JPH09218493A - Treatment of silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent voids in fixing or deterioration in the remaining colors of a photosensitive material after treated, or to prevent defective drying or contamination of a photosensitive material or production of precipitation in an automatic developing machine by incorporating a specified compd. into a fixing agent and carrying out a washing process by a multistage counterflow method. SOLUTION: A photosensitive material is treated with a liquid prepared by dissolving a solid treating agent in an automatic developing machine having a developing process, a fixing process, a washing process in two or more stages, and a drying process. In this treating method, a compd. expressed by X-CH2 -(CR1 R2 )n -CH2 -Y is incorporated into the fixing agent, and the washing process is carried out by a multistage counterflow method with two or more stages. In formula, X and Y are halogen atoms, hydroxyl groups, sulfonate groups or carboxyl groups, R1 and R2 are hydrogen atom or hydroxyl groups, (n) is an integer 0 to 3. By the multistage counterflow method, the washing tank of the automatic developing machine is divided into at least two and the washing process is carried out in these tanks. For example, three tanks 31-33 are used for a three-stage counter flow method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more specifically, it does not deteriorate fixing loss and residual color even with a low replenishing fixing solution and washing water, and causes poor drying, stains, and automatic developing machines. The present invention relates to a method for processing a silver halide photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive material) which does not generate a precipitate.

[0002]

BACKGROUND OF THE INVENTION Black-and-white light-sensitive materials are developed, fixed, and exposed after exposure.
An image is obtained by washing with water or stabilizing treatment. At that time, fixing is usually performed with a fixing solution containing thiosulfate as a fixing agent. It is also well known that a water-soluble aluminum compound is added to a fixing solution to subject a light-sensitive material to a film hardening treatment in a fixing step to reduce the load in a subsequent stabilization and washing step and a drying step, and improve transportability. Yes, it is widely practiced.

Processing is generally carried out by an automatic developing machine having a developing section, a fixing section, a water washing section or a stabilizing bath section and a drying section.
In the case of processing with such an automatic processor, a large increase in washing water due to an increase in the amount of processing in recent years has become a problem, and the movement to take water saving measures is increasing year by year. As one of the countermeasures, a multi-stage countercurrent system in which the washing tank is divided into two or more stages to perform the washing treatment is known. However, in the case of using the multi-stage countercurrent method, the recent problems of ultra-rapid processing and low replenishment have caused a problem that the fixing missing property is significantly reduced due to the reduction of the processing time. Further, by reducing the replenishing amount of the washing solution, the residual color property of the processed light-sensitive material is significantly deteriorated, and there are disadvantages such as discoloration to brown. In addition, a large amount of used washing water is discharged as it is, and most of it is not used thereafter, and it is strongly desired to be reused.

On the other hand, a method of replenishing the treatment agent is generally adopted to keep the activity of the treatment liquid in the treatment tank constant, and the treatment agent replenishing method is a treatment agent (concentration kit or powder). The method of preparing in advance a replenisher solution in which) is dissolved is widely used. Specifically, the treatment work is performed while supplying the replenisher solution prepared in advance to the replenishment tank into the treatment tank at appropriate times, but providing the replenishment tank has a problem of taking up space. In addition, as another problem, the replenisher is thickened as the replenishment and the rapid processing are promoted, and the solubility is usually limited.
Therefore, there are many practical problems such as storage stability of the replenisher, for example, crystal precipitation.

In the light-sensitive material, it is usually 1 m in order to prevent fatigue of the processing solution due to continuous processing or air oxidation.
It has been usual to process while replenishing 300 ml or more of development replenisher and 450 ml or more of fixing replenisher per ² times. However, in recent years, the disposal of processing solutions has become a problem with the increase in processing volume, and the replenishment rate of processing solutions has been reduced due to the need to prevent environmental pollution. The thiosulfate concentration is increased, which causes a white precipitate to be generated by reacting with various ions existing in industrial water and tap water used in the treatment process.

In order to prevent this, a method of adding boric acid or polybasic acid to a fixing solution or the like is known, but the effect is not sufficient, and sufficient measures cannot be taken at present. A white precipitate adheres to the fixing roller and the inner wall of the tank, which causes abnormal rotation of the roller, stains on the photosensitive material, and in some cases causes damage. Further, since a high-concentration fixer is stored in the replenishing tank for a long period of time, the concentration further progresses depending on the storage condition, and white precipitates are likely to occur in the replenisher.

If the replenishing amount of the fixing solution is reduced, the fixing hardening film becomes insufficient due to fatigue and consumption during running,
As a result, the film comes out in a damp state without completely drying. Furthermore, when the processed image is stored, the color tone of the image silver loses pure black and discolors to brown, and the residual color property is extremely deteriorated, resulting in a serious problem.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to eliminate the fixing loss and residual color of the photosensitive material after the processing step even if the replenishing amounts of the fixing solution and the washing solution are reduced in the processing step of the photosensitive material. It is an object of the present invention to provide a method for processing a light-sensitive material which does not deteriorate the properties and does not cause defective drying or stains of the light-sensitive material and a precipitate in the automatic developing machine.

[0009]

The above object of the present invention is achieved by the following means.

In a method of processing a light-sensitive material, which is processed by using a liquid in which a solid processing agent is dissolved by an automatic processor processing including a developing step, a fixing step, a washing step of two or more steps, and a drying step, A method of processing a light-sensitive material, comprising a compound represented by the general formula (1), wherein the washing step is a multi-stage countercurrent method having two or more stages.

The method for processing a light-sensitive material according to the above item, characterized in that a part or all of the overflow liquid in the washing step is used as a diluting liquid in the fixing tank.

The method for processing a light-sensitive material as described in the above item 1 or 2, wherein a solid processing agent formed from two or more kinds of compounds is processed with a fixing agent containing metabisulfite and an Al compound.

[0013] Any one of the above items 1 to 3, which is treated with a solid fixing agent produced by a dry freezing method.
Item 6. The method for processing a light-sensitive material according to the item.

The replenishing amount of the washing liquid in the washing process is 500 m
l / m ² or less, The method for processing a light-sensitive material described in any one of the above items 1 to 4.

The method for processing a light-sensitive material according to any one of items 1 to 3, wherein the washing solution contains a chelating agent and a bactericide.

Hereinafter, the present invention will be described in detail.

A preferred structure of the general formula (1) is a compound represented by the following general formula (2).

General formula (2) HO—CH ₂ — (CH—OH) _n —CH ₂ —OH n = 3 to 8 These compounds have structural isomers, and the present invention includes all of them.

Specific examples of the compound represented by the general formula (2) preferably used in the present invention are shown below.
The present invention is not limited to these.

2-1 Cl—CH ₂ — (CHOH) ₄ —CH ₂ —Cl 2-2 Cl—CH ₂ — (CHOH) ₈ —CH ₂ —Cl 2-3 HOOC—CH ₂ — (CHOH) ₃ — _{CH 2 COOH 2-4 HOOC-CH 2} - (CHOH) 4 -CH 2 COOH 2-5 HOCH 2 - (CHOH) 3 -CH 2 OH 2-6 HOCH 2 - (CHOH) 4 -CH 2 OH 2-7 HOCH ₂ — (CHOH) ₆ —CH ₂ OH 2-8 HOCH ₂ — (CHOH) ₈ —CH ₂ OH Among these, 2-6 structural isomers D-mannitol and D-sorbitol are particularly preferred.

The fixing starter solution may be prepared by diluting a commonly used concentrated solution kit with water, or by dissolving a solid processing agent alone or a mixture formed from two or more compounds with water. You can use it. As the replenisher, it is preferable to use a solid processing agent formed of two or more kinds of compounds alone or as a mixture, dissolved in water.

The fixer is an aqueous solution containing thiosulfate,
The pH of the fixing start solution is 4.0 or more, preferably 4.2 to
It is 5.5, More preferably, it is 4.6-5.3.
As the fixing agent, sodium thiosulfate or ammonium thiosulfate can be used, which contains thiosulfate ion and ammonium ion as essential components, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally 0.1 to about 6 mol /
l.

The fixing solution preferably contains a water-soluble aluminum salt which acts as a hardening agent, and examples thereof include aluminum sulfate and potassium alum. If desired, a preservative (eg, sulfite or bisulfite), a pH adjuster (eg, sulfuric acid or sodium hydroxide), a chelating agent having a water softening agent and JP-A-62-7 can be used in the fixing solution.
The compound described in No. 8551 can be included. As a preservative, metabisulfite is preferable.

As the metabisulfite compound contained in the fixing agent, sodium metabisulfite, potassium metabisulfite and the like are preferable, and sodium metabisulfite is particularly preferable. The amount added per liter of the treatment liquid is 0.1
10 g / l is preferable, and 1 to 10 g is particularly preferable.

The solid processing agent of the present invention refers to a solid formed by molding two or more kinds of components constituting the fixing solution, and one solid containing all the fixing components or two or more solids fixing. It may be one that can constitute the component. The solid processing agent may be at least one solid formed by molding at least two kinds of compounds, and may be a single substance other than the molded solid.

Next, the freeze-drying method will be described. Freeze-drying is a method in which the raw material is frozen and the frozen ice is sublimated and evaporated to obtain a dried product. The drying method is one in which ice or a eutectic is formed by freezing to remove water from the hydrolyzed product, and water is removed from the raw material by sublimation of ice. The moisture adsorbed in the raw material is removed by raising the temperature in another drying method or in a freeze dryer.

As the solid processing agent, a powdery one prepared by a spray-drying method, a freeze-drying method and granulation (extrusion granulation, fluidized-bed granulation, tumbling granulation) granular (average particle size) 0.1 mm to 10 mm, especially 9 of the front particles
0% particle size is within ± 40% of the average particle size), and it is in the form of tablets that are compression molded. Particularly preferred forms are granules and tablets. The solid processing agent may contain compounds necessary for molding such as a binder and a lubricant.

On the other hand, after the treatment agent kit is manufactured and before the treatment agent is used, oxygen permeates from the packaging material to oxidize the treatment components, so that the packaging material of the present invention is It is desirable that the oxygen permeability is low. Polyethylene terephthalate (PET), nylon (Ny), vinylidene chloride-coated nylon, ethylene vinyl acetate (EVA), vinyl chloride, aluminum foil or aluminum oxide vapor-deposited film is laminated as a material having low oxygen permeability. The above materials, and the materials obtained by laminating these materials in multiple layers. In particular, the oxygen permeability of these packaging materials is 50 ml / atm · m ² · 25 ° C · da.
It is preferably y or less for stability with time in the kit state.

The fixer replenishing amount of the present invention is intended to reduce the economical burden of waste liquid treatment and the running cost of the user. In addition, it is possible to downsize the automatic processor by reducing the space of the replenishment tank. Preferred replenishment rate is 350 ml / m ² or less 25
ml / m ² or more, especially 250 ml / m ² or less 50 ml / m
^Two or more are preferred.

The multi-stage countercurrent washing is a step in which the washing tank of the automatic processor is divided into at least two to carry out the washing treatment. By dividing the washing bath, it is possible to minimize the concentration of the fixing solution in the washing bath that finally passes after fixing.

FIG. 1 is an explanatory view of processing steps of an automatic developing machine adopting the multi-stage water washing method of the present invention. In FIG.
1 is a developing tank, 2 is a fixing tank, and the washing tanks are 31, 32
And 33, three-stage countercurrent washing method. 4 is a drying section, 7
Is a dehumidifier, and water is supplied from the water supply tank 5 supplied from the water supply unit 51 through the pipe 6 to the developing tank 1 through the pipe 61 and the washing tank 33 through the pipe 62, and the fixing tank is washed with water. Countercurrent from the tank 33 to the washing tank 31 and washing tank 3
The overflow washing solution from 1 is used as dilution water.

The chelating agent contained in the washing solution is EDTA,
Citric acid, boric acid, etc., and the addition amount is 0.1 per liter.
It is preferably 5 to 100 g, more preferably 1 to 50 g. The bactericide contained therein is particularly preferably isothiazone, preferably 0.5 to 100 g, and more preferably 1 to 50 g per liter.

An object of the present invention is to reduce the economical burden of the washing process and the running cost of the user by reducing the supplement amount of the washing water as much as possible. In addition, it is possible to further reduce the economic burden by using the wash water of the overflow generated by the replenishment as the diluting liquid of the solid processing agent.
The replenishing amount is preferably 50 to 500 ml / m ² , and more preferably 200 to 500 ml / m ² .

The amount of the treating agent added at one time is 0.1 to 5
0 g is preferable, 1 to 20 g is preferable for the developing solution, and 5 to 50 g is preferable for the fixing solution. When the solid processing agent in this range is directly put into the processing tank of a general small automatic developing machine and slowly dissolved But it doesn't affect the picture condition. This is because the solid processing agent does not dissolve rapidly but dissolves slowly, so even if the amount added at one time is large, the composition is balanced with the amount consumed during processing and stable photographic performance is exhibited. . It was found that the photographic performance could be kept constant by injecting the replenishing water along with the dissolution. The treatment liquid is always regulated to the treatment temperature,
It is maintained at a nearly constant temperature. That is, since the dissolution speed is almost constant, the calculated addition of the solid processing agent and the balance of the components are achieved.

[0035]

The present invention will be specifically described below with reference to examples. Note that, needless to say, the present invention is not limited to the embodiments described below.

Example 1 A black-and-white light-sensitive material was prepared according to the following formulation. Then, this photosensitive material was exposed to a blackening rate of 50% and halogenated by using a modified developing machine GR-26SR manufactured by Konica Corporation using a developing solution and a fixing solution having the following formulations. The replenishing amounts of the developing solution and the fixing solution per 1 m ^{2 of the} silver photographic light-sensitive material were processed as shown in Table 1 for 200 days per day for 10 days, and the solution was used as a running solution.

(Preparation of Silver Halide Emulsion A) Silver chlorobromide core grains having an average thickness of 0.05 μm and an average diameter of 0.15 μm, which are 70 mol% of silver chloride and the rest of which is silver bromide, are prepared by the simultaneous mixing method. did. Add K ₃ RuCl ₆ to silver 1 when mixing core particles
8 × 10 ⁻⁸ mol was added per mol. In this core particle,
The shell was attached using the double-blending method. At that time, K ₂ IrC
l ₆ was added 3 × 10 ^-7 mol per 1 mol of silver. The obtained emulsion has an average thickness of 0.10 μm and an average diameter of 0.25 μm.
Core / shell monodisperse (variation coefficient 10%) of (10
Silver chloroiodobromide having 0) plane as the main plane (90 mol% of silver chloride, 0.2 mol% of silver iodobromide, and the rest consisting of silver bromide)
The emulsion was a tabular grain emulsion. Then, JP-A-2-28013
No. 9 described in Japanese Unexamined Patent Publication (Kokai) No. 2-2 (the modified gelatin wherein the amino group in the gelatin is substituted with phenylcarbamyl).
Desalting was carried out using the exemplified compound G-8) of No. 80139, page 287 (3). The EAg after desalting was 190 mV at 50 ° C.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene was added to the resulting emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5. .6, adjust to EAg123mV,
After adding 2 × 10 ^-5 mol of chloroauric acid, add 3 × of inorganic sulfur
Chemical ripening was performed at a temperature of 60 ° C. until the maximum sensitivity was obtained by adding 10 ⁻⁶ mol. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was used in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole and 3 × 10 ^-4 mol per mol of silver and gelatin. Was added.

(Preparation of silver halide emulsion B) 60 mol% of silver chloride, 2.5 mol% of silver iodide and the rest of silver bromide having an average thickness of 0.05 μm and an average diameter of 0.
15 μm silver chloroiodobromide core grains were prepared. When the core particles were mixed, K ₃ RhBr ₅ was added in an amount of 2 × 10 ^-8 mol per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 1 per mol of silver.
^0-7 mol was added. The resulting emulsion has an average thickness of 0.10 μm.
m, average diameter 0.42 μm, core / shell type monodisperse (variation coefficient: 10%) silver chloroiodobromide (90 mol% silver chloride, 0.5 mol% silver iodobromide, the rest being silver bromide). ) It was a tabular grain emulsion. Then, the modified gelatin described in JP-A-2-280139 (a gelatin in which an amino group in gelatin is substituted with phenylcarbamyl, for example, JP-A-2-280139)
No. 287 (3) page, exemplary compound G-8) was used for desalting. The EAg after desalting was 180 mV at 50 ° C.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene was added to the resulting emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. After adjusting the pH to 5.6 and EAg123 mV and adding 2 × 10 ⁻⁵ mol of chloroauric acid, N, N,
3'10 ^-5 mol of N'-trimethyl-N'-heptafluoroselenourea was added and chemical ripening was carried out at a temperature of 60 ° C until maximum sensitivity was obtained. After aging, 4-hydroxy-6-
Methyl-1,3,3a7-tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 1-phenyl-5-mercaptotetrazole in an amount of 3 × 10 ⁻⁴ mol, and gelatin.

(Preparation of photosensitive material for printing plate making scanner for HeNe laser light source) On one undercoat layer of the above-mentioned support, a gelatin undercoat layer of the following Formulation 1 was used in which the amount of gelatin was 0.
As will be 5 g / m ^2, amount of silver 1.5 g / m ² of silver halide emulsion layers 1 formulation 2 thereon, the amount of gelatin is 0.5
g / m at ^2, the following formulation 3 of the coating solution of gelatin weight of 0.3 g / m ² as a further intermediate protective layer thereon
In addition, a silver halide emulsion layer 2 of Formula 4 was added on top of the above so that the silver amount was 1.4 g / m ² , and the gelatin amount was 0.4 g.
/ M such that ^2, further amount of gelatin coating solution having the following formulation 5 is simultaneous multilayer coating so as to be 0.6 g / m ^2.
On the other side of the undercoat layer, a backing layer of the following formulation 6 was formed so that the amount of gelatin was 0.6 g / m ^2, and a hydrophobic polymer layer of the following formulation 7 was formed on the backing layer, and the following formulation was also formed on the hydrophobic polymer layer. The backing protective layer of No. 8 has a gelatin content of 0.4 g / m ²
A sample was obtained by simultaneous multilayer coating with the emulsion layer side.

Formulation 1 (Composition of gelatin undercoat layer) Gelatin 0.5 g / m ² Solid dispersion fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (Sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A Silver amount 1.5 g / m ² Solid of dye AD-8 Dispersed fine particles (average particle size 0.1 μm) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye d-2 5 mg / m ² hydrazine derivative HY -1 20 mg / m ² Nucleation accelerator: Exemplified compound AM-1 40 mg / m ² Redox compound: RE-1 20 mg / m ² Compound e 100 mg / m ² Latex polymer f 0.5 g / m ² Hardener g 5 mg / m ² S-1 0.7 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 30 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ² formulation 3 (Intermediate layer composition) Gelatin 0.3 g / m ² S-1 2 mg / m ² Formulation 4 (Silver halide emulsion layer 2 composition) Silver halide emulsion B Silver amount 1.4 g / m ² Sensitizing dye d-1 3 mg / m ² Sensitizing dye d-2 3 mg / m ² Hydrazine derivative HY-2 20 mg / m ² Nucleation accelerator AM-1 40 mg / m ² Redox compound: RE-1 20 mg / m ² 2-Mercapto-6- Hydroxypurine 5 mg / m ² EDTA 20 mg / m ² latex polymer f 0.5 g / m ² S-1 1.7 mg / m ² Formulation 5 (emulsion protective layer composition) Gelatin 0.6 g / m ² Solid dispersion of dye b (Average grain ^{0.1μm) 40mg / m 2 S-} 1 12mg / m 2 Matting agent: average particle size 3.5μm monodisperse silica 25 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² colloidal silica (average particle size 0.05 μm) 10 mg / m ² hardener j 30 mg / m ² formulation 6 (backing layer composition) gelatin 0.6 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 sodium polystyrene sulfonate 20 mg / m ² compound i 100 mg / m ² formulation 7 (hydrophobic polymer layer composition) latex (methyl methacrylate: acrylic acid) = 97: 3) 1.0g / m 2 hardener g 6 mg / m ² formulation 8 (backing protective layer) gelatin 0.4 g / m ² matting agent: mean Monodispersed polymethyl methacrylate 50 mg / m ² Sodium diameter 5 [mu] m - di - (2-ethylhexyl) - sulfosuccinate 10 mg / m ² Surfactant h 1 mg / m ² Dye ^{k 20mg / m 2 H- (OCH} 2 CH 2 ) _68- OH 50 mg / m ² Hardener j 20 mg / m ²

[0043]

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[0044]

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[0045]

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[0046]

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(Treatment liquid formulation) Start developer (HAD-S) Use liquid 1 lmin Pure water 300 ml DTPA / 5Na (diethylenetriamine 5 acetic acid 5Na) 1.45 g Sodium sulfite 52 g Potassium carbonate 55 g 8-Mercaptoadenine 0.06 g Diethylene glycol 50 g 5-methylbenzotriazole 0.21 g 1-phenyl-5-mercaptotetrazole 0.03 g Dimezone S 0.87 g Hydroquinone 20 g Sodium erythorbate 5 g KOH (55% aqueous solution) and 400 ml (p).
H10.45). When using it, use pure water 60
0 ml and 400 ml of the above concentrated liquid are mixed and used.

Preparation of replenishing developed tablet (HAD-JR) (Preparation of granulated product A part) Working liquid 1 l DTPA / 5Na 1.45 g Sodium metasulfite 21.3 g Potassium bromide 2.0 g Sodium carbonate 65 g 1-phenyl -5-Mercaptotetrazole 0.03 g Lithium hydroxide 12 g D-mannitol (trade name: Kao) 5 g D-sorbitol 3.5 g The above materials are mixed in a commercially available bandam mill for 30 minutes, and further with a commercially available stirring granulator. After granulating for 10 minutes at room temperature, the internal pressure was lowered to about 5 mmHg using a batch-type freeze dryer, and then cooled. Then, the mixture was treated at −20 ° C. for 12 hours and dried until the water content became 1% to obtain a granulated A part.

(Preparation of Granulated Material B Parts) Working Liquid 1 Lmin 8-Mercaptoadenine 0.09 g Dimezone S 1.4 g 5-Methylbenzotriazole 0.27 g Sodium metabisulfite 10.7 g Sodium erythorbate 7.5 g Hydroquinone 21 g D-sorbitol 2.0 g The above materials were mixed in a commercially available bandam mill for 30 minutes and further granulated for 10 minutes at room temperature with a commercially available stirring granulator, and then a batch-type freeze dryer was used, and the internal pressure was about 5 mmHg. And then cooled. Then, the mixture was treated at −20 ° C. for 12 hours and dried until the water content became 1% to obtain a granulated B part.

1-of the above-mentioned A parts and B parts and lubricants
2.0 g of sodium octanesulfonate was added and thoroughly mixed for 10 minutes, and the resulting mixture was compressed by 1.5 ton / m ² using a Masina UD / DFE30 / 40 tablet machine manufactured by Masina Co., Ltd. Twenty tablets each having a thickness of 30 mm and a thickness of 10 mm were obtained.

Starting Fixing Solution (HAF-S) Working Solution 1 Lmin Pure Water 120 ml Ammonium Thiosulfate 140 g (10% Na Salt: Hoechst) Sodium Sulfite 22 g Boric Acid 10 g Tartaric Acid 3 g Sodium Acetate / Trihydrate 37.8 g Acetic Acid (90) % Aqueous solution) 13.5 g Aluminum sulfate-18-hydrate 18 g 50% sulfuric acid aqueous solution and pure water 333 ml (pH 4.
81). When used, 667 ml of pure water and 333 ml of the above concentrated liquid are mixed and used. Starting solution pH
It is 4.85.

Preparation of replenishing fixed tablet (preparation of fixing A part tablet) Replenishing solution 1 liter Ammonium thiosulfate 140 g (10% Na salt: Hoechst) sodium bisulfite 4.5 g sodium sulfite 8.5 g sodium acetate 17 g pine flow ( (Product name: Matsutani Chemical Co., Ltd.) 17 g The above materials are mixed in a commercially available bandam mill for 30 minutes, and further granulated for 10 minutes at room temperature with a commercially available stirring granulator, and then a batch-type freeze dryer is used, and the internal pressure is about 5 mmHg. And then cooled. And it processed at -20 degreeC for 12 hours, it dried until the water content became 1%, and the fixing A part was obtained. Sodium 1-octanesulfonate 2.0 as part A and lubricant
g and thoroughly mixed for 10 minutes, and the resulting mixture was compressed to 1.5 tons / m ² using a Machine UD / DFE30 / 40 tabletting machine manufactured by Machinea Co., Ltd.
20 tablets each having a thickness of 10 mm and a thickness of 10 mm (1 l of the replenisher) were obtained.

(Preparation of fixing B part tablet) Replenisher 1 lmin Boric acid 6 g Tartaric acid 3 g Succinic acid 21 g Sodium metabisulfite Amount shown in Table 1 Aluminum sulfate octahydrate 12 g Compound (1) 6.3 g Commercially available material After mixing in a band dam mill for 30 minutes and further granulating with a commercially available stirring granulator at room temperature for 10 minutes, the internal pressure was lowered to about 5 mmHg using a batch-type freeze dryer and then cooled. Then, it was treated at -20 ° C for 12 hours and dried until the water content became 1% to obtain a fixing B part.

The above B part and 0.3 g of sodium 1-octanesulfonate as a lubricant were added and mixed thoroughly for 10 minutes.
Masina UD / DF manufactured by Masina Co., Ltd.
Using an E30.40 tableting device, 1.5 tablets of 1.5 ton / m ² were compressed to form 9 tablets (diameter: 30 mm, thickness: 10 mm) (2 l of replenisher).

Developers prepared above (18 tablets of A, B of B
8 tablets) and fixer (45 tablets A, 9 tablets B) each made of polyethylene (oxygen permeability: 40 ml)
/ Atm · m ² · 25 ° C · day), a polypropylene cap was placed on the lid, and the aluminum foil bag was stored at 50 ° C and 70% for 2 weeks.

When the above-mentioned tablets were used, they were dissolved in water using a mixer to make 2 l. The pH of the fixing replenisher
Was adjusted to a pH shown in Table 1 with a 50% sulfuric acid aqueous solution and a 30% sodium hydroxide aqueous solution. Development replenisher pH is 1
0.72.

The entire size of the light-sensitive material prepared above (5
08 × 610 mm) 130 ml of developing replenisher per sheet,
2,000 sheets of fixing replenisher (130 ml)
The exposed area of the sheet was 20% of the total area). The automatic developing machine was modified from GR-26SR (made by Konica Corp.), the replenishment parts of the developing tank and the fixing tank were modified so that the solid processing agent could be added, and the washing method was a three-stage countercurrent flow as shown in FIG. The original flush water replenishment amount of GR-26SR is 5.3l
/ M is ² those changed to 300 ml / m ^2, yet was assumed to use a washing water for dilution of the fixing replenisher.

Treatment condition Process Temperature Time Image 35 ° C. 30 seconds Fixing 34 ° C. 20 seconds Water washing Normal temperature 20 seconds Drying 45 ° C. 20 seconds Line speed (conveyance speed) 984 mm / min (rinse liquid for washing) Preparation) EDTA.2Na 40 g KOH 23 g K ₂ CO ₃ 12 g Potassium sulfite 110 g Sunbag-P (Sanai Petroleum) 20 g The above water is added to make a total volume of 1 l.

(Evaluation of Stain Inside the Fixing Tank and Roller Section) Stain after the running test was evaluated as follows from A to
The evaluation was made in 5 grades of E.

A: No stain B: Slightly deposited on the roller C: Precipitated on the roller D: Precipitated on the roller and suspended in the fixing tank E: Precipitated on the roller, inside the fixing tank Precipitation A and B were judged to be practical levels.

(Evaluation of Color Remaining Property) Ten sheets of unexposed light-sensitive material were processed with the processing solution after running processing, and the remaining color was visually observed.
The grade was evaluated. 5 is a good level and 1 is a poor level.

(Evaluation of Drying Property) 20 sheets of unexposed light-sensitive material were continuously processed with the processing solution after running processing, and the degree of drying was examined by touching with a hand, and the evaluation was carried out in 5 grades.

A: Completely dry b: Completely dry but slightly cold c: Dry but slightly moist d: Moist and adheres to another film e: Complete Among the above, a, b, and c are practical levels.

(Evaluation of Fixation Omission) The unexposed light-sensitive material was continuously processed on 20 sheets of the processing solution after the running treatment, and the fixation omission property was visually evaluated in three stages.

A: Fixing is completely missing and transparent B: Fixing is missing but slightly lacking transparency C: Fixing is not missing Among the above, A and B are at practical levels. .

The above results are shown in Table 1.

[0067]

[Table 1]

From this, it can be seen that the use of the processing method of the present invention improves the roller stain, the drying property, the residual color property, and the fixing missing property, and obtains good performance.

Example 2 Evaluations were made in the same manner as in Example 1 except that the replenishment amount of the washing water or the rinse solution was changed as shown in Table 2.

[0070]

[Table 2]

From this, it is understood that the use of the processing method of the present invention improves the roller stain, the drying property, the residual color property, and the fixing missing property, and the good performance can be obtained.

Example 3 Examples 1 and 2 except that the developing agent was changed as follows.
The evaluation was performed in the same manner as described above.

(Developer formulation) Pure water 300 g Potassium carbonate 89 g Potassium hydrogen carbonate 52 g Na erythorbate (Na isoascorbate) 25 g Dimezone S 2.8 g DTPA.5Na (40 wt%) 3.63 g Potassium bromide 2.5 g 5 -Methylbenzotriazole 0.55 g 2-Mercaptohypoxanthine 0.06 g Sodium sulfite 15.0 g Finally, it was made up to 500 ml with pure water. The pH was adjusted to 10.15 with potassium hydroxide. This concentrated liquid is diluted with water to 2.0.
The starting solution (pH 9.8) was prepared by diluting the solution twice.

(Preparation of Development Replenishing Tablet) Operation (A) 4000 g of developing agent Na erythorbate, dimezone S
300 g is ground in a commercial Van Dam mill until the average particle size is 10 μm. About 7 at room temperature in a commercial stirred granulator
After granulating by adding 200 ml of water for 1 minute, the internal pressure was lowered to about 5 mmHg using a batch-type freeze dryer and then cooled. Then, treat at -20 ° C for 12 hours,
It was dried until the water content became 1% to obtain a granulated product A part.

Operation (B) Potassium carbonate 14000 g, sodium sulfite 1500
g, disodium triamine pentaacetic acid pentasodium 145
g, PEG6000, 400g and Mannit 800g
Is ground to a mean particle size of 10 μm in a commercially available bandam mill. Approximately 7 minutes at room temperature in a commercial stirred granulator, 2
After granulating by adding 00 ml of water, the internal pressure was lowered to about 5 mmHg using a batch-type freeze dryer and then cooled. Then, it is treated at -20 ° C for 12 hours, and the water content is 1%.
And dried to obtain granulated B parts.

Operation (C) 250 g of potassium bromide, 60 g of 5-methylbenzotriazole, 5 g of 2-mercaptohypoxanthine and 6 g of pine flow (manufactured by Matsutani Chemical Co., Ltd.) were crushed in the same manner as in (A),
Mix and granulate. The amount of water added was 16 ml, and after granulation,
As in (A), the water content of the granulated product was almost completely removed to obtain a granulated product C part.

Operation (D) The granulated product (granules) sample prepared in the above operations (A) to (C) was subjected to 1 at room temperature using a commercially available cross rotary mixer.
Mix for 0 minutes and add N-myristoylalanine sodium to 0.2.
Add 9 g and mix for 3 minutes. The mixed granules thus obtained were continuously tableted with a rotary tableting machine (Kikusui Seisakusho Clean Press Collect H18) to give a developing supplement tablet sample having a diameter of 30 mm, a thickness of 15 mm and a weight of 21.5 g. I got 1000 pieces.

[0078]

[Table 3]

From the above, it can be seen that the use of the processing method of the present invention improves the roller stain, the drying property, the residual color property, and the fixing missing property, and obtains good performance.

[0080]

According to the present invention, even when the replenishing amount of the fixing solution and the washing solution is reduced in the processing step of the light-sensitive material, the fixing missing property and the residual color property of the light-sensitive material after the processing step are not deteriorated,
Moreover, it was possible to provide a method for processing a light-sensitive material which does not cause defective drying or stains on the light-sensitive material, or a precipitate in the automatic developing machine.

[Brief description of drawings]

FIG. 1 is an explanatory view of a processing step of an automatic processor adopting a multi-stage water washing method of the present invention.

[Explanation of symbols]

 1 Development Tank 2 Fixing Tank 31, 32, 33 Water Wash Tank 4 Drying Section 5 Water Supply Tank 51 Water Supply Unit 6, 61, 62 Piping 7 Dehumidifier

Claims (6)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material, which is processed by a liquid in which a solid processing agent is dissolved by an automatic processor processing including a developing step, a fixing step, a washing step of two or more steps, and a drying step. In the fixing agent, the following general formula (1)
A method of processing a silver halide photographic light-sensitive material, which comprises a compound represented by the following formula, and the water washing step is a multi-stage countercurrent system of two or more stages. Formula _{(1) X-CH 2 -} (CR 1 R 2) in _n -CH ₂ -Y [wherein, X, Y represents a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxyl group, R _1, R ₂ Represents a hydrogen atom and a hydroxyl group. n represents an integer of 3 to 10. ] 2. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein a part or all of the overflow solution in the water washing step is used as a diluting solution in the fixing tank. 3. A halogenating agent according to claim 1, wherein a solid processing agent formed from two or more kinds of compounds is treated with a fixing agent containing metabisulfite and an Al compound. Processing method of silver photographic light-sensitive material. 4. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the method is a solid fixing agent prepared by a dry freezing method. 5. The replenishing amount of the washing solution in the washing step is 500 ml.
/ M ² or less, the method for processing a silver halide photographic light-sensitive material according to any one of claims 1 to 4. 6. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the washing solution contains a chelating agent and a bactericide.