JPH08211570A - Method for continuously processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a method for continuously processing a silver halide photographic sensitive material without the developability (variation of sensitivity, etc.), fixability and dryability being deteriorated even when the material is processed continuously at a high speed. CONSTITUTION: A silver halide photographic sensitive material is continuously processed as follows. Namely, the material is dipped in a developer in a developing tank and developed, and the material is dipped in a fixer and fixed. Another processing stage is not substantially provided between the developing and fixing stage, and a solid developer contg. a developing agent and a sulfite and a developing diluent are supplied to the developer and a solid fixing agent contg. a fixer and a fixing diluent to the fixer in accordance with the amt. of the silver halide photographic sensitive material to be processed. The amt. of the sulfite in the solid fixing agent to be supplied to the fixer is controlled to 0-0.05mol per 1l of the diluent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a continuous processing method for a silver halide photographic light-sensitive material, and more particularly to a continuous processing method for a silver halide photographic light-sensitive material which does not deteriorate in fixability and drying property even when continuously processed at high speed. Is.

[0002]

2. Description of the Related Art At present, many processing agents are sold as concentrated solutions to be used after diluting them. However, the concentrated liquid is heavy and has a large volume, so transportation cost, storage space,
The demand for improving work efficiency has increased. A solid processing agent is considered as a means for solving this. The solid processing agent can reduce the amount of the packaging material used and is preferable from the environmental aspect.

[0003]

However, there is a problem that it takes a long time to dissolve. That is, when the treatment agent is replenished in the treatment tank with the solid component and the diluting water, the dissolution rate of the solid component is slow, so that the amount of the undissolved treatment agent increases and the treatment performance deteriorates. Especially in recent years, there is a strong demand for rapid processing, and the development processing is less than 30 seconds and the processing amount is 100 m ² /
Massive processing such as time is being performed. When such rapid and continuous processing is performed, there is a drawback that the dissolution delay is particularly remarkable and the processing performance is deteriorated.

The deterioration of the processing performance caused by the dissolution delay of the processing agent includes the deterioration of the fixing property and the drying property of the fixing solution, and the fluctuation of the sensitivity of the developing solution. On the other hand, means such as the shape of the solid processing agent and the crushing of the solid processing agent in an automatic processor have been mentioned, but they have not been sufficient.

Therefore, an object of the present invention is to provide a continuous processing method for a silver halide photographic light-sensitive material which does not deteriorate the developability (variation in sensitivity, etc.), fixing property and drying property even when continuously processed at high speed. is there.

[0006]

The above object of the present invention has been achieved by the following constitution.

(1) In a method of continuously processing a silver halide photographic light-sensitive material, a development processing step in which the light-sensitive material is immersed in a development processing solution in a development processing tank, and fixing in a fixing processing tank There is provided a fixing processing step which is carried out by immersing the photosensitive material which has been subjected to the development processing in a processing solution, and substantially no other processing step is provided between the development processing step and the fixing processing step. Depending on the processing amount of photographic light-sensitive material,
A developing solid processing agent and a developing diluent containing a developing agent and a sulfite in the developing processing solution, and a fixing solid processing agent and a fixing diluent containing a fixing agent in the fixing processing solution are supplied, The amount of sulfurous acid in the fixing solid processing agent supplied to the fixing processing liquid is 0 to 0.
A continuous processing method for a silver halide photographic light-sensitive material, characterized in that the content is 05 mol.

(2) The silver halide photographic light-sensitive material according to (1), wherein the amount of sulfurous acid in the developing solid processing agent supplied to the developing processing solution is 0.3 mol or more per 1 l of the developing diluting solution. Continuous processing method for materials.

(3) The amount of the fixing diluting liquid is 300 cc per 1 m ² of the processing amount of the silver halide photographic light-sensitive material.
The method for continuously processing a silver halide photographic light-sensitive material as described in (1), characterized in that:

(4) The amount of the developing diluting solution is 300 cc per 1 m ² of the processing amount of the silver halide photographic light-sensitive material.
The method for continuously processing a silver halide photographic light-sensitive material as described in (1), characterized in that:

(5) A photographic processing method in which a silver halide photographic light-sensitive material after exposure is processed by energizing a processing solution in contact with a solution containing an electrolyte through at least anions.
A continuous processing method for a silver halide photographic light-sensitive material, characterized in that a solid processing agent for a silver halide photographic light-sensitive material is directly charged into a bath of the processing liquid.

(6) A photographic processing method in which a silver halide photographic light-sensitive material after exposure is processed by energizing a processing solution in contact with a solution containing an electrolyte through at least anions.
Further, the continuous processing method for a silver halide photographic light-sensitive material as described in (1), (2), (3) or (4), wherein the solid processing agent for silver halide photographic light-sensitive material is directly charged into the bath of the processing liquid. .

(7) The continuous processing method for a silver halide photographic light-sensitive material as described in (5) or (6), wherein the amount of dissolution replenishing water of the directly added solid processing agent is 300 cc / m ² or less.

(8) The continuous processing method of a silver halide photographic light-sensitive material as described in (5), (6) or (7), wherein the processing speed of the silver halide photographic light-sensitive material is 20 m ² / hour or more.

That is, in the present invention, a means for increasing the dissolution rate by reducing the amount of sulfurous acid in the fixing agent, and a method for recovering the deteriorated fixing property by specifying the ratio of potassium ion and sodium ion in the sulfite salt of the developing solution. means,
And, the above object was achieved by means of increasing the dissolution rate by removing unnecessary salts in the treatment liquid.

The fixing agent contains a sulfite (sulfite component) as a preservative of thiosulfate. Since the dissolution rate of the sulfurous acid component is slow, it has a great adverse effect on the dissolution rate (solubility) of the solid processing agent, and therefore the amount thereof is preferably as small as possible. On the other hand, the developing solution also contains a sulfurous acid component as a preservative of the developing solution, and the developing solution is contained in the film by the developing treatment and brought into the fixing tank. Therefore, the developing solution is supplied with sulfurous acid from the developing solution, so that a small amount of sulfurous acid component is required for replenishment. In particular, when the replenishing amount of the fixing solution is small, the ratio of the carried-in developing solution to the fixing solution becomes high, and the sulfurous acid component replenished to the fixing solution can be smaller. In the conventional liquid agent kit, not only the state of the used liquid but also thiosulfuric acid is liquid even in the state of the kit, so that it is oxidized and decomposed, so that the sulfurous acid component is necessary to prevent oxidation. On the other hand, when the fixing agent is a solid processing agent, the decomposition of thiosulfuric acid is greatly reduced, so it is not necessary to suppress it by adding the sulfurous acid component, and the sulfurous acid component can be reduced in the solid kit state.

As another means for improving the solubility, it can be achieved by removing excess salts through the anion exchange membrane. That is, when the development process is performed, unnecessary potassium halide and sodium are generated in the development, and the salt strength increases. Even in the fixing solution, the silver halide is dissolved and the developing solution is brought in, so that unnecessary salts are increased and the salt strength is increased. By focusing on this point and removing unnecessary ions, the dissolution rate of the solid processing agent could be increased. This improves the deteriorated processability. That is, fluctuations such as a decrease in sensitivity were suppressed in the development, and deterioration in the fixability due to the dissolution delay of the main agent and deterioration in the drying property due to the dissolution delay of the aluminum component were suppressed in the fixing.

Further, the deterioration of the fixability due to the dissolution delay of the solid processing agent was improved by specifying the ratio of potassium ion and sodium ion of the sulfite of the developing solution. Sodium ions were preferred because the fixability deteriorates when the potassium ions of the developing solution are brought into the fixing solution. However, the use of sodium ions was not a preferable method in the case of a liquid concentrate kit because the kit volume was increased in terms of solubility. However, in the case of a solid solid processing agent, even if the potassium sulfite of the solid developer is changed to sodium in order to improve the fixing property deterioration, the volume of the solid processing agent does not increase and the fixing property deterioration is improved without any problem. Was done. The object of the present invention has been achieved as described above.

The present invention will be specifically described below.

The solid processing agent as referred to in the present invention is a powder processing agent as described above or a solid processing agent such as tablets, pills, granules, etc., which have been subjected to a moisture-proof treatment if necessary.

The powder in the present invention refers to an aggregate of fine crystal grains. The granules referred to in the present invention are obtained by subjecting a powder to a granulation step, and mean granules having a particle diameter of 50 to 5000 μm. The tablet in the present invention refers to a powder or granules compression-molded into a certain shape.

As a cause of fluctuations in photographic performance, it is effective to reduce the opening coefficient of the developer in the automatic processor. Particularly, the aperture coefficient is preferably 80 cm ² / l or less. That is, when the opening coefficient exceeds 80 cm ² / l, the undissolved solid processing agent or the concentrated liquid immediately after dissolution is easily subjected to air oxidation, resulting in the generation of insoluble matter or scum, which is then processed by the automatic processing machine or processed. Although problems such as contamination of the light-sensitive material occur, these problems are solved when the opening coefficient is 80 cm ² / l or less.
The opening coefficient referred to here is represented by the contact area with the air per unit volume of the processing liquid, and the unit is (cm ² / l). In the present invention, the aperture coefficient is preferably 80 cm ² / l or less, more preferably 50 to ³ cm ² / l, and further preferably 35 to 10 cm ² / l.

The opening coefficient is generally reduced by using a resin or the like for blocking the air as a floating pig.
No. 131138, No. 63-216050, No. 63-2
The size can be reduced by the slit type developing device described in No. 35940.

Further, in the automatic developing machine of the present invention, even if the photosensitive material conveying means is stopped after the development processing of the photosensitive material is completed, it is necessary for the processing agent to be dissolved from the time of the stop. It is preferable that the pump is continuously driven for a predetermined time to circulate the processing liquid. It is preferable that the time for which the pump is driven from the end of the development processing is within 2 hours,
The range of 10 minutes to 70 minutes is particularly preferable, and the range of 15 minutes to 50 minutes is particularly preferable in this range. If this time is too long, it is not preferable from various viewpoints such as usability, energy saving, deterioration of the processing liquid, and clogging of the filter.
Conversely, if it is too short, the dissolution of the solid processing agent will be insufficient.

To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is preliminarily formed on the surface of the photographic processing agent. Arbitrary means such as forming a coating layer by spraying (see JP-A-4-29136 and 4-8)
No. 5535, No. 4-85536, No. 4-85533
Nos. 4-85534 and 4-172341).

A preferable tablet manufacturing method is a method in which a solid processing agent in powder form is granulated and then a tableting step is performed to form the tablet. There is an advantage that the solubility and the storability are improved and the photographic performance becomes stable as compared with the solid processing agent formed by the tableting step by simply mixing the solid processing agent components.

As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation are used. Can be done.
In order to form tablets, the average particle size of the obtained granules is 100 to 800 μm in that when the granules are mixed and compressed under pressure, nonuniformity of the components, so-called segregation does not easily occur.
It is preferable to use the above-mentioned one, more preferably 200
˜750 μm. Furthermore, the particle size distribution is 6 for granulated particles.
It is preferable that 0% or more is within a deviation of ± 100 to 150 μm. When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a preketching machine can be used. The solid processing agent obtained by compression under pressure can have any shape, but from the viewpoint of productivity and handleability, or from the problem of dust when used on the user side, a cylindrical type, a so-called tablet is used. preferable.

More preferably, during granulation, the above-mentioned effects become more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

The method for producing the tablet treating agent is described in, for example, JP-A-51-61837, JP-A-54-155038 and JP-A-52-51838.
-88025, British Patent No. 1,213,808 and the like can be produced by a general method, further granule treating agent,
For example, JP-A Nos. 2-109042 and 2-10904.
It can be produced by a general method described in No. 3, No. 3-39735 and No. 3-39739. Further, the powder treating agent can be prepared by a general method as described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861. Can be manufactured.

The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g / cm ³ ~2.5g / cm ³ is preferably 1. 0 g
/ Cm ³ in terms of strength of the obtained solid matter,
If it is less than 2.5 g / cm ³ , it is more preferable in terms of solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

The solid processing agent used in the present invention is a developer,
Although it is used as a fixing agent, a rinsing agent, and the like for a photographic processing agent, it is the developer that has a large effect of stabilizing the photographic performance of the present invention.

It is within the scope of the present invention to solidify only one part of a certain treating agent in the solid treating agent used in the present invention, but preferably all components of the treating agent are solidified. is there. It is desirable that each component be molded as a separate solid processing agent and packaged in the same manner. It is also desirable that the individual components are packaged in the order in which they are periodically added repeatedly in a package.

It is preferable to add all the processing agents to be replenished to the respective processing tanks as solid processing agents according to the processing amount information.
When replenishment water is required, it is replenished based on the throughput information or other replenishment water control information. In this case, the liquid to be replenished in the processing tank can be only replenishing water. That is, when there are two or more types of processing tanks that need to be replenished, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the automatic developing machine can be made compact. The replenishing water tank may be placed outside or may be built in the automatic developing machine, and it is preferable to install the replenishing water tank from the viewpoint of space saving.

When the developer is solidified, all the alkali agents and reducing agents are solid-state processing agents, and in the case of tablets, at least 3 agents and most preferably 1 agent is used. It is a preferred embodiment of the agent. When two or more agents are divided into solid processing agents, it is preferable that the plurality of tablets or granules be packed in the same package.

In the present invention, the following materials may be used as the package of the solid processing agent.

As the synthetic resin material, polyethylene (either high pressure method or low pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, nylon (stretched or unstretched), polychlorinated Vinylidene, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate (PET), other polyesters, acrylonitrile butadiene copolymer, epoxy-phosphoric acid resin (JP-A-63-63037)
And the polymers described in JP-A-57-32952). Alternatively, pulp may be used.

Although these are preferably made of a single material, when they are used as a film, the films are laminated and adhered, but may be a coating layer or a single layer.

Further, it is more preferable to use various gas barrier films such as using aluminum foil or aluminum vapor-deposited synthetic resin between the above synthetic resin films.

The oxygen permeability of these packaging materials is 50 ml in order to preserve the solid processing agent and prevent the generation of stains.
/ M ² 24 hr · atm or less (at 20 ° C. and 65% RH),
It is more preferably 30 ml / m ² 24 hr · atm or less.

The total thickness of these laminated films or single layers is 1 to 3000 μm, more preferably 10 to 2000.
μm, and more preferably 50 to 1000 μm.

The above synthetic resin film may be a single layer (polymer) resin film, or a laminate of two or more (polymer)
It may be a resin film.

Examples of the one-layer polymer resin film suitable for the conditions of the present invention include (1) polyethylene terephthalate (PET) having a thickness of 0.1 mm or more, and (2) acrylonitrile butadiene copolymerization having a thickness of 0.3 mm or more. Combined (3) Hydrochloric acid rubber with a thickness of 0.1 mm or more
Among them, polyethylene terephthalate is excellent in alkali resistance and acid resistance, and thus can be suitably used in the present invention.

Next, as a laminated polymer resin film which meets the conditions of the present invention, for example, (4) PET / polyvinyl alcohol / ethylene copolymer (Eval) / polyethylene (PE) (5) oriented polypropylene (OPP) ) / Eval / P
E (6) Unstretched polypropylene (CPP) / Eval /
PE (7) Nylon (N) / Aluminum foil (Al) / PE (8) PET / Al / PE (9) Cellophane / PE / Al / PE (10) Al / Paper / PE (11) PET / PE / Al / PE (12) N / PE / Al / PE (13) Paper / PE / Al / PE (14) PET / Al / PET / Polypropylene (P
P) (15) PET / Al / PET / High Density Polyethylene (HDPE) (16) PET / Al / PE / Low Density Polyethylene (LDPE) (17) Eval / PP (18) PET / Al / PP (19) Paper / Al / PE (20) PE / PVDC coated nylon / PE / Ethyl vinyl acetate / polyethylene condensate (EVA) (21) PE / PVDC coated N / PE (22) EVA / PE / Aluminum deposited nylon / PE /
EVA (23) Aluminum vapor deposition nylon / N / PE / EVA (24) OPP / PVDC coat N / PE (25) PE / PVDC coat N / PE (26) OPP / Eval / LDPE (27) OPP / Eval / CPP ( 28) PET / EVAL / LDPE (29) ON (stretched nylon) / EVAL / LDPE (30) CN (unstretched nylon) / EVAL / LDP
E, etc., among which (20) to (30) are preferably used.

As a more specific structure of the packaging material, if the side in contact with the treating agent is the inner surface, PE / mainly paperboard / PE / Al / epoxy-phosphoric acid resin layer / polyester resin in this order from the inner surface. Layer / PE PE / K-nylon / PE or adhesive / Al / PE /
Paperboard / PE PE / vinylon / PE or adhesive / Al / PE / paperboard / PE PE / vinylidene chloride / PE or adhesive / Al / PE
/ Paperboard / PE PE / Polyester / PE or Adhesive / Al / PE /
Paperboard / PE Polypropylene / K-Nylon / Polypropylene / Al
/ Polypropylene / paperboard / polypropylene etc.

As a method for moisture-proof packaging of tablets and granules, there are 4-way seal, 3-way seal stick (pillow package, gusset package) PTP cartridge.

The four-way seal, three-way seal, and stick (pillow, gusset) packaging are different in the form, and the above materials are used, but when used in the peel-open system, a sealant agent is laminated to provide peel-open suitability. .

The peel-open method generally includes a cohesive failure method, an interface peeling method, and an interlayer peeling method.

The cohesive failure method is an adhesive called hot melt, which is used as a sealant in a heat-sealing lacquer, and peels off due to internal cohesive failure of the sealant layer during opening.

The surface-active peeling method is a method of peeling at the interface between films, in which the sealing film (sealant) and the adherend are not completely fused and can be peeled with an appropriate strength. The sealant is a film in which an adhesive resin is mixed, and polyethylene, polypropylene or a copolymer thereof, a polyester type, or the like can be selected depending on the material of the adherend.

Further, the delamination method is one in which the sealant is peeled between the layers of the laminate film by using a multilayer coextrusion film such as a laminate film.

In the present invention, the peel-open method using a film is preferably the interlaminar peeling method or the interfacial peeling method.

Since such a sealant is thin,
Usually, other films such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester (polyethylene terephthalate), polyvinyl chloride, nylon, eval, aluminum are laminated and used, but considering moisture resistance, environmental friendliness and matching with contents. Polyethylene, polypropylene, polyester, EVAL and the like are preferable. In consideration of printability, the outermost surface is preferably unstretched polypropylene polyester, paper or the like.

As the sealant film, for example, Tohcello, CMPS film, Dainippon Ink Diffran PP-100, PS-300 or Toppan Printing LTS is used.
There are films, Sun-seal FR, Sun-seal MS, etc. made by San-A Chemical Co., Ltd., and as the type already laminated with polyester, Declan C-1600T, C-1
There are 602T and the like.

PTP is a packaging form in which a solid processing agent is put into a sheet of PVC, CPP or the like which is molded as a kind of blister packaging and heat sealed with an aluminum sealing material.

Environmentally, PVC is not used as a forming material, and recently A-PET and highly moisture-proof PP (for example, TAS) are used.
-1130, TAS-2230, TAS-3230: Taisei Kako Co., Ltd. are preferably used.

When the treating agent is packaged or bound or coated with a water-soluble film or a binder, the water-soluble film or the binder may be a polyvinyl alcohol type, a methyl cellulose type, a polyethylene oxide type, a starch type, a polyvinyl pyrrolidone type, Hydroxypropyl cellulose type, pullulan type, dextran type and gum arabic type,
Films or binders composed of polyvinyl acetate-based, hydroxyethyl cellulose-based, carboxyethyl cellulose-based, carboxymethyl hydroxyethyl cellulose sodium salt-based, poly (alkyl) oxazoline-based, polyethylene glycol-based substrates are preferably used, and among these, In particular, polyvinyl alcohol type and pullulan type are more preferably used from the viewpoint of the effect of coating or binding.

The preferred polyvinyl alcohol is a very good film-forming material and has good strength and flexibility under most conditions. Commercially available polyvinyl alcohol compositions cast as films vary in molecular weight and degree of hydrolysis, but preferably have a molecular weight of about 10,000 to about 100,000. The degree of hydrolysis is the rate at which the acetic acid ester group of polyvinyl alcohol is replaced with a hydroxyl group. For film applications, the range of hydrolysis is usually about 70% to 100%. Thus, the term polyvinyl alcohol usually includes polyvinyl acetate compounds.

The method for producing these water-soluble films is described in, for example, JP-A-2-124945 and JP-A-61-17343.
No. 8, 60-158245, and JP-A-2-86638.
JP-A-57-117867 and JP-A-2-7565.
No. 0, JP-A-59-226018, 63-2187.
No. 41 and No. 54-13565, etc., but it is produced by a general method.

Further, as these water-soluble films, those commercially available under the names of Solbron (manufactured by Aicello Chemical Co., Ltd.), Hi-Selon (manufactured by Nigo Film Co., Ltd.) or Pullulan (manufactured by Hayashibara Co., Ltd.) can be used. Also, Chris Craft Industries (Chris Craft In
dustries) Inc. The 7-000 series polyvinyl alcohol films available from the MONO-SOL Division of the Company dissolve in water temperatures of about 34 ° F. to about 200 ° F., are harmless and exhibit a high degree of chemical resistance, and are particularly preferred. Used.

The thickness of the above water-soluble film is preferably 10 to 120 μm, more preferably 15 to 80 μm, in view of storage stability of the solid processing agent, dissolution time of the water-soluble film and crystal precipitation in an automatic processor. Those having 20 to 60 μm are particularly preferably used.

The water-soluble film is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process are facilitated, but also the covering effect is more excellently achieved.

Further, the tensile strength of the water-soluble film is 0.
5 × 10 6 to 50 × 10 6 kg / m ² is preferable, 1 × 10 6 to 25 × 10 6 kg / m ² is particularly preferable, and 1.5 × 10 6 to 10 × 10 6 kg / m ² is particularly preferable. These tensile strengths are measured by the method described in JIS Z-1521.

Further, the photographic processing agent packaged or bound or coated with a water-soluble film or a binding agent is used in storage, transportation, and handling during storage, transportation, and handling. Humidity in the atmosphere such as high humidity, rain, and fog, and water. In order to prevent damage caused by splashing or accidental contact with water due to wet hands, it is preferable to be packaged in a moisture-proof packaging material having a film thickness of 10 to 15
A film having a thickness of 0 μ is preferable, and a moisture-proof packaging material is a polyolefin film such as polyethylene terephthalate, polyethylene, or polypropylene, kraft paper, wax paper, moisture-resistant cellophane, glassine, polyester, polystyrene, or polyvinyl chloride, which can have a moisture resistance effect with polyethylene.
Polyvinylidene chloride, polyamide, polycarbonate,
At least one selected from acrylonitrile-based and metal foils such as aluminum and metallized polymer films is preferable, and a composite material using these may be used.

In the practice of the present invention, it is also preferable that the moisture-proof packaging material is a degradable plastic, particularly a biodegradable or photodegradable plastic.

Examples of the biodegradable plastics include natural polymers, polymers produced by microorganisms, synthetic polymers with good biodegradability, blending of biodegradable natural polymers with plastics, and photodegradable plastics are ,
Examples thereof include a group that is excited by ultraviolet rays and has a group that is linked to cleavage in the main chain. Further, other than the above-mentioned polymers, those having two functions of photodegradability and biodegradability at the same time can be favorably used.

The specific representative examples are as follows.

Examples of biodegradable plastics include natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. Microorganism-produced polymer PHB-PHV (3-hydroxybutyrate and 3-hydroxyvalerate). (Copolymer with rate) as a component
pol ", microbial-produced cellulose and other biodegradable synthetic polymers polyvinyl alcohol, polycaprolactone, etc. or their copolymers or mixtures Blending biodegradable natural polymers into plastics As biodegradable natural polymers , Starch, and cellulose, which have shape-disintegrating properties in addition to plastic.

Further, examples of improving the photodegradability of plastics include the introduction of a carbonyl group for photodisintegration and the addition of an ultraviolet absorber to accelerate the disintegration.

Regarding such degradable plastic,
"Science and Industry" Vol. 64, No. 10, pp. 478-484 (1990), "Functional Materials", July 1990, No. 23
What is generally described on page-34 etc. can be used. Also, Biopol (manufactured by ICI), E
co (Eco) (made by Union Carbide), E
colite (Eco Plastic)
Co., Ltd., Ecostar (St. Law)
Commercially available disassembled plastics such as Rence Starch) and Knuckle P (Nihon Unicar) can be used.

The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² 24 hr or less, more preferably 5 g · mm / m ² 24 hr or less.

In the present invention, as the means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, JP-B-63-137773 and 63-9 are used.
There are known methods such as 7522 and No. 1-85732, but the point is that any method can be used as long as it has at least the function of supplying tablets to the processing tank. Further, when the solid processing agent is granules or powder, it is disclosed in Japanese Utility Model Publication No. 62-81964,
63-84151, JP-A-1-292375, the gravity drop method described in JP-A-63-105159, and JP-A-6-105159.
The method using a screw or a screw described in JP-A-3-195345 and the like is a known method, but the method is not limited thereto.

However, the preferable method is, as a supply means for supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent which is previously weighed and divided and packaged is opened according to the processing amount of the photosensitive material, and the package is opened. A method of taking it out is possible. Specifically, the solid processing agent is sandwiched and housed in a package composed of at least two packaging materials by a predetermined amount, preferably one replenishment amount, and the package is separated in two directions or the package A part of it is opened so that it can be taken out. The solid processing agent that can be taken out can be easily supplied to the processing tank having the filtering means by spontaneous fall. A predetermined amount of the solid processing agent is housed in a package that is divided and hermetically sealed so that the air permeability between the solid processing agent and the adjacent solid processing agent is blocked. Therefore, moisture resistance is guaranteed unless the package is opened.

As an embodiment, it is conceivable that a package composed of at least two packaging materials sandwiching the solid processing agent is adhered or adhered to each other at their contact surfaces so that the periphery of the solid processing agent can be separated. . By pulling the respective packaging materials sandwiching the solid processing agent in different directions, the closely contacted or adhered contact surfaces are separated, and the solid processing agent can be taken out.

As another embodiment, it is conceivable that at least one of the packages made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term "opening" as used herein means a cut or break that leaves a part of the packaging material. As the unsealing method, the solid processing agent is forcibly pushed out by applying a compressive force from the packaging body on the non-opening side to the packaging body which can be opened through the solid processing agent, or on the packaging body on the openable side. It is considered that the solid processing agent can be taken out by making a cut with a sharp member.

The supply start signal is obtained by detecting the processing amount information. The supply stop signal is obtained by detecting the information that the supply of the predetermined amount is completed. Further, when the treatment agent is packaged and needs to be opened, the driving means for separating or opening based on the obtained supply start signal operates, and the driving means for separating or opening based on the supply stop signal is It can be controlled to stop.

The above-mentioned solid processing agent supplying means has a control means for charging a fixed amount of the solid processing agent according to the processing amount information of the photosensitive material, which is an important requirement in the present invention.
That is, in the automatic developing machine of the present invention, it is necessary to keep the component concentration in each processing tank constant and to stabilize photographic performance. What is the processing amount information of silver halide photographic light-sensitive materials?
It is a value proportional to the processing amount of the silver halide photographic light-sensitive material processed with the processing solution, the processing amount of the processed silver halide photographic light-sensitive material, or the processing amount of the silver halide photographic light-sensitive material being processed. It indicates indirectly or directly the amount of reduction of the treating agent in the liquid. It may be detected before or after the photosensitive material is carried into the processing liquid, or at any timing during immersion in the processing liquid. Further, it may be a physical parameter such as the concentration of the composition in the treatment liquid or a change in the concentration, pH and specific gravity. Further, it may be the amount of the treatment liquid which is discharged to the outside after drying.

The solid processing agent of the present invention may be placed in a processing tank, but preferably, it is communicated with a processing section for processing a light-sensitive material, and a processing solution flows between the processing section and the processing section. It is preferable that the structure is such that the dissolved components move to the processing section because there is a certain amount of processing liquid circulation between the processing section and the processing section. The solid processing agent is preferably added to the temperature-controlled processing liquid.

Generally, the temperature of an automatic developing machine is controlled, so that the temperature of the processing liquid is controlled by an electric heater. As a general method, a heat exchange part is provided in an auxiliary tank connected to the treatment layer, a heater is installed, and a pump is arranged in this replenishment tank to feed the liquid from the treatment tank in a constant circulation amount and to keep the temperature constant. There is.

Usually, a filter is arranged for the purpose of removing the crystalline foreign matter that is mixed in the processing liquid or is generated by crystallization, and plays a role of removing the foreign matter.

The most preferable method is to add the solid processing agent to a place where the temperature is adjusted, such as a place communicating with the processing section such as this auxiliary tank. This is because the insoluble component in the processing agent that has been added is blocked from the processing section by the filter section, and it is possible to prevent solids from flowing into the processing section and adhering to the photosensitive material, etc. It will be good.

Further, in the case where the processing agent input section is provided in the processing tank together with the processing section, it is preferable to devise a shield or the like so that the insoluble portion does not come into direct contact with the film or the like.

As for the material of the filter, the filtering device and the like, all materials used in general automatic developing machines can be used in the present invention, and the special structure and material do not influence the effect of the present invention.

In order not to impair the stability of processing performance such as a decrease in sensitivity and a decrease in γ, the amount of the processing liquid in the processing tank is preferably 7 l or more. More preferably, it is 10 l or more. Especially, the developer in the developing tank is 7
A value of 1 or more contributes to the effect.

The number of times of circulation of the treatment liquid circulated by the circulation means in the present invention is preferably 0.5 to 2.0 times / min, particularly 0.8 to 2.0 times / min, and further 1.0 to
2.0 times / min is preferable. This accelerates the dissolution of the solid processing agent, prevents the formation of lumps of the high-concentration liquid, prevents the concentration unevenness of the processed photosensitive material, and prevents the generation of insufficiently processed photosensitive material. It can be prevented. Here, the number of circulations indicates the flow rate of the liquid to be circulated, and it is defined as once when the liquid amount corresponding to the total liquid amount in the processing tank flows.

The solid treating agent according to the present invention is added to the treatment tank separately from the replenishing water, and the replenishing water is supplied from the replenishing water tank.

The antifungal means of the refill water tank of the present invention will be described. When the replacement rate in the replenishing water tank is reduced and the residence time of water becomes long, water scales are generated, and there is a problem in that the water rots for 2-3 weeks and a bad odor is generated. Further, if the generated water scale is replenished as it is, it will adhere to the surface of the photographic light-sensitive material or the solid processing agent and cause development unevenness in the case of a developing tank and poor fixing in the case of a fixing tank, which will significantly reduce the commercial value. There is. Therefore, in order to remove this water stain, it has to be washed regularly, which is very troublesome. Therefore, the water supply tank of the present invention has a mildewproof means. This antifungal means can be achieved by at least one means selected from the following group.

(Group) Chelating agent adding means Antifungal agent adding means Deionization processing means Ultraviolet irradiation means Magnetic processing means Ultrasonic processing means Electrolytic sterilization means Silver ion releasing means Air foaming means Active oxygen releasing means By contact with porous material Means Addition of other harmless fungi to prevent the growth of harmful fungi These means will be specifically described. The chelating agent and bactericide used as the antifungal means in the present invention are described in L. E. FIG. W
est "Water Quality Criteri
a "Photo. Sci. and Eng., vo1.
9, No. 6, 398 (1965), M.S. E. FIG. Bea
ch “Microbiological Growth”
in Motion-Picture Process
ing "SMPTE Journal, vol.85,
mar. (1976), R.S. O. Deegan “Pho
topprocessing Wash Water B
iocides "J.Imaging Tech.vo
l. 10, No. 6, 239 Dec (1984), JP-A Nos. 57-8542, 58-105145, 5
The compounds described in 7-157244, 62-220951 and the like can be used.

Examples of the chelating agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), 2-hydroxy-4-sulfophenol and 2-hydroxy-3. , 5-disulfophenol is preferable, and as the bactericide, phenol compounds, thiazole compounds and benztriazole compounds are preferable. Specifically, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-one
3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, sodium o-phenylphenol, and benztriazole are mentioned as preferable compounds.
It is preferable that these compounds are in the form of tablets if they are packaged in a package, and if they are divided and weighed in advance, they are individually packaged in an amount to be added at one time.

Means for adding these may be added by hand by the pharmacist, but preferably the solid processing agent supply device of the present invention is installed, and addition is carried out by this, and more preferably, detection is made in the rehydration tank. It is preferable from the viewpoint of maintenance-free that the water is added automatically when the tank is equipped and the water is replenished to a certain amount in the tank.

In the present invention, the means for modifying water with an ion exchange resin can be carried out based on the means described in JP-A-61-131632.

As the ion-exchange resin, various known cation-exchange resins (strongly acidic cation-exchange resin, weakly acid-acidic cation-exchange resin) described in Kokai Giho, Kogi No. 90-473, etc.
And various anion exchange resins (strongly basic anion exchange resins)
And these can be used alone or in combination. Usually, it is preferable to use a strongly acidic H type cation exchange resin and a weakly basic OH type anion exchange resin. It may be attached to the water replenishment tank or the water may be improved elsewhere.

Preferred ion exchange resins for strong acid are DIAION SK1B SK102, SK104, S.
K106, SK110, SK112, and SK116 (Mitsubishi Kasei Co., Ltd.), and preferred OH type strongly basic anion exchange resins are DIAION PA406 and PA40.
8, PA412, PA416, PA418 (Mitsubishi Kasei Co., Ltd.).

In the present invention, the means for irradiating with ultraviolet rays can be implemented by the means described in JP-A-60-263939. As the ultraviolet irradiation device, a product manufactured by Kindai Bio Research Institute (headquarters Kobe City) is small and can be preferably used.
The means for applying the magnetic field of the present invention is disclosed in JP-A-60-26393
It can be carried out by the means described in Japanese Patent No. The means for applying ultrasonic waves of the present invention can be implemented by the means described in JP-A-60-263940. The means for applying electrolysis of the present invention can be implemented by the means described in JP-A-3-22468. The means for releasing silver ions of the present invention include a means for putting a silver foil or a silver plate in a water replenishing tank, a means for coating the inner wall with silver, and a means for putting a silver ion releasing compound.

In the present invention, the air bubbling means may be a very simple means for blowing bubbles into the replenishment water tank, and is appropriately selected according to the size of the replenishment water tank. From the viewpoints of compactness and economy, the means for preventing the generation of scales and microorganisms is preferably selected from, and more preferably selected from.

The silver ion-releasing compound used in the above means is an organic acid such as silver chloride, silver bromide, silver iodide, silver oxide, silver sulfate, silver nitrate, silver acetate, silver oxalate, silver behenate or silver maleate. Specific examples include silver.

These silver compounds include those having a SiO ₂ —Na ₂ O type glass body having a network structure as a base structure component, a methane type SiO ₄ tetrahedron and Al.
In the present invention, a zeolite body having a three-dimensional skeleton structure in which O ₄ tetrahedra have one oxygen atom in common with each other and the silver compound is contained therein is preferably used in the present invention.

These silver compounds, and the zeolite bodies and glass bodies containing the compounds can be obtained as commercially available products, for example, Bio-Sure SG (Kinki Pipe Giken Co., Ltd.), Opa Pharma (Switzerland) Opagent Tablets (Opargent
Tablets and Zeomic (Ze manufactured by Sinanen Zeomic Co., Ltd.)
mic) and the like.

Further, the silver compound according to the present invention and the zeolite or glass body containing the compound can be used in various shapes. For example, it may be in the form of powder, spheres, pellets, fibers, or filters, or these may be kneaded into fibers such as cotton, wool, polyester, etc. before use. As a specific example of these, Saniter 30 (SANITER3) manufactured by Kuraray Co., Ltd.
0) and the like.

Of these, a filter-like or spherical one is one of the preferred embodiments in the present invention.

Furthermore, it is also one of the preferred embodiments of the present invention to use the silver compound or the zeolite or glass containing the compound in a water permeable container such as a plastic case or tea bag. . In addition to these, Clinker 205 manufactured by Nichiban Kenkyusho Co., Ltd. and Pacific Chemical's rackin can also be preferably used.

The solid processing agent used in the present invention includes, as a binder, saccharides (monosaccharides, polysaccharides in which a plurality of monosaccharides are glycoside-bonded to each other, and those described in Japanese Patent Application No. 6-91987 (pages 23 to 30)). Decomposition products) are preferred, and those selected from dextrins and sugar alcohols are particularly preferably used. There is little change in shape during long-term storage, troubles occur during addition, and usability is improved.

For the solid processing agent used in the present invention, it is preferable to use acylated amino acids described in Japanese Patent Application No. 5-186254 (pages 9 to 15) as lubricants. A solid processing agent can be stably manufactured without compromising strength,
Little deterioration of solubility, storage stability and dust generation are improved.

The solid processing agent used in the present invention includes, as a coating agent, Japanese Patent Application No. 6-70860 (14-33).
Page) hydroxylamines, phenylcarboxylic acids, phenylsulfonic acids, hydroxyl group- or carboxyl group-introduced alkyl (or alkenyl) carboxylic acids, sulfites, water-soluble polymers (polyalkylene glycol, methacrylic acid betaine-type polymers) etc),
It is preferable to use sugars. There is little generation of fine powder, little deterioration of solubility, excellent storage stability, and stable photographic performance can be maintained.

In the developer used in the present invention, in addition to dihydroxybenzenes, aminophenols and pyrazolidones described in Japanese Patent Application No. 4-286232 (pages 19 to 20) as developing agents, JP-A-5-165161 is used. The described reductones are also preferably used. Among the pyrazolidones to be used, those substituted at the 4-position (dimesone, dimeson S, etc.) are particularly preferable because their water solubility and the solid treating agent themselves do not change over time.

In order not to impair the stability of processing performance, the concentration of the developing agent is preferably 0.5 mol% or more. More preferably, it is 1.0 mol% or more.

As the preservative, in addition to the sulfite described in Japanese Patent Application No. 4-286232, an organic reducing agent can be used as the preservative. In addition, Japanese Patent Application No. 4-586323 (page 20)
The chelating agent described and the bisulfite adduct of the hardening agent described in the same (page 21) can be used. Further, as a silver sludge inhibitor, Japanese Patent Application No. 4-92947 and Japanese Patent Application No. 5-96118.
It is also preferable to add the compound represented by (general formula [4-a] [4-b]). Addition of a cyclodextrin compound is also preferable, and the compounds described in JP-A No. 1-124853 are particularly preferable.

An amine compound may be added to the developer of the present invention, and the compounds described in US Pat. No. 4,269,929 are particularly preferable.

The developer used in the present invention requires the use of a buffering agent, and examples of the buffering agent include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, and tripotassium phosphate. , Dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate),
Examples thereof include potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

As a development accelerator, Japanese Patent Publication No. 37-160
No. 88, No. 37-5987, No. 38-7826, No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813,247, and the like, JP-A-52-49829. No. and ibid. 50-15554
P-phenylenediamine compounds, quaternary ammonium salts represented by JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, US Patent 2,61
P-aminophenols described in Nos. 0,122 and 4,119,462, U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796, and 3,253. 919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, and amine compounds described in Japanese Patent Publication Nos. 37-16088 and 37-16088. 42-25201
No. 3, U.S. Pat. No. 3,128,183, Japanese Patent Publication No. 41-11
431, 42-23883 and U.S. Pat. No. 3,53
No. 2,501 and other polyalkylene oxides,
In addition, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, A nitrogen-containing heterocyclic compound such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine can be mentioned as a representative example 1-phenyl-5-mercaptotetrazole.

Further, in the developer composition used in the present invention, if necessary, methyl cellosolve, methanol,
Acetone, dimethylformamide, cyclodextrin compound, other Japanese Patent Publication Nos. 47-33378 and 44-9
The compounds described in JP-A No. 509 can be used as an organic solvent for increasing the solubility of the developing agent.

Furthermore, other various additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators can be used.

A compound known as a fixing agent can be added to the fixing agent used in the present invention. Fixing agents and chelating agents, p
An H buffer, a hardener, a preservative and the like can be added, and these are described in, for example, JP-A-4-242246 (page 4) and JP-A-5-11.
Those described in 3632 (pages 2 to 4) can be used. In addition, as a hardener, a chelating agent described in Japanese Patent Application No. 4-586323 (page 20), a bisulfite adduct of the hardener described in the same (page 21), or a known fixing accelerator can be used.

Prior to the treatment, it is also preferable to add a starter, and it is also preferable to solidify and add the starter. As the starter, in addition to organic acids such as polycarboxylic acid compounds, halides of alkaline earth metals such as KBr, organic inhibitors, and development accelerators are used.

In the present invention, the sulfite salt is a salt of sulfite, which includes sodium sulfite, potassium sulfite,
Water-soluble substances such as lithium sulfite and ammonium sulfite are preferable, and sodium sulfite and potassium sulfite are particularly preferable.

The sulfite concentration in the present invention means the sulfite concentration when the solid processing agent is completely dissolved in the corresponding amount of the diluent.

The sulfite concentration of the developer used in the present invention is preferably 0.3 mol / l or more, particularly preferably 0.45 mol / l or more and 1.5 mol / l or less.

The sulfite concentration of the fixing agent used in the present invention is preferably 0.05 mol / l or less, particularly preferably 0.005 mol / l or more and 0.03 mol / l or less.

The replenishing amount of the diluting solution of the fixing solution used in the present invention is preferably 300 cc / m ² or less, and particularly preferably 50.
It is cc / m ² or more and 150 cc / m ² or less.

In the present invention, the diluting liquid is a liquid to be replenished in the processing tank together with the solid processing agent, and tap water is preferable. Alternatively, a liquid obtained by distilling the processing waste liquid may be used.

In the present invention, the sulfite salt of the developer is present so as to satisfy the following formula. In other words, the molar ratio of sodium sulfite to potassium sulfite of the developer component added as a solid component is represented by the following formula. Says to be satisfied.

[(MNa) / (MK)]> 1 [wherein, MNa: the number of moles of sodium sulfite contained in 1 g of the solid developer MK: represents the number of moles of potassium sulfite contained in 1 g of the solid developer. The silver halide photographic light-sensitive material used in the present invention is not particularly limited, but the following are preferably used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method.
For example, Research Disclosure (RD) No.
17643 (December 1978), 22 to 23, page 1
・ Emulsion preparation method
on and types) and the same (RD) No. 18
716 (November, 1979) -Page 648. In addition, for example, T. H. Jam
es "The theory of the photo"
"graphic process" 4th edition, Macm
Illan, Inc. (1977) pages 38-104, G. F. Dauffin's "Photoemulsion Chemistry""P
photographic emulation Chem
istry ", published by Focal press (196
6 years), P. Glafkides "Physics and Chemistry of Photography" Chimie et physique photo
graphique ", published by Paul Montel (1967), VL Zelikman et al.," Making and Coat of Photographic Emulsions ".
ing Photographic Emulsio
n ", published by Focal press (1964) and the like.

Preferred silver halide emulsions are, for example, JP-A-59-177535 and JP-A-61-8.
No. 02237, No. 61-132943, No. 63-49.
751 and Japanese Patent Application No. 63-238225, and the like, high internal iodine type monodisperse particles can be mentioned. Crystal habits are cubic, 14-sided, 8-sided and the intermediate (11
The 1) plane and the (100) plane may be arbitrarily mixed.

The crystal structure of silver halide may be such that the inside and the outside have different silver halide compositions. A preferred embodiment of the emulsion is a core / shell type monodisperse emulsion having a two-layer structure comprising a high iodine core portion and a low iodine shell layer. The silver iodide content in the high iodine portion is 20 to 40 mol%, and particularly preferably 20 to 30 mol%. Examples of these include, for example, J. Photo. Sic. 12.24
Pages 2-251 (1963), JP-A-48-36890.
No. 52-16364, No. 55-142329,
58-49938, British Patent 1,413,748.
U.S. Pat. Nos. 3,574,628 and 3,655,3.
94, British Patent 1,027,146, US Patent 3,
505,068, 4,444,877, JP-A-6
It is described in gazettes such as 0-14331.

Another silver halide emulsion preferably used in the present invention is a tabular grain having an average aspect ratio of more than 1. The advantage of such tabular grains is that the spectral sensitization efficiency can be improved and the graininess and sharpness of images can be improved. For example, British Patent 2,112,157, US Pat. No. 4,439,520, 4,433,048
Issue No. 4,414,310 Issue No. 4,434,226
No. 58-113927 and 58-12792.
No. 1, 63-138342, 63-284272.
No. 63-305343 and the like, and the emulsion can be prepared by the methods described in these publications.

Particularly, Japanese Patent Application No. 4-289002 (1 to 3)
Page), JP-A-59-177535 (pages 2 to 5), Japanese Patent Application No. 4-277369 (pages 5 to 6), JP-A-62-42.
Those described in No. 146 (14 to 15) are preferably used.

Still another preferred silver halide emulsion used in the present invention is silver chlorobromide or silver chloride having a silver chloride content of 50% or more.

In order not to impair the stability of processing performance, a silver halide emulsion having a silver iodide content of 0.5 mol% or less is preferable. More preferably, it is 0.4 mol% or less.

The above-mentioned emulsion is either a surface latent image type that forms a latent image on the surface of the grain, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. May be. In these emulsions, a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, or the like may be used at the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method in order to remove soluble salts. As a preferred washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B No. 35-16086, or G3, G8, etc., as an aggregation high molecular weight agent described in JP-A No. 63-158644 is used. The method used is mentioned as a particularly preferable desalting method. The chemical ripening method of the emulsion used in the light-sensitive material of the present invention is preferably gold sensitization, sulfur sensitization, reduction sensitization, sensitization with a chalcogen compound, or a combination thereof.

The emulsion of the light-sensitive material used in the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. A hydrazine compound may be added, and the compound of Japanese Patent Application No. 5-134743 is preferable, and the compounds of general formula (5) and general formulas (7) and (8) are particularly preferable as the nucleation accelerator. A tetrazolium salt may be added, and those described in JP-A-2-250050 are particularly preferable. Other known additives include, for example, Research Disclosure No. 176
43 (December 1978), the same No. 18716 (19
1979) and the same No. The compound described in 308119 (December 1989) is mentioned. The types of compounds and the places where they are described in these three Research Disclosures are listed below.

Additives RD-17643 RD-18716 RD-308119 Page classification Page classification Page classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agents 26 to 7 XI 650 Right 1005 to 6 XI Antistatic agent 27 XII 650 Right 1006 to 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9
XVI binder 26 XXII 1003-4 IX support 28 XVII 1009 XVII Examples of the support that can be used in the light-sensitive material according to the present invention include, for example, RD-17643, page 28 and RD.
The thing described in page 1009 of -308119 is mentioned.

A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer. Further, a crossover cut layer or an antistatic layer may be provided.

In order not to impair the stability of processing performance, the amount of silver halide coated on the light-sensitive material should be 3 or less.
It is preferably g / m ² or less. The total amount of gelatin in the light-sensitive material is 4 g / m ² or less, more preferably 3.6.
When it is at most g / m ² , the processing stability will be improved.

Emulsion layers may be present on both sides of the support,
It may be on only one side. In the case of both sides, both sides may have the same performance or different performances.

FIG. 1 is a plan view showing an example of a processing apparatus used in the present invention. In the processing apparatus shown in FIG. 1, an anion exchange membrane (A membrane) 26, 3 is provided between the cathode and the anode for both development and fixing.
6 and cation exchange membranes (K membranes) 25 and 35 are alternately partitioned, and cathode chambers (N chambers) 24 and 34, anode chambers (A chamber)
21, 31, one or more concentrating chambers (C chambers) 22, 32 and one or more desalting chambers (D chambers) 23, 33 are arranged.

First, the liquid tank 20 will be described. The developer waste liquid is circulated in the desalting chamber (D chamber) 23 by a pump 28, while the cathode chamber (N chamber) 24 and the anode chamber (A chamber) 2 are circulated.
1. In the concentrating chamber (C chamber) 22, when an electrolyte solution such as sodium sulfate is circulated from a tank 27 by a pump 29 and a direct current is passed between the cathode and the anode, the halide ions in the waste liquid are anion exchange membranes. Desalination chamber (D
It is moved from the chamber 23 to the concentration chamber (C chamber) 22 and removed. The halide ions collected in the concentrating chamber (C chamber) 22 cannot move from the concentrating chamber (C chamber) 22 because they cannot pass through the cation exchange membrane (K membrane) 25 even if they want to move to the anode side. Therefore, the halide ions can be efficiently removed.

As shown in FIG. 1, the processing device is the developer 11
A developing tank 11 filled with 0, a fixing tank 12 filled with a fixing solution 120, and a washing tank 13 are provided. The photosensitive material 10 such as an X-ray film is conveyed to each processing tank for development, fixing,
Each treatment of washing with water is performed.

The developing tank 11 and the fixing tank 12 are provided with respective tanks and liquid tanks 20 and 30 through which liquids can freely flow. Then, in each of the liquid tanks 20 and 30, anion exchange membranes (A membranes) 26 and 36 are arranged so as to divide each tank into two or more chambers.

The desalting chamber (D chamber) 23 in the liquid tank 20 is filled with the developing solution 110, and is configured to be freely flowable with the developing tank through a connecting pipe or the like. Concentration chamber (C chamber) in liquid tank 20
22 is filled with the electrolytic chamber solution 270. With such a configuration, the developing solution 110 and the electrolyte solution 27
0 is in contact with the anion exchange membrane (A membrane) 26.
In the cathode chamber (N chamber) 24 in the liquid tank 20, the cathode is
An anode is immersed in the chamber 21.

The liquid tank 30 is similar to the liquid tank 20. The desalting chamber (D chamber) 33 is filled with the fixing liquid 120, and the concentrating chamber (C chamber) 32 is filled with the electrolyte 370.
These are in contact with each other through the anion exchange membrane 36.

Further, the liquid tank 20 may be a processing apparatus having only a cathode chamber (N chamber) and an anode chamber (A chamber). In this case, the cathode chamber (N
Chamber) and the electrolyte solution 270 in the anode chamber (A chamber)
And the space between the cathode chamber (N chamber) and the anode chamber (A chamber) is completely covered by an anion exchange membrane (A membrane).

Further, the liquid tank 30 may be a processing apparatus having only a cathode chamber (N chamber) and an anode chamber (A chamber). In this case, the cathode chamber (N
Chamber) and the electrolytic solution 370 in the anode chamber (A chamber)
And the space between the cathode chamber (N chamber) and the anode chamber (A chamber) is completely covered by an anion exchange membrane (A membrane).

By energizing, the halide ions in the treatment liquid are moved and removed from the cathode chambers (N chambers) 24 and 34 through the anion exchange membrane to the anode chambers (A chambers) 26 and 36, respectively.

When energized, the current density is 0.02 to 3 A / dm.
² , preferably a voltage of 0.05 to 1.2 A / dm ² is applied. The applied voltage is conceptually 0.05 to 100 V, preferably 0.1 to 10 V, though it is completely different depending on the liquid used, the form of the processing apparatus, the electrode distance, the nature and type of the diaphragm.

The initial value of the membrane voltage is usually 0.5 to 2
It is 0 V (membrane resistance 0.5 to 30 Ω).

By applying such an electric current during the processing of the photosensitive material, halide ions such as Br − accumulated in the developing solution or the fixing solution by the processing can be moved to the counter electrode through the anion exchange membrane. Therefore, the halide ion in the processing liquid can be maintained constant, and the oxidized processing component such as the developing agent is reduced to recover the processing ability, and a constant processing performance can be obtained.

In the present invention, current is supplied with a constant current, but in this case, a unit volume (for example, 1 l) of the processing liquid is used.
It is preferable to manage the per-current (current density) so as to be constant. In this case, specifically, time management may be performed. Further, when electricity is being supplied (for example, at a constant voltage without controlling voltage or current), it may be managed using an integrating ammeter or the like. This is because the movement of halide ions and the oxidation in the bleaching solution act with an efficiency of 80 to 99% with respect to the amount of electricity passed.

The current density at this time is usually 0.5 to 5
It is set to 0 A / l, preferably 1 to 10 A / l. By performing such management, the amount of movement of anions can be controlled to be more constant.

At this time, the amount of electricity required for recovering the developing power of the developing solution depends on the adjustment of the energization time. This amount of electricity depends on the coating silver amount of the light-sensitive material and the pre-bath of the light-sensitive material. It may be determined according to the amount of items brought in.

As the anion exchange membrane used in the present invention, any one may be used as long as it selectively permeates anions, and commercially available ones can be used as they are.

Thus, as the anion exchange membrane, Se
Lemion AMV / AMR (Made by Asahi Glass), Acip
lex A201, A172 (manufactured by Asahi Kasei), Neose
pta AM-1 to 3 (manufactured by Tokuyama Soda), Ionac M
A-3148 (manufactured by Ionac Chemicals), N
Epton AR103PZL (manufactured by Ionics) or the like can also be used, but in particular, the present invention aims at the permeation of halide ions such as Br-, and therefore Selmion ASV / A that selectively permeates monovalent anions.
SR (Made by Asahi Glass), Neosepta AFN-7, N
It is preferable to use a commercially available product under the trade name such as eosepta ACS (manufactured by Tokuyama Soda).

In the present invention, the above-mentioned anion exchange membrane is a generic term for a membrane that selectively permeates anions, and in this sense, the pore diameter is 0.2 to 20.
It also includes porous ceramics of μm.

The processing solution to which the present invention is applied is specifically a color developing solution, a first black-and-white developing solution for reversal processing, a fixing solution or the like in a color photograph, and a black-and-white image in a black-and-white photograph. Examples include developing solutions and fixing solutions. With these processing solutions, it is necessary to prevent the accumulation of halide ions eluted from the emulsion layer of the light-sensitive material as the processing progresses.

On the other hand, the solution containing the electrolyte in which the anode is dipped may be a treatment liquid or a solution prepared separately, and this solution prepared separately is called an electrolyte solution. Examples of the processing liquid include a processing liquid having a bleaching ability such as a bleaching liquid. In the bleaching solution, by combining with a color developing solution or a fixing solution, a halide ion is transferred from the developing solution or the fixing solution to the bleaching solution, and further, the bleaching agent in the reduced state is oxidized at the anode, whereby the bleaching solution itself The processing performance can be restored.

The electrolyte used in the electrolyte solution is not particularly limited, but may be NaCl, KCl, LiCl,
HaBr such as NaBr, KBr, KI, Na ₂ S
Sulfates such as O ₄ , K ₂ SO ₄ , KNO ₃ , NaNO ₃ , NH ₄
It is preferable to use nitrates such as NO ₃ and carbonates such as Na ₂ CO ₃ and K ₂ CO ₃ .

When nitrate is used among the above various salts, the nitrate ion is replenished, so that the replenishment of the corrosion inhibitor and the bleaching accelerator can be reduced or eliminated in some cases.

When a sulfate is used, the sulfate ion is replenished, so that the acid replenishment for lowering the pH can be reduced or even eliminated in some cases.

When a carbonate is used, the carbonate ion is replenished, so that the pH buffer and the acid can be replenished in a reduced amount or in some cases eliminated.

The concentration of the electrolyte in the electrolyte solution at this time may be 0.1 to 30%, preferably 0.5 to 20%.

Then, the anion exchange membrane may be appropriately selected depending on the electrolyte solution.

The cathode used in the present invention may be any electric conductor or semiconductor that can withstand long-term use, but stainless steel is particularly preferable. The anode may be made of an insoluble material and an electric conductor, and specific examples thereof include carbon (graphite), lead dioxide, platinum, gold and titanium steel, and stainless steel may be used depending on the case. The shape of the both poles is preferably a plate-like shape, a mesh-like plate-like shape, or a plate-like shape with projections, which is easy to install in the tank. The size may be appropriately selected depending on the tank capacity.

In the present invention, the amount of replenishing water for dissolution of the solid processing agent to be added is 300 cc / m ² or less, preferably 5
It is 0 cc / m ^{2 to} 150 cc / m ² .

In the present invention, the processing speed of the silver halide photographic light-sensitive material is 20 m ² / hr or more, preferably 30 m ² / hr or more.
m is ² / ^{hr~100m 2} / hr.

[0165]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 First, a photosensitive material for evaluation was prepared as follows.

<< Preparation of Photosensitive Material >><Preparation of Seed Emulsion-1> Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 Potassium bromide 841 g Water 2825 ml D1 1.75N Potassium bromide aqueous solution The following silver potential control amount 42 ° C. Japanese Patent Publication Nos. 58-58288 and 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
And 464.3 ml of each of Solution C1 were added by the simultaneous mixing method over 1.5 minutes to perform nucleation.

After stopping the addition of the solution B1 and the solution C1, it took 60 minutes to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then re-solution. B1 and solution C1 were each mixed by the simultaneous mixing method at 55.4.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was made + using the solution D1.
It was controlled to be 8 mv and +16 mv.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains have an average thickness of 0.064 μm and an average grain size of 0.064 μm. Diameter (circle diameter conversion)
Was confirmed to be 0.595 μm with an electron microscope. The variation coefficient of thickness was 40%, and the variation coefficient of distance between twin planes was 42%.

<Preparation of Em-1> A tabular silver halide emulsion Em-1 was prepared by using seed emulsion-1 and the following four kinds of solutions.
Was prepared.

A2 ossein gelatin 34.03 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.25 ml Emulsion-1 1.218 mol equivalent Equal to 3150 ml with water B2 Potassium bromide 1734 g Water Finish to 3644 ml with C2 Silver nitrate 2478 g Finish with water to 4165 ml D2 Fine grain emulsion consisting of 3% by weight of gelatin and silver iodide grains (average grain size 0.05μ) Equivalent to 0.080 mol * 0.06 mol To 6.64 liters of a 5.0% by weight gelatin aqueous solution containing potassium iodide, 2 liters of an aqueous solution each containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After forming the particles, p using an aqueous solution of sodium carbonate
The H was adjusted to 6.0.

Solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and a part of solution B2, a part of solution C2 and a half amount of solution D2 were added thereto by a simultaneous mixing method over 5 minutes. Then, half of the remaining amount of the solution B2 and the solution C2 is continuously added over 37 minutes, and then a part of the solution B2, a part of the solution C2 and the remaining whole amount of the solution D2 are added over 15 minutes, and finally, The remaining total amount of the solutions B2 and C2 was added thereto over 33 minutes. During this time, pH was 5.8 and pAg was
I kept it at 8.8 from beginning to end. Here, the addition rates of the solution B2 and the solution C2 were changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate.

Further, the above solution D2 was added to the total silver amount of 0.
Halogen substitution was carried out by adding 15 mol% equivalent.

After the addition is complete, the emulsion is cooled to 40.degree.
As an aggregating polymer agent, 1800 ml of a 13.8% (weight) modified gelatin aqueous solution modified with a phenylcarbamoyl group (substitution rate 90%) was added and stirred for 3 minutes. afterwards,
A 56% (weight) aqueous acetic acid solution was added to adjust the pH of the emulsion to 4.6, the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then, 9.0 l of distilled water at 40 ° C. was added, and the supernatant was drained after standing with stirring, 11.25 l of distilled water was further added, and the supernatant was drained after standing with stirring. Subsequently, a gelatin aqueous solution and a sodium carbonate 10% (weight) aqueous solution were added to adjust the pH to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, the pH was 5.80 at 40 ° C,
The pAg was adjusted to 8.06.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μm and the average thickness was 0.2.
5 μm, average aspect ratio of about 4.5, width of particle size distribution 1
It was 8.1% of tabular silver halide grains. The average distance between twin planes is 0.020 μm, and grains having a ratio between twin planes and thickness of 5 or more account for 97% (number) of all tabular silver halide grains and 10 or more grains. Was 49%, and particles of 15 or more accounted for 17%.

Next, after the above emulsion (Em-1) was heated to 60 ° C., a predetermined amount of the spectral sensitizing dye was added as a solid fine particle dispersion, and then adenine, ammonium thiocyanate, chloroauric acid and thioauric acid were added. Add a mixed aqueous solution of sodium sulfate and a dispersion of triphenylphosphine selenide,
After 60 minutes, a silver iodide fine grain emulsion was added, and ripening was carried out for a total of 2 hours. At the end of aging, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The above-mentioned additive and its addition amount (AgX1
Per mole) is shown below.

5,5′-Dichloro-9-ethyl-3,3′-di- (sulfopropyl) -oxacarbocyanine sodium salt anhydrous 2.0 mg 5,5′-di- (butoxycarbonyl) -3, 3'-Di- (4-sulfobutyl) -benzimidazolocarbocyanin sodium salt anhydrate 120 mg Adenine 15 mg Ammonium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg Silver iodide fine particles 280 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 500 mg A solid fine particle dispersion of a spectral sensitizing dye is disclosed in Japanese Patent Application No. 4-994.
It was prepared by a method similar to that described in No. 37. That is, it was obtained by adding a predetermined amount of the spectral sensitizing dye to water whose temperature had been adjusted to 27 ° C. in advance and stirring the mixture with a high-speed stirrer (dissolver) at 3,500 rpm for 30 to 120 minutes.

A dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C. and stirred to completely dissolve it. On the other hand 3.8 kg of photographic gelatin
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% sodium dodecylbenzene sulfonate aqueous solution was added thereto. Next, these two liquids were mixed and dispersed at 50 ° C. for 30 minutes at a peripheral speed of the dispersing blade of 40 m / sec using a high-speed stirring type disperser having a dissolver having a diameter of 10 cm. Immediately after that, the residual concentration of ethyl acetate was reduced to 0.3 under reduced pressure.
Ethyl acetate was removed while stirring until the content became not more than wt%. Then, dilute this dispersion with pure water to obtain 80 kg.
Finished. A part of the thus obtained dispersion was collected and used in the above experiment.

The average iodine content of the outermost surface of the silver halide grains contained in the silver halide emulsion (Em-1) by the addition of the above silver iodide fine particles was about 4 mol%.

Next, the following additives were added to the emulsion thus sensitized to prepare an emulsion layer coating solution. At the same time, a protective layer coating solution was also prepared.

Next, from below, on both sides of a support in which the following transverse light-shielding layer was previously coated on both sides of a polyethylene terephthalate film base for X-rays (thickness: 175 μm) colored blue with a concentration of 0.15. The emulsion layer coating solution and the protective layer coating solution were simultaneously multilayer coated in the following predetermined coating amounts and dried.

First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzene sulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2, 4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² second layer (emulsion layer) Compound (G) obtained by adding the following various additives to the emulsion 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl- catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35mg / ^{m 2} styrene - maleic acid copolymer 80 mg / ^{m 2} sodium polystyrenesulfonate anhydride 0 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl - triphenyl - phosphonium chloride 20 mg / m ² 1,3-dihydroxybenzene-4-sulfonic acid ammonium 500 mg / m ² 2-mercaptobenzimidazole - Sodium 5-sulfonate 5 mg / m ² compound (H) 0.5 mg / m ² n-C ₄ H ₉ OCH ₂ CH (OH) CH ₂ —N (CH ₂ COOH) ₂ 350 mg / m ² compound (M) 5 mg / M ² compound (N) 5 mg / m ² colloidal silica 0.5 g / m ² latex (L) 0.2 g / m ² dextrin (average molecular weight 1000) 0.2 g / m ² However, as gelatin, 1.0 g / m ² It was adjusted to be m ² .

Third Layer (Protective Layer) Gelatin 0.8 g / m ² Polymethylmethacrylate matting agent (area average particle size 7.0 μm) 50 mg / m ² formaldehyde 20 mg / m ² 2,4-dichloro-6- Hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonylmethyl ether 36 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² poly Sodium acrylate 30 mg / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² Compound (O) 50 mg / m ² Compound (S-2) 5 mg / m ² C ₉ F ₁₉ —O— (CH ₂ CH ₂ O) ₁₁ —H 3 mg / m ² C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) [(CH ₂ CH ₂ O) ₁₅ H] 2 mg / m ² C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) [(CH ₂ CH ₂ O) _{4 - (CH 2) 4 sO} 3 Na ] 1 mg / m ² in addition, the amount with the material is one-sided partial silver coverage was adjusted to 1.6 g / m ² as a one-sided min.

[0186]

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[0187]

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[0188]

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<< Preparation of Treatment Agent >> The following procedure (A),
Operation (A) in which a developing replenishing tablet was prepared according to (B): 3000 g of hydroquinone as a developing agent was ground in a commercially available bandam mill until the average particle size became 10 μm. To this fine powder, sodium sulfite and potassium sulfite in the amounts shown in Table 1 and dimezone S1000g were added and mixed in a mill for 30 minutes, and then in a commercially available stirring granulator at room temperature for about 10 minutes at 30 m.
After granulating by adding 1 liter of water, the granulated product is dried in a fluidized bed dryer at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product. 100 g of polyethylene glycol 6000 was added to the granules thus prepared at 25 ° C. for 4 hours.
After uniformly mixing for 10 minutes using a mixer in a room where the humidity was adjusted to 0% RH or less, the obtained mixture was transferred to a tablet press using a tablet press modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho KK The filling amount was set to the amount shown in Table 1 and compression tableting was performed, and 2500 developing replenishing tablets A-1 to
A-6 agent was prepared.

Operation (B) DTPA 100 g, potassium carbonate 4000 g, 5-methylbenzotriazole 10 g, 1-phenyl-5-mercaptotetrazole 7 g, 2-mercaptohypoxanthine 5 g, KOH 200 g, N-acetyl-D, L-penicillamine were operated. It grind | pulverizes and granulates like (A). The amount of water added was 30.0 ml, and after granulation, the granulated product was dried for 30 minutes at 50 ° C. to almost completely remove water. The mixture thus obtained was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount per tablet was 1.73 g and the mixture was compressed to 250
0 developing replenishing tablet B agents were prepared.

Next, a fixing supplementary tablet was prepared by the following procedure.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
(0 weight ratio) 14,000 g, and the amount of sodium sulfite shown in Table 2 is pulverized in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Then, in the same manner as in (A), the amount of water added is 50
Granulate to 0 ml. After granulation, granulate at 60 ° C for 3
The granules are dried for 0 minutes to almost completely remove water. In this way, 4 g of sodium N-lauroylalanine is added to the adjusted granulated product, and mixed for 3 minutes using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Next, the mixture thus obtained was compressed into tablets using a tableting machine modified from Tough Pressto Correct 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was the amount shown in Table 2 and 2500
Individual fixing replenishment tablets C-1 to C-4 were prepared.

Operation (D) 1000 g of boric acid, 150 aluminum sulphate-18-hydrate
0 g, sodium hydrogen acetate (dried by mixing glacial acetic acid and sodium acetate in equal moles) 3000 g, tartaric acid 200
Then, g is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 100 ml, and after granulation, the granules are dried for 30 minutes to almost completely remove the water content. Thus, 4 g of sodium N-lauroylalanine was added to the thus-prepared mixture, and the mixture was mixed for 3 minutes, and then the obtained mixture was used per tablet by a tableting machine which was modified from Kikusui Seisakusho Co., Ltd. Tuffpress Collect 1527HU. Was compressed into tablets to prepare 1250 fixing replenishment tablets D agent.

Developer starter Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make 1 L.

At the start of processing of the developing solution (starting of running), 16.5 l of developing solution prepared by diluting the developing tablet with diluting water
On the other hand, the developing tank was filled with the solution obtained by adding 330 ml of the starter as the starting solution to start the processing. The pH of the developer containing the starter was 10.45.

At the start of the processing of the fixing solution (starting of running), the fixing solution prepared as follows was used as the starting solution (fixing start solution) to fill the fixing tank and start the processing.

Fixer Formula Part-A (for 18 l finishing) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethylamino) -Ethyl-5-mercaptotetrazole 18g Part-B Aluminum sulphate 800g Part A and Part B were added at the same time to about 5 liters of water, and water was added while stirring and dissolving to make 18 liters, sulfuric acid and NaOH.
Was used to adjust the pH to 4.4.

<< Processing of Light-Sensitive Material >> The light-sensitive material prepared above was exposed to light so that the optical density after development was 1.0, and running (cut into 2,000 sheets) was performed. For running, an automatic processor SRX-502 equipped with a solid processing agent charging member and modified so as to be processed at a processing speed of 25 seconds was used.

During the running, the developing solution contained a light-sensitive material of 0.6.
^Two A and B agents each and 2 ml of water and 76 ml of water were added per 2 m ² . When each of A and B was dissolved in 38 ml of water, the pH was 10.70, and the sulfite concentration showed the values shown in Table 1. The fixing solution contains the amount of dilution water shown in Table 3 and the above C agent,
D agent was added. Two agents C and one agent D were added to 74 ml of diluted water. The sulfite concentration at that time is shown in Table 2.

The addition rate of water to each treatment agent was started almost at the same time as the addition of the treatment agent, and was added in approximately proportion to the dissolution rate of the treatment agent.

[0201] << Evaluation >><Evaluation of Fixability> Using the obtained running fixing solution,
Time to clear visually (clearing time)
Was measured and the fixability was evaluated. The fixing temperature is 25
° C.

<Evaluation of Dryability> Using the thus obtained running liquid, the film immediately before being squeezed after entering the drying zone after passing through the developing-fixing-water washing step was taken out and subjected to the following measurements.

The time taken for the surface temperature to reach 30 ° C. was measured with a surface thermometer while blowing hot air onto the film taken out with a commercially available dryer.

The results are shown in Table 3.

[0205]

[Table 1]

[0206]

[Table 2]

[0207]

[Table 3]

As is clear from Table 3, the present invention improves the fixing property and the drying property. Especially, the effect is great by removing the fixing sulfurous acid. It is also effective to reduce the replenishment amount of the fixing dilution water.

Example 2 Using the fixing start solution of Example 1 and the fixing solution A prepared as described below, the depositability and the fixability by storage were compared.

Fixer formulation Part-A (for 18 l finishing) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethylamino) -ethyl- 5-Mercaptotetrazole 18g Part-B Aluminum sulphate 800g PartA and PartB are added simultaneously to about 5l of water, and water is added while stirring and dissolving to make 18l, sulfuric acid and NaOH.
Was used to adjust the pH to 4.4.

A fixing start solution, a fixing solution, and a running solution (No. 2 in Table 3 of Example 1) left at 34 ° C. for 15 days were evaluated.

<Evaluation Method of Precipitability> The precipitability was visually evaluated according to the following criteria.

1: No occurrence 2: Slight occurrence 3: Large occurrence <Fixability> The fixability was visually evaluated by the time until it became transparent (clearing time). Evaluation of Fixability The film was the film used in Example 1 and the fixing temperature was 25 ° C.

The results are shown in Table 4.

[0215]

[Table 4]

As is clear from Table 4, according to the present invention, the depositability of the fixer at the start of processing and the fixability upon storage are excellent.

Example 3 (Preparation of Silver Halide Emulsion B) At the time of mixing using the simultaneous mixing method, 8 × 10 ⁻⁵ mol of rhodium hexachloride complex was added per 1 mol of silver, and after desalting by a conventional method, the average grain size was changed. An emulsion of monodisperse (variation coefficient 10%) silver chlorobromide (99 mol% silver chloride, balance silver bromide) cubic grains having a diameter of 0.10 μm was obtained.

4-Hydroxy-6-methyl-3,3,3a7-tetrazaindene, potassium bromide and citric acid were added to the resulting emulsion to add inorganic sulfur to 3 per mol of silver.
Chemical aging was carried out at a temperature of 60 ° C. until the maximum sensitivity was reached by adding × 10 ^-6 mol. After the ripening, 3 × 10 ⁻⁴ mol of 4-hydroxy-6-methyl-3,3,3a7-tetrazaindene and 1-phenyl-5-mercaptotetrazole and gelatin were added.

(Preparation of silver halide photographic light-sensitive material) On one undercoat layer of a polyethylene terephthalate film having a thickness of 75 μm and subjected to the antistatic treatment described in Example 1 of JP-A-3-92175, the following formulation The gelatin subbing layer of No. 7 had a gelatin content of 0.5 g / m ² , and the silver halide emulsion of Formula 8 had a silver content of 2.5 g / m ^2.
m ² and the amount of gelatin were 1.0 g / m ^2, and a coating solution of the following formulation 9 was further applied as a protective layer on the upper layer so that the amount of gelatin was 0.4 g / m ² . or,
A backing layer having the following formulation 10 was provided on the opposite undercoat layer so that the amount of gelatin was 0.4 g / m ^2, and a polymer layer having the following formulation 11 was further provided thereon, and the following formulation 1 was also provided thereon.
Two backing protective layers were provided by simultaneous multilayer coating so that the amount of gelatin was 0.4 g / m ² .

Formulation 7 (gelatin undercoat layer composition) Gelatin 0.5 g / m ² Dye b (ball mill-dispersed into powder having a particle size of 0.01 μm) 20 mg / m ² Dye c (ball mill-dispersed particle size) 0.01 μm powder) 10 mg / m ² Dye 1 (ball mill-dispersed powder 0.01 μm particle size) 80 mg / m ² Styrene-maleic acid copolymer hydrophilic polymer Viscous agent 10 mg / m ² S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Formulation 8 (silver halide emulsion layer composition) tetrazolium compound T-5 30 mg / m ² dodecyl Sodium benzenesulfonate 10 mg / m ² 5-methylbenzotriazole 10 mg / m ² Compound m 6 mg / m ² Latex polymer f 1.0 g / m ² Hardener g 40 m g / m ² S-1 0.7 mg / m ² Styrene-maleic acid copolymer hydrophilic polymer (thickener) 20 mg / m ² Formulation 9 (emulsion protective layer composition) Gelatin 0.5 g / m ² Dye c (Powder having a particle size of 0.01 μm by ball mill dispersion) 100 mg / m ² S-1 12 mg / m ² matting agent (monodispersed silica having an average particle size of 3.0 μm) 15 mg / m ² matting agent (average Monodisperse silica having a particle size of 8.0 μm) 20 mg / m ² 1,3-vinylsulfonyl-2-propanol 50 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 20 mg / m ² Formulation 10 (Backing layer composition) Gelatin 0.4 g / m ² S-1 5 mg / m ² Latex polymer f 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 70 mg / m ² Styrene-maleic acid Hydrophilic polymer (thickener) of copolymer 20 mg / m ² compound i 100 mg / m ² formulation 11 (polymer layer composition) latex n (styrene: butadiene: acrylic acid = 30: 65: 5) 1.0 g / m ² Hardener g 10 mg / m ² Formulation 12 (backing protective layer) Gelatin 0.4 g / m ² Matting agent (monodisperse polymethylmethacrylate having an average particle size of 5 μm) 50 mg / m ² Sodium-di- (2-ethylhexyl) -Sulfosuccinate 10 mg / m ² Surfactant h 1 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Hardener g 40 mg / m ²

[0221]

[Chemical 4]

[0222]

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[0223]

[Chemical 6]

[0224]

[Chemical 7]

The photosensitive material prepared as described above was used in the same manner as in Example 1 except that GR26SR (manufactured by Konica) was used as an automatic developing machine in which a 5 liter replenishing agent charging tank and a water replenishing nozzle were connected. Then, the fixability and dryness were evaluated.

The processing time is shown below.

[0227]

[0228]

[Table 5]

As is clear from Table 5, the present invention improves the fixability and dryability. Especially, the effect is great by removing sulfurous acid for fixing, and it is also effective to reduce the dilution water for fixing.

Example 4 Developer Potassium carbonate 40 g Hydroquinone 30 g Dimezone S 10 g Diethylenetriamine pentaacetic acid 5Na (DTPA) 1 g 5-Methylbenzotriazole 0.1 g 1-Phenyl-5-mercaptotetrazole 0.07 g 2-Mercaptohypoxanthine 0.05 g Sodium sulfite 30.00 g Potassium sulfite 25 g KOH 2 g Diethylene glycol 50 g N-acetyl-D, L-penicillamine 0.1 g These are dissolved in 300 ml of water and finally 400 m with pure water.
finished to 1. This concentrate was diluted to 1 liter with water to prepare a replenisher. The pH of this replenisher was 10.70.

Sodium thiosulfate 42.0 g Potassium thiosulfate 98.0 g Sodium sulfite 15.0 g Boric acid 10.0 g Sodium hydrogen acetate 30.0 g Glacial acetic acid 17.3 g Sodium acetate 12.7 g Tartaric acid 2.0 g These are 400 ml of water. Dissolve in and finally with pure water 500m
finished to 1. This concentrate was diluted to 1 liter with water to prepare a replenisher. The pH of this replenisher was 4.50.

Tablets for development replenishment were prepared according to the following procedures (A) and (B).

Operation (A) 3000 g of hydroquinone as a developing agent is ground in a commercially available bandam mill until the average particle size becomes 10 μm. 3000g of sodium sulfite and 2 of potassium sulfite are added to this fine powder.
000 g and Dimezone S1000 g were added and mixed in a mill for 30 minutes, and then in a commercial stirred granulator at room temperature for about 10 minutes,
After granulating by adding 30 ml of water, the granulated product is dried in a fluidized bed dryer at 40 ° C. for 2 hours to remove almost completely the water content of the granulated product. In this way, 100 g of polyethylene glycol 6000 was added to the prepared granules.
After uniformly mixing for 10 minutes in a room controlled at 5 ° C. and 40% RH or less, the resulting mixture was mixed with a tabletting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Tablet compression was performed by setting the filling amount per tablet to 3.84 g to prepare 2,500 development-supplementing tablet A agents.

Operation (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH, N-acetyl-D, L-.
Penicillamine is crushed and granulated in the same manner as in the operation (A). The amount of water added was 30.0 ml, and after granulation, the granulated product was dried for 30 minutes at 50 ° C. to almost completely remove water. The mixture thus obtained was compressed into tablets with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount per tablet was 1.73 g and the mixture was compressed to 25
00 developing replenishing tablet B agents were prepared.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is pulverized in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), add 500 m of water.
Granulate with l. After the granulation, the granulated product is dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product. In this way, 4 g of sodium N-lauroylalanine is added to the prepared granulated product, and mixed for 3 minutes using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Next, the mixture thus obtained was compressed into tablets with a filling amount of 6.202 g per tablet by a tableting machine modified from Tough Pressto Correct 1527HU manufactured by Kikusui Seisakusho Co., Ltd., and 2500 fixing replenishing tablets C were prepared. The agent was created.

Operation (D) 1000 g of boric acid, 150 parts of aluminum sulfate and 18 hydrates
0 g, sodium hydrogen acetate (dried by mixing glacial acetic acid and sodium acetate in equal moles) 3000 g, tartaric acid 200
Then, g is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 100 ml, and after granulation, the granules are dried for 30 minutes to almost completely remove the water content. In this way, 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and the mixture was mixed for 3 minutes, and then the obtained mixture was used per tablet by a tablet machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. Was compressed into tablets to prepare 1250 fixing replenishment tablets D agent.

Developer starter Glacial acetic acid 2.98 g KBr 4.0 g The developer obtained by adding 20 cc of starter to 1 liter of the development starter had a pH of 10.45.

The developing solution was prepared by adding ² each of the above-mentioned agents A and B and water per 0.62 m ² of the light-sensitive material as shown in Tables 6 to 9. When each of A and B was dissolved in 38 ml of water, the pH was 10.70. 0.6 for the fixing solution
Each 2 m ² of the above C agent, 1 D agent and 74 water
ml was added (treatment condition A).

For comparison, development processing was performed using a liquid agent. The processing conditions are such that the replenishment amounts of the developing solution and the fixing solution are 0.
The solid treatment was performed in the same manner as the solid treatment except that the amount was 40 ml per 62 m ² (treatment condition B).

<Evaluation of dissolution rate (dissolved state) of solid processing agent> Modified SRX-50 equipped with a solid processing agent charging member
The developer prepared using the above-mentioned replenishing tablets A and B and a starter are put into a developing tank of No. 2 (developing machine B) and pH is set to 10.4.
Adjusted to 5. A fixing solution prepared using the above-mentioned replenishing tablets C and D was also added to the fixing tank and adjusted to pH 4.50.
Using this automatic developing machine, the light-sensitive material (film) previously prepared in Example 1 was exposed to an optical density of 1.0 after development and continuously processed for 1 hour. At this time, processing was performed while replenishing tablets A and B in the developing tank and replenishing tablets C and D in the fixing tank.

The amount of water dissolved in the treating agent at this time is shown in Table 6 to Table 9.
It was shown to.

After the treatment, the state of the solid treatment agent is Dev tank, F
Immediately after continuous treatment in both ix tanks, the rack was raised and visually evaluated for solid matter in the tank and in the roller portions of the rack.

1 A small amount of finely divided solid processing agent is present, but a slight amount 2 A large amount of finely divided solid processing agent remains 3 A large amount of solid processing agent remains large <Evaluation of sensitivity> Fluorescent intensifying screen KO-250
Sensitometry was performed by a distance method (Konica Corp.) at a tube voltage of 90 KVp, 20 mA for 0.05 seconds to irradiate X-rays, and the sensitivity was determined and shown in Tables 6 to 9. The sensitivity value was obtained as the reciprocal of the X-ray dose required to obtain the density of fog +1.0, and the result was that sample No. It was expressed as relative sensitivity when the sensitivity after one run was 100.

<Evaluation of Residual Silver> Under the same processing conditions as above, the unexposed film was processed without exposure to obtain a sample for evaluating residual silver. The residual silver was evaluated by the following method.

Residual silver evaluation liquid (sodium sulfide 2.6 ×
An aqueous solution (10 ⁻³ mol / liter) is dripped at 5 points on the residual silver evaluation film.

After leaving for 3 minutes, the liquid was wiped off thoroughly, and after leaving at room temperature and normal humidity for 15 hours, it was left with an interference filter of spectral filter 436 ± 10 nm using a photo densitometer PDA-65 (manufactured by Konica Corp.). The blue light transmission densities of the portion below the silver evaluation droplet and the portion not dropped were measured, and the difference was used as a measure of the residual silver. That is, the larger this difference is, the higher the residual silver concentration in the processed film is.

The automatic processor SRX-502 used in the first embodiment.
Three kinds of products (made by Konica Corporation) modified as shown below were used.

Automatic machine A: Micro Acylyzer G3 (manufactured by Asahi Kasei Corp., tabletop electrodialysis (desalination) tank)
Automatic machine SR using cartridge AC-210-800
X-502 is further modified by adding a solid processing agent charging member so that the number of processed sheets is as shown in Table 6 when continuously processed for 1 hour. Develop machine B: Develop machine SRX-502 with solid processing agent. Remodeled so as to have the number of treatments shown in Table 6 when it is continuously treated for 1 hour with a charging member Developed machine C: When continuously treated for one hour on the machine SRX-502, the number of treatments shown in Table 6 Remodeled to be

[0249]

[Table 6]

As can be seen from Table 6, when the halogen was removed from the treatment liquid, the dissolution rate did not deteriorate even if the solid treatment agent was directly added, and the treatment failure did not occur.

Automatic machine GR-26SR used in the second embodiment.
Three kinds of products (made by Konica Corporation) modified as shown below were used.

Automatic machine A: Micro Acylyzer G3 (manufactured by Asahi Kasei Corporation, tabletop electrodialysis (desalination) tank)
Automatic machine GR using cartridge AC-210-800
-26SR is further modified by adding a solid processing agent charging member so that the number of processed materials is as shown in Table 7 when continuously processed for 1 hour. Develop machine B: Add solid processing agent to Develop machine GR-26SR. Remodeled so that the number of processed materials will be as shown in Table 7 when it is continuously processed for 1 hour. Automatic machine C: When the automatic processing machine GR-26SR is continuously processed for 1 hour. Modified to be

[0253]

[Table 7]

As can be seen from Table 7, when the halogen was removed from the treatment liquid, the dissolution rate did not deteriorate even when the solid treatment agent was directly added, and the treatment failure did not occur.

The automatic developing machine LD-220QT used in the third embodiment.
Three types of products (made by Dainippon Screen Co., Ltd.) modified as shown below were used.

Automatic machine A: Micro Acylyzer G3 (manufactured by Asahi Kasei Corporation, tabletop electrodialysis (desalination) tank)
Develop LD using cartridge AC-210-800
-220QT is further equipped with a solid processing agent charging member, 1
Remodeled so that the number of sheets can be processed as shown in Table 8 when continuously processed for a time. Develop machine B: When a continuous processing agent was added to the Develop machine LD-220QT for 1 hour and continuously processed, described in Table 8. Remodeled so that the number of processed sheets of the machine is C: Reproduced so that the number of processed sheets shown in Table 8 is obtained when the machine of LD-220QT is continuously processed for 1 hour.

[0257]

[Table 8]

As can be seen from Table 8, when the halogen is removed from the treatment liquid, the dissolution rate is not deteriorated even if the solid treatment agent is directly added, and the treatment failure does not occur.

As shown below, the automatic developing machine GR-27 (manufactured by Konica Corp.) used in Example 4 was modified to use three types.

Machine A: Microacylizer G3 (Asahi Kasei Corporation) with cartridge AC-210-8
An automatic developing machine GR-27 using 00 was further modified with a solid processing agent charging member so that the number of processed sheets was as shown in Table 9 when continuously processed for 1 hour. Automatic developing machine B: automatic developing machine GR -27 is a solid processing agent charging member and is modified so that the number of processed sheets is as shown in Table 9 when continuously processed for 1 hour. Developed machine C: When continuously processed on Developed machine GR-27 for 1 hour. Items modified so that the number of processed sheets listed in Table 9 is obtained.

[0261]

[Table 9]

As can be seen from Table 9, when the halogen was removed from the treatment liquid, the dissolution rate was not deteriorated and the treatment failure did not occur even when the solid treatment agent was directly added.

Example 5 Preparation of Photosensitive Material Preparation of Seed Emulsion-21 Seed Emulsion-21 was prepared as follows.

A21 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B21 2.5N silver nitrate aqueous solution 2825 ml C21 odor Potassium bromide 841 g Finish with water to 2825 ml D21 1.75N potassium bromide aqueous solution The following silver potential control amount at 42 ° C. Japanese Patent Publication Nos. 58-58288 and 58-5828
Solution A21 was mixed with Solution B using the mixing stirrer shown in No. 9.
21 and solution C21 (464.3 ml each) were added by the simultaneous mixing method over 1.5 minutes to perform nucleation.

After stopping the addition of solution B21 and solution C21, it took 60 minutes to raise the temperature of solution A21 to 60 ° C.
And adjust the pH to 5.0 with 3% KOH,
Solution B21 and solution C21 were again added by the simultaneous mixing method at a flow rate of 55.4 ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during this temperature increase from 42 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B21 and C21 was +8 mv each using the solution D21. And +16 mv.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains have an average thickness of 0.064 μm and an average grain size of 0.064 μm. Diameter (circle diameter conversion)
Was confirmed to be 0.595 μm with an electron microscope. The variation coefficient of thickness was 40%, and the variation coefficient of distance between twin planes was 42%.

Preparation of Em-21 Tabular silver halide emulsion Em-21 was prepared using seed emulsion-21 and the following four kinds of solutions.

A22 ossein gelatin 34.03 g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol) 2.25 ml seed emulsion-21 1.218 mol equivalent Water is made up to 3150 ml.

B22 Potassium bromide 1734 g Water to make 3644 ml.

C22 Silver Nitrate 2478 g Water to make up 4165 ml.

D22 Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μ) * 5.0% by weight aqueous gelatin solution 6 containing 0.06 mol of potassium iodide 6 To 0.64 liter, 2 liters each of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide was added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After forming the particles, p using an aqueous solution of sodium carbonate
H was adjusted to 6.0.

Solution A22 was vigorously stirred in the reaction vessel while maintaining it at 60 ° C., and a part of solution B22 and solution C2 were stirred therein.
Part 2 and solution D22 were added by the simultaneous mixing method over 5 minutes, then half of the remaining amount of solution B22 and solution C22 was added over 37 minutes, and then solution B22 was added.
Part of the solution C22 and a part of the solution C22 and the remaining total amount of the solution D22 were added over 15 minutes, and finally the remaining total amount of the solutions B22 and C22 were added over 33 minutes. During this time, the pH is 5.8.
In addition, pAg was kept at 8.8 throughout. Where solution B2
The addition rates of 2 and the solution C22 were changed in a function-like manner with respect to time so as to match the critical growth rate.

The addition amount of the solution D22 was adjusted so as to have the halogen composition shown in Table 10 below.

After the addition is complete, the emulsion is cooled to 40.degree.
As an aggregating polymer agent, 1800 ml of a 13.8% (weight) modified gelatin aqueous solution modified with a phenylcarbamoyl group (substitution rate 90%) was added and stirred for 3 minutes. afterwards,
A 56% (weight) aqueous acetic acid solution was added to adjust the pH of the emulsion to 4.6, the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then, 9.0 l of distilled water at 40 ° C. was added, and the supernatant was drained after standing with stirring, 11.25 l of distilled water was further added, and the supernatant was drained after standing with stirring. Subsequently, a gelatin aqueous solution and a sodium carbonate 10% (weight) aqueous solution were added to adjust the pH to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, the pH was 5.80 at 40 ° C,
The pAg was adjusted to 8.06.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.91 μm and the average thickness was 0.2.
0 μm, average aspect ratio about 4.5, width of particle size distribution 1
It was 8.1% of tabular silver halide grains. The average distance between twin planes is 0.020 μm, and grains having a ratio between twin planes and thickness of 5 or more account for 97% (number) of all tabular silver halide grains and 10 or more grains. Was 49%, and particles of 15 or more accounted for 17%.

Next, after the above emulsion (Em-21) was heated to 60 ° C., a predetermined amount of the spectral sensitizing dye was added as a solid fine particle dispersion, and then adenine, ammonium thiocyanate, chloroauric acid and thioauric acid were added. A mixed aqueous solution of sodium sulfate and a dispersion of triphenylphosphine selenide were added, and after 60 minutes, a silver iodide fine grain emulsion (equivalent to 0.3 mol% in terms of silver halide composition) was added, and a total of 2 hours was added. Aged. At the end of aging, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer.

The above-mentioned additive and its addition amount (AgX1
Per mole) is shown below.

Spectral sensitizing dye (I) 2.0 mg Spectral sensitizing dye (II) 120 mg Adenine 15 mg Ammonium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg 4- Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 2000 mg

[0279]

Embedded image

A solid fine particle dispersion of a spectral sensitizing dye was prepared by a method according to the method described in Japanese Patent Application No. 4-99437. That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature was previously adjusted to 27 ° C.
Obtained by stirring at 00 rpm for 30-120 minutes.

A dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C. and stirred to completely dissolve it. On the other hand, 3.8 kg of photographic gelatin
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% sodium dodecylbenzenesulfonate aqueous solution was added to the solution. Next, these two liquids were mixed and dispersed at 50 ° C. for 30 minutes at a peripheral speed of the dispersing blade of 40 m / sec using a high-speed stirring type disperser having a dissolver having a diameter of 10 cm. Immediately after that, the residual concentration of ethyl acetate was reduced to 0.3 under reduced pressure.
Ethyl acetate was removed while stirring until the content became not more than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the thus obtained dispersion was collected and used in the above experiment.

Next, the following additives were added to the emulsion thus sensitized to prepare an emulsion layer coating solution. At the same time, a protective layer coating solution was also prepared.

Next, the following transverse light-shielding layers were previously coated on both sides of a polyethylene terephthalate film base for X-rays (thickness: 175 μm), which was colored blue at a concentration of 0.15, and the above was applied to both sides of the support from the bottom. The emulsion layer coating solution and the protective layer coating solution were simultaneously coated in multiple layers to give the following prescribed coating amounts, and dried.

First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 180 mg / m ² Gelatin 0.15 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2, 4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² second layer (emulsion layer) The following various additives were added to the emulsion per mol of silver.

2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg t-butyl-catechol 70 mg polyvinylpyrrolidone (molecular weight 10,000) 800 mg styrene-maleic anhydride copolymer 2000 mg Sodium polystyrene sulfonate 1000 mg Trimethylolpropane 8000 mg Nitrophenyl-triphenyl-phosphonium chloride 50 mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 1500 mg 2-Mercaptobenzimidazole-5-sodium sulfonate 10 mg n-C ₄ H ₉ OCH _{2 CH (OH) CH 2 N} (CH 2 COOH) 2 700mg colloidal silica 1000mg latex (L) 800 mg dextrin (average molecular weight 1000) 00mg However, gelatin was adjusted to 1.25 g / m ^2.

[0286] The third layer (protective layer) matting agent 50 mg / m ² consisting of gelatin 0.5 g / m ² Polymethyl methacrylate (area average particle diameter 7.0 .mu.m) Formaldehyde 20 mg / m ² 2,4-dichloro-6- Hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonylmethyl ether 36 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² _{C 9 F 19 -O- (CH 2} CH 2 O) 11 -H 3mg / m 2 C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2 O) 15 -H 2mg / m 2 C 8 _{F 17 SO 2 N (C 3} H 7) (CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na 1mg / m 2 it is noted that the amount with the material is one-sided partial silver coverage sided min As the amount shown below It was manufactured.

[0287]

[Chemical 9]

Next, a development replenishing tablet was prepared according to the following procedure (A, B).

Operation (A) 4000 g of hydroquinone as a developing agent is pulverized in a commercially available bandam mill until the average particle size becomes 10 μm. 3000g of sodium sulfite and 2 of potassium sulfite are added to this fine powder.
500 g, 2000 g of 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone were added and 3 in the mill
After mixing for 0 minutes and granulating by adding 30 ml of water in a commercial stirred granulator at room temperature for about 10 minutes, the granulate is dried in a fluid bed dryer at 40 ° C. for 2 hours. To almost completely remove the water content of the granulated product. 100 g of polyethylene glycol 6000 was added to the granulated product thus prepared.
Was evenly mixed for 10 minutes in a room whose humidity was adjusted to 25 ° C and 40% RH or less, and then the obtained mixture was mixed with a tableting machine which was modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho. Filling amount per tablet 3.84g
After that, the tablets were compressed and compressed into 2,500 developing replenishment tablets A.
Two agents were made.

Operation (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH, 10 g of N-acetyl-D, L-penicillamine. Is pulverized and granulated in the same manner as in the operation (A). The amount of water added was 30.0 ml, and after granulation, the granulated product was dried for 30 minutes at 50 ° C. to almost completely remove water.
The mixture thus obtained was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 1.73 g and 2500 developing replenishers were used. Tablet B2 was prepared.

Next, fixing replenishing tablets were prepared by the following operations (C) and (D).

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is pulverized in the same manner as in the operation (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in the operation (A), the amount of water added is adjusted to 500 ml and granulation is performed. After granulation, granulate at 60 ℃
And dried for 30 minutes to almost completely remove the water content of the granulated product. To the granulated product thus prepared, 4 g of sodium N-lauroylalanine was added, and the mixture was added at 25 ° C. and 40% RH.
Mix for 3 minutes using a mixer in a conditioned room below. Next, the obtained mixture was compressed into tablets with a tableting machine which was modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 6.202 g.
2500 fixing replenishment tablets C2 were prepared.

Operation (D) 1000 g of boric acid, 150 parts of aluminum sulfate-18 hydrate
0 g, sodium hydrogen acetate (dried by mixing equimolar amounts of glacial acetic acid and sodium acetate) 3000 g, tartaric acid 200
Then, g is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 100 ml, and after granulation, the granules are dried for 30 minutes to almost completely remove the water content. To the thus-prepared product, 4 g of sodium N-lauroylalanine was added, and the mixture was mixed for 3 minutes, and then the obtained mixture was used per tablet by a tableting machine which was modified from Kikusui Seisakusho Co., Ltd. Tough Pressed Collect 1527HU. Was compressed to 4.562 g to prepare 1250 fixing replenishment tablets D2.

Developer starter Glacial acetic acid
2.98 g KBr 4.0 g Water was added to make 1 L.

At the start of the processing of the developing solution (starting of running), 25 tablets each of the developing replenishing tablets A2 and B2 were diluted with diluting water to 1 L. Developer 16.5 adjusted at this ratio
The developing tank was filled with a solution obtained by adding 330 ml of a starter to L as a starting solution, and fixing processing replenishment tablets C2 (25 tablets) and D2 at the start of the processing of the fixing solution (start of running).
(12.5 tablets) was diluted with diluting water to adjust to 1 L, and the fixing tank was filled with 9.2 L of the fixing solution adjusted at this ratio to start the processing.

The pH of the developer containing the starter is 1
It was 0.45.

The light-sensitive material prepared above was exposed to light so that the optical density after development was 1.0, and running was carried out. For running, an automatic developing machine SRX-502 equipped with a solid processing agent charging member, modified so as to be processed at a processing speed of 25 seconds, and further modified with a developing and fixing tank capacity were used. The amount of developer set here is 1
The amount of the fixing liquid is 6.5 L and the amount of the fixing liquid is 9.2 L.

During running, the developing solution contained a light-sensitive material of 0.6.
2 ml each of the above A2 and B2 agents and 38 ml of water per 2 m ²
Was added. The pH when the A2 and B2 agents were dissolved in 20 ml of water was 10.70. The fixing solution contains ^two C2 agents and one D2 agent per 0.62 m ² of the light-sensitive material.
37 ml of water and water were added.

Processing conditions Current image 35 ° C. 8.2 sec Settling 33 ° C. 5 sec Water wash Normal temperature 4.5 sec Squeeze 1.6 sec Dry 40 ° C. 5.7 sec Total 25 sec (Evaluation of sensitivity and fog) 40% at 50 ℃
After leaving it for 12 hours in an RH environment, it was wedge-exposed with a tungsten light source, processed with the above-mentioned automatic developing machine, and the sensitivity was measured as the reciprocal of the light amount to obtain a fog density + 1.0.

(Evaluation of Sensitivity and γ Fluctuation) The above-prepared sample was cut into a size of 4 pieces, and an exposure amount that blackened half of the coated silver amount was given, and then 4 mol of silver was developed in a unit time. The processing was carried out by the above-mentioned automatic developing machine at a processing interval. At this time,
Immediately before starting the treatment, and 30 minutes after starting the treatment, the wedge-exposed sample was treated to obtain sensitivity, γ (Fog
+ 0.25-Fog + 2.0) was measured and the difference was calculated.

(Evaluation of Silver Color Tone) The sample prepared above was exposed to a density of 1.2 and developed, and the color tone of the blackened silver was sensory-evaluated in five levels.

Rank 3 indicates the lower limit of practical use in the market,
Rank 5 shows a preferable level in which the finish is cold black.

The results obtained are shown in Table 10.

[0304]

[Table 10]

As can be seen from the above results, when the developing solution in the developing tank is 7 liters or more, the silver halide coating amount of the photosensitive material is 3 g / m ² or less, and the silver iodide content is 0.5 mol% or less. It can be seen that if there is, there is an effect on the processing stability. Further, this effect is remarkably exhibited when the number of moles of silver halide in the light-sensitive material developed per unit time is 0.8 to 5 moles.

[0306]

According to the present invention, a solid processing agent for a silver halide photographic light-sensitive material and a silver halide photographic light-sensitive material which do not deteriorate in developability (change in sensitivity, etc.), fixing property and drying property even when continuously processed at high speed. It was possible to provide a continuous processing method of

[Brief description of drawings]

FIG. 1 is a plan view showing an example of a processing apparatus according to the present invention.

[Explanation of symbols]

 11 Development tank 12 Fixing tank 13 Washing tank 20,30 Liquid tank 21,31 Anode chamber 22,32 Concentrated liquid 23,33 Desalination chamber 24,34 Cathode chamber 25,35 Cation exchange membrane 26,36 Anion exchange membrane 110 Developer 120 Fixer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location G03C 5/38 5/395 (72) Inventor Shoji Nishio 1 Sakuramachi, Hino City, Tokyo Konica Stock Association In-house

Claims (8)

[Claims] 1. A method of continuously processing a silver halide photographic light-sensitive material, a development processing step of dipping the light-sensitive material in a development processing solution in a development processing tank, and a fixing processing in a fixing processing tank. A silver halide photograph having a fixing processing step which is carried out by immersing the photosensitive material which has been subjected to the developing processing in a liquid, and substantially no other processing step is provided between the developing processing step and the fixing processing step. A solid processing agent for development containing a developing agent and a sulfite in the development processing solution and a diluting solution for development, and a solid processing agent for fixing containing a fixing agent in the fixing processing solution according to the throughput of the light-sensitive material. And a fixing diluting liquid are supplied, and the amount of sulfurous acid in the fixing solid processing agent supplied to the fixing processing liquid is 0 to 0.05 m with respect to 1 l of the fixing diluting liquid.
and a continuous processing method of a silver halide photographic light-sensitive material. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the amount of sulfurous acid in the developing solid processing agent supplied to the developing processing solution is 0.3 mol or more per 1 l of the developing diluting solution. Continuous processing method. 3. The continuous processing of a silver halide photographic light-sensitive material according to claim 1, wherein the amount of the fixing diluting liquid is 300 cc or less per 1 m ² of the processing amount of the silver halide photographic light-sensitive material. Method. 4. The continuous processing of the silver halide photographic light-sensitive material according to claim 1, wherein the amount of the developing diluent is 300 cc or less per 1 m ² of the processing amount of the silver halide photographic light-sensitive material. Method. 5. A treatment liquid which comes into contact with a liquid containing an electrolyte,
It is a photographic processing method in which an exposed silver halide photographic light-sensitive material is processed by being energized through at least anions, and a solid processing agent for silver halide photographic light-sensitive material is directly put into a tank of the processing solution. A method for continuously processing a silver halide photographic light-sensitive material, comprising: 6. A treatment liquid which comes into contact with a liquid containing an electrolyte,
A photographic processing method in which an exposed silver halide photographic light-sensitive material is processed by energizing at least through anions, and a solid processing agent for silver halide photographic light-sensitive material is directly put into a tank of the processing solution. Item 5. A continuous processing method for a silver halide photographic light-sensitive material as described in 1, 2, 3 or 4. 7. The continuous processing method for a silver halide photographic light-sensitive material according to claim 5, wherein the amount of replenishing replenishing water of the solid processing agent to be directly added is 300 cc / m ² or less. 8. The continuous processing method of a silver halide photographic light-sensitive material according to claim 5, 6 or 7, wherein the processing speed of the silver halide photographic light-sensitive material is 20 m ² / hour or more.