JP2000241950A - Treatment of silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate contamination, scale and silver sludge in a washing tank while saving water, to prevent deterioration in the dot quality of a film and to prevent contamination on a drying roller by carrying out a washing process or a stabilizing process in the presence of hydrogen peroxide while recovering silver. SOLUTION: When a silver halide photographic material is developed, fixed, washed or stabilized in an automatic developing machine equipped with a developing tank, fixing tank, washing tank or stabilizing tank, the washing process or stabilizing process is carried out in the presence of hydrogen peroxide while recovering silver. In this method, any type of an electrode electrolytic method of a silver recovering device may be used. The silver recovering device may be directly connected to recover silver such that the device as an external device is connected to the machine through pipes to recover silver from a waste liquid, or direct electrodes or cylindrical electrodes may be assembled in the fixing tank to directly electrolyze the liquid. The method of direct electrolysis is advantageous because the amount of silver in the fixing tank can always and directly be controlled.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a silver halide photographic material which is effective in saving water.

[0002]

2. Description of the Related Art A silver halide photographic material (hereinafter simply referred to as a "photosensitive material") is subjected to processes such as development, desilvering, washing and stabilization after exposure. 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 film.

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 the actual situation is that washing is performed using a large amount of washing water as ever.

[0004] In the water saving system, in order to reduce the amount of washing water and to prevent the generation of scale, a filter is removed, a disinfectant is added, or thiosulfate as a fixing agent is fixed with hydrogen peroxide. Some attempts have been made to purify the salt (hypo) and bacteria, and to purify the bacteria with silver and fungicides to prevent the growth of bacteria, and some of them have been commercialized.

[0005]

However, since the concentration of silver in the fixer in the washing water has increased due to the low replenishment, the problem has arisen that the hypo is decomposed and silver sludge is generated. . In addition, if the purifying agent used for it is reduced, scale will be generated,
When the amount is increased, silver sludge is generated, so that a difficult problem such as competition between silver sludge and water scale has arisen.

In addition, silver and gelatin solidify while adjusting to suppress both silver sludge and scale, and the piping becomes clogged, and when the automatic developing machine is started up in the morning, silver sludge sticks to the processing film. A serious problem and a difficult problem such as discoloration due to remaining hypo have arisen, and a solution has been strongly demanded.

On the other hand, as a means of saving water, there has appeared a method in which a washing tank is divided into a plurality of parts and a multistage countercurrent washing method is performed. Multi-stage washing has poor rotation of water, and is more likely to produce water stains than the single-tank washing method. When hydrogen peroxide was used as a purifying agent to destroy the hypo, many users came to be interrupted due to the generation of silver sludge.

[0008] In addition, serious problems such as the deterioration of the halftone dot quality of the film and the occurrence of stains on the dry roller of the film due to the deposits caused by the contamination of the transfer roller have arisen.

The present invention has been made in view of the above circumstances, and an object of the present invention is to prevent water, water, dirt, scale, and silver sludge from being generated in a washing tank, thereby deteriorating the halftone dot quality of a film. It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material which does not cause contamination of a drying roller.

[0010]

The object of the present invention is to develop, fix, wash or stabilize a silver halide photographic material using an automatic developing machine having a developing tank, a fixing tank, a washing tank or a stabilizing tank. Processing method of silver halide photographic light-sensitive material which is washed or stabilized in the presence of hydrogen peroxide while recovering silver in the presence of hydrogen peroxide; developing tank, fixing tank, water-washing tank for silver halide photographic light-sensitive material Or, when developing, fixing, washing or stabilizing using an automatic developing machine having a stabilizing tank, the halogen to be washed or stabilized in the presence of hydrogen peroxide in two or more washing tanks or stabilizing tanks. Processing method of silver halide photographic light-sensitive material, automatic processor having washing tank (migration washing) between at least one processing tank, developing, fixing, washing with water In carrying out the chemical treatment, an automatic developing machine having a developing tank, a fixing tank, a washing tank or a stabilizing tank, and a washing tank (migration washing) provided between at least one of the processing tanks is used. A method for processing a silver halide photographic light-sensitive material to be washed or stabilized in the presence of the silver halide photographic light-sensitive material.Development and fixing of the silver halide photographic light-sensitive material using an automatic developing machine having a developing tank, a fixing tank, a washing tank or a stabilizing tank. A washing method or a stabilizing treatment, a method for treating a silver halide photographic material which is washed or stabilized in the presence of hydrogen peroxide and the compound represented by the general formula (1), The concentration of hydrogen peroxide in the washing tank or the stabilizing tank is 0.0001 to 0.5% by weight, and the aqueous hydrogen peroxide supplied to the washing tank or the stabilizing tank is prepared from a kit concentrate. The hydrogen peroxide concentration of the liquid is 2-3 Either a weight percent, dissolving the hydrogen peroxide Kit concentrate directly washing tank or stabilizing tank is accomplished by.

Hereinafter, the present invention will be described in detail.

One embodiment of the present invention is characterized in that washing or stabilization treatment is performed in the presence of hydrogen peroxide while recovering silver.

The electrode electrolysis method of the silver recovery apparatus used in the present invention may be of any type. For example, a method using a rotating cylindrical electrode, which has been widely used, is disclosed in US Pat.
No. 4,455, a method using a spiral cathode, and a fluidized bed electrolysis method filled with non-conductive particles disclosed in JP-A-53-65218. A silver recovery device is connected to the outside through a pipe to recover silver by indirect connection such as recovering silver from waste liquid, and a direct electrolysis is performed by incorporating an electrode or a cylindrical electrode directly into the fixing tank. However, those which perform direct electrolysis are more advantageous in that they can always directly control the amount of silver in the fixing tank. Therefore, those which directly perform electrolysis are preferable. For use in current miniaturized automatic processors, miniaturize the rotating cylinder and embed it in the bottom or side of the processing tank to directly electrolyze or use a miniaturized spiral cathode. Are preferred.

Also, the method described in JP-A-56-696261 can be applied to a method in which an anode is separated by a cornea and a liquid having a composition different from that of a fixing solution is used for the anode film. Further, a method of contacting with an ion exchange resin after recovering electrolytic silver (German Patent Application No. 2,741,080) can also be applied. In the processing method of the present invention, the pre-bath of the washing solution or the stabilizing solution is the fixing solution, and most of the silver salt is dissolved therein.

As another silver recovery method, there is a method of removing a filter. However, silver stains are immediately accumulated in a running process or the like, and the effect is insufficient.
Not preferred.

In the present invention, the silver recovery apparatus is mounted in a washing tank or a stabilizing tank, but it may be mounted in a fixing tank together with the washing tank or the stabilizing tank.

A second aspect of the present invention is characterized in that there are two or more washing tanks or stabilizing tanks, and the washing or stabilizing treatment is performed in the presence of hydrogen peroxide. When two or more washing tanks or stabilization tanks are provided, it has been known for a long time.
It is preferable to use a multi-stage countercurrent method as a means for reducing the replenisher amount of the washing water. 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.

In a third aspect of the present invention, a water washing or stabilization treatment is carried out in the presence of hydrogen peroxide using an automatic developing machine provided with a washing tank (crossover washing) between at least one of the processing tanks. It is characterized by doing.

As a method of migratory washing which can be adopted in the present invention, a small washing tank or a small groove is formed between the developing tank and the fixing tank, and the film processed in the developing tank passes through that portion. is there. If this part is called a transfer cleaning tank, the transfer cleaning tank may be a complete processing tank with rollers etc., but a groove is created for miniaturization and simplification,
It may be one that allows running water to pass through that part.
The running water may be tap water or distilled water, but may be an acidic solution such as acetic acid that is weak for stopping development, or may be a stabilizing solution used for stabilization after development and fixing. good. The washing liquid in the transfer washing may be used by circulating and discarded in the developing waste liquid or the fixing waste liquid tank.However, the water supplied as washing water is once passed through the transfer washing tank, and then added to the washing tank and the washing water is added. It may be used as. In this case, the washing water may enter the washing tank after it has passed through the washing tank once, or it has a pre-branched passage for migration washing and washing water only. You may enter the washing tank after entering. In addition, even if the cleaning water used for the cross-over cleaning is circulated, as long as it satisfies the discharge standard based on the Environmental Sewerage Law, it can be flowed into the sewer through a washing tank. The transfer washing tank can be used not only between the above-mentioned developing tank and the fixing tank, but also between the fixing tank and the washing tank, and between the multiple developing tank, the fixing tank, and the multiple washing tank. it can.

In the above-described second embodiment of the present invention, it is effective to carry out the crossover cleaning.

A fourth aspect of the present invention is characterized in that a washing or stabilizing treatment is carried out in the presence of hydrogen peroxide and a compound represented by the general formula (1).

In the general formula (1), R ₁ and R ₂ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (for example,
Methyl group, ethyl group, propyl group). Where R ₁
And R ₂ are not simultaneously hydrogen atoms, and both are preferably alkyl groups. R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, or a propyl group); and R ₅ represents a hydroxyl group (including a metal salt), an amino group, or a carbon atom. Alkyl groups of formulas 1 to 3 (for example, methyl group, ethyl group, propyl group)
Represents R ₆ and R ₇ each represent a hydrogen atom, a carbon atom number of 1 to 5;
(E.g., a methyl group, an ethyl group, a propyl group), an acyl group having 18 or less carbon atoms, usually 2 to 18 (e.g., an acetyl group, a propionyl group) or -COO
Representing the M ₁₀ group. Here, M ₁₀ represents a hydrogen atom, carbon atom 1
And represents an alkyl group of 4 to 4, an alkali metal atom, an aryl group or an alkyl group having 15 or less carbon atoms, usually 7 to 15 carbon atoms. However, R ₆ and R ₇ are not simultaneously hydrogen atoms. M ₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. k is 0, 1 or 2.

Hereinafter, specific examples of the compound represented by the general formula (1) will be shown.

[0024]

Embedded image

Of these, 1-1 is particularly preferred.

In the present invention, a supply means for automatically supplying hydrogen peroxide based on information on the photosensitive material processing area is provided as a regeneration or purification means in a washing or stabilizing tank of an automatic developing machine for processing a photosensitive material. Is preferred. Hydrogen peroxide is added to decompose hypo that is brought into the washing or stabilization tank.However, if the contamination concentration reaches a certain level due to accumulation of eluted components from the photosensitive material, water must be replaced. Therefore, it has a drainage means equipped with a means for measuring the concentration of contamination so that at least a part of the washing water or the stabilizing solution can be drained, and in a specification in which hydrogen peroxide is sent when a certain concentration of contamination, that is, a certain treatment area is reached. Preferably, there is.

In the present invention, the concentration of hydrogen peroxide in the washing tank or stabilizing tank is preferably 0.0001 to 0.5% by weight, more preferably 0.0003 to 0.3% by weight. The hydrogen peroxide solution to be supplied to the washing tank or the stabilization tank is prepared from the kit concentrate, and the hydrogen peroxide concentration of the concentrate is 2 to 35% by weight, or the hydrogen peroxide kit concentrate is directly washed with water. It is preferable to dissolve in a tank or a stabilizing tank.

From the viewpoint of rapid processing, the total processing time (Dry to dry) from when the leading end of the photosensitive material is inserted into the automatic developing machine to when it comes out of the drying zone is preferably from 10 to 60 seconds. Preferably it is 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 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 the like) 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.

Further, as the automatic developing machine, those employing the following methods or functions 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".

The treating agent used in the present invention may be supplied in any form such as a powder, a paste, granules, tablets, a concentrated solution, and a used solution. Is preferred. When used as a starting solution, they are adjusted and used 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.

Examples of the sulfite and metabisulfite used as a preservative of the developer include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is used in an amount of 0.25 mol / L or more, particularly preferably 0.4 mol / L or more.

An alkali agent (eg, sodium hydroxide or potassium hydroxide) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) are added to the developer. Preferably. The pH buffer is preferably a carbonate, and the amount of the carbonate added is preferably 0.5 to 2.5 mol per liter, and more preferably 0.5 to 2.5 mol per liter.
75 to 1.5 mol. If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (for example, ethylenediamine tetraethylene) Acetic acid or an alkali metal salt thereof, nitrilotriacetate, polyphosphate, etc.), a development accelerator (for example, U.S. Pat. No. 2,304,025, Japanese Patent Publication No. 47-4554)
No. 1), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent can be added. The pH of the developer is 7.5
Preferably, it is adjusted to at least 10.5. More preferably, the pH is 8.5 or more and 10.4 or less.

The waste developing solution 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 photosensitive material 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 which can be added to the developer are additionally added. You can do it. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that 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 a light-sensitive material, for example, in an emulsion layer or a layer adjacent thereto, and is used in an activator processing solution for processing the light-sensitive material in an aqueous alkali solution to perform development. Is also good. 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 starter may be used by diluting a commonly used concentrated liquid 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. As for the replenisher, it is preferable to use a solid processing agent formed from two or more compounds alone or as a mixture dissolved 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 4.4 to 6.9. 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 used can be changed as appropriate, and is generally from 0.1 to about 6.0 mol / L.

The fixing solution may optionally contain a preservative (eg,
Sulfites, bisulfites), pH adjusters (eg, sulfuric acid,
Sodium hydroxide), a chelating agent having the function of a curing softener, and the compounds described in JP-A-62-78551.

In the processing of the light-sensitive material, the processing is performed while replenishing a fixed amount of processing solution in proportion to the area of the light-sensitive material in order to reduce the amount of waste liquid. The replenishment amount of the developer, the replenishment amount of the fixing solution, and the replenishment amount of the stabilizing solution are respectively 32 to 325 ml / m
² , preferably 65 to 130 ml / m ² .

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

As used herein, the term "solid processing agent" refers to a solid formed of two or more components constituting the processing solution. One type of solid includes all components of the processing solution, or two or more types of solids include the processing solution. May be one that can constitute the above-mentioned component. In the solid processing agent, at least one solid in which at least two or more compounds are formed may be used, 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, granulating and then drying to obtain granules, and a method of forming the solid processing agent, 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 preferably 0% or more and 2% or less based on the total amount of the raw materials.

A briquetting machine is an example of a system in which raw materials are directly compression-molded without 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.

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 following techniques are preferably employed for the black-and-white silver halide photographic light-sensitive material to be processed in the present invention.

1) Solid dispersed fine particles of a dye: JP-A-7-
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).

[0050]

EXAMPLES Example 1 The present invention will be specifically described below with reference to examples. In addition,
As a matter of course, the present invention is not limited to the embodiments described below.

<< 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 prepared from silver bromide. Average thickness 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 RuCl 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 an aggregating 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 redispersion, the pH was adjusted to 5.80 pAg at 8.06 at 40 ° C. After desalting, the EAg of this emulsion was 50 ° C.
Was 190 mv.

To the obtained 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 added to adjust the pH to 5%. .6, adjusted to EAg123mv,
After adding 1 × 10 ^-3 mol of sodium P-toluenethiosulfonate, 350 mg of chloramine T per mol of silver was added.
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 aging, 4-hydroxy-6-methyl-
1,3,3a7-tetrazaindene is added in an amount of 2 per mole of silver.
× 10 ^-3 mol, 3 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole and 300 mg of potassium iodide were added.

(Preparation of Silver Halide Emulsion B) Using a double jet method, 60 mol% of silver chloride, 2.5 mol% of silver iodide, and the balance consisting of silver bromide having 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 obtained emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% silver chloride, 0.5 mol% silver iodobromide) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. , The remainder being silver bromide). Then, JP-A-2-280139
Described in Japanese Unexamined Patent Publication (Kokai) No. 2-28, for example, a modified gelatin wherein the amino group in the gelatin is substituted with phenylcarbamyl.
Desalting was performed using Exemplified Compound G-8) described in No. 0139, 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. PH 5.6 and EAg 123 mv, and after adding 2 × 10 ⁻⁵ mol of chloroauric acid, N, N,
N'-trimethyl-N'-heptafluoroselenourea was added in an amount of 3 × 10 ^-5 mol and chemically ripened at a temperature of 60 ° C. until the 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.

On one subbing layer of the undercoated support, a gelatin subbing layer of the following formula 1 was further formed, a silver halide emulsion layer 1 of the formula 2 was further formed thereon, and an intermediate protective layer was further formed thereon as an intermediate protective layer. Coating solution No. 3 and a silver halide emulsion layer 2 of Formulation 4 thereon, and a coating solution of Formulation 5 below were simultaneously coated thereon. On the other side of the undercoat layer, a backing layer of the following formula 6 is coated, a hydrophobic polymer layer of the following formula 7 is further coated thereon, and a backing protective layer of the following formula 8 is further coated on the backing layer simultaneously with the emulsion layer side. To obtain a sample.

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 Prescription 2 (composition of silver halide emulsion layer 1) Gelatin 0.5 g / m ² Silver halide emulsion A Silver amount 1.5 g / m 2 ^In order to obtain a solid dispersion fine particle of dye a (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 20mg / m ² nucleation accelerator: AM-1 40mg / m ² redox compound: RE-1 20mg / m ² compound e 100 mg / m ² latex port Mer 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. 05 μm) 10 mg / m ² prescription 3 (intermediate layer composition) gelatin 0.3 g / m ² S-12 2 mg / m ² prescription 4 (silver halide emulsion layer 2 composition) Gelatin amount 0.4 g / m ² silver halide emulsion B silver amount 1.4 g / sensitizing dyes as m becomes ² 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 0.6g / M ² Solid dispersion of dye b (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-vinyl Sulfonyl-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 Formula 7 ( Hydrophobic polymer layer composition) Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² Hardener g 6 mg / m ² Formulation 8 (backing protective layer) Zera Tin 0.4 g / m ² matting agent: monodispersed 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

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<< Preparation of Solid Developer Kit (10 L of Working Solution)
Min.) >> (Pretreatment of material) MIKRO-PULVERIZER A manufactured by Hosokawa Micron Co., Ltd.
It was pulverized with a P-B pulverizer at a mesh of 8 mm and a rotation speed of 25 Hz.

8 Mercaptoadenine was pulverized with the same pulverizer at a mesh of 8 mm and a rotation speed of 50 Hz.

The KBr was crushed by the same crusher to a mesh of 8 mm.
Grinding was performed at a rotation speed of 50 Hz.

(Mixing of Materials) A commercially available V-type mixer (capacity 2
00L), the following formulation was mixed for 10 minutes.

Sodium erythorbic acid (the above-mentioned pulverized product) 163 kg Dimezone S 3.5 kg 8 mercaptoadenine (the above-mentioned pulverized substance) 0.3 kg diethylenetriaminepentaacetic acid 11 kg KBr (the above-mentioned pulverized substance) 6.5 kg sorbitol 5 kg The obtained mixture When 50 g of each component was sampled and analyzed from arbitrary points (5 places), the concentration of each component was within ± 5% of the above prescribed value, and the components were sufficiently uniformly mixed.

(Molding) Using a compression granulator Briquetter BSS-IV manufactured by Shinto Kogyo Co., Ltd., the above mixture was used to form a pocket having a shape of 5.0 mmΦ × 1.2 mm (Depth), a roller rotation speed of 20 rpm, and a feeder. The molding was performed at a rotation speed of 50 rpm. The obtained plate-like molded product is crushed with a classifier,
It was divided into 2.4-7.0 mm granules and 2.4 mm or less fine powder (fractions of 7.0 mm or more were crushed). Also 2.4mm
About the following fine powder, it mixed with the said mixture and returned to the compression molding machine again and shape | molded. As a result, the granule DA was about 95
kg.

(Preparation of Raw Materials) The following raw materials are prepared,
Pretreatment was performed.

Mixture of sodium sulfite / 1-phenyl-5-mercaptotetrazole / benzotriazole 18 g of 1-phenyl-5mercaptotetrazole and benzotriazole 78 in 400 ml of ethyl alcohol
g was dissolved. The resulting solution was added dropwise in small amounts to 20 kg of sodium sulfite being rotated by a mixer, and the rotation was continued until the solution was sufficiently dried. The obtained mixture was sampled at 10 g points from arbitrary points (five places) and analyzed. As a result, 1-phenyl-5mercaptotetrazole and benzotriazole were sufficiently homogeneously mixed. Let the obtained mixture be M-1.

Potassium carbonate / sodium carbonate / anhydrous /
Mixing of lithium hydroxide and 1H ₂ O Using a commercially available V-type mixer (capacity 200 L), 56 kg of potassium carbonate, 42 kg of sodium carbonate, ₂ kg of lithium hydroxide and 1 H ₂ O (22 k in the case of using comparative example HQ)
g) was mixed for 10 minutes. Let the obtained mixture be M-2.

(Packing: 10 L kit for use solution) A raw material mixture and a molded product were filled in a standing pouch in the following order, and sealed with a heat sealer.

Mixture M-2 600 g (bottom layer) Mixture M-1 663.2 g (middle layer) Granules DA 399 g (top layer) This kit was finished and the pH after dissolving in 10 L was 9.8. In the case of using HQ of the comparative example, the pH was 10.70.

<Preparation of a solid fixing agent kit (use solution 100
L)) (Pretreatment of material) Sodium 1-octanesulfonate was added to MIKRO-PULVERIZE manufactured by Hosokawa Micron Corporation.
RAP-B crusher, mesh 4mm, rotation speed 60H
crushed with z.

(Mixing of Materials) A commercially available V-type mixer (capacity 2
00L), the following formulation was mixed for 10 minutes.

15 kg of sodium thiosulfate 2.2 kg of sodium sulfite 50 g of 8-mercaptoadenine 1 kg of sodium 1-octanesulfonate (the above ground product) was added to the obtained mixture, and the mixture was further mixed for 5 minutes.

(Molding) Using a compression granulator Briquetter BSS-IV, manufactured by Shinto Kogyo Co., Ltd., the above mixture was used to form a pocket having a shape of 5.0 mmΦ × 1.2 mm (Depth), a roller rotation speed of 30 rpm, and a feeder. The molding was performed at a rotation speed of 67 rpm. The obtained plate-like molded product is crushed with a classifier,
It was divided into 2.4-7.0 mm granules and 2.4 mm or less fine powder (fractions of 7.0 mm or more were crushed). Also 2.4mm
About the following fine powder, it mixed with the said mixture and returned to the compression molding machine again and shape | molded. Thus, granule FA was obtained.

(Mixing of Materials) A commercially available V-type mixer (capacity 2
00L), the following formulation was mixed for 10 minutes.

Trisodium citrate dihydrate 2.94 kg Sodium gluconate 0.5 kg Succinic acid 1.2 kg (Molding) The above mixture was used with a compression granulator Briquetta BSS-IV manufactured by Shinto Kogyo Co., Ltd. 5.0m pocket shape
mΦ × 1.2 mm (Depth), roller rotation speed 30
The molding was performed at a feeder rotation speed of 67 rpm. The obtained plate-like molded product was crushed by a classifier, and 2.4 to 7.0.
mm and granules of up to 2.4 mm (7.0 m
m or more are crushed). The fine powder having a size of 2.4 mm or less was mixed with the above-mentioned mixture and returned to the compression molding machine to be molded. Thus, granules FB were obtained.

(Packaging) The standing pouches were filled with molded articles in the following order.

Granule FB (bottom layer) Granule FA (top layer) 100 L of this was packaged in a 10 L kit. Finish 1
The pH after dissolution in 0 L was 5.6.

The black-and-white silver halide photographic light-sensitive material prepared according to the above formula was exposed so as to have a blackening ratio of 5%, and an automatic developing machine GR- made by Konica Corporation equipped with a purifying agent replenishing device was installed.
The 960 washing tank was modified and a silver recovery device was installed. Further, a mixer SM-10 manufactured by Konica Corporation, which was modified so that granules could be added for replenishment of a developer and a fixer, was mounted.

Then, the silver halide photographic light-sensitive material 1 was prepared by using the above-prepared developer and fixing agent, and a water-washing purifier.
130 ml of the developing replenisher and the fixing replenisher were replenished in the amounts shown in the table per m ² , and 500 sheets were processed per day for four months to obtain a running solution.

Further, each time a sheet film of a large total size (508 mm × 610 mm) is inserted so that the hydrogen peroxide concentration becomes the concentration shown in the table, replenishment is carried out from the purifying agent kit to the washing tank, and 5 L each time 7 sheets are processed. Was supplied, and the concentration was adjusted so that the inside of the washing tank had the concentration shown in the table. Also remodeled to be able to change the line speed up to 2.0 times,
High-speed processing has been enabled.

(Purifying agent formulation) 35% by weight of hydrogen peroxide solution 171.5 g Salicylic acid 0.1 g 5-Chloro-2-methyl-4isothiazoline-3one 15.0 g Polypropylene glycol 3.1 g Finished to 1 L using pure water Was. The kit configuration was 10 L. When used, it is added to tap water to a predetermined concentration and used as washing water.

(Processing conditions) Step Temperature Time Developing 38 ° C. 12 seconds Fixing 38 ° C. 12 seconds Washing 25 ° C. 8 seconds Drying 48 ° C. 9 seconds (Evaluation of silver sludge stain generated in the washing tank) Dirt generated in the washing tank after running 5 visually as follows
It was evaluated on a scale.

A: No precipitate at all and the liquid is clear B: No precipitate at all C: No precipitate occurs, but there is dirt D: Slight precipitate E: Precipitate accumulates at the bottom C or more is practical Yes.

(Evaluation of halftone dot quality) A 50% halftone image was output with a scanner FTR-5055 manufactured by Dainippon Screen Co., Ltd. Was evaluated. The highest rank was set to 5, and the rank was lowered and evaluated to 4, 3, 2, 1 according to the dot quality. Ranks 1 and 2 are levels that are not practically desirable.

(Precipitation / scale in the fixing tank and the washing tank) The degree of precipitation generated in the washing tank after running was visually evaluated in five steps as follows.

A: No precipitation, no precipitation / scale, and the liquid 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 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 practical.

(Dry roller stain) The degree of stain generated on the dry roller after running was visually evaluated on a five-point scale as follows.

A: There is no stain B: There is almost no stain, but a little stain is found at the end C: There is a little stain but the film has no problem D: The stain is generated on the roller as a whole In some cases, the film adheres to the film. E: C or more is practically usable, where the dirt accumulates on the roller as a whole and the treated film becomes a level that cannot be used practically.

Table 1 shows the above results.

[0095]

[Table 1]

Example 2 A black-and-white silver halide photographic light-sensitive material prepared in the same manner as in Example 1 was exposed so as to have a blackening ratio of 10%, and was manufactured by Konica Corp. Developing machine GR-
The 960 washing tank was modified into a two-stage multi-stage countercurrent tank, and a washing tank having a width of 2.0 cm was formed between the developing tank and the fixing tank. Further, a mixer SM-10 manufactured by Konica Corporation, which was modified so that granules could be added for replenishment of a developer and a fixer, was mounted.

Each time a sheet film of a large size (508 mm × 610 mm) was inserted, the washing tank was replenished from the purifying agent kit so that the hydrogen peroxide concentration was as shown in Table 2, and every time 7 sheets were processed. 5 L of water was supplied, and the concentration in the washing tank was adjusted so as to be the concentration shown in the table.

Using the above-mentioned developer, fixing agent and stabilizing solution, 130 ml of developing replenisher and 130 ml of fixing replenisher were replenished per 1 m ^{2 of the} silver halide photographic light-sensitive material to process 500 sheets per day for four months. Then, the liquid was used as a running liquid. The line speed has been modified so that it can be varied up to 2.0 times, so that high-speed processing is possible.

(Processing conditions) Step Temperature Time Developing 38 ° C. 12 seconds Fixing 38 ° C. 12 seconds Stabilization 1 Room temperature 6 seconds Stabilization 2 Room temperature 6 seconds Drying 48 ° C. 9 seconds The results of the same evaluation as in Example 1 are shown. It is shown in FIG.

[0100]

[Table 2]

Example 3 The black-and-white silver halide photographic material was exposed to a blackening ratio of 5%, and the granules could be introduced into an automatic developing machine GR-960 manufactured by Konica Corporation equipped with a purifier replenisher. A modified mixer SM-10 manufactured by Konica Corporation was installed.

Further, a washing tank having a width of 2.0 cm was formed between the developing tank and the fixing tank, and processing was performed so that a washing liquid could be flowed through the washing tank.

Then, using the developer, fixing agent and water-purifying agent having the above formulation, 1 m of silver halide photographic material was prepared.
^The replenisher was replenished with 130 ml of developer replenisher and fixer replenisher in the amounts shown in the table, and 500 sheets were processed per day for four months, and the resulting solution was used as a running solution.

Each time a sheet film of large total size (508 mm × 610 mm) is inserted, the washing tank is replenished from the purifying agent kit so that the hydrogen peroxide concentration becomes the concentration shown in the table, and 5 L each time 7 sheets are processed. , And the concentration was adjusted so that the inside of the washing tank had the concentration shown in the table. Also remodeled to be able to change the line speed up to 2.0 times,
High-speed processing has been enabled.

(Processing conditions) Step Temperature Time Developing 38 ° C for 12 seconds Fixing 38 ° C for 12 seconds Washing 25 ° C for 8 seconds Drying 48 ° C for 9 seconds Except that the purifying agent was changed to the following liquid agent, the experiment and experiment were conducted in the same manner as in Example 1. evaluated.

(Purifying agent formulation) 35% by weight aqueous hydrogen peroxide 171.5 g Salicylic acid 0.1 g 5-Chloro-2-methyl-4isothiazoline-3one 15.0 g Polypropylene glycol 3.1 g Compound of general formula (1) 12 It finished to 1L using 0.0g 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.

Table 3 shows the results.

[0108]

[Table 3]

[0109]

As demonstrated in the examples, according to the treatment method of the present invention, even if the washing water is reduced, no dirt, scale or silver sludge is generated in the washing tank, and the dot quality of the film is deteriorated. No contamination of the drying roller occurs.

Claims (8)

[Claims] 1. A method for developing, fixing, washing or stabilizing a silver halide photographic material using an automatic developing machine having a developing tank, a fixing tank, a washing tank or a stabilizing tank, in the presence of hydrogen peroxide. And a washing or stabilizing treatment while recovering silver. 2. A washing tank or stabilizing tank for developing, fixing, washing or stabilizing a silver halide photographic material using an automatic developing machine having a developing tank, a fixing tank, a washing tank or a stabilizing tank. A water-washing or stabilizing treatment in the presence of hydrogen peroxide in two or more tanks. 3. The method for processing a silver halide photographic material according to claim 1, wherein the automatic developing machine has a washing tank (crossover washing) between at least one of the processing tanks. 4. A method for developing, fixing, washing or stabilizing a silver halide photographic light-sensitive material, comprising a developing tank, a fixing tank, a washing tank or a stabilizing tank, and at least one between each processing tank. A method for processing a silver halide photographic light-sensitive material, comprising performing water washing or stabilizing treatment in the presence of hydrogen peroxide using an automatic developing machine provided with a washing tank (crossover washing). 5. A method for developing, fixing, washing or stabilizing a silver halide photographic material using an automatic developing machine having a developing tank, a fixing tank, a washing tank or a stabilizing tank. A method for processing a silver halide photographic material, comprising washing or stabilizing in the presence of a compound represented by the formula (1). Embedded image [Wherein, R ₁ and R ₂ each represent a hydrogen atom or a carbon atom
3 represents an alkyl group. However, R ₁ and R ₂ are not hydrogen atoms at the same time. R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₅ represents a hydroxyl group,
Represents an amino group or an alkyl group having 1 to 3 carbon atoms. R
₆ and R ₇ each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having 18 or less carbon atoms, or a —COOM ₁₀ group. Here, M ₁₀ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom, an aryl group or a carbon atom having 15 or less alkyl groups. However, R ₆ and R ₇ are not simultaneously hydrogen atoms. M ₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. k is 0, 1 or 2. ] 6. The halogenation according to claim 1, wherein the concentration of hydrogen peroxide in the washing tank or the stabilization tank is 0.0001 to 0.5% by weight. Processing method of silver photographic photosensitive material. 7. The hydrogen peroxide solution supplied to the washing tank or the stabilizing tank is prepared from a kit concentrate, and the hydrogen peroxide concentration of the concentrate is 2 to 35% by weight. 7. The method for processing a silver halide photographic light-sensitive material according to 1, 2, 3, 4, 5, or 6. 8. The method according to claim 1, wherein the concentrated solution of the hydrogen peroxide kit is directly dissolved in a washing tank or a stabilizing tank.
7. The method for processing a silver halide photographic material according to 3, 4, 5 or 6.