5 is a structural perspective view of the bottle. The bottle 1300 has a container body 1302. The upper end of the container body 1302 is an inclined portion whose diameter is gradually reduced, and is in contact with the mouth 1306. The mouth 1306 is formed in a cylindrical shape with a male screw 1304 on the outer periphery. The upper end of the mouth 1306 is open, and the above-mentioned replenisher can be taken in and out through the opening. The mouth 13
A polyethylene sheet 1308 as a sealing member is arranged at the upper end of the reference numeral 06. In the present embodiment, the polyethylene sheet 1308 has a cross-shaped tear, and is formed in a shape that is easily pierced by a constricted hole nozzle described later.

(Operation in the Present Embodiment) Next, the operation in the present embodiment will be described mainly with reference to FIGS. For example, when the photographic printing paper P is developed in the developing tank 74 of FIG. 1, the replenishing pump (370 in FIG. 4) is operated in accordance with the development, and the developing replenisher once stored in the replenishing tank 347 is developed. The replenisher is sent to the tank 74 and replenished with a deteriorated amount of the developing replenisher used for processing in the developing tank 74. The bleach-fix solution in the bleach-fix tank was also used in the bleach replenisher tank 3.
This is the same in that replenishment is performed from the fixing replenishment tank 49 and the fixing replenishment tank 351 to compensate for the deterioration due to use. In FIG. 4, when the liquid level in the replenishing tank 347 becomes equal to or less than a predetermined amount, the float switch 360 detects this, and
An instruction to supply the replenisher to the replenisher tank 347 is displayed on the monitor 460, the control device is operated, the motor 328 is driven, the pipe 324 connected to the holder 316 is moved downward, and the perforation nozzle 346 is moved. (The washing nozzle 346 is also pierced at the tip thereof and is also called a piercing nozzle.) In the direction in which the bottle approaches the bottle 203, the polyethylene sheet (1314 in FIG. 5) of the mouth (1314 in FIG. 5) of the cap 208 is moved.
08).

From this state, the perforation nozzle 346 further approaches by the driving force of the motor 328, and the perforation nozzle 34
6 breaks through the polyethylene sheet (1308 in FIG. 5) to open the polyethylene sheet (1308 in FIG. 5), and the replenisher (developer) inside the container body (1302 in FIG. 5) flows down. In this way, the bottle (130 in FIG. 5)
The replenishing agent discharged from 0) is supplied to the replenishing tank 347 via the receiving port 352 or a pipe.

As shown in FIGS. 3 and 4, the casing 10A
A water storage tank 426 is provided therein, and the water stored in this tank is used for washing water for developing the photosensitive material, diluting water for diluting the processing agent for preparing the processing solution, or after the processing agent flows out. It is used as cleaning water for cleaning the containers 203, 205, and 207. The piping 434 at the bottom of the water storage tank 426 sends the washing water to the washing tank 79. Piping 4 from the bottom
Reference numeral 36 denotes a cleaning agent container cleaning valve 450 connected via a container cleaning pump 440 on the way, and a distal end thereof connected to a cleaning nozzle 346. Similarly, cleaning nozzles 346, 348, 35 for the bleaching agent container and the fixing agent container.
The pipe is provided so as to send the cleaning water to the pipe 0 (not shown). After being used as washing water, these washing waters are sent to a replenishing tank and become a part of dilution water for preparing a treatment liquid.

On the other hand, after the treatment agent composition is discharged from the container, the cleaning water supplied from the pipe 436 is jetted from each cleaning nozzle into an empty container to perform cleaning. The washing wastewater is discharged to each replenishment tank and used as a part of the dilution water.

Here, the bottle 203 according to the present embodiment
The operator operates the bottle 130 by opening the opening / closing door 302.
0 (in a form in which the normal treatment agent composition kit is collectively put in a storage case), the door 302 is closed, and the motor 328 in FIG. 4 is simply operated. Polyethylene sheet (130 in FIG. 5)
The work of perforating 8) to replenish the processing agent into the replenishing tank 347 is automatically performed inside the closed replenishing unit 300. Therefore, the troublesome work of refilling the bottle 203 by hand by the operator is not required, and the processing agent is not scattered at the time of opening and refilling, and the hands and clothes of the operator are not stained. .

Referring to the recycling of the bottle shown in FIG. 5, the removed empty bottle 1300 (203 in FIGS. 3 and 4) is recycled. In this case, the cap 1310 (208 in FIG. 3) is used. Is the container body 1
The polyethylene sheet 1308 is detached from the opening 1306 of the base 302, and the polyethylene sheet 1308 can be separated and collected separately for each material, or can be collectively collected as HDPE depending on the similarity of the materials. In FIG. 5, if there are accompanying members such as the container body 1302, the cap 1310, and the polyethylene sheet 1308, each of them is an independent separate part, including these members, and the polyethylene sheet 1308 for assembling them is the container body 1302. To the mouth 1306. Therefore, the cap 13
10 to remove the polyethylene sheet 130
6 can be easily removed and separated. Alternatively, the cap 1310 may be omitted because there is a polyethylene sheet 1308 at the mouth. In still another embodiment, a seal member may be provided in place of the polyethylene sheet, and packing may be provided if necessary. In addition,
A seal 1308 in FIG. 5 is representative of each of the above-described closure methods such as a polyethylene sheet.

[Treatment Agent Composition] The treatment agent composition container of the present invention contains, in addition to the concentrated liquid treatment agent composition commonly used in the art,
The present invention is also applicable to a slurry, a granule, and a powdery processing agent composition and a processing agent composition including a tablet. For one development processing step, usually, a developer composition and a processing composition for a silver removal step are assembled as a kit, and the latter can be further divided into a bleaching composition and a fixing composition. Many,
The container of the present invention can be used for any of these compositions. In addition, there are additional processing baths such as a washing substitute stabilizing bath and an image stabilizing bath, and a processing agent therefor may be included. Additional processing baths such as a washing substitute stabilizing bath and an image stabilizing bath are not necessarily the object of the present invention because their concentration is extremely low as compared with the processing baths in the developing step and the silver removing step. A treatment composition container can be used.

The developer composition filled in the container of the present invention contains an alkaline continuous phase liquid containing the components contained in a usual color developer in a dissolved state, and the components as a slurry-like dispersion. Suspensions or compositions in the form of granules, powders or tablets. Among them, a color developing agent is contained. In the present invention, as described above, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline and 4-amino-3- Methyl-N-ethyl-
N- (β-methanesulfamidoethyl) aniline or a salt thereof, or another p-phenylenediamine type color developing agent may be added as an auxiliary color developing agent. In recent years, some black-and-white photosensitive materials have been added so that a coupler is colored so as to develop black, and a black-and-white image is formed using a general-purpose general color developing solution. The composition is also applied to the processing of this type of photosensitive material. Since the color-developing agent causes coloring of the container when subjected to oxidation, the container of the present invention is particularly effective when used in a developer composition.

The form of the treating agent of the present invention is described in
-234289 or JP-A-10-234289
A slurry-like treating agent containing a water-soluble polymer described in JP-A-39426 can be mentioned as a preferable application object.

[0053]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 In Example 1, the effect of each component of the container for a developer composition of the present invention is shown for a prismatic container. (1) Container-Container molding The shape of the used developer / developer composition container is schematically shown in Fig. 5, and the dimensions are according to the following specifications. Size and height of cross section of columnar part 75mm x 75mm x 2
50 mm (height) Height from the mouth to the base 270 mm Height to the top of the head 310 mm Average thickness of the container 0.5 mm (Note) The average thickness is the average thickness of the container over the surface area of the columnar portion of the container. -Material and molding method of container As shown in Table 1, the material and molding method of the container were changed to 13 kinds of tests. PE, PET, PP in the column of material in Table 1
And PVC are abbreviations of polyethylene, polyethylene terephthalate, polypropylene and polyvinyl chloride, respectively, and the column of MI is a melt index value (10 minutes) measured at 190 ° C under a load of 2.16 kg according to ASTM D1238. Per gram).
The unit of the water supply pressure is kg / cm ² .

(2) Preparation of Processing Agent Composition Three containers each of the above 13 types were prepared, and a color developer composition, a bleaching agent composition, and a fixing agent composition were each prepared.
Fill 300ml each, color developer, bleach,
A kit in the form of a fixing agent container was prepared, and the kit was housed in a set of three cardboard boxes, and was packaged in the same manner as an actual product in the form of a cartridge.

Formulation of color developing composition: Filling amount 1300 ml Optical brightener A (described below) 12.0 g Optical brightener B (described below) 12.0 g Dimethylpolysiloxane-based surfactant 0.35 g ( Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Ethylenediaminetetraacetic acid 15.0 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 30.0 g Tri (isopropanol) amine 30.0 g Potassium hydroxide 18 0.5 g sodium hydroxide 24.0 g sodium sulfite 0.60 g potassium bromide 0.04 g polyethylene glycol 400 30.0 g 4-amino-3-methyl-N-ethyl-N- (β-methanesulfamidoethyl) aniline 3/2 Sulfate monohydrate 60.0 g Potassium carbonate 100.0 g pH 13.0 Add water The total amount of Te 1 liter

[0057]

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[0058]

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Formulation of bleach composition: filling amount 1300 ml nitric acid (67%) 98.7 g imidazole 75.0 g iron (III) ammonium ethylenediaminetetraacetate dihydrate 210.0 g ethylenediaminetetraacetic acid 7.5 g 1,2 -Benzoisothiazolin-3-one 0.15 g m-carboxybenzenesulfinic acid 50.0 g Ammonia water (27%) 40.0 g Water was added to add 1 liter pH (adjusted with ammonia and nitric acid) 6.0

Formulation of fixing agent composition: Filling amount 1300 ml Ammonium thiosulfate solution (750 g / liter) 580.0 g Ethylenediaminetetraacetic acid 9.0 g Ammonium bisulfite solution (70%) 285.0 g Imidazole 7.5 g ammonia water (27 %) 53.5 g 1 liter by adding water pH (adjusted with aqueous ammonia and acetic acid) 5.9

[0061]

[Table 1]

The above composition was filled in a container, and each one was loaded in a set of three into a cardboard cartridge, then set in a processor, and the replenisher was adjusted by opening, washing, and dilution. The adjustment amount of the replenishment amount after adding water is as follows. Color developer replenisher 5.0 liters pH 12.5 Bleach replenisher 2.0 liters pH 6.0 Fixer replenisher 2.0 liters pH 6.0

(3) Test method-Container filling and aging test The above-mentioned developer composition was added to containers 1 to 13 shown in Table 1 for 13 times.
The mouth filled with 00 ml was sealed by sealing a grooved seal 1308 with a packing and a cap as shown in FIG. The container containing the developer composition, the bleaching agent composition, and the fixing agent composition was packed into a container case of a cardboard box, and then the temperature was 40 ° C and the relative humidity was 7 ° C.
It was aged for 6 months in a 0% constant temperature and humidity chamber.

Opening of Container, Discharging of Composition and Washing The temporal sample of the above-mentioned processing agent composition container was mounted on the processing agent container mounting portion of the automatic developing machine shown in FIG. The container was opened, the composition was discharged, and the inner wall of the container was washed. Nozzle (Nozzle 346 in FIG. 3)
The largest part of the diameter is 20 mm and its length is 50 mm, and this nozzle breaks the seal, discharges the composition to the developing replenisher tank, and then sprays water from the tip of the nozzle under the following conditions. Figure 1 shows the operation of cleaning the inside of the empty container
The processing was performed by an automatic developing machine described in Nos. 1 to 4. The water outlet at the tip of the nozzle is conically opened at an angle of 30 ° to the vertical axis, and the depth of the outlet is 5 mm. Further, as shown in Table 1, the water supply pressure was set to 0.3, 0.5, 1.2, 3.0.
The washing was carried out by changing to kg / cm ² and continuously jetting until the jetted water amount became 0.3 liter.

Observation and evaluation method After the preparation of the processing agent described above, filling in a container, assembling in a cartridge, aging with heating, mounting in a developing machine, discharging the contents, and washing, the washing is carried out for 30 minutes. Conversely, for each container that was maintained and drained, the cleaning state inside the container was visually observed. The observation results were classified and evaluated as follows.付 着 Neither deposit nor coloring is observed. ○ There is no adhering matter, but there is slight coloring. Δ: Slight deposits and slight coloring. X: The deposits are clearly left partially, and there is a little coloration. XX: Deposits remain on the entire surface and there is clear coloring. In Table 1, the results of the container for the developer composition in which the effect of the container of the present invention is remarkably exhibited are shown in the rightmost column as ◎, △, Δ, ×, XX.
It is described in.

(4) Test Results In Table 1, the underlined parts are outside the requirements of the present invention. Tests 2 to 6 in which a container manufactured by injection blow molding of HDPE having a density and a melt index value specified in the present invention was used and the container was washed at a water supply pressure of 0.5 kg / cm ² or more were all performed. ◎ or ○, showing good results. Tests 9 and 10 in which the molding method was changed to the direct blow method were also judged to be Δ, which was within the scope of the present invention and practical, but was inferior to those of the injection blow molded tests 2 to 6. there were. On the other hand, a comparative example (Test 1) in which the water supply pressure is weak even for HDPE whose density and melt index meet the conditions of the present invention, or a comparative example (Test 7) using LDPE having a low density even when the water supply pressure is within the range of the invention. In Comparative Example (Test 8) having a low melt index also in HDPE and HDPE, a colored residue was generated. Examples of containers using materials other than polyethylene (Test 11)
In all of the cases (13) to (13), adhesion of colored residue was observed.
That is, the effect of the invention is exhibited when the HDPE container having a specific range of density and melt index value is washed under the condition of the specific water supply pressure, and the effect is obtained when the container is formed by the injection blow method. Was shown to be more prominent.

[Supplementary Explanation] The automatic developing machine used in conducting the test of Example 1 above, the specification method of the developer composition,
The processing agent cartridge, the replenishment method, and other related items will be described.

(1) Configuration of Automatic Developing Machine The automatic developing machine shown in FIGS. 1 to 4 is a printer processor which continuously performs printing and development for color photographic paper (color paper). A container for a processing agent composition intended for application to a printer processor of this type is used. The container for a processing agent composition of the present invention is, as shown in Example 3, another automatic developing machine such as a color negative. It can also be applied to a treating agent composition for use. In this case, the same effects as those described in the above embodiment can be obtained. Also, from the viewpoint of clean operation without touching the liquid, Japanese Patent Application Laid-Open Nos. 6-308700, 7-125829, and 8-
It is preferable to introduce an automatic cleaning mechanism for processing racks and rollers described in No. 82907. Japanese Patent No. 1891588 and Japanese Patent Application Laid-Open No.
It is also preferable to employ a vertical multi-stage water washing method described in Japanese Patent No. 68787. Needless to say, the processing agent composition container of the present invention is a mechanism capable of producing prints of various sizes by the same automatic developing machine. If the size is E or E, the system can also be applied to an automatic developing machine having a so-called size sorting mechanism in which a three-line transport system can be selected. The time from printing exposure of color paper by the printer unit to entering the developing tank is usually from 2 seconds to 1 second.
Minutes, often 3 to 30 seconds.

(2) Supplement on Container In order to ensure quality, ensure safety, prevent deterioration, etc., it is desirable to make the cap of the container difficult to open so that it is not accidentally or intentionally opened. It is. The method of making it difficult to open may be any conceivable method, but in a preferred embodiment, a protrusion for preventing reverse rotation is provided at the lower end of the spiral screw groove provided on the mouth, and the cap is fitted into the cap. A screw hole is provided for the screw, and when the cap is completely screwed in, when the projection falls into the fastener, the screw cannot be further rotated.This ratchet type fastener is not a screw rotation, but a cap screw. There is a ratchet type in which a fastening operation is performed in a vertical direction by being pushed from top to bottom. Further, in the case where a seal is provided at the mouth portion and sealing is performed, it is preferable to provide a groove in the seal so that the seal can be easily pierced when the opening nozzle comes into contact with the seal. The shape of the groove is preferably the cross shape shown in the above embodiment or the swastika shape, and the depth of the groove is also 0.2 to 0.8 mm, preferably 0.3 to 0.8 in consideration of the thickness of the sealing member.
Engraved to 0.7mm. Further, when the container is opened by the perforated nozzle, the material of the container is a flexible thin HDPE, so that the position of the container in the vertical direction may be rubbed by the pressure of the nozzle, and the opening operation may not be smoothly performed. It is desired to fix the position of the mouth and secure its length without deforming the neck. For that purpose, it is preferable to have a projection for positioning the mouth in the vertical direction and a projection for securing the neck interval. Both projections may be provided on the cap, or in the case of a sealing method without a cap, both may be provided on the container body side, and one may be provided on the cap side and the other may be provided on the body side. The details of the container opening mechanism are described in JP-A-8-248606.

(3) Packaging state of kit FIG. 6 is a perspective view of an example of a processing agent cartridge to which the present invention is applied. The processing agent kit is conveniently in the form of a cartridge stored in a processing agent storage case. In the embodiment shown in Example 1, the developer composition,
A test was carried out by mounting a cartridge in the form of a product in which a kit comprising each of the bleaching agent composition and the fixing agent composition in a cardboard storage case was attached to an automatic developing machine (in FIG. The developer composition container 203, the bleaching composition container 205, and the fixing agent composition container 207 are housed to constitute the processing agent cartridge 202). An example of the actual appearance is shown in a schematic perspective view of the cartridge in the form of a product in FIG. The storage box used for this cartridge is a rectangular parallelepiped box type provided with an opening at the top so that the neck of the container comes out, and its outer dimensions are 85 mm in width and 24 mm in width.
0 mm and height 285 mm. The area occupied by the treatment agent composition container in the cross-sectional area of the inside of the cardboard storage case of the cartridge cut by the columnar portion of the container in the horizontal plane is 94% of the cross-sectional area of the cardboard storage case.
Met. That is, they are packed and stored so that there are few voids. The cardboard used had a thickness of 4 mm and was coated with a non-slip varnish.

(4) Kit Dilution Method To prepare the replenisher by diluting the contents of the kit, FIG.
And as described in FIG. 4, the seal at the mouth of each composition container is pierced by the opening nozzle, the contents are discharged to the replenishing tank, and then the inside of the emptied container is sprayed from the nozzle. Washed with water. In Example 1, the amount of the cleaning water was 300 ml while the treatment agent composition in the container was 1300 ml. On the other hand, the actual replenisher contains 1300 ml of developer composition, 3700 ml of dilution water, and 1 bleach composition.
The dilution water is 700 ml for 300 ml, and the dilution water is 700 ml for 1300 ml of the fixing agent composition. In each case, the washing water is used as a part of the dilution water. The dilution water is sent from the three-way valve 450 to the replenishing tank via the pipe 442 from the above, and the dilution of the specified amount is performed to prepare a replenishing solution.
At this time, the treatment agent composition and the dilution water are mixed and stirred by the water flow of the dilution water to form a uniform replenisher.

(5) Suitability of Form of Processing Agent Composition and Cleaning Ability of Container Material The container after opening the processing agent composition container must be sufficiently cleaned thoroughly in order to recycle the container. In some cases, the composition is partially coagulated and solidified and stays inside the container, which makes it difficult to discharge the composition from the container. Also,
The components of the composition may also penetrate into the interior of the container material and may not be easily washed out. Such problems may occur when the composition is a homogeneous liquid, but are particularly likely when the composition is in the form of powder, granules, tablets or slurries.

To solve this problem, first, an HD having a density and a melt index specified in the present invention is used.
It is effective to use a container made by injection-molding PE. In addition, a container manufactured using high-density polyethylene (HDPE) having a flow ratio of 20 to 30 is more preferable because the container wall surface has high smoothness and a high cleaning effect. The flow ratio is a value obtained by dividing the flow rate (melt flow rate) of a resin measured at 190 ° C. under a load of 11200 g by the flow rate measured under a load of 1120 g at the same temperature according to the method specified in ASTM D1238. It is.

Aggregation and solidification of the treating agent composition and adsorption to the inner wall of the container are likely to occur when the treating agent composition is in the form of powder, granules, tablets or slurries as described above. Metal carbonates such as sodium and sodium carbonate, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, alkali metal sulfites, alkali metal borate, alkali metal thiosulfates, ammonium thiosulfates, and color development It is remarkably recognized when a black-and-white developing agent such as a main agent and hydroquinone is contained.
Therefore, when the treatment agent composition is in such a state and configuration, the effect is particularly large if the container has the above-mentioned material specifications.

The effective spray cleaning conditions not only for the treatment composition in the form of a homogeneous solution but also in the form of powders, granules, tablets or slurries are described in terms of the spray angle (θ: The angle and the aspect ratio of the treatment agent container are also important. C is the internal height of the treatment agent container (height from the mouth of the inverted container to the opposite bottom), A is the short side (inner method), and L is the long side (inner method) if the bottom is rectangular. To B,
Assuming that the height from the mouth of the inverted container at the position where the lower end portion of the cleaning liquid sprayed on the inner surface of the container hits the inner wall is C1,
It is desirable that B / A = 1 to 1.5, and it is more desirable that A = B. Further, it may be a cylindrical container. A <C and B <C are preferably satisfied.
/ B = 2 to 5 is preferred. When the columnar portion of the container is a columnar container, it is preferable that the ratio with the height C when the inner diameter of the cross section of the columnar portion is B is in the above relationship. The injection angle (θ) is within 60 °, preferably 10 to 50 °, and particularly preferably 15 to 45 °. If the injection angle is too large, the upper part of the container is not easily washed, and if it is too small, the impact on the container wall is low and the efficiency is inefficient. C1 is の of C
Or less, while the absolute value is 100
mm or less, preferably 70 mm or less, more preferably 5 mm or less.
0 mm or less is good. However, it is preferable to be above the shoulder (that is, the columnar portion).

(6) Container Cleaning Type and Cleaning Effect The treating agent composition container needs to be sufficiently cleaned for recycling after use. The cleaning effect is closely related to the cleaning type of the opening and cleaning device. Has to do with. In particular,
After washing the inside of the container from which the composition has been discharged, a two-stage washing in which the mouth of the container is further washed and a jet washing in which washing water is intermittently jetted are effective. This is a cleaning method that can be used for stoppers and cleaning devices. Hereinafter, these two types of cleaning will be described.

(6a) Two-Step Cleaning Method and Apparatus for Inside of Container and Around the Mouth A description will be given of two-step cleaning with a high cleaning effect with respect to the opening and cleaning apparatus. In this cleaning method, insoluble coagulated solidified substances and constituents are remarkably adsorbed to the inner wall of the container at the mouth and surrounding area of the container, so in addition to cleaning the inner wall of the container, the mouth is washed separately. It is.

The components and functions of the cleaning type opening / closing apparatus are as follows. 1) It comes into contact with the sealing member provided at the mouth of the container from the outside,
There is a plug member for opening the sealing member to discharge the treatment agent composition, and a cleaning member having a cleaning nozzle for spraying cleaning water to clean the inside of the container. 2) There is a moving mechanism for moving the container or the cleaning member so that the cleaning member is positioned below the outside of the mouth of the container when the cleaning of the inside of the container is completed. 3) A cleaning mechanism is provided for cleaning the periphery of the container opening by injecting cleaning water from the injection hole of the cleaning member after moving the container or the cleaning member.

In this apparatus, the cleaning operation is performed in two stages, i.e., cleaning of the inner wall of the empty container and cleaning of the periphery of the container opening. Not only that, the inside and outside parts (including the cap) of particularly dirty mouths are also cleaned, so that containers can be recycled, and at the same time, clean handling and safety of empty containers are ensured.

Referring to FIGS. 3 and 4, the opening / cleaning member opens the sealing member at the mouth of the treatment agent composition container and discharges the composition to the lower dissolution tank / replenisher tank from the stage where it is discharged. The mode of the step cleaning will be described. After a lapse of a predetermined time (the time when the processing agent almost flows out of the container and is stored in advance in the control device 460) from the opening, the liquid sending pump 440 operates,
The switching cock 442 is switched, the electromagnetic valve (washing valve) 450 is opened, and the washing water is sprayed from the water storage tank 426 to the inner wall of the container from the spray nozzle 214 attached to the opening / cleaning member 346.

When the cleaning of the inside of the container 203 is completed, in the present embodiment, another two water supply pipes (for a bleach replenisher and a fixer replenisher) are separated from the switching cock 442.
However, the cleaning water is also sent to the respective cleaning nozzles via the respective electromagnetic valves, and the containers 205 and 207 from which the bleaching agent composition and the fixing agent composition are respectively discharged are also cleaned. In this way, for each of the containers from which the treating agent composition has been discharged, the washing water is jetted from the washing nozzle into the empty container to perform washing.

After the predetermined cleaning of the inside of the container is completed, the electromagnetic valve 45
Each solenoid valve such as 0 is closed, and then the liquid sending pump 442
Stops, the opening motor 328 is driven, and at the same time, the second cleaning program timer is started. The opening motor 328 moves the entire mounting base together with the sliding member 324 upward.
When it arrives below the outside of the mouth of No. 3 (the positional relationship shown in FIG. 3), it stops at that position by the time management of the timer. Next, the liquid supply pump 440 is started, the electromagnetic valve 450 is opened, and the injection nozzle 214 injects washing water around the mouth to perform washing. The area around the mouth is contaminated with the internal and external parts and the broken pieces of the ruptured sealing member due to the splash and powder of the composition. Cleaning around the mouth of the container 203, ie, the second
When the cleaning is completed, in the present embodiment, as in the case of the first cleaning, another two water supply pipes separated from the switching cock 442 send the cleaning water to the respective cleaning nozzles via the respective solenoid valves. Therefore, the container 205 after the treatment agent is discharged,
Cleaning around the mouth 207 is sequentially performed. In this way, the cleaning water from each cleaning nozzle cleans the inside and the mouth of each treatment agent composition container to a level at which the containers can be recycled. It goes without saying that two-stage cleaning of each of the containers 203, 205 and 207 can be performed in parallel by arranging the solenoid valves and operating sequences in such a manner.

The distance between the injection hole of the cleaning nozzle, the cap and the mouth in the second cleaning is determined by the injection pressure, the cap of the container,
Depending on the size of the mouth, etc., it is 1 to 80 mm, preferably 2 to 10 mm. The angle of spraying the washing water in the second washing, the intermittent repetitive spraying, the amount of the spraying water, and the like are conveniently the same as those for the jet washing inside the container, but may be changed.

After the completion of the second cleaning, the opening motor 328
The sliding member 324 is again controlled by the time management of the timer.
At the same time, the entire mounting base is moved upward, and when the microswitch 334 detects the upper limit position of the mounting base, that is, the initial position, the mounting base is stopped at that position, and a series of opening and cleaning operations is completed. The washing water used for washing flows down the container wall, flows down from the mouth to the outside of the container, flows into the dissolving tank 347 (other processing agent compositions also flow into the respective dissolving tanks), and dilutes the diluted water. Used as a part.

(6b) Method and Apparatus for Intermittent Injection Cleaning of Rinse Water For effective cleaning of the container, the above-described two-step cleaning is particularly effective for removing dirt on the mouth. For the cleaning of the mouth part in the two-stage cleaning, cleaning performed by dividing the washing water and intermittently spraying it is particularly effective. As in the previous section, the description will be made based on FIGS. 3 and 4, but the description will focus on the operation of the opening and cleaning apparatus in the case of intermittent cleaning in order to avoid duplication with the previous section. After the cap is opened, the control device 46 is required in advance for the treatment agent to almost flow out of the container.
When the set time stored in 0 elapses, the liquid sending pump 440
Is activated, and the switching cock 442 is opened and the cleaning member 34 is opened.
6 and the solenoid valve operation program timer of the control device 460 starts. In the solenoid valve operation program timer, an opening time, a closing time, and the number of times of opening and closing of the solenoid valve are set. The electromagnetic valve (washing valve) 450 sends the washing water from the water storage tank 426 to the spray nozzle 214 attached to the opening / cleaning member 346 according to the program, and the spray nozzle 214 sprays the wash water to the inner wall of the container. When the cleaning nozzle finishes the spray cleaning for the predetermined spray time, pause interval and number of sprays set in the program timer, and the program timer is closed, the developer composition container 20
The opening and washing of 3 is completed.

When the cleaning of the inside of the container 203 is completed, in this embodiment, another two water supply pipes (for a bleach replenisher and a fixer replenisher) are separated from the switching cock 442.
However, the cleaning water is also sent to the respective cleaning nozzles via the respective electromagnetic valves, and the containers 205 and 207 from which the bleaching agent composition and the fixing agent composition are respectively discharged are also cleaned. All of the washing operations are performed with the same injection time, pause time, and number of injections set as in the above-described opening and washing operation of the developer composition container. In this manner, for each of the containers from which the treating agent composition has been discharged, the cleaning water is intermittently and repeatedly injected into the empty container from the cleaning nozzle to perform the cleaning. The washing water used for washing flows down the container wall, flows down from the mouth to the outside of the container, flows into the dissolving tank 347 (other processing agent compositions also flow into the respective dissolving tanks), and dilutes the diluted water. Used as a part.

After the predetermined cleaning of the inside of the container is completed,
When the liquid supply pump 440 is stopped, the opening motor 328 is driven, and the sliding member 32 is closed.
When the micro switch 334 detects the upper limit position of the mounting base, that is, the initial position, the stop is stopped at that position, and a series of opening and cleaning operations is completed.

The washing performed by spraying water into the inside of the container and around the mouth is intermittent by dividing the spray of washing water into a plurality of sprays, rather than spraying the same amount of wash water continuously at one time. In this case, it is possible to remove the deposits on the vessel wall much more effectively by adopting the method of the repetitive spray cleaning. If the washing water is continuously sprayed, the washing water that blows up and the falling washing water may interfere with each other and reduce the washing efficiency. However, if the washing water is intermittently sprayed, this effect is prevented and the washing efficiency is reduced. improves. Further, when the injection interval is set to 1 second or more, it is preferable that the washing water is discharged out of the container between the injections.

It is effective to divide the number of washings into three or more. Preferably, the number is preferably 3 to 10 times. However, the amount of water per injection is 5 to
Preferably it is 100 ml. Many injections with less than 5 milliliters (the injection interval becomes shorter),
In the cleaning method of jetting a small number of times at 100 milliliters or more, the cleaning effect is slightly improved compared to the case where the divided cleaning is not performed. The total amount of washing water is arbitrary as long as it is smaller than the amount of water added to the treating agent composition for preparing a treatment solution such as a replenisher in a dissolution tank.
0-500 ml. The difference between the amount of water added to prepare the replenisher in the dissolution tank and the amount of dilution water is added directly to the dissolution tank. In that case, an agitation effect at the time of pouring into the dissolution tank is expected.

In the control device 460, the program for intermittently washing by dividing the washing water is designed by selecting an appropriate level from the following injection time, pause time, number of injections and washing water amount. The injection time of the washing water is set in the range of 0.1 to 60 seconds, preferably 1.0 to 10.0 seconds. The dwell time between injections is 1.0-10 seconds, preferably 1-1.
It is set in the range of 0.0 seconds. The jet speed of the washing water when the solenoid valve is open is set in the range of 1.0 to 100 ml / sec, preferably 5 to 30.0 ml / sec. As described above, the number of injections is 3 to 10
The number of injections is preferably one, and the amount of water injected at one time is preferably 5 to 100 ml.

(7) Preparation and storage of replenisher in replenisher / dissolution tank The replenisher / dissolution tank 347 shown in FIG. 4 as a simple rectangular figure is supplemented. In this embodiment, this tank functions as both a dissolving tank and a replenishing tank. This section supplements the operation of this tank. FIG. 7 is schematically rewritten to functionally describe the replenishing tank shown as the replenishing tank 347 in FIGS. 1 and 4, and the replenishing tank itself is a cylindrical tank made of polyvinyl chloride resin. . The treating agent discharged from the treating agent container and the washing wastewater that has washed the container are introduced from the upper portion through the treating agent inlet 501 into a portion of the replenisher tank at the bottom where residual liquid is present. Part of the dilution water to be added to the treatment agent is washing water for the container, and the rest flows from the water storage tank (426 in FIG. 4) to the bottom of the tank by opening and closing the electromagnetic valve 502 as described above. At this time, since the dilution water flows in a large amount in a short time by the liquid sending pump, the water flow stirs and mixes with the treatment agent. Therefore, it is not always necessary to provide a stirring device. The replenishment from the replenishment tank to the processing tank is performed by a replenishment system (368 in FIG. 4) indicated by P in FIG. During off-peak periods and in small developing laboratories, the amount of photosensitive material processed per day is small, and the replenisher once prepared may stay in the replenisher for a long time. It is advisable to take measures to prevent this. In order to prevent the replenisher from being deteriorated by air oxidation while being stored in the replenisher tank, a floating lid 503 made of a vinyl chloride resin is provided on the surface of the replenisher so as to be in contact with air. I have.

(8) Replenishment Control Method of Batch-Replenishing Treatment Agents As described above, the operation of putting each treatment agent into the replenishment tank and preparing the replenisher solution can be performed collectively from the viewpoint of work management. This is also advantageous from the viewpoint of processing management. As a method, the amount of the replenisher used is set in advance by associating in advance the amount of the replenisher replenished at a time and the amount of the photosensitive material that can be processed with the amount of the replenisher. When the amount reaches the amount, the replenishment amount is corrected by comparing the prescribed processing amount of the photosensitive material corresponding to the amount and the actual processing amount of the photosensitive material with the replenisher,
It is necessary to match the preset processing amount of the photosensitive material with the supply timing. This makes it possible to reliably process a predetermined amount of the photosensitive material with a processing solution in the processing tank in which the replenisher is replenished and the activity is maintained.

If an error occurs in the replenishing means (for example, fatigue of a pump, clogging of a pipe, or the like), a replenishing amount of a specific replenishing solution may not coincide with a corresponding predetermined photosensitive material processing amount. The correction operation of the replenishing apparatus of the present invention in that case will be described separately for a specific replenishing tank (generally, a developing replenishing tank) and another replenishing tank (for example, a bleach-fixing replenishing tank).

First, when the remaining amount of the specific replenisher reaches the sensor for detecting the lower limit liquid level (360 in FIG. 4), the remaining amount of the specific replenisher (in this case, the developer replenisher in this case) is set to the prescribed value. The replenisher used from the time the value reached the lower limit level sensor this time corresponds to the replenishment amount of the replenisher in one time to the replenishment tank, and the processing of the photosensitive material corresponding to the replenishment amount The amount is specified. Therefore, when the remaining amount reaches the lower limit liquid level sensor, the actual processing amount from the previous arrival at the lower limit liquid level sensor to the current lower limit liquid level sensor is read, and this processing amount and the replenishment amount of the replenisher (that is, one kit The amount of replenisher in the specific replenisher tank is corrected next time so that the two values match each other.

Next, the replenishment and processing amount of other replenishers (in this case, the bleach replenisher and the fixing replenisher) will be described. When the remaining amount of the specific replenisher reaches the specified value, that is, the lower limit liquid level sensor, and when the remaining amount of the other replenisher does not reach the specified value, that is, the lower limit liquid level sensor of the processing tank, Until the remaining amount of the replenisher reaches the specified value, the replenisher is forcibly replenished, and the next replenishment amount of the replenisher is corrected based on the information of the forcibly replenished amount. Specifically, since the amount of the replenisher liquid that was actually replenished to the treatment tank before the forced replenishment is performed from the amount of the replenisher liquid that was forcibly replenished and the prepared amount of the replenisher liquid at that time, this amount, The amount of replenishment of the replenisher for the next time is corrected by comparing the amount of the replenisher with the actual amount of processing of the photosensitive material during the replenishment.

If the remaining amount of another replenisher reaches the specified value before the remaining amount of the specific replenisher reaches the specified value, that is, the lower limit liquid level sensor, the replenishment of the replenisher is stopped. In addition, the actual processing amount of the photosensitive material processed until the replenisher reaches the specified value is compared with the specified processing amount corresponding to the replenishment amount of the replenisher, and the next replenishment amount of the replenisher is determined. to correct. Therefore, in the next processing, correction is performed so that the specified processing amount of the photosensitive material corresponding to the amount of the replenisher replenished for the specific replenisher and the other replenishers also matches the actual processing amount. . Such a correction operation is performed each time the replenisher is supplied to the replenisher tank and diluted with water to prepare a replenisher, so that correct replenishment management is maintained.

In the above-described method, the replenishment amount for the next time is corrected by comparing the replenishment amount of the processing agent with the actual processing amount of the photosensitive material processed by the processing agent. When the specified processing amount of the photosensitive material is processed, the next replenishment amount can be corrected by comparing the specified replenishment amount corresponding to the replenishment amount of the processing agent with the actual usage fee of the replenisher.

(9) Processing Specifications Color paper is developed according to the following process specifications. The following formulation is a typical example of a minilab printer processor PP125 manufactured by Fuji Photo Film Co., Ltd.
This is a processing step when imagewise exposure is performed using 8AR and subsequently color development processing is performed.

Processing Step Temperature Time Replenishment amount ^* Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ℃ 20 seconds-Rinse (3) ** 38.0 ° C 20 seconds-Rinse (4) ** 38.0 ° C 20 seconds 121 ml Drying 80 ° C 30 seconds (Note) * Replenishment amount per 1 m ^{2 of} photosensitive material ** A rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is attached to the rinse (3), and the rinse liquid is taken out of the rinse (3) and sent to the reverse osmosis module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. Rinsing was carried out in a 4-tank countercurrent system from (1) to (4).

The replenisher for developing was added to the developing tank at a rate of 45 ml per 1 m ² of the light-sensitive material.
Each bleach-fix tank is replenished at a rate of 17.5 ml.

The color paper is treated at 40 ° C.
It is preferable to shorten the entire process by high-temperature treatment at 70 ° C. and a high developing agent concentration of 7 g / l or more. Specifically, each of the steps of color development, bleach-fixing, washing or rinsing or stabilization, and drying is shortened from 10 seconds to 15 seconds, and ultrashort processing in which all steps are within 40 seconds to 60 seconds can be preferably applied.

(10) Startup Kit The developing machine normally operates continuously. During that time, a processing solution called a mother liquor or a tank solution is always stored in the processing tank, and the amount consumed by the developing process is replenished. Then, a steady operation is performed, but before starting the operation, it is necessary to fill each processing tank with the respective mother liquor. This mother liquor is called the start mother liquor, but its preparation is carried out directly in the treatment tank. That is, the mixing and dilution of the starting mother liquor preparation are performed in each processing tank according to the following prescription and the mother liquor is completed.

• Color developing solution starting mother liquor P1A 1.1 liter P1S 1.2 liters Water 10.0 liters pH 10.15 • Bleaching-fixing solution starting mother liquor P2A 2.0 liters P2B 2.0 liters Water 8.0 liters pH 6.0

• Formulation of P1A: Same as the developer composition described above. • Formulation of P1S: 6.1 g of diethylenetriaminepentaacetic acid 68.3 g of potassium carbonate 68.3 g of disodium-N, N-bis (sulfonatoethyl) Hydroxylamine 22.0 g Sodium bicarbonate 64.5 g Potassium chloride 120.0 g Potassium bromide 0.25 g Add water 1.0 liter pH 9.25 Formulation of P2A Bleach composition as described above Same ・ Prescription of P2B Same as the fixing agent composition described above

(11) Photosensitive Material Used for Development Process [Preparation of Photosensitive Material Sample] A corona discharge treatment was applied to the surface of a support in which both sides of a paper were coated with polyethylene resin, and then sodium dodecylbenzenesulfonate was used. Was provided, and a first to seventh photographic constituent layers were sequentially coated to prepare a silver halide color photographic light-sensitive material having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows. The average grain size of the emulsion shown below is the average value of the converted diameter of the grain area measured by the so-called projection area method.

(Preparation of Coating Solution) Preparation of Coating Solution for Fifth Layer 12 g of cyan coupler A having the following structure, 100 g of cyan coupler B, 50 g of cyan coupler C, 62 g of color image stabilizer (Cpd-6), and color image stabilization Agent (Cpd-7) 13
g, color image stabilizer (Cpd-9) 38 g, color image stabilizer (C
pd-14) 12 g, color image stabilizer (Cpd-15) 11
0 g, 62 g of color image stabilizer (Cpd-16), 74 g of color image stabilizer (Cpd-17), color image stabilizer (Cpd-18)
74 g and 40 g of a color image stabilizer (Cpd-19) are dissolved in 140 g of a solvent (Solv-5) and 350 ml of ethyl acetate, and this solution is dissolved in 650 of a 10% aqueous solution of gelatin containing 200 ml of 10% sodium dodecylbenzenesulfonate.
The resulting mixture was emulsified and dispersed in 0 g to prepare an emulsified dispersion C.

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On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-sized emulsion C having an average grain size of 0.50 μm and small-sized emulsion C having an average grain size of 0.41 μm (silver molar ratio). The coefficient of variation was 0.09 and 0.11, respectively, and 0.5 mol% of silver bromide was locally contained in a part of the surface of silver chloride-based grains in each size emulsion.) . This emulsion contains the following red-sensitive sensitizing dyes G and H in an amount of 6.0 × 10 ⁻⁵ mol per mol of silver for the large-size emulsion C, and 6.0 × 10 ^-5 mol for the small-size emulsion C per mol of silver. 9.0 × 10 ^-5 mol is added. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. Emulsified dispersion C and silver chlorobromide emulsion C
Were mixed and dissolved to prepare a fifth layer coating solution having the composition described below.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Ab-1, Ab-2 , Ab-3 and Ab-4 the total amount respectively 15.0 mg / m ² in each layer, 60.0mg / m ^2,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

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The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

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(Sensitizing dyes A, B and C were used in an amount of 1.4 ×
^10-4 moles, ^1.7x each for small size emulsions
10 ^-4 mol was added. Green sensitive emulsion layer

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMol of sensitizing dye F per mol of silver halide.
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for size emulsion^-FourMole was added. ) Red-sensitive emulsion layer

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(Sensitizing dyes G and H were converted to silver halide 1
6.0 × 1 per mole for large size emulsions
0 ^-5 mol, respectively 9.0 × 1 to the small size emulsion
0 ^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

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Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and
1- (3-methylureidophenyl) was added to the red-sensitive emulsion layer.
) -5-mercaptotetrazole
3.3 × 10 per mole of silver halide^-FourMol, 1.0 × 10^-3
Mol and 5.9 × 10^-FourMole was added. Furthermore, the second
Layer, the fourth layer, the sixth layer and the seventh layer, respectively.
mg / m ^Two 0.2 mg / m^Two , 0.6 mg / m^Two ,
0.1mg / m^Two Was added so that Blue sensitivity
4-hydroxy-6 to the emulsion layer and the green-sensitive emulsion layer
-Methyl-1,3,3a, 7-tetrazaindene
1 × 10 per mol of silver halide^-FourMole, 2
× 10^-FourMole was added. Also, methacrylate is added to the red-sensitive emulsion layer.
Copolymer of phosphoric acid and butyl acrylate (weight ratio 1: 1, flat
Average molecular weight of 200,000 to 400,000) is added to 0.05 g /
m^TwoWas added. In addition, the second, fourth and sixth layers
Catechol-3,5-disulfonate disodium
6mg / m each^Two, 6mg / m^Two, 18mg / m^TwoBecomes
Was added as follows. Also, to prevent irradiation
In addition, the following dyes are shown in the emulsion layer
Was added.

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content of 16% by weight, ZnO; content of 4% by weight) and a fluorescent whitening agent (4,4'-bis (benzoxazolyl) stilbene and 4,4-bis (5-methylbenzoxazolyl) stilbene 8/2 (weight ratio): 0.05% by weight), including bluish dye (ultramarine)

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large-size emulsion A having an average grain size of 0.72 μm and small-size emulsion A having a 0.60 μm emulsion (silver molar ratio) The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. ) 0.26 Gelatin 1.35 Yellow coupler (ExY) 0.62 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0 .08 Solvent (Solv-1) 0.23

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.45 μm and small-size emulsion B of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride.) 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-1) 0.05 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.02 UV absorption Agent (UV-4) 0.04 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer ( Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Image stabilizer (Cpd-10) 0.01 Color Image Stabilizer (Cpd-11) 0.0001 solvent (Solv-3) 0.11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-size emulsion C having an average grain size of 0.50 μm and small-size emulsion C of 0.41 μm (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.11 Gelatin 1.16 Cyan coupler A 0.012 Cyan coupler B 0.100 Cyan coupler C 0.050 Color image stabilizer (Cpd-6) 0.062 Color image stabilizer (Cpd-7) 0.013 colors Image stabilizer (Cpd-9) 0.038 Color image stabilizer (Cpd-14) 0.012 Color image stabilizer (Cpd-15) 0.110 Color image stabilizer (Cpd-16) 0.062 Color image stabilizer Agent (Cpd-17) 0.074 Image stabilizer (Cpd-18) 0.074 Color Image Stabilizer (Cpd-19) 0.040 solvent (Solv-5) 0.140

Sixth layer (UV absorbing layer) Gelatin 0.66 UV absorbing agent (UV-1) 0.19 UV absorbing agent (UV-2) 0.06 UV absorbing agent (UV-3) 0.06 UV absorbing Agent (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.09 Solvent (Solv-7) 0.25

Seventh layer (protective layer) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

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(12) Exposure Method to Photosensitive Material In the printer portion shown in the right half of the printer processor in FIG. 1, surface exposure is performed from a halogen lamp light source through a developed negative. On the other hand, as another mode, the image of the developed negative is read, the sensor is scanned, the image information is electrically read, the electrical image information is converted into digital data, and the image is corrected by applying image processing by a computer. Alternatively, the exposure may be performed using a laser beam modulated with the converted information by converting the corrected image information into an analog signal.

By this method, it is possible to perform printing with corrected overexposure and underexposure of the developed negative, and over / under exposure of the subject contrast. The outline of this process will be described with reference to FIGS. FIG. 8 shows an image output device 8 for a color image reproducing system for reproducing a color image on a color paper based on image data processed by the image processing device, and a printer processor for receiving the laser output and producing a color print. FIG.

In FIG. 8, the negative digital image information subjected to the image processing is sent to the data memory 80 via the interface 78 and the CPU 79 for controlling the image output device 8.
A D / A converter 81 for converting image data into an analog signal, a laser light irradiating means 82, and a modulator driving means 83 for outputting a modulation signal for modulating the intensity of the laser light. Performs modulation exposure.

FIG. 9 is a schematic diagram of the laser light irradiating means 82 shown in FIG. 8. The laser light irradiating means 82 includes semiconductor laser light sources 84a, 84b, and 84c, and emits laser light emitted from the semiconductor laser light source 84b. The light is converted into green laser light having a wavelength of 532 nm by the wavelength conversion means 85, and the laser light emitted by the semiconductor laser light source 84 c is converted by the wavelength conversion means 86 into blue laser light having a wavelength of 473 nm.

6 emitted from the semiconductor laser light source 84a
Red laser light of any wavelength between 70 nm and 690 nm,
The green laser light whose wavelength has been converted by the wavelength converting means 85 and the blue laser light whose wavelength has been converted by the wavelength converting means 86 are respectively converted into an acousto-optic modulator (AO).
M) and the like so as to be incident on the optical modulators 87R, 87G, 87B.
B is configured such that a modulation signal is input from the modulator driving unit 83 and the intensity of the laser beam is modulated according to the modulation signal. At this time, if the semiconductor laser light source 84a can operate at high speed, the optical modulator 87R can be omitted by directly modulating the semiconductor laser light source 84a.

The laser light whose intensity has been modulated by the light modulators 87R, 87G, 87B is reflected by the reflection mirror 88R,
The polygon mirror 89 is reflected by 88G and 88B.
Incident on. Here, the paper is transported at a speed of about 75 mm per second, the scanning line density is 600 lines per inch, and each pixel is modulated every 100 nsec.

The color paper 90 exposed by the laser beam is sent to the developing section 94, where the color paper 90 is subjected to a predetermined color developing process, a bleach-fixing process, and a washing process. The color image is reproduced on the paper 90. A color developing tank 94, a bleach-fixing tank 95, and a washing tank 96 are used to perform a color developing process, a bleach-fixing process, and a washing process on the color paper 90.
Is sent to a drying unit 97, and after being dried, one frame of one frame is driven by a cutter 98 driven in synchronization with the conveyance of the color paper 90 based on a reference hole formed in a side edge of the color paper 90. It is cut into a length corresponding to the color image recorded on the film F or one color paper P, sent to the sorter 99, and accumulated in a number corresponding to one film F or for each customer. Is configured.

[Example 2] In Example 2, the results of a test on the effect of the material of the container in Example 1 by changing the floating fixing agent are shown. The container used was an HDPE container (density of sample No. 3 in Table 1 of Example 1 as an example of the present invention).
0.966), and LD of sample No. 7 in Table 1 as a comparative example.
The same method as that of Example 1 except that a PE container (density 0.922) was used and a composition using an iron (III) complex salt of ethylenediaminedisuccinic acid having the following composition was used as a bleach-fixing treatment composition. Was tested.

Formulation of bleach-fixing composition: filling amount 100
0 ml A treatment agent was prepared by concentrating the following basic formulation (use solution formulation) five-fold and filled in the treatment agent bottle. This treating agent is a slurry composition in which a suspension exists.

[Basic prescription] Ammonium thiosulfate solution (750 g / liter) 0.61 mol sodium sulfite 0.17 mol iron (III) · ethylenediaminedisuccinate complex (SS form) ^* 0.11 mol ethylenediaminedisuccinate complex ( (SS form) 0.011 mol Acetic acid 0.08 mol pH adjustment (ammonia or acetic acid) 6.0 1 liter by adding water (Note 1) *: SS form means SS form of optical isomer.

The test results are shown in Table 1 within the scope of the present invention.
In the No. 3 HDPE container, the cleaning effect of the solution was ◎ on the same evaluation scale as in Example 1, and in the No. 7 LDPE container of the comparative example, it was ×. Therefore, even in the case of a highly concentrated bleach-fix processing composition in which the bleach-fix solution is in a slurry state and the type of the bleach is different, HDPE having the material requirements of the present invention has excellent dischargeability and detergency. It was confirmed that.

[Supplementary Explanation] Here, the bleach-fix solution used in Example 2 is slightly supplemented. The bleach-fixing solution is unstable due to the coexistence of an iron (III) complex as an oxidizing agent and a reducing thiosulfate. One-part construction is generally difficult, and usually has two parts, a bleach part and a fixing part. The bleach-fix processing composition used in the present example was changed to 1 by changing the bleaching agent.
It is a bleach-fixing agent treating agent composition which is stable in part composition and realizes stability and simplicity without defects such as bleaching fog, incomplete coloring of a dye and incomplete removal of silver.

The bleach-fixing agent represented by the above formula contains, as a main component, either or both of iron (III) / ethylenediamine disuccinate complex and iron (III) / ethylenediamine diglutamic acid complex as a bleaching agent. And a one-part concentrated bleach-fixing agent filled in a container having an oxygen supply rate of 10 ml / hr or less per liter of the filler.

In particular, 50 mol% or more of ethylenediaminedisuccinic acid and ethylenediaminediglutamic acid constituting the iron (III) · ethylenediaminedisuccinic acid complex salt and the iron (III) · ethylenediaminediglutamic acid complex salt, respectively, comprise at least 50 mol% of the optical isomer (S, S) A bleach-fixing composition comprising a body is preferred.

As the bleaching agent, at least one compound selected from the group consisting of ethylenediaminedisuccinic acid and ethylenediaminediglutamic acid occupies 50 to 100 mol% of the prebleaching agent as the main bleaching agent.
A group consisting of iron (III) complex salts of-(2-carboxylateethyl) -L-aspartic acid, β-alanine diacetate, methyliminodiacetic acid, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminemonosuccinic acid, and ethylenediaminetetraacetic acid At least one compound selected from the group consisting of 0 to 50 mol% as a second bleaching agent.

The characteristics of the above bleach-fixing composition can be summarized as follows: a specific iron (III) complex salt compound was used as a bleaching agent which was stable for a long time even in a system coexisting with the fixing agent; The stability of the processing agent is further enhanced by using an HDPE container having polyethylene as a single constituent resin, and the bleach-fix processing agent can be designed in a one-part configuration. That is, its stability is maintained.

Example 3 In Example 3, the effect of each component of the container for a developer composition of the present invention is shown for color negative development. The sample No. in Table 1 of Example 1 was used. Three
The same materials as those prepared in the above and the following processing agent were charged into the container for the developing composition, and the same evaluation as in Example 1 was performed. As a result, good results were obtained.

Color developing composition: filling amount 1320 ml diethylenetriaminepentaacetic acid 8.0 g 4,5-dihydroxybenzene-1,3-disulphonic acid disodium salt 0.30 g potassium hydroxide 6.24 g sodium sulfite 0.109 Mol sodium-N, N-bis (sulfonatoethyl) hydroxylamine 13.6 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 15.7 g potassium carbonate 91.7 g Water was added and the total amount was 440 ml. Specific gravity (25 ° C) 1.100 pH 10.5

Bleach composition: filling amount 850 ml ammonium nitrate 29.4 g maleic acid 75.6 g succinic acid 63.5 g imidazole 35.3 g 1,3-diaminopropanetetraacetic acid ferric complex (1 ammonium salt) 208.2 g odor Ammonium chloride 81.1 g Add water and add 850 ml

Fixing agent composition: Filling amount 1320 ml Ammonium thiosulfate 560.0 g Ammonium bisulfite 39.0 g Imidazole 35.0 g Ethylenediaminetetraacetic acid 9.0 g Mercaptotriazole 2.0 g Water was added to 887.0 ml Specific gravity 1.307 pH7 .0

In addition to the above, a stabilizer and a development preservative were prepared by filling the following containers with a processing agent. Container: prism type 75 mm x 75 mm x 105 mm (column height) x 1
25 mm (height to the base of the neck) × 155 mm (height to the top of the head) Stabilizer composition: filling amount 500 ml 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 75.0 g 1,2,4-triazole 130.0 g p-toluenesulfinic acid 3.0 g p-nonylphenoxypolyglycidol (glycidol average degree of polymerization 10) 20.0 g 1,2-benzoisothiazolin-3-one 5.0 g water was added. 1 liter pH 8.3 Developer preservative: filling amount 500 ml hydroxylamine sulfate 180.0 g water 1 liter pH 3.3

After the processing agent composition prepared as described above was filled in a container, one of each of the color developer composition, the bleaching agent composition and the fixing agent composition was set as a set and loaded into a cardboard cartridge. . In addition, the stabilizer composition and the developer preservative were filled in a container, and then each was similarly loaded into a cardboard cartridge.

The treatment composition thus adjusted was prepared in Example 1.
In the same manner as described above, the replenisher was prepared by loading into a processor, opening the cap, washing, and diluting. The finished amount of the replenisher to which the water for washing and dilution has been added is as follows. Color developing replenisher 3.0 liter Bleaching replenisher 1.0 liter Fixing replenisher 1.5 liter Stable replenisher 1.9 liter Developer preservative replenisher 1.8 liter In addition, color developing replenisher 3.0 liter A mechanism is provided in which 180 ml of a developer preservative replenisher is automatically added.

Startup Kit Adjustment of Color Developer Start Mother Solution Adjustment in the processor's color developer tank: 2.7 liters of the above color developer composition 105 ml of the above developer preservative 105 ml of the following starter 450 ml of water In addition 9.0 L Starter: Potassium hydroxide 1.0 g Potassium carbonate 40.0 g Sodium bicarbonate 28.0 g Potassium bromide 9.6 g Potassium iodide 0.01 g Water is added to 450 mL pH 9.6

・ Adjustment of bleaching solution start mother liquor Adjustment in processor bleaching solution tank 2.3 liters of bleaching agent as described above with addition of water 4.0 liters ・ Adjustment of fixing agent starting mother liquor Fixing solution tank of processor (1) ), Adjusted in (2) 1.2 g of the above-mentioned fixing agent composition 4.0 liters by adding water ・ Adjustment of the mother liquor for starting the stabilizing solution Adjustment Stabilizer composition 20 ml 2.0 liters with water

Processing Step Specifications Process Processing Time Processing Temperature Replenishment Color Developing 3 minutes 5 seconds 38.0 ° C 15 ml Bleaching 50 seconds 38.0 ° C 5 ml Setting (1) 50 seconds 38.0 ° C Setting (2) 50 seconds 38.0 ° C 5ml * Stable (1) 30 seconds 38.0 ° C Stable (2) 20 seconds 38.0 ° C Stable (3) 20 seconds 38.0 ° C 1.0ml ** Dry 1 minute 30 seconds 60 ° C (*: Separate piping, (Replenish 15 ml of stabilizer overflow) (**: Refill 24 ml of water with a separate pipe)

[Supplementary Explanation] The automatic developing machine used in conducting the test of Example 3 above, the method of using the developer composition,
The processing agent cartridge, the replenishment method, and other related items will be described.

(1) Configuration of Automatic Developing Machine An automatic developing machine for a color negative having an automatic cleaning mechanism has a function of simultaneously loading and replenishing a processing agent cartridge as in the first embodiment. A bleach replenisher prepared by diluting the color developer composition and the bleach composition according to the mold processing is replenished to a bleaching tank, and a fixing replenisher prepared by diluting the fixing agent composition is replenished to a fixing tank. . The replenishment method is basically the same as the processor part of the above-described printer processor for color paper, and the structure is assembled so as to be compatible with the color negative processing. However, the principle is the same.

(2) Water saving method that can be added to multi-stage countercurrent washing The developing apparatus used in the present embodiment saves water more than the so-called multistage countercurrent washing system. The water saving method is performed in a replenisher tank, and the washing water used for the fixing agent composition is used as dilution water in the tank without adversely affecting the photographic processing performance. That is, the automatic processing apparatus used has a developing tank, a bleaching tank, a fixing tank, and a three-stage multi-stage countercurrent type washing tank, and the concentrated fixing replenisher is supplied to the fixing tank. The developing apparatus is configured so that the rinsing water is replenished to the last tank of the rinsing tank, and the photographic photosensitive material is sequentially immersed in a developing tank, a processing solution tank having a fixing ability, and a rinsing or stabilizing bath. And a pump for sending the washing water in the tank from the second tank of the multistage countercurrent washing tank to the fixing tank. The pump for supplying the washing water of the second washing tank to the fixing tank operates according to the processing amount information from the detecting means for detecting the processing amount of the photosensitive material. When the supply of water is required, the washing water and the fixing replenisher composition are supplied by a signal from the liquid level detecting means of the replenisher tank.

Further, the development processing apparatus has a stop time of the apparatus,
Control means for calculating the amount of moisture evaporated from the fixing tank based on operating state information comprising pause time and photosensitive material processing time and working environment information comprising temperature and humidity of the developing work place; and A pump for feeding the washing water in the second washing tank to the fixing tank based on the given information on the amount of evaporated water from the fixing tank also has a mechanism that operates to compensate for the amount of evaporated water.

Further, the second washing tank has a piping system which receives the supply of washing water directly from the washing water storage tank, and feeds an amount of washing water for compensating the evaporation amount from the washing tank to the fixing tank. After that, it is possible to directly supply an amount of washing water equivalent to the amount of liquid sent from the washing water storage tank to the second washing tank.

The amount of washing water to be pumped from the washing tank to the fixing tank is at least 50% of the amount of washing water or the replenisher of the stabilizing solution supplied to the final washing tank, that is, 50% of the supplied washing water. The above is reused as the dilution water for preparing the fixing replenisher, and water is saved by that amount. A basic feature of this developing apparatus is that a processing liquid tank having a fixing ability for washing water or a stabilizing solution in a washing or stabilizing bath (the second washing bath in the apparatus of this embodiment) except for the first tank and the last tank. Is provided with a liquid sending pump so as to send the liquid to the pump.

In the conventionally known development processing method in which the washing water in the first washing tank is added to the fixing tank as dilution water for the replenisher, a streak-like silver streaking stain or roller transfer stain on the surface of the photosensitive material may occur. Problems such as a decrease in accuracy of the liquid sending pump occur. However, in the method according to the present embodiment in which the washing water in the second washing tank is added, the dilution water is supplied without such problems.

Further, (1) the concentrated fixing agent and the second
The case of the present invention in which the washing water in the washing tank is separately replenished to the fixing tank, the case of (2) the conventional method of replenishing a replenisher prepared by previously mixing a concentrated fixing agent with fresh water, and (2) 3) Differences in photographic properties including desilvering property and adhesion of dirt are recognized between the three replenishment methods when the replenisher prepared by mixing the above fixing agent with the washing water in the second washing tank is replenished. I couldn't. That is, in the fixing agent replenishing method of the present embodiment, the washing water can be reused without affecting the processing quality, and the amount discharged as waste liquid is reduced by the reused amount.

(3) Light-sensitive material used in the processing: An undercoated cellulose triacetate film support was
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.155 Silver Iodobromide Emulsion P Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-3 0.002 1. Cpd-2 0.001 HBS-1 0.004 HBS-2 0.002 Second layer (second antihalation layer) Black colloidal silver Silver 0.066 Gelatin 0.407 ExM-1 0.050 ExF-1 0 × 10 ⁻³ HBS-1 0.074 Solid disperse dye ExF-2 0.015 Solid disperse dye ExF-3 0.020

Third layer (intermediate layer) Silver iodobromide emulsion O 0.020 ExC-2 0.022 polyethyl acrylate latex 0.085 gelatin 0.294 Fourth layer (low-sensitivity red-sensitive emulsion layer) Silver Emulsion A Silver 0.323 ExS-1 5.5 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 2.4 × 10 ^-4 ExC-1 0.109 ExC-3 0.044 ExC -4 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.17 Gelatin 0.80

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion B Silver 0.28 Silver Iodobromide Emulsion C Silver 0.54 ExS-1 5.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 2.0 × 10 ^-4 ExC-1 0.14 ExC-2 0.026 ExC-3 0.020 ExC-4 0.12 ExC-5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18 6th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.47 ExS-1 3.7 × 10 ^-4 ExS-2 1 × 10 ^-5 ExS-3 1.8 × 10 ^-4 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY-5 0.0. 008 Cpd-2 0.046 Cpd-4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12

Seventh layer (intermediate layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.83 Gelatin 0.84 Eighth layer (to red sensitive layer) Layer giving multilayer effect) Silver iodobromide emulsion E 0.560 ExS-6 1.7 × 10 ^-4 ExS-10 4.6 × 10 ^-4 Cpd-4 0.030 ExM-2 0.096 ExM- 3 0.028 ExY-1 0.031 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58

Ninth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion F silver 0.39 silver iodobromide emulsion G silver 0.28 silver iodobromide emulsion H silver 0.35 ExS-4 2.4 × 10 ^-5 ExS-5 1.0 × 10 ^-4 ExS-6 3.9 × 10 ^-4 ExS-7 7.7 × 10 ^-5 ExS-8 3.3 × 10 ^-4 ExM-2 0.36 ExM-3 0.045 HBS-1 0.28 HBS-3 0.01 HSB-4 0.27 Gelatin 1.39 10th layer (Medium speed green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 0.45 ExS -4 5.3 × 10 ^-5 ExS-7 1.5 × 10 ^-4 ExS-8 6.3 × 10 ^-4 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY-1 0.006 ExM-4 0.028 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 gelatin 0.44

Eleventh layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I silver 0.19 silver iodobromide emulsion J silver 0.80 ExS-4 4.1 × 10 ^-5 ExS-7 1.1 × 10 ^-4 ExS-8 4.9 × 10 ^-4 ExC-6 0.004 ExM-1 0.016 ExM-3 0.036 ExM-4 0.020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 Cpd-3 0.004 Cpd-4 0.007 HBS-1 0.18 Polyethyl acrylate latex 0.099 Gelatin 1.11

Twelfth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.047 Cpd-1 0.16 Solid Disperse Dye ExF-5 0.020 Solid Disperse Dye ExF-6 0.020 Oil-soluble Dye ExF-7 010 HBS-1 0.082 Gelatin 1.057 13th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion K silver 0.18 Silver iodobromide emulsion L Silver 0.20 Silver iodobromide emulsion M Silver 0 0.07 ExS-9 4.4 × 10 ^-4 ExS-10 4.0 × 10 ^-4 ExC-1 0.041 ExC-8 0.012 ExY-1 0.035 ExY-2 0.71 ExY-30 .10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.24 Gelatin 1.41

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion N silver 0.75 ExS-9 3.6 × 10 ^-4 ExC-1 0.013 ExY-2 0.31 ExY-30 .05 ExY-6 0.062 Cpd-2 0.075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.91 Fifteenth layer (first protective layer) Silver iodobromide emulsion O Silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F-18 0.009 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3

Sixteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-30 .05 S-1 0.20 Gelatin 0.75 Further, each layer may have a preservability, a processing property, a pressure resistance, an antifungal property.
In order to improve antibacterial properties, antistatic properties and coatability, W-
1 to W-5, B-4 to B-6, F-1 to F
-18 and iron, lead, gold, platinum, palladium, iridium, ruthenium, and rhodium salts. The coating solution for the eighth layer was 8.5 × 10 ^-3 g per mol of silver halide, and the coating solution for the eleventh layer was 7.9 × 10 ^-3 g.
^A sample was prepared by adding ^-3 grams of calcium with an aqueous solution of calcium nitrate.

Table 1 below shows the AgI content, grain size, surface iodine content and the like of the emulsions represented by the above-mentioned abbreviations. The surface iodine content can be determined by XPS as follows. The sample was transferred to -115 in a 1x10 torr transfer vacuum.
C., and irradiated with MgKα as a probe X-ray at an X-ray source voltage of 8 kV and an X-ray current of 20 mA.
2, measured for Br3d and I3d5 / 2 electrons, the integrated intensity of the measured peak was corrected by a sensitivity factor, and the iodine content of the surface was determined from the intensity ratio.

[0181]

[Table 2]

In Table 2, (1) Emulsions L to O were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

(2) Emulsions A to O are described in JP-A-3-23745.
According to the example of No. 0, gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer.

(3) Preparation of tabular grains is disclosed in
According to the example of 58 426, low molecular weight gelatin is used.

(4) JP-A-3-2374 for tabular grains
Dislocation lines as described in No. 50 have been observed using a high voltage electron microscope.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were put into a 700 ml pot mill. , Dye ExF-
2 and 5.0 g of zirconium oxide beads (diameter 1 mm)
500 ml was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles is 0.4
It was 4 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameter of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
m. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP-A-549,489A. The average particle size was 0.06 μm.

The solid dispersion of ExF-7 was dispersed by the following method.

To 1400 g of an ExF-7 wet cake containing 30% of water, 70 g of water and W-2 were added, and the mixture was stirred.
70 g of xF-7 was added and stirred, and the concentration of ExF-7 was 30%.
Slurry. Next, 1700 ml of zirconia beads having an average particle size of 0.5 mm was filled into Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd., and the peripheral speed was about 10 m / sec, and the discharge rate was 0.5 liter / min.
For 8 hours.

The compounds used for forming each of the above layers are as shown below.

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(4) General description of the photosensitive material to which the present invention can be applied in the development processing Examples 1 and 2 and Example 3 show the configurations of the color paper and the color negative film to which the present invention is applied, respectively.
The photosensitive material to which the processing agent using the container of the present invention is applied during the development processing is not limited to these. Hereinafter, a photosensitive material to which a development process is performed according to the present invention will be described.

The light-sensitive silver halide emulsion in the light-sensitive material as a positive material such as color paper has a silver chloride content of at least 95 mol%, the balance being silver bromide, and substantially no silver iodide. It preferably comprises silver halide grains. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less, more preferably 0 mol%. From the viewpoint of rapid processing, the silver halide emulsion is preferably a silver halide emulsion having a silver chloride content of 98 mol% or more.
Among such silver halides, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable since high sensitivity can be obtained and photographic performance can be stabilized.

The silver halide emulsion contained in at least one photosensitive silver halide emulsion layer has a coefficient of variation in grain size distribution (standard deviation of grain size distribution divided by average grain size) of 15% or less. Some are preferred and 1
Monodispersed emulsions of 0% or less are more preferred. It is preferable to use two or more of the above monodispersed emulsions in the same layer for the purpose of obtaining a wide latitude. At this time, the monodispersed emulsions preferably differ in average grain size by 15% or more, more preferably 20 to 60%, and even more preferably 25 to 50%. The sensitivity difference between the monodispersed emulsions is preferably from 0.15 to 0.50 logE, more preferably from 0.20 to 0.40 logE, even more preferably from 0.25 to 0.35 logE. . Further, the silver halide emulsion may be subjected to conventionally known chemical sensitization and / or physical sensitization, and among them, gold sensitization is particularly preferable.

In order to obtain a positive image for the purpose of the present invention, iron and / or ruthenium and / or osmium compounds are added to silver chlorobromide having a silver chloride content of not less than 95 mol% which is substantially free of silver iodide. 1 × 10 per mole of silver halide
^-5 to 1 × 10 ^-3 mol, and a silver halide emulsion containing 1 × 10 ^-7 to 1 × 10 ^-5 mol of an iridium compound per mol of silver halide in a silver bromide localized phase. It is effective to use.

For a color photographic material for photographing purposes, for example, a multilayer color negative film or a color reversal film, tabular grains having a silver iodobromide internal structure or non-tabular multi-structure grains are mainly used. Preferred silver halide is about 30
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing not more than mol% of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion Production (Emulsion p.
reparation and types) ”and No. 18716
(November 1979), p. 648, ibid. 30710
5 (11/1989), pages 863 to 865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemie et Phisique Photographique,
Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, Focal Press (GFDuffin, Photographi)
c Emulsion Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zeligman et al., Published by Focal Press (VLZelikman, et al., Making and Coating Ph.
otographic Emulsion, Focal Press, 1964).

US Pat. Nos. 3,574,628 and 3,655,
Monodisperse emulsions described in 394 and GB 1,413,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are written by Gatoff, Photographic Science and Engineering (Gutoff, Photographic Sciencean).
d Engineering), Vol. 14, pp. 248-257 (197
0); US Pat. Nos. 4,434,226 and 4,414,31
0, 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, or the inside and outside may be composed of different halogen compositions,
It may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
This preparation method is described in JP-A-59-133542. Although the thickness of the shell of this emulsion varies depending on the development process and the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is RD No. 17643,
No. No. 18716 and the same No. 307105, and the corresponding portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions different in at least one property of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion,
They can be mixed and used in the same layer. US4,0
82,553, fogged silver halide grains, US Pat. No. 4,626,498, JP-A-59-214.
It is preferable to apply the silver halide grains and the colloidal silver having the inside of the grains described in 852 to a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term “silver halide particles having a fogged interior or surface” refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of the unexposed portions and exposed portions of the photosensitive material. The preparation method is US 4,626,49
8, described in JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. Any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used as the silver halide having the inside or the surface of the grain fogged. The average grain size of these fogged silver halide grains is 0.1.
It is preferably from 0.01 to 0.75 μm, particularly preferably from 0.05 to 0.6 μm. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or number of silver halide grains is ± 40% of the average grain size).
Having a particle diameter within the range described above).

As the silver halide photographic light-sensitive material for printing and photographing which is the object of the present invention, conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transmissive support include transparent films such as cellulose nitrate film and polyethylene terephthalate, and 2,6-naphthalenedicarboxylic acid (NDC).
The one in which an information recording layer such as a magnetic layer is provided on a polyester of A) and ethylene glycol (EG) or a polyester of NDCA, terephthalic acid and EG is preferably used. For the purposes of the present invention, a reflective support is preferred, in particular laminated with a plurality of polyethylene or polyester layers, such a water-resistant resin layer (laminate layer)
A reflective support containing at least one layer of a white pigment such as titanium oxide is preferred.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio in the case of mixing with the water-resistant resin is preferably 0.0005 to 3% by weight with respect to the resin, and more preferably 0.1 to 3% by weight.
001 to 0.5% by weight. A body in which a hydrophilic colloid layer containing a white pigment is provided on the body may be used. Also,
The reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface. The light-sensitive material according to the present invention is provided with a dye capable of being decolorized by a treatment described in European Patent EP 0,337,490 A2, pp. 27-76, in a hydrophilic colloid layer for the purpose of improving the sharpness of an image. Of these, oxonol-based dyes) are used in the photosensitive material.
Titanium oxide added so that the optical reflection density at 0 nm becomes 0.70 or more, or surface-treated with a divalent or tetravalent alcohol (for example, trimethylolethane) in the water-resistant resin layer of the support. Is preferably contained in an amount of 12% by weight or more (more preferably 14% by weight or more).

The light-sensitive material according to the present invention is protected against various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image as described in JP-A-63-271247. It is preferred to add a fungicide.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods applied for processing this light-sensitive material And processing additives, EP 0,355,660 A2, JP-A-2-33144 and JP-A-62
Those described in the specification of U.S. Pat. No. 215272 or those listed in Table 3 below are preferably used.

[0220]

[Table 3]

The photosensitive material of the present invention has a great effect of the invention such as improvement of whiteness of a white background when it contains a pyrrolotriazole type coupler. However, a photosensitive material containing a cyan coupler other than this coupler may also be used. It is an application of the method of the present invention. The cyan, magenta or yellow coupler is impregnated with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of a high boiling organic solvent as described in the preceding table, or It is preferable to dissolve it together with a water-insoluble and organic solvent-soluble polymer and emulsify and disperse in a hydrophilic colloid aqueous solution. Preferred water-insoluble and organic solvent-soluble polymers are described in U.S. Pat. No. 4,857,449, column 7 to column 7.
Homopolymers or copolymers described in column 15 and pages 12 to 30 of WO 88/00723 can be mentioned. In particular, a methacrylate or acrylamide polymer is particularly preferred in terms of color image stability and the like.

Among the pyrrolotriazole type couplers,
A pyrrolotriazole cyan coupler represented by the following general formula (I) is preferably used.

[0223]

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(Wherein, Z^a, Z^bIs -C (R^Three)
= Or -N =. Where Z^a, Z^bAny of
Is -N = and the other is -C (R^Three) =. R¹ You
And R ^Two Is the Hammett's substituent constant σ_pvalue
Represents an electron withdrawing group of 0.20 or more;¹ And R^Two Σ
_pThe sum of the values is 0.65 or more. R^ThreeIs a hydrogen atom or
Represents a substituent. X is a hydrogen atom or a color developing agent
Lists groups that can be removed in the coupling reaction with the oxidant.
You. R¹ , R^Two , R^ThreeOr, the group of X is a divalent group.
Or a homopolymer by bonding with a multimer or polymer
Alternatively, a copolymer may be formed. )

The cyan coupler of the general formula (I) will be described. The Hammett's substituent constant σ _p used for the structure of the general formula (I) will be briefly described. Hammett's rule was used by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
Empirical rule, which is widely accepted today. The substituent constants determined by Hammett's rule include σ _p and σ _m values, which can be found in many common books. For example, JADean
Hen, "Lange's Handbook of Chemistry", 12th edition, 1
997 (Mc Graw-Hill) and extra edition of "Chemistry", 12
No. 2, pages 96 to 103, 1979 (Nankodo). In the present invention, each substituent is limited or described by Hammett's substituent constant σ _p, but this is limited to only those substituents having a value known in the literature, which can be found in the above-mentioned books. Not to mention the meaning, but it goes without saying that even if the value is unknown in the literature, it also includes a substituent that would be included in the range when measured based on the Hammett rule. Although the compound represented by the general formula (I) of the present invention is not a benzene derivative, the σ _p value is used as a measure of the electronic effect of the substituent regardless of the substitution position. In the present invention, the σ _p value will be used in this sense in the future. The term "lipophilic" as used in the present invention means that the solubility in water at room temperature is 10% or less.

In the present specification, the term "aliphatic" may be linear or branched and may be saturated or unsaturated, and is used to include cyclic ones. Examples thereof include alkyl, alkenyl and alkynyl. , Cycloalkyl, or cycloalkenyl, which may further have a substituent. In addition, aromatic represents aryl, which may further have a substituent. Heterocycle (heterocycle) has a heteroatom in the ring, and also includes an aromatic group. And may further have a substituent. The substituents in the present specification and the substituents which may be present on these aliphatic, aromatic, and heterocyclic rings may be any groups that can be substituted unless otherwise specified, and include, for example, an aliphatic group and an aromatic group. Group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, aliphatic Carbamoyl group, aromatic carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic flufamoyl group, aromatic sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, aliphatic amino group, aromatic amino group, Aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic thio group, aromatic thio group, mercapto group, hydroxy group, cyano group, nitro It can be exemplified group, hydroxyamino group, a halogen atom or the like.

Hereinafter, the cyan coupler represented by formula (I) of the present invention will be described in detail. Z ^a and Z ^b each a -C (R ³⁾ = or an -N =. However, Z either ^a and Z ^b are -N =, the other is -C (R ³⁾ =
It is.

R ³ represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group. Group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxy Carbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group,
Examples include a phosphonyl group, an aryloxycarbonyl group, and an acyl group. These groups may be further substituted with substituents as exemplified for R ³ .

More specifically, R ³ is a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), an alkyl group (eg, a linear or branched alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). Group, alkynyl group, cycloalkyl group, cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl group (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 4-tetradecanamidophenyl), a heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl,
2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy,
2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t
-Butylphenoxy, 3-nitrophenoxy, 3-t-
Butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamido, benzamido, tetradecanamido, 2- (2,4
-Di-t-amylphenoxy) butanamide, 4- (3
-T-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl)
Phenoxy didecaneamide), an alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5
-Dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {2- (3-t-butyl-4)
-Hydroxyphenoxy) dodecaneamide {anilino), a ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), a sulfamoylamino group (eg, N, N-dipropylsulfamoylamino, N-methyl) -N-decylsulfamoylamino), an alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio,
3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (for example,
Phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonyl) Amino), a sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), a carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N-
(2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-
Di-t-amylphenoxy) propyl @ carbamoyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2
-Dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group ( For example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl),
Heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy- 4-propanoylphenylazo), an acyloxy group (eg, acetoxy), a carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryl An oxycarbonylamino group (for example, phenoxycarbonylamino), an imide group (for example, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2, 4 Di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), a sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphospho) Nyl, octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl), and an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl).

R ³ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, or an alkoxycarbonylamino group. , Sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group Can be mentioned.

More preferably, they are an alkyl group or an aryl group, more preferably, from the viewpoint of cohesion, an alkyl group or an aryl group having at least one substituent, and further preferably, at least one alkyl group or an alkoxy group. , A sulfonyl group, a sulfamoyl group, a carbamoyl group, an acylamide group or an alkyl group or an aryl group having a sulfonamide group as a substituent. Particularly preferred is an alkyl group or an aryl group having at least one alkyl group, acylamide group or sulfonamide group as a substituent. When these substituents are present in the aryl group, it is more preferable to have them at least in the ortho or para position.

The cyan coupler is an electron-withdrawing group in which both R ¹ and R ² are 0.20 or more and the sum of the σ _p values of R ¹ and R ² is 0.65 or more. It develops as a color. The sum of the σ _p values of R ¹ and R ² is preferably 0.70 or more, and the upper limit is 2.
It is about 0.

R ¹ and R ² are Hammett's substituent constant σ _p
An electron-withdrawing group having a value of 0.20 or more. Preferably,
It is an electron-withdrawing group of 0.30 or more. The upper limit is 1.
It is an electron-withdrawing group of 0 or less.

Specific examples of R ¹ and R ² which are electron-withdrawing groups having a σ _p value of 0.20 or more include acyl, acyloxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, Nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group An alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σ _p value of 0.20 or more; Heterocyclic group, halogen atom, azo group, or Renoshianeto group, and the like. Among these substituents, the group which can have a substituent may further have a substituent as described for R ³ .

If R ¹ and R ² are described in more detail, σ _p
Examples of the electron-withdrawing group having a value of 0.20 or more include an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), an acyloxy group (eg, acetoxy), a carbamoyl group (eg, carbamoyl) , N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dibutylcarbamoyl, N
-(2-dodecyloxyethyl) carbamoyl, N-
(4-n-pentadecanamido) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3
-(2,4-di-t-amylphenoxy) propyl} carbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, iso-propyloxycarbonyl, tert-butyloxycarbonyl, iso-
Butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (eg, dimethylphosphono), diarylphosphono group (E.g., diphenylphosphono), diarylphosphinyl group (e.g., diphenylphosphinyl), alkylsulfinyl group (e.g., 3-phenoxypropylsulfinyl), arylsulfinyl group (e.g.,
3-pentadecylphenylsulfinyl), alkylsulfonyl group (eg, methanesulfonyl, octanesulfonyl), arylsulfonyl group (eg, benzenesulfonyl, toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), acylthio Groups (eg, acetylthio, benzoylthio), sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-
(2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), thiocyanate group, thiocarbonyl group (eg, methylthiocarbonyl, phenylthiocarbonyl), alkyl halide Groups (eg, trifluoromethane, heptafluoropropane), halogenated alkoxy groups (eg, trifluoromethyloxy), halogenated aryloxy groups (eg, pentafluorophenyloxy), halogenated alkylamino groups (eg, N, N-
Di- (trifluoromethyl) amino), a halogenated alkylthio group (for example, difluoromethylthio, 1,1,2,2
2-tetrafluoroethane ethylthiomethyl), an aryl group substituted with sigma _p 0.20 or more other electron withdrawing group (e.g., 2,
4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl), a heterocyclic group (for example, 2-
Benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl), halogen atom (eg, chlorine atom, bromine atom), azo group (eg, phenylazo)
Or a selenocyanate group. Among these substituents, the group which can have a substituent may further have a substituent as described for R ³ .

R ¹ and R ² are preferably acyl, acyloxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfinyl, arylsulfinyl, Alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkyloxy group, halogenated alkylthio group,
A halogenated aryloxy group, two or more σ _p 0.20
An aryl group substituted with the other electron-withdrawing group and a heterocyclic group can be exemplified. More preferred are an alkoxycarbonyl group, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group and a halogenated alkyl group. Most preferred as R ¹ is a cyano group. Particularly preferred as R ² is an alkoxycarbonyl group, and most preferred is a branched alkoxycarbonyl group (especially a cycloalkoxycarbonyl group).

X represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of a color developing agent. When the group capable of leaving is specifically described, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl group Or arylsulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, carbamoyloxy group, heterocyclic carbonyloxy group, A 5- or 6-membered nitrogen-containing heterocyclic group, an imide group, an arylazo group, and the like;
These groups may be further substituted with a group permitted as a substituent of R ³ . Here, examples of the oxidized form of the color developing agent include, in addition to the known aromatic primary amine color developing agent, hydrazine developing agents such as carbamoylhydrazine developing agents and sulfamoylhydrazine developing agents. . Preferred are aromatic primary amine color developing agents.

More specifically, halogen atoms (eg, fluorine, chlorine, bromine), alkoxy groups (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methanesulfonylethoxy, ethoxycarbonylmethoxy), aryl An oxy group (e.g., 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (eg, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl Sulfonyloxy group (for example, methanesulfonyloxy, toluenesulfonyloxy), acylamino group (for example, dichloroacetylamino, heptafluorobutyrylamino), alkyl or arylsulfonamide group (for example, methanesulfonylamino,
Trifluoromethanesulfonylamino, p-toluenesulfonylamino), alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), alkyl,
Aryl or heterocyclic thio groups (e.g. dodecylthio, 1-carboxydodecylthio, phenylthio, 2-
Butoxy-5-t-octylphenylthio, tetrazolylthio), carbamoylamino group (eg, N-methylcarbamoylamino, N-phenylcarbamoylamino), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, N-ethylcarbamoyl) Oxy, N-ethyl-N-phenylcarbamoyloxy),
Heterocyclic carbonyloxy group (eg, morpholinocarbonyloxy, piperidinocarbonyloxy), 5- or 6-membered nitrogen-containing heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2
-Dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo) and the like. X is an aldehyde or ketone as a leaving group bonded via a carbon atom.
It may take the form of a bis-type coupler obtained by condensing an equivalent coupler. X may contain a photographically useful group such as a development inhibitor and a development accelerator.

Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an alkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a heterocyclic carbonyloxy group, and a nitrogen atom at the coupling active position. A 5- or 6-membered nitrogen-containing heterocyclic group bonded by an atom. More preferred X is a halogen atom, an alkyl or arylthio group, an alkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a heterocyclic carbonyloxy group, and particularly preferred are a carbamoyloxy group and a heterocyclic carbonyloxy group. It is.

In the cyan coupler represented by the general formula (I), the group of R ¹ , R ² , R ³ or X becomes a divalent group, and is bonded to a dimer or higher multimer or a polymer chain. A homopolymer or a copolymer may be formed. A homopolymer or a copolymer bonded to a polymer chain is a typical example of an addition polymer having a cyan coupler residue represented by the general formula (I), homo- or copolymer of an ethylenically unsaturated compound. . in this case,
One or more cyan coloring repeating units having a cyan coupler residue represented by the general formula (I) may be contained in the polymer, and one or two non-coloring ethylene-type monomers may be used as a copolymer component. It may be a copolymer containing more than one species. The cyan coloring repeating unit having a cyan coupler residue represented by the general formula (I) is preferably represented by the following general formula (P).

[0241]

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In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A represents -CONH-, -COO-
Or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, and L represents -CONH-, -NHCONH-,
-NHCOO-, -NHCO-, -OCONH-, -NH-, -COO
-, - OCO -, - CO -, - O -, - S -, - SO 2 -, -
It represents NHSO ₂ — or —SO ₂ NH—. a, b, and c represent 0 or 1. Q is R of the compound represented by the general formula (I)
¹ , represents a cyan coupler residue from which a hydrogen atom has been removed from R ² , R ³ or X. As the polymer, a copolymer of a cyan-color-forming monomer represented by a coupler unit of the general formula (I) and a non-color-forming ethylene-like monomer that does not couple with an oxidation product of a developing agent is preferable.

Examples of the non-color-forming ethylenic monomer which does not couple with the oxidation product of the developing agent include acrylic acid and α-
Chloroacrylic acid, α-alkylacrylic acid (eg, methacrylic acid) Amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methyl acrylate) , Ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β- Hydroxy methacrylate), vinyl esters (eg, vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile , Methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinylalkyl ether (eg, vinyl ethyl ether) ), Maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylilipyridine and 2- and -4-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters and maleic esters. The non-color-forming ethylene type monomer used here can be used in combination of two or more kinds. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetone acrylamide can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above-mentioned general formula (I) has the physical properties of the copolymer formed and / or Alternatively, it can be selected such that the chemical properties, such as solubility, the compatibility of the photographic colloid composition with the binder, such as gelatin, its flexibility, thermal stability, etc., are favorably affected.

In order to incorporate a cyan coupler into a silver halide light-sensitive material, preferably into a red-sensitive silver halide emulsion layer, it is preferable to use a so-called inner coupler.
For that purpose, at least one group of R ¹ , R ² , R ³ and X is preferably a so-called ballast group (preferably having a total carbon number of 10 or more), and more preferably having a carbon number of 10 to 50. . Particularly, it is preferable that R ³ has a ballast group. The cyan coupler represented by the general formula (I) is more preferably a compound having a structure represented by the following general formula (II).

[0247]

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In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different and each represents a hydrogen atom or a substituent. As the substituent, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aryl group is preferable, and more preferable ones are described below. R ¹¹ and R ^{12 each} preferably represent an aliphatic group, for example, a linear, branched or cyclic alkyl group, aralkyl group, alkenyl group, alkynyl group or cycloalkenyl group having 1 to 36 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, t-butyl, t
-Represents amyl, t-octyl, tridecyl, cyclopentyl, cyclohexyl. The aliphatic group more preferably has 1 to 12 carbon atoms. R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or an aliphatic group. Examples of the aliphatic group include the groups described above for R ¹¹ and R ¹² . R ¹³ , R ¹⁴ , R
¹⁵ is particularly preferably a hydrogen atom.

Z represents a group necessary for forming a 5- to 8-membered ring,
Represents a group of non-metallic atoms, and this ring may be substituted, may be a saturated ring or may have an unsaturated bond.
Preferred non-metallic atoms include a nitrogen atom, an oxygen atom, a sulfur atom and a carbon atom, and more preferably a carbon atom. Examples of the ring formed by Z include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring,
Cyclooctane ring, cyclohexene ring, piperazine ring,
Examples thereof include an oxane ring and a thiane ring, and these rings may be substituted with a substituent represented by R ³ described above. Preferably the ring formed by Z is a cyclohexane ring which may be substituted, especially preferably, 4-position substituted with a substituent as represented by an alkyl group (the aforementioned R ³ having 1 to 24 carbon atoms A cyclohexane ring substituted with

R ^{3 in} formula (II) has the same meaning as R ^{3 in} formula (I), particularly preferably an alkyl group or an aryl group, and more preferably a substituted aryl group. From the viewpoint of carbon number, in the case of an alkyl group, preferably,
1 to 36, and in the case of an aryl group, preferably
6 to 36. Among the aryl groups, those in which the alkoxy group is substituted at the ortho position of the bond position to the coupler mother nucleus are not preferred because the light fastness of the dye derived from the coupler is low. In that regard, the substituents on the aryl group may be substituted or
Unsubstituted alkyl groups are preferred, and among them, unsubstituted alkyl groups are most preferred. Particularly, an unsubstituted alkyl group having 1 to 30 carbon atoms is preferable.

X ² represents a hydrogen atom or a substituent. The substituent is X ² -C (=
O) Groups which promote the elimination of the O- group are preferred. X ² is preferably a heterocyclic ring, a substituted or unsubstituted amino group, or an aryl group. The hetero ring is preferably a 5- to 8-membered ring having a nitrogen atom, an oxygen atom, or a sulfur atom and having 1 to 36 carbon atoms. More preferably,
A 5- or 6-membered ring bonded by a nitrogen atom, of which a 6-membered ring is particularly preferred. These rings may form a condensed ring with a benzene ring or a hetero ring. Specific examples include imidazole, pyrazole, triazole, lactam compounds, piperidine, pyrrolidine, pyrrole, morpholine,
Pyrazolidine, thiazolidine, pyrazoline and the like, preferably, morpholine, piperidine,
Particularly, morpholine is preferred. Examples of the substituent of the substituted amino group include an aliphatic group, an aryl group and a heterocyclic group. Examples of the aliphatic group include the substituents of R ^{3 described} above, and further include a cyano group, an alkoxy group (eg, methoxy), an alkoxycarbonyl group (eg, ethoxycarbonyl), a chlorine atom, a hydroxyl group, a carboxyl group, and the like. May be substituted. As the substituted amino group,
Disubstitution is preferred over monosubstitution. As the substituent, an alkyl group is preferable.

The aryl group preferably has 6 to 36 carbon atoms, and more preferably a monocyclic ring. Specific examples include phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, 4-dichlorophenyl and the like. The cyan coupler represented by the general formula (II) has an oil-solubilizing group in the molecule and is easily soluble in a high-boiling organic solvent, and the coupler itself and the coupler and a color-forming reducing agent (developer) are oxidized. The dye formed by the ring is preferably non-diffusible in the hydrophilic colloid layer. In the coupler represented by the general formula (II), R ³ may contain a coupler residue represented by the general formula (II) to form a dimer or higher multimer,
³ may contain a polymer chain and form a homopolymer or a copolymer. A typical example of the homopolymer or copolymer containing a polymer chain is an addition polymer having a coupler residue represented by the general formula (II), homo- or copolymer of an ethylenically unsaturated compound. In this case, the polymer may contain one or more kinds of cyan coloring repeating units having a coupler residue represented by the general formula (II), and an acrylic acid ester, a methacrylic acid ester, or a maleic acid ester as a copolymer component. It may be a copolymer containing one or more non-color-forming ethylenic monomers that do not couple with the oxidation product of an aromatic primary amine developer such as phenol. Hereinafter, specific examples of the cyan coupler defined by the general formula (I) of the present invention are shown, but the invention is not limited thereto.

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[0254]

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[0255]

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[0256]

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[0257]

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[0258]

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[0259]

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[0260]

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[0261]

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[0262]

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[0263]

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[0264]

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[0265]

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The compound represented by formula (I) can be prepared by a known method, for example, as described in JP-A-5-150423 and 5-2.
No. 55333, No. 5-202004, No. 7-4837
No. 6, 9-189988 can be synthesized.

The light-sensitive material to which the present invention is applied includes a color image preservability improving compound as described in European Patent EP 0,277,589 A2, a pyrazoloazole coupler,
It is preferable to use in combination with the above pyrrolotriazole coupler and acylacetamide type yellow coupler.

Examples of the cyan coupler include phenol couplers and naphthol couplers described in the publicly known documents in the above table, as well as JP-A-2-33144.
JP, EP 0333185 A2, JP-A-6
4-32260, European Patent EP 0 456 226 A1, European Patent EP 0 484 909, European Patent EP
You may use the cyan coupler of the specification of 0488248 and EP0491197A1.

Examples of the magenta coupler include 5-pyrazolone-based magenta couplers as described in the publicly known documents in the above table, and also described in International Publication Nos. WO92 / 18901, WO92 / 18902 and WO92 / 18903. Are also preferred. In addition to these 5-pyrazolone magenta couplers, known pyrazoloazole type couplers are used in the present invention. Among them, hue and image stability,
The pyrazolo described in JP-A-61-65245, JP-A-61-65246, JP-A-61-14254, and EP-A-226,849A and EP-A-294,785A in terms of coloring properties and the like. The use of azole couplers is preferred.

As the yellow coupler, known acylacetanilide-type couplers are preferably used. Among them, European Patent EP0447969A and JP-A-5-15-1 can be used.
07701, JP-A-5-113462, European Patent E
The couplers described in P-0482552A and EP-0524540A are preferably used.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,
570, EP 96,873B, DE 3,234,533
Are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456, 257 A1 (particularly Y on page 84).
C-86), yellow colored magenta coupler ExM-7 (p. 202) and EX-1 (249) described in the EP.
EX-7 (page 251), US Pat. No. 4,833,069.
Magenta colored cyan couplers CC-9 (column 8), CC-13 (column 10), US Pat.
7,136 (2) (column 8), WO92 / 1157
Colorless masking couplers of formula (A) of claim 1 of claim 5 (especially the exemplified compounds on pages 36 to 45) are preferred.

Examples of the compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound: E
Formulas (I), (II), and P378, 236A1.
Compounds represented by (III) and (IV) (particularly T-101
(Page 30), T-104 (page 31), T-113 (36
Page), T-131 (page 45), T-144 (page 51),
T-158 (p. 58)), EP 436, 938 A2, 7
Compounds represented by formula (I) described on page (particularly D-49)
(Page 51)), the compound represented by the formula (1) of EP568,037A (especially (23) (page 11)), EP44
Formulas (I), (II) and (II) described on pages 5 to 6 of U.S. Pat.
Compounds represented by I) (especially I- (1) on page 29);

Bleaching accelerator releasing compound: EP 310,12
Compounds represented by formulas (I) and (I ') on page 5 of 5A2 (especially (60) and (61) on page 61) and JP-A-6-59.
411. The compound represented by the formula (C) of claim 1 (particularly (7) (p. 7); Ligand releasing compound: US 4,55)
Compound represented by LIG-X described in claim 1 of 5,478 (especially, a compound on lines 21 to 41 of column 12); Leuco dye releasing compound: US Pat.
Compounds 1 to 6 of columns 3 to 8; fluorescent dye releasing compounds:
C0UP-DY of claim 1 of US 4,774,181
Compound represented by E (particularly, compound 1 in columns 7-10)
-11); Development accelerator or fogging agent releasing compound: US
Formulas (1), (2) in column 3 of 4,656,123,
The compound represented by (3) (particularly, (I-2) in column 25
2)) and EP450, 637A2, page 75, 36-38.
ExZK-2 in row: Compound that releases a group that becomes a dye only after leaving: a compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (especially, Y-1 to Y- in columns 25 to 36) 19).

The following are preferred as additives other than the coupler. Dispersion medium of oil-soluble organic compound:
215272 P-3, 5, 16, 19, 25, 30,
42, 49, 54, 55, 66, 81, 85, 86, 9
Latex for impregnating an oil-soluble organic compound: latex described in US Pat. No. 4,199,363; oxidized developing agent scavenger: US Pat.
606, column 54, lines 54 to 62, compounds of formula (I) (especially I-, (1), (2), (6), (12) (columns 4 to 5), US Pat. No. 4,923,787 Column 2 of 5
Formulas on lines 10 to 10 (especially compound 1 (column 3); Stain inhibitor: Formulas (I) to (III) on page 4, lines 30 to 33 of EP298321A, particularly I-47, 72, III-1, 27
(Pages 24 to 48); Anti-fading agent: A-6, 7, 20, 21, 23, 24, 25, 26, 3 of EP298321A
0, 37, 40, 42, 48, 63, 90, 92, 9
4,164 (pp. 69-118), US 5,122,44
4, columns 25-38 II-1 to III-23, especially III-
10, EP 471347A, pages 8 to 12 I-1 to III
Column 4, especially II-2, US 5,139,931
A-1 to 48 of 2 to 40, especially A-39 and 42; a material for reducing the amount of a color-enhancing agent or color-mixing inhibitor used: EP
I1 to II-15, especially I-46 on pages 5 to 24 of 411324A; formalin scavenger: EP 47793
SCV-1 to 28 on page 24 to 29 of 2A, especially SCV-
8;

Hardener: H-1,4,6,8,14 on page 17 of JP-A-1-214845, US Pat. No. 4,618,573
(H-1 to 54) represented by Formulas (VII) to (XII) in columns 13 to 23 of JP-A-2-214852.
Compounds represented by the formula (6) at the lower right of the page (H-1 to 7)
6), particularly compounds described in claim 1 of H-14, US Pat. No. 3,325,287; development inhibitor precursors: P-24, 37, 39 of JP-A-62-168139 (6-7)
Compounds described in claim 1 of US Pat. No. 5,019,492, especially 28, 29 of column 7; preservative, fungicide: U
I-4 to I-3 of columns 3 to 15 of S4,923,790
-43, especially II-1, 9, 10, 18, III-25; stabilizer, antifoggant: I-1 to (14) of columns 6 to 16 of US 4,923,793, especially I-1,60 ,
(2), (13), column 25 of US 4,952,483
Compounds 1 to 65, especially 36: Chemical sensitizer: triphenylphosphine selenide, JP-A-5-40324
Compound 50 of the formula:

Dye: 15-1 of JP-A-3-156450
A-1 to b-20 on page 8, especially a-1, 12, 18, 2
7, 35, 36, b-5, pp. 27 to 29, V-1 to V-2
3, especially F-1, I-F-II-43 on pages 33 to 55 of EP 445627A, especially F-I-11 and F-II.
VIII, pages III-I to EP-157153A, pages 17-28.
36, especially III-1,3, WO88 / 04794, 8-
26, a microcrystalline dispersion of Dye-1 to 124, EP319
Compounds 1 to 22 of 999A, pages 6 to 11, especially compounds 1, compounds D-1 to 87 of formulas (1) to (3) of EP519306A (pages 3 to 28), US Pat.
68,622 compounds of formula (I) 1-22
(Columns 3 to 10), compounds (1) to (31) represented by formula (I) of US Pat. No. 4,923,788 (column 2
9); UV absorber: Formula (1) of JP-A-46-3335
Compounds (18b) to (18r), 101-
427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) represented by formula (I) and compounds HBT-1 to 10 (1) represented by formula (III) in EP520938A.
4), compounds (1) to (31) represented by the formula (1) in EP521823A (columns 2-9).

The processing agent according to the present invention can be applied to general-purpose or cinema-use color negative films. In addition, Tokuhei 2-32615, Tokuhei 3-3978
4 is suitable for the film unit with a lens. Suitable supports that can be used in the present invention are described, for example, in RD. No. No. 17643, page 28; 18
716 from page 647 right column to page 648 page left column, and N
o. As described on page 879 of 307105, it is preferred to use a polyester support.

The color negative film used in the processing agent according to the present invention preferably has a magnetic recording layer.
The magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. The magnetic particles used in the present invention include a ferromagnetic iron oxide such as γFe ₂ O ₃ , Co-coated γFe
₂ O ₃ , Co-coated magnetite, Co-containing magnetite,
Ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co deposited γFe
Co-coated ferromagnetic iron oxide such as ₂ O ₃ is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. In terms of specific surface area, S _BET is preferably 20 m ² / g or more,
Particularly preferred is 30 m ² / g or more. Saturation magnetization (σ
s) is preferably from 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A /
m, particularly preferably 4.0 × 10 ^{4 to} 2.5 × 1
0 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-160332. JP-A-4-2
No. 59911, 5-81652 No.
Magnetic particles coated with an organic substance can also be used.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. US Pat. Nos. 5,336,589 and 5,25 for photosensitive materials having a magnetic recording layer
0,404, 5,229,259, 5,215,8
74, EP 466,130.

The polyester support will be described, and the details, including the photosensitive material, treatment, cartridge and examples described later, are described in Published Technical Report, Official Technical Publication No. 94-6023 (Invention Association; 1994.3.13.). Have been. The polyester used in the present invention is formed by using diol and aromatic dicarboxylic acid as essential components. As aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, and terephthalic acid are used. Acid, isophthalic acid,
Examples of phthalic acid and diol include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid.
Among them, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is from 0.1 hour to 1500 hours, and more preferably from 0.5 hour to 200 hours. The heat treatment of the support may be performed in a roll form, or may be performed while transporting the support in a web form. The surface is provided with irregularities (for example, Sn
(Conductive inorganic fine particles such as O ₂ and Sb ₂ O ₅ are applied), and the surface state may be improved. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be carried out at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), or after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. In order to prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

The light-sensitive material to which the present invention is applied has an emulsion layer
The total thickness of all the hydrophilic colloid layers on the side having
Or less, more preferably 23 μm or less.
And more preferably 18 μm or less, particularly preferably 16 μm or less.
preferable. The film swelling speed T _1/2Is preferably 30 seconds or less
And more preferably 20 seconds or less. T_1/2Is a color developer
Maximum swelling film thickness reached when treated at 30 ° C for 3 minutes and 15 seconds
When the saturated film thickness is 90% of the film thickness, the film thickness itself is １ ／.
Is defined as the time to reach. Film thickness is 25 ° C relative humidity
Film thickness measured under 55% humidity control (2 days), T
_1/2Is a photograph by A. Green
Science and Engineering (Photog)
r.Sci.Eng.), 19, 2, 124-129.
Measurement by using a swellometer
Can be determined. T_1/2Is hard on gelatin as a binder
Add film agent or change aging condition after application
Can be adjusted. The swelling ratio is 1
50-400% is preferred. The swelling ratio and the condition mentioned earlier
From the maximum swollen film thickness under the condition, the formula: (maximum swollen film thickness−film)
Thickness) / film thickness. The light-sensitive material of the present invention comprises
On the side opposite to the side having the agent layer, the total dry film thickness is 2 μm or more.
Provide a 20μm hydrophilic colloid layer (called back layer)
Preferably. This back layer has the aforementioned light absorption
Agent, filter dye, UV absorber, antistatic
Agents, hardeners, binders, plasticizers, lubricants, coating aids,
It is preferable to include a surfactant. This back layer
Is preferably 150 to 500%.

To adhere the support and the light-sensitive material constituting layer,
Surface treatment is preferred. Chemical treatment, mechanical treatment,
Corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment,
Surface activation treatments such as glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the undercoating method will be described. It may be a single layer or two or more layers. As a binder for the undercoat layer,
Starting from copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., polyethylene imine, epoxy resin, grafting Gelatin, nitrocellulose and gelatin are included.
Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, as a gelatin hardener, chromium salt (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6) are used.
-Hydroxy-S-triazine), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

Also, an antistatic agent is preferably used.
Examples of such antistatic agents include carboxylic acids and carboxylate salts, polymers containing sulfonates, cationic polymers,
An ionic surfactant compound can be mentioned.

The most preferred antistatic agent is Zn.
O, TiO_Two, SnO_Two, Al_TwoO_Three, In_TwoO_Three, SiO_Two, MgO, BaO,
MoO_Three, V_TwoO_FiveAt least one volume resistivity selected from
Is 10 ⁷Ωcm or less, more preferably 10^FiveΩcm or less
Particle size 0.001 ~ 1.0μm crystalline metal oxide
Of these composite oxides (Sb, P, B, In, S, Si, C, etc.)
Particles, sol-like metal oxides or composites thereof
These are oxide fine particles.

The content in the light-sensitive material is 5 to 500 mg / m ²
And particularly preferably 10 to 350 mg / m ² . The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 1/1.
00 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25
° C, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.

Examples of usable slip agents include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethylsiloxane,
Polydiethylsiloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The photosensitive material preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrower, and the average particle size is 0.9 to 1.1.
It is preferable that 90% or more of the total number of particles be contained during the doubling. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), Polystyrene particles (0.25μm), colloidal silica (0.03μm)
Is mentioned.

Next, the film cartridge will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic.

Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are disclosed in
37, 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same as the current 135 size, and it is effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less in order to reduce the size of the camera.
The volume of a cartridge case, 30cm ³ or less, preferably 25
It is preferably set to not more than cm ³ . The weight of plastic used for patrone and patrone case can range from 5g to 15g
g is preferred.

Further, a patrone that rotates the spool to feed the film may be used. Alternatively, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction. They are
Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a photographic film that has been subjected to development processing.
Further, the raw film and the developed photographic film may be stored in the same new patrone, or may be different patrones.

The color photographic light-sensitive material is also suitable as a negative film for an advanced photo system (hereinafter, referred to as an AP system), and NEXIA A, NEXIA F, manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film). NEXI
Films processed into the AP system format like AH (in order, ISO 200/100/400) and stored in a special cartridge can be mentioned. These AP system cartridge films are used by loading them into an AP system camera such as the EPION series (e.g., EPION 300Z) manufactured by Fujifilm. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super color slim made by Fujifilm.

[0295] The film photographed in these manners is printed through the following steps in the minilab system. (1) Reception (exposed cartridge film received from customer) (2) Detaching process (transfer film from cartridge to intermediate cartridge for developing process) (3) Film development (4) Retouching process (developed negative (Return the film to the original cartridge.) (5) Print (continuous automatic printing of C / H / P 3 type prints and index prints on color paper (preferably SUPER FA8 made by FUJIFILM)) (6) Verification and shipment (The cartridge and index print are collated by ID number and shipped together with the print.) These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / FA-238 and Fujifilm Digital Lab System Frontier. preferable. Minilab Champion's film processors include FP922AL / FP562B / FP562B, AL / FP362B / FP362B, AL, and the recommended chemical is Fujicolor Justit CN-1.
6L and CN-16Q. As a printer processor,
PP3008AR / PP3008A / PP1828AR / PP1828A / PP1258AR / PP1258A
/ PP728AR / PP728A, and the recommended treatment chemicals are Fujicolor Justit CP-47L and CP-40FAII. Frontier System, Scanner & Image Processor
SP-1000 and laser printer & paper processor
LP-1000P or laser printer LP-1000W is used. The detacher used in the detaching step and the reattacher used in the rear attaching step are preferably DT200 / DT100 and AT200 / AT100 of Fujifilm, respectively.

[0296]

As described above, by using the developer composition container having the shape and material specified in the present invention, the colorant adheres little to the inner wall of the container even if the composition is aged, and the stain is removed by washing. By removing the container, the container can be reused, and furthermore, handling in a small-scale developing facility is easy, and workability is simplified. Therefore, it can be incorporated into an automatic developing machine and incorporated in a system for automatically preparing a replenisher, washing a container, and the like.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing a printer processor of one embodiment using a developer composition container of the present invention.

FIG. 2 is a perspective view showing a printer processor of one embodiment using the developer composition container of the present invention.

FIG. 3 is a front view of the vicinity of a mounting portion of the treatment agent composition container.

FIG. 4 is a configuration diagram of a developing replenisher system of a replenishing unit.

FIG. 5 is an exploded perspective view of a developer composition container according to one embodiment of the present invention.

FIG. 6 is a perspective view of a product form using the developer composition container of the present invention. FIG.

FIG. 7 is a diagram showing the structure of the replenishing tank shown in FIG.

FIG. 8 is a diagram schematically showing an image output device.

FIG. 9 shows a laser beam irradiation unit of the image output device.

[Explanation of symbols]

 73 Photosensitive material processing amount detection means 122 Display device (alarm means) 202 Processing agent composition kit 204 Processing agent composition storage case 346 PIR cleaning nozzle 347 P1R replenishment tank 348 P2RA cleaning nozzle 349 P2RA replenishment tank 350 P2RB cleaning nozzle 351 P2RB replenishment Tank 358 Upper level sensor 360 Lower limit level sensor 1300 Container for developer composition 1302 Container main body 1304 Male screw (screw part) 1308 Seal member 1310 Cap 1312 Bottom part when loaded 1314 Mouth

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) B29L 22:00

Claims (2)

[Claims] Claims: 1. A container for a photographic processing agent composition which is used by being attached to an automatic developing machine having a function of washing the inside of the container, wherein the container is attached and the processing agent composition in the container is discharged. The inside of the container is washed with washing water having a water supply pressure to the washing nozzle of 0.5 to 3.0 kg / cm ² and a density of 0.9.
51 to 0.969 g / cm ³ and a melt index of 0.3 to 7.0 g / 10 min (ASTM D123
8. A container for a photographic developer composition, wherein high-density polyethylene having a temperature of 90 ° C. and a load of 2.16 kg) is made of a single resin material. 2. The container for a photographic developer composition according to claim 1, wherein the container is manufactured by an injection blow molding method.