JPH11242313A - Treatment of silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treating device and a treating method of a silver halide photographic sensitive material by which even when the amt. of washing water is largely decreased, dirt or dross in a washing tank are not caused. SOLUTION: In the processes to develop, fix, wash or stabilize a silver halide photographic sensitive material by using an automatic developing machine having a developing tank, a fixing tank and washing tanks of 5 to 40 L total volume, the amt. of the fixing liquid brought by the photosensitive material from the fixing tank to the washing tank is specified to 10 to 60 ml per 1 m<2> , and the replenishing amt. of the fixing liquid is specified to 65 to 325 ml per 1 m<2> of the photosensitive material. After the treatment is completed, the inside of the washing tank is washed with water or a stabilizer.

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 which does not produce scale or stains in a washing tank.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material) is exposed, developed, desilvered, washed,
It is processed by steps such as stabilization. Processing is usually performed by an automatic developing machine, and a method of replenishing a replenisher in order to keep the activity of the processing solution constant is generally widely used. The replenishment of the replenisher is intended to dilute the eluate from the light-sensitive material, correct the amount of evaporation, and replenish the consumed components. In the water washing step, ordinary tap water is usually supplied to wash out and remove the fixing components remaining inside the processed photosensitive material.

[0003] Although there is a movement to save water by suppressing the use of a large amount of water for energy saving, there is a problem that scale is generated in the washing water, and it is inevitable to use a large amount of washing water to some extent. It was a situation. Some attempts have been made, such as removing the filter or adding a bactericide to prevent water scale during water saving.
The effect is inadequate.

On the other hand, in recent years, environmental problems have become remarkable, and the amount of waste liquid discharged in large quantities has become a problem even in processing using an automatic developing machine. Therefore, in order to reduce the total waste liquid amount, it is necessary to reduce the replenishment amount of the processing agent. However, if the replenishment amount of the fixing solution is reduced, the fixing solution becomes contaminated with gelatin and eluted substances eluted from the photosensitive material. The problem has arisen. Further, it is carried into the washing tank, and dirt, scale, etc. are generated inside the washing tank, which has a great effect on the photosensitive material to be processed. In addition, dirty water hits the roller, and the resulting deposits cause an extra load on the drying roller and the drive motor, degrading the dot quality of the film, generating abnormal noise, and causing the motor to A serious problem such as breakdown has occurred.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which does not cause dirt or scale in a washing tank. That is.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to develop and fix a silver halide photographic light-sensitive material using an automatic developing machine having a developing tank, a fixing tank and a washing tank having a total capacity of 5 to 40 L. In carrying out the washing or stabilizing treatment, the amount of the fixing solution of the photosensitive material brought into the washing tank from the fixing tank is reduced by 1%.
m ² per 10～60Ml, and as the photosensitive material 1 m ² per 65~325ml processed fixing replenishing amount, the silver halide photographic light-sensitive material of the interior of the washing tank after the process is completed is washed with water or stabilizing solution The treatment method, the concentration of hydrogen peroxide in the washing tank is 0.0003 to 0.3% by weight, and the concentration of hydrogen peroxide in the kit concentrate supplied to the washing tank is 2 to 35% by weight. And dissolving the hydrogen peroxide kit concentrate directly in a washing tank.

That is, the present inventors wash the inside of the washing tank of the automatic developing machine with water or a stabilizing solution every time the running process is completed, so that the fixing replenishment rate is 65 to 325 ml / m2.
^The present inventors have found that it can be reduced to ^2, and have reached the present invention.

Hereinafter, the present invention will be described in detail.

The automatic developing machine for carrying out the processing method of the present invention has a capacity of 5 to 40 L for the entire washing tank, and uses hydrogen peroxide as an oxidizing agent to decompose thiosulfate brought into the washing tank. Oxidizing agent supply means for automatically supplying based on information of the photosensitive material processing area as a washing tank regeneration or purification means, and when the contamination concentration becomes accumulation of elution components and the like from the photosensitive material, At least part of the washing water can be drained to replace the water,
It is desirable to have drainage means having concentration measuring means.

When the amount of the fixing solution of the photosensitive material brought into the washing tank from the fixing tank is 10 to 60 ml per 1 m ² ,
Reduce the concentration of hydrogen peroxide in the washing tank to 0.0003 to 0.3.
% By weight, and a hydrogen peroxide concentration of 2-3.
An oxidizing agent supply means for directly dissolving a 5% by weight of the kit concentrate in the washing tank is preferable.

Next, the treating agent that can be used in the present invention will be described.

The treating agent used in the present invention may be supplied in any form such as powder, paste, granules, tablets, concentrated solution, and used solution. Is preferred. When used as a starting liquid, they are used by adjusting them by dissolving them in water as specified. When used as a replenisher, it may be used by mixing and dissolving it with water in advance, or may be used by directly charging it into an automatic developing machine.

The developing solution contains a preservative (sodium sulfite,
Potassium sulfite, ammonium sulfite, sulfites such as sodium metabisulfite, metabisulfite), alkaline agents (sodium hydroxide, potassium hydroxide, etc.) and pH buffering agents (for example, carbonate, phosphate, borate, boric acid, Acetic acid, citric acid, alkanolamine, etc.) are preferably added. Sulfite is 0.25 mol / L or more, preferably 0.1 mol / L or more.
Used at 4 mol / L or more. The pH buffer is preferably a carbonate, and the amount of the carbonate added is preferably 0.5 mol or more and 2.5 mol or less per liter, more preferably 0.75 mol / L.
It is in the range of not less than 1 mol and not more than 1.5 mol. If necessary, dissolution aids (polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (nonionic surfactants including polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, defoaming Agents, antifoggants (halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (ethylenediaminetetraacetic acid or its alkali) Metal salts, nitrilotriacetates, polyphosphates, etc.), development accelerators (US Pat. No. 2,304,025)
, A compound described in JP-B-47-45541), a hardening agent (glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent. The pH of the developer is preferably adjusted to 7.5 or more and less than 11.5. More preferably, the pH is 8.5 or more and 11.0 or less.

The developing waste liquid can be regenerated by energizing. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The light-sensitive material according to the present invention can be processed while energizing. At that time, various additives added to the developer,
For example, a preservative, an alkali agent, a pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor and the like which can be added to the developer can be added. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. At this time, an additive which can be added to the developing solution as described above can be added. In the case where the waste developer is recycled, the transition agent complex is preferably used as the developing agent of the developer used.

As a special type of development processing, a developing agent is contained in the light-sensitive material, for example, in the emulsion layer or in a layer adjacent thereto,
It may be used as an activator processing solution for processing a photosensitive material in an alkaline aqueous solution to perform development. Further, a light-sensitive material containing a developing agent in a light-sensitive material, for example, in an emulsion layer or in a layer adjacent thereto may be processed with a developer. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions.

The fixing starting solution may be used by diluting a commonly used concentrated solution kit with water, or by dissolving a single or mixture of solid processing agents formed from two or more compounds in water. May be used. Regarding the replenisher, it is preferable to use a solid processing agent formed from two or more compounds alone or as a mixture by dissolving in water.

The fixing solution is an aqueous solution containing a thiosulfate, and the pH of the fixing initiating solution is 4.0 or more, preferably 4.2 to 7.0.
0, and more preferably 4.2 to 5.5. As fixing agents, sodium thiosulfate and ammonium thiosulfate can be used, and thiosulfate ions are an essential component. Sodium thiosulfate is particularly preferred for the purpose of preventing generation of odor. The amount of the fixing agent to be used can be appropriately changed, and is generally 0.1 to about 6 mol / L.

The fixing solution may optionally contain a preservative (for example,
Sulfites, bisulfites), pH adjusters (eg, sulfuric acid,
Sodium hydroxide), a chelating agent capable of softening water and compounds described in JP-A-62-78551.

In the processing of the present invention, the replenishing amount of the developing solution, the replenishing amount of the fixing solution, and the replenishing amount of the stabilizing solution are 65 to 325 ml / m ^{2 of the} photosensitive material, respectively, in order to reduce the amount of waste liquid.
And more preferably 65 to 130 per m ²
ml.

The replenishing amount of the developing solution and the replenishing amount of the fixing solution are, specifically, the replenishing amounts of the developing solution and the fixing solution when the same solution is replenished. This is the total amount of each concentrated solution and water when replenishing with the solution diluted in. When the solid processing agent is replenished with a solution dissolved in water, the replenishing amount is the total amount of each solid processing agent volume and water volume, and when the solid processing agent and water are separately replenished, the replenishing amount is It is the total amount of each solid processing agent volume and water volume.

The solid processing agent used in the present invention may be a solid formed of two or more components constituting the processing liquid, a single solid containing all of the processing liquid components, or a processing liquid containing two or more solid components. However, it is preferable that there is at least one solid formed of at least two compounds, and a single substance other than the formed solid may be used.

As a method for preparing a solid processing agent, a method of adding water to perform granulation and then drying to obtain granules and molding the mixture, a method of performing granulation with a small amount of water added, or a method of completely adding water There is a method in which molding is performed directly without a drying step without the addition of a polymer. The amount of water added is 0 to the amount of the whole material.
Preferably it is 2%. A briquetting machine is an example of a system in which a raw material is directly compression-molded without performing granulation to form a granular solid processing agent. As a means for granulating, there is a method using a commonly used stirring granulator or Henschel mixer.

From the viewpoint of rapid processing, in the present invention,
The total processing time (Dry to dr) from when the tip of the photosensitive material is inserted into the automatic developing machine to when it comes out of the drying zone
y) is preferably from 10 to 90 seconds, more preferably from 15 to 50 seconds. In order to stably process a large amount of photosensitive material of 100 m ² or more, the development time is preferably 2 to 30 seconds, more preferably 5 to 18 seconds.

As the automatic developing machine, a heat transfer material of 60 ° C. or more (heat roller of 60 ° C. to 130 ° C.) or 150 ° C.
The above radiating objects (tungsten, carbon, nichrome, zirconium oxide, a mixture of yttrium oxide, thorium oxide, silicon carbide, etc.) are directly heated to radiate heat, and heat energy from a resistance heating body is made of copper, stainless steel, nickel, various ceramics, etc. (Which emit infrared rays by transmitting to a radiator) and have a drying zone.

As the automatic developing machine, an automatic developing machine having the following method or function can be preferably used.

Deodorizing device: JP-A-64-37560, page 544 (2), upper left column to page 545 (3), upper left column Washing water regeneration purifying agent and device: JP-A-6-25035
No. 2, page (3), paragraph "0011" to paragraph (8), page "0058" Wastewater treatment method: JP-A-2-64638, No. 388
(2) Bottom left column to page 391 (5) Bottom left column Rinse bath between developing bath and fixing bath: JP-A-4-313
No. 749, page (18), paragraph "0054" to page (21), paragraph "0065" Replenishing water replenishment method: JP-A-1-281446, No. 25
0 (2) lower left column to lower right column Detect dry air temperature and humidity to control drying air: JP-A-1-315745, page 496 (2), lower right column to 50th
1 (7) lower right column and JP-A-2-108051-58
8 (2) lower left column to 589 (3) lower left column Silver recovery from fixing waste solution: JP-A-6-27623, page (4), paragraph "0012" to page (7), "0071".

In the case where two or more stabilizing tanks are provided, it is preferable to use a multi-stage countercurrent method as a means for reducing the replenisher amount of the washing water, which has been known before. If this multi-stage countercurrent method is used, the photosensitive material after fixing is gradually contacted and processed in a clean direction, that is, a processing solution that is not stained with the fixing solution, so that more efficient water washing is performed.

The replenishing amount of the silver halide in the silver halide photographic light-sensitive material subjected to the processing of the present invention is preferably silver chloride, silver chlorobromide or silver chloroiodobromide having a silver chloride content of 60 mol% or more. Good for reduction and rapid processing.

The average grain size of the silver halide grains is 1.2 μm.
Hereinafter, 0.1 to 0.8 μm is particularly preferable. Further, it is preferable that the particle size distribution is narrow, and it is preferable to use a so-called monodispersed emulsion. Further, an emulsion composed of tabular grains having a (100) plane as a main plane is preferred. Such emulsions are described in U.S. Pat. Nos. 5,264,337, 5,314,798 and 5,320,958. Can be obtained with reference to the description in Further, in order to obtain high illuminance characteristics, iridium is doped in a range of 10 ^-9 to 10 ^-3 mol per 1 mol of silver halide, and at least one selected from rhodium, ruthenium, osmium and rhenium in order to harden the emulsion. It is preferable to dope one kind in the range of 10 ^-9 to 10 ^-3 mol per mol of silver halide.

The silver halide emulsion can be subjected to known chemical sensitization such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization.

The silver halide photographic light-sensitive material subjected to the processing of the present invention preferably employs the following techniques.

1) Solid dispersed fine particles of a dye:
No. 5629, page (3), paragraph "0017" to page (16), paragraph "0042" 2) Compound having an acid group: JP-A-62-237445.
No. 292 (8), lower left column, 11th line to 309 (25)
3rd line, lower right column of the page 3) Acidic polymer: JP-A-6-186659, (1)
0) page paragraph “0036” to page (17) page “006”
2) 4) Sensitizing dye Paragraph "0017" on page (3) of JP-A-5-224330
To page (13), paragraph “0040” JP-A-6-194777, page (11), paragraph “004”
2 "to (22)" 0094 "JP-A-6-242533, page (2), paragraph" 0015 "
To page (8), paragraph “0034” JP-A-6-337492, page (3), paragraph “0012”
To page (34), paragraph “0056” JP-A-6-337494, page (4), paragraph “0013”
To page (14), paragraph "0039" 5) Supersensitizer JP-A-6-347938, page (3), paragraph "0011"
To page (16), paragraph “0066” 6) Hydrazine derivative JP-A-7-114126, page (23), paragraph “011”
1) to page (32), paragraph “0157” 7) Nucleation accelerator JP-A-7-114126, page (32), paragraph “015”
8 "to page (36), paragraph" 0169 "8) Tetrazolium compound JP-A-6-208188, page (8), paragraph" 0059 "
To page (10), paragraph "0067" 9) Pyridinium compounds JP-A-7-110556, page (5), paragraph "0028"
10) Redox compounds JP-A-4-245243, 235 (7) to 250
(22) 11) Syndiotactic polystyrene support JP-A-3-131843, pages 324 (2) to 327
(5) Page About other additives, for example, Research Disclosure No. No. 17643 (December 1978); No. 18716 (November 1979) and the same No. 3
08119 (December, 1989).

[0033]

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 <Preparation of silver halide photographic light-sensitive material for printing plate making scanner for He-Ne laser light source> (Preparation of silver halide emulsion A) 70 mol% of silver chloride was obtained by a double jet method, and the rest was odor. Average thickness of silver halide 0.05
μm, silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. At the time of mixing the core particles, 8 × 10 ⁻⁸ mol of K ₃ RhCl ₆ was added 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 × 10 ⁻⁷ mol per mol of silver. The obtained emulsion was silver / chloroiodobromide (90 mol% of silver chloride) having a core / shell type monodisperse (coefficient of variation: 10%) having a (100) plane as a main plane having an average thickness of 0.10 μm and an average diameter of 0.25 μm. , 0.2 mol% of silver iodide, the balance being silver bromide).

The emulsion was cooled to 40 ° C. and modified with a phenylcarbamoyl group as a flocculant polymer (substitution rate: 90%).
1800 ml of a 13.8% by weight aqueous solution of modified gelatin
Was added and stirred for 3 minutes. Thereafter, an aqueous solution of 56% by weight of acetic acid was added to adjust the pH of the emulsion to 4.6, and the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation.

Thereafter, 9.0 L of distilled water at 40 ° C. was added, the supernatant was drained after stirring and standing, and 11.25 L of distilled water was further added. After stirring and standing, the supernatant was drained. Subsequently, an aqueous gelatin solution and a 10% by weight aqueous sodium carbonate solution were added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes to redisperse. After the redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C. After desalting, the EAg of this emulsion was 50 ° C.
At 190 mV.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. The pH was adjusted to 5.6 and the EAg to 123 mV, and sodium p-toluenethiosulfonate was adjusted to 1 × 10 ^−3.
After the addition of mol, chloramine T was added at 350 m per mol of silver.
g, 0.6 mg of inorganic sulfur (S ₈ ) and 6 mg of trichloroaurate were added and chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained.

After completion of aging, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene per mol of silver was 2 × 10 ⁻³ mol, 1-phenyl-5-mercaptotetrazole was 3 × 10 ⁻⁴ mol, and potassium iodide was 300 mg.
Was added.

(Preparation of Silver Halide Emulsion B) Using a simultaneous mixing method, 60 mol% of silver chloride, 2.5 mol% of silver iodide, and the remainder made of silver bromide have an average thickness of 0.05 μm and an average diameter of 0.1 mol.
15 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 1 per mole of silver.
^0-8 moles were added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% silver chloride, 0.5 mol% silver iodide) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. The remainder was tabular grain emulsions (composed of silver bromide). Then, desalting was performed using a modified gelatin G-8 (in which the amino group in the gelatin was substituted with phenylcarbamyl) described in JP-A-2-280139, page 287 (3). The EAg after desalting was 190 mV at 50 ° C.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. The pH was adjusted to 5.6 and the EAg to 123 mV, and 2 × 10 ⁻⁵ mol of chloroauric acid was added.
3 × 10 ⁻⁵ mol of N′-trimethyl-N′-hepta-fluoroselenourea was added, and chemical ripening was carried out at a temperature of 60 ° C. until the maximum sensitivity was obtained. 4-hydroxy-6 after aging
-Methyl-1,3,3a, 7-tetrazaindene was converted to silver 1
2 × 10 ⁻³ mol per mol, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and gelatin were added.

On one subbing layer of the support, the following formulation 1
A silver halide emulsion layer 1 of Formulation 2 was further coated with a silver undercoat layer having a silver amount of 1.5 g / m ² and a gelatin amount of 0.5 g / m ^{2 so} that the gelatin undercoat layer had a gelatin amount of 0.5 g / m ² . ^The silver halide emulsion layer 2 of Formula 4 was further coated thereon with a coating solution of Formula 3 below as an intermediate protective layer so that the amount of gelatin was 0.3 g / m ^2. 1.4 g /
m ^2, as the amount of gelatin is 0.4 g / m ^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 further coated with a hydrophobic polymer layer of the following formulation 7 so that the amount of gelatin was 0.6 g / m ² , and further a further formulation of the following A sample was obtained by simultaneously coating the backing protective layer No. 8 with the emulsion layer so that the amount of gelatin became 0.4 g / m ² .

Formulation 1 (Gelatin undercoat layer composition) Gelatin 0.5 g / m ² Solid dispersed 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 (Silver halide emulsion layer 1 composition) Gelatin amount 0.5 g / m ² Silver halide emulsion A Silver amount 1.5 g / as becomes m ² dye a solid dispersion fine particles (average particle size 0.1 [mu] m) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye ^d-2 5mg / m 2 hydrazine derivative HY-1 20mg / m ² nucleation accelerator exemplified compound AM-1 40mg / m ² redox compound: RE-1 20mg / m ² compound e 100 mg / m ² latte Box polymer f 0.5 g / m ² hardener ^{g 5mg / m 2 S-1} 0.7mg / m 2 2- mercapto-6-hydroxy purine ^{5mg / m 2 EDTA 30mg / m} 2 Colloidal silica (average particle diameter 0 0.05 mg) 10 mg / m ² Prescription 3 (intermediate layer composition) Gelatin 0.3 g / m ² S-1 2 mg / m ² Prescription 4 (silver halide emulsion layer 2 composition) Silver halide emulsion B Silver amount 1.4 g / gelatin amount which become m ² 0.4g / m ² sensitizing dye d-1 6mg / m ² hydrazine derivative ^HY-2 20mg / m 2 nucleation accelerator AM-1 40mg / 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 Dye b solid dispersion (average particle size 0.1 μm) 40 mg / m ² S-1 12 mg / m ² matting agent: monodisperse silica having an average particle size of 3.5 μm 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 Prescription 7 (Composition of hydrophobic polymer layer) Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² Hardener g 6 mg / m ² Formulation 8 (Backing protective layer) Latin 0.4 g / m ² matting agent: monodisperse polymethyl methacrylate 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 dye k 20 mg / 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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<Preparation of Developer> (Preparation of Developer A Part) 1 L of Working Solution 8-mercaptoadenine 0.09 g Dimezone S (1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone) 3 g 5-methylbenzotriazole 0.26 g sodium sulfite 7.1 g hydroquinone 24 g D-sorbitol 5.0 g (preparation of developer B part) 1 L of working solution DTPA / 5Na 4.35 g sodium carbonate 28.77 g potassium carbonate 37.5 g Potassium bromide 2.0 g Sodium sulfite 49.5 g LiOH.H ₂ O 8.8 g D-mannitol (trade name: Kao) 11.7 g D-sorbitol 5 g <Preparation of fixing agent> (Preparation of fixing agent A part) 1 L liquid sodium thiosulfate 150 g sodium sulfite 2 g citric acid Sodium dihydrate 19.4 g Pine flow (trade name: Matsutani Chemical) 9 g (Preparation of fixing agent B part) 1 L of working solution Sodium gluconate 5 g Succinic acid 11.9 g Trisodium citrate dihydrate 10 g D-mannitol 2 0.5 g D-Sorbit 1.2 g Macrogol PEG # 4000 0.75 g Each material of the developer and the fixing agent was added to each part in a commercially available Henschel mixer with 0.5% by weight of water and added at room temperature.
Granulation was performed for minutes to obtain each granulated material.

Sodium 1-octanesulfonate was added to each of the developer granules A parts and B parts and the fixer granules A parts and B parts by 2% by weight, and the respective A and B parts were added for 10 minutes. The mixture was thoroughly mixed, and the resulting mixture was compressed to a diameter of 30 m by compression and compression at 1.5 ton / m ² using a machine UD / DFE30 / 40 tableting machine manufactured by Masina.
m, a tablet having a thickness of 10 mm and a weight of 10 g were obtained.

4 L of the developer prepared above (17 A,
B45) and 4 L of the fixing agent (72 A, 16 B) were each placed in an aluminum foil bag and stored at 20 ° C. and 20% environment for 2 weeks.

When the above tablets were used, they were dissolved in water using a mixer SM-10 manufactured by Konica Corporation and finished to 4 L.

The pH when the developer is dissolved is 10.
7. The pH when the fixing agent was dissolved was 5.4.

<Preparation of stabilizing solution used in the present invention> 35% by weight aqueous hydrogen peroxide Added so as to have an amount shown in Table 1 Salicylic acid 1.0 g 5-Chloro-2-methyl-4 isothiazoline-3one 1.5 g Finished to 1 L using pure water. The kit configuration was 10 L. When used, it is added to tap water to a predetermined concentration and used as washing water.

The black-and-white silver halide photographic light-sensitive material prepared according to the above-mentioned formula was exposed so as to have a blackening ratio of 10%, and the water was washed in a two-tank multi-stage countercurrent in an automatic developing machine GR-960 manufactured by Konica Corporation. The tank was modified and equipped with a mixer SM-10 manufactured by Konica Corporation. Using the developer, fixing agent and stabilizing solution of the above formulation, 130 ml of a developing replenisher per 1 m ^{2 of} silver halide photographic material, fixing was performed. The replenisher was replenished with the amount shown in the table, and 500 sheets were treated per day for 4 months, and the resulting solution was used as a running solution. In the experiment according to the present invention, the interior of the washing tank was washed with water or a stabilizing solution for 30 days after these treatments were completed every day.
Washed for minutes.

Each time a sheet film of large total size (508 mm × 610 mm) was inserted, the stabilizing solution kit was refilled into the washing tank so that the hydrogen peroxide concentration was as shown in the table. The density was adjusted so that the density was as shown in FIG.

[0055] <Evaluation of dot quality> He-N manufactured by Dainippon Screen Co., Ltd.
The midpoint (target 50%) exposed by a halftone dot (FM screen) of a random pattern of 8 μm with the e-laser SG-747RU was observed with a 100-power loupe to evaluate the halftone dot quality (clearness). The highest rank is 5, and depending on the dot quality,
The ranks were reduced to 3, 2, and 1 and evaluated. Ranks 1 and 2 are levels that are not practically desirable.

<Evaluation of transportability> The transportability when discharged from the drying section of the automatic developing machine after running is as follows.
Grading was performed.

A: The film comes out smoothly. B: The film comes out without any problem, but there is no problem. C: The film comes out with a little noise, but the humming sound comes from the drying roller drive motor. D: Abnormal noise during film transport and humming from the drying roller drive motor. E: Loud noise during film transport and the drying roller drive motor stops. A and b are practical levels.

<Evaluation of dirt on the drying roller> The degree of dirt generated on the drying roller after running was visually evaluated in five stages as follows.

A: No dirt B: Little dirt, but a little dirt on the edge C: Some dirt, but no problem on film D: Dirt on the roller as a whole In some cases, the film adhered to the film. E: C or higher, at which dirt accumulated on the roller as a whole and the treated film was at an unusable level, was judged to be practicable.

<Evaluation of precipitation and scale in the washing tank> The degree of precipitation generated in the washing tank after running was visually evaluated in five stages as follows.

A: No precipitation, no precipitation / scale, and the solution is clear. B: No precipitation / precipitation, and almost no scale. C: No precipitation, but a small amount of scale on the inner wall of the washing tank. Adhesion. P: Practically acceptable D: Slight precipitation occurs and scale is partially generated E: Precipitation accumulates at the bottom and scale is generated as a whole C or more is considered to be practical.

Table 1 shows the above results.

[0063]

[Table 1]

From the results shown in the table, it is considered that in the comparative experiment, the processed photographic material was adversely affected. However, in the experiment of the present invention, good results were obtained and were sufficiently practical.

Example 2 An experiment and evaluation were conducted in the same manner as in Example 1 except that the developer and the fixing agent were changed from tablets to liquids as shown below.

(Developer Formulation) 1 L of Working Solution Pure Water 300 ml DTPA / 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 KOH (55% aqueous solution) and pure water 400 ml (p
H10.45). When using pure water 60
0 ml and the above concentrated solution (400 ml) are mixed and used (use solution pH 10.40).

(Fixing Solution Formulation) 1 L of working solution Pure water 120 ml Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g 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 4.0)
81). When used, 667 ml of pure water and 333 ml of the above concentrated liquid are mixed and used (pH of the used liquid).
4.85).

Table 2 shows the results.

[0069]

[Table 2]

Table 2 shows that good results were obtained in the experiments of the present invention, and that they were sufficiently practical.

[0071]

According to the processing method of the present invention, it is possible to greatly reduce the occurrence of scale, dirt, and deterioration of the quality of the processed film.

Claims (4)

[Claims] 1. A fixing tank for developing, fixing, washing or stabilizing a silver halide photographic light-sensitive material using an automatic developing machine having a developing tank, a fixing tank, and a washing tank having a total volume of 5 to 40 L. The amount of the fixing solution of the photosensitive material brought into the washing tank from 10 to 60 ml per 1 m ² , and the amount of fixer replenished is 65 to 325 m per 1 m ^{2 of the} photosensitive material to be processed.
(1) A method for processing a silver halide photographic light-sensitive material, wherein after the processing is completed, the inside of the washing tank is washed with water or a stabilizing solution. 2. The method for processing a silver halide photographic material according to claim 1, wherein the concentration of hydrogen peroxide in the washing tank is 0.0003 to 0.3% by weight. 3. A method for processing a silver halide photographic light-sensitive material according to claim 2, wherein the concentration of hydrogen peroxide in the kit concentrated solution supplied to the washing tank is 2 to 35% by weight. . 4. The method for processing a silver halide photographic material according to claim 3, wherein the concentrated solution of the hydrogen peroxide kit is directly dissolved in a washing tank.