JPH10177243A - Method for processing black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for the black-and-while silver halide photographic sensitive material prevented from occurrence of precipitates due to a fixing solution and deterioration of image storage stability and any problem on residual dye stains in the case of executing stabilization processing in a processing system containing a water-soluble aluminum salt as a hardening agent for the fixing solution and reducing a replenishing amount for the fixing solution and utilizing a part or all of the overflow of the stabilization processing solution. SOLUTION: A part or all of the overflow of the stabilization processing solution is reused for the fixing replenishing solution when the black-and-white silver halide photographic sensitive material is processed with the fixing solution containing the water-soluble aluminum salt and then processed with the stabilization processing solution, and a replenishing amount for the fixing solution is <=260cc/m<2> of the photosensitive material to be processed and the stabilization processing solution contains a chelating agent having a stability constant of >=8 and, preferably, an antimolding agent.

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 black-and-white silver halide photographic material, and more particularly to a method for processing a black-and-white silver halide photographic material which can reduce the amount of replenished fixing and is particularly suitable for the field of printing plate making. .

[0002]

2. Description of the Related Art A photosensitive material for plate making (hereinafter simply referred to as "photosensitive material") is generally an automatic developing machine having at least a developing section, a fixing section, a washing section or a stabilizing bath section, and a drying section after exposure. In general, each step is processed while a replenisher is being replenished.

[0003] In recent years, the London Treaty has been concluded for the purpose of protecting the global environment, and the dumping of photographic processing wastewater into the ocean has been prohibited in Japan since January 1, 1996. For this reason, the photographic industry has made efforts to reduce the photographic processing waste liquid to the utmost limit. In the printing plate making field, there is a great demand for reducing the waste liquid by reducing the replenishment amount of the processing liquid, and various studies have been made.

One of them is disclosed in Japanese Patent Application Laid-Open No. 60-235133.
As described in JP-A No. 63-129343, a stabilizing treatment is performed in place of washing to remove the washing waste liquid, and part or all of the overflow of the stabilizing treatment solution is used as a fixing replenisher. That is, the fixing replenishment amount is reduced.

[0005]

In a fixing solution for a black-and-white silver halide photographic light-sensitive material, in particular, a fixing solution for printing plate making, a water-soluble aluminum salt is used as a hardening agent to maintain the image strength after processing. Often contained. If a stabilization process is used in such a processing system to reduce the amount of fixing replenishment and if part or all of the overflow of the stabilizing solution is used as the fixing replenisher, sedimentation occurs in the fixing solution, However, there is a problem that the image storability deteriorates and the residual color becomes strong.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fixing system containing a water-soluble aluminum salt as a hardening agent, using a stabilizing treatment,
Even if the amount of fixing replenishment is reduced and part or all of the overflow of the stabilizing processing solution is used for the fixing replenishing solution, it does not cause problems such as occurrence of precipitation in the fixing solution, deterioration of image storability and residual color. An object of the present invention is to provide a method for processing a black-and-white silver halide photographic light-sensitive material.

[0007]

The object of the present invention is to provide a method for treating a black-and-white silver halide photographic material with a stabilizing solution after treating it with a fixing solution containing a water-soluble aluminum salt. Part or all of the overflow is used as a fixer replenisher, and the fixer replenisher is replenished at a rate of 260 cc or less per m ^{2 of the} light-sensitive material to be processed. A black-and-white silver halide photograph containing a compound represented by the general formula (1) Z-SM or a gelatin hardening agent, which is a processing solution imparted with antifungal properties containing at least 8 chelating agents. This is achieved by a method for processing a light-sensitive material, a fixing replenisher used for preparing the fixing replenisher being a solid processing agent, and a light-sensitive material to be processed containing a quaternary onium compound.

That is, the inventor of the present invention has stated that the stabilized treatment liquid is a treatment liquid provided with a fungicidal property, which contains a chelating agent having a chelate stability constant for ferric ion of 8 or more.
A treatment in which a water-soluble aluminum salt is contained as a hardening agent in a fixing solution by adopting any one of a structure containing a compound represented by the general formula (1) Z-SM or a gelatin hardener. The system uses a stabilizing process to reduce the replenishment rate of the fixing material to 260 cc or less per m ^{2 of the} photosensitive material to be processed, and to use a part or all of the overflow of the stabilizing processing solution for the replenishing solution. The present invention has been found to be able to solve the problem of the occurrence of precipitation in the liquid, the deterioration of image storability, and the problem of residual color, leading to the present invention.

Hereinafter, the present invention will be described in detail for each item.

<< Stabilizing Solution >> The stabilizing solution of the present invention contains a solution having a chelate stability constant of 8 or more with respect to ferric ion (Fe ³⁺ ). Here, the chelate stability constant is defined as L.C. G. FIG. Sillen, A .; E. FIG. Mart
, "Stability Constants"
of Metal Complexes ", The
Chemical Society, London (19
64). S. Chaberek, A .; E. FIG. Martel
l, "Organic Sequestering"
Agents ", Willley (1959) and the like.

In the present invention, examples of the chelating agent having a chelating stability constant for iron ions of 8 or more include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent, a polyhydroxy compound and the like. Typical compounds include ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid,
Ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, Ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-
1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate,
Examples thereof include sodium tetrapolyphosphate and sodium hexametaphosphate. Particularly preferred are, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and 1,3.
-Diaminopropanol tetraacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylene diamine triacetic acid, 2
-Phosphonoptan-1,2,4-tricarboxylic acid, 1,
1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1-diphosphonic acid, -Hydroxyethylidene-1,1-diphosphonic acid and salts thereof.

Good results can be obtained when the amount of these chelating agents used is in the range of 0.01 to 100 g, preferably 0.05 to 50 g per liter of the stabilizing solution.

Means for imparting antifungal properties are not particularly limited as long as the stabilized processing solution does not adversely affect the developing and fixing performance and the quality of the processed light-sensitive material can be maintained satisfactorily. It is selected from ultraviolet irradiation, application of a magnetic field, ion exchange, and addition of a fungicide. Most preferably, a fungicide is used.

The magnetic field is obtained by using a permanent magnet made of ferromagnetic iron, cobalt or nickel, or by applying a direct current to a coil or the like, and applying a stabilizing treatment solution or a replenisher thereof to the generated magnetic field. Let it pass. It is preferable to employ a method in which a permanent magnet is fixed to part or all of the inside or outside of the circulation system pipe and the stabilizing treatment liquid is circulated.

The ultraviolet irradiation is carried out using a commercially available ultraviolet lamp (preferably having a tube output of 5 to 800 W), an ultraviolet irradiation device, or the like.
350 nm is preferred.

The ion exchange is performed by passing the stabilizing solution through a hot-bed column filled with a commercially available H-type strongly acidic cation exchange resin and an OH-type strongly basic exchange resin.

A method using ultraviolet light is disclosed in
The method using a magnetic field is described in detail in JP-A-60-263940, and the method using an ion exchange resin is described in detail in Japanese Patent Application No. 61-131632.

The fungicides used in the present invention include thiazolyl benzimidazole compounds, isothiazolone compounds, chlorophenol compounds, bromophenol compounds, thiocyanic acid and isothiocyanic acid compounds, acid azide compounds, Diazine and triazine compounds, thiourea compounds, alkylguanidine compounds, quaternary ammonium salts, organotin and organozinc compounds, cyclohexylphenol compounds, imidazole and benzimidazole compounds, sulfamide compounds, chlorinated sodium isocyanurate, etc. Active halogenated compounds, chelating agents, sulfite compounds, antibiotics represented by penicillin and the like can be mentioned. In addition, L. E. FIG.
West, “Water Quality Crite
ria "Phot. Sci. and Eng., Vo
l. 9, No. 6 (1965): JP-A-55-111942, JP-A-57-8524, and JP-A-57-524.
Nos. 157244, 58-105145 and 59-
Various fungicides described in No. 126533; "Chemistry of fungicides and fungi" written by Hiroshi Horiguchi and published by Sankyo Publishing Co., Ltd. (Showa 57);
Year)).

The following are specific examples of the antifungal agent, but the invention is not limited thereto.

1) 5-chloro-2-methyl-4-isothiazolin-3-one 2) 2- (4-thiazolyl) benzimidazole 3) methyl isothiocyanate 4) 3,5-dichloro-4'-fluorothiocarba Nilide 5) 4-Chloro-3,5-dimethylphenol 6) 2,4,6-Trichlorophenol 7) Sodium dehydroacetate 8) Sulfanilamide 9) 3,4,5-Tribromosalicylanilide 10) Potassium sorbate 11) Benzoalkonium chloride 12) 1-Bromo-3-chloro-5,6-dimethylhydantoin 13) Monochloroacetamide 14) Monobromoacetamide 15) Monoiodoacetamide 16) Benzimidazole 17) Cyclohexylphenol 18) 2-Octylisothiazoline -3-on 9) Ethylenediaminetetraacetic acid 20) Nitrilo-N, N, N-trimethylenephosphonic acid 21) 1-Hydroxyethane-1,1-diphosphonic acid 22) Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 23) Chlorinated sodium isocyanurate 24) 2-Methyl-4-isothiazolin-3-one 25) 10,10'-oxybisphenoxyarsine 26) 1,2-Benzoisothiazolin-3-one These compounds are disclosed in U.S. Pat. No. 2,767,172,
No. 2,767,173, No. 2,767,174, No. 2,870,015, British Patent No. 848,130,
It can be synthesized with reference to French Patent No. 1,555,416 and the like. Furthermore, Predentol ON, Permachem PD, Topside 800, Topside EG5, Topside 300, Topside 600 (all manufactured by Permachem Asia), Fineside J-700 (Tokyo Fine Chemical), ProzelGXL (IC) .I company).

These antifungal agents are used in an amount of about 0.01 to 50 g, preferably 0.05 to 50 g per liter of the stabilized solution.
Used at 20 g.

As a means for imparting antifungal properties, an oxidizing agent can be used. Examples of the oxidizing agent that can be used include metal or nonmetal oxides, oxyacids or salts thereof, peroxides, and compounds containing an organic acid system. Sulfuric acid, nitrous acid, nitric acid, hypochlorous acid and the like are preferably used as the oxyacid, and hydrogen peroxide, fentonic acid reagent and the like, and ozone are preferably used as the peroxide.

The stabilizing solution of the present invention contains a compound represented by the general formula (1).

In the general formula (1), the alkyl group represented by Z preferably has 1 to 30 carbon atoms, particularly a straight-chain, branched or cyclic alkyl group having 2 to 20 carbon atoms. May have a substituent other than the above substituent.
The aromatic group represented by Z is preferably a monocyclic or condensed ring having 6 to 32 carbon atoms, and may have a substituent in addition to the substituent. The heterocyclic group represented by Z is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms, and has 1 to 6 heteroatoms in one ring independently selected from nitrogen, oxygen and sulfur. It is a 5- or 6-membered ring and may have a substituent other than the above. However, when the heterocyclic group is tetrazole, it does not have a substituted or unsubstituted naphthyl group as a substituent. Among the compounds represented by the general formula (1), a compound in which Z is a heterocyclic group having two or more nitrogen atoms is preferable.

The ammonium group preferably has 2 carbon atoms.
0 or less and the substituent is a substituted or unsubstituted straight chain,
It represents a branched or cyclic alkyl group (eg, methyl group, ethyl group, benzyl group, ethoxypropyl group, cyclohexyl group), substituted or unsubstituted phenyl group, and naphthyl group.

Further preferred compounds represented by the general formula (1) are compounds represented by the following general formula (1-a).

[0027]

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In the formula, Z 'is an unsaturated 5 having a nitrogen atom.
Membered heterocycle or 6-membered heterocycle (pyrrole ring, imidazole ring, pyrazole ring, pyrimidine ring, pyridazine ring,
A group required to form a pyrazine ring, etc.), a compound having at least one -SM group or thione group and a hydroxyl group, -COOM group, -SO ₃ M
And at least one substituent selected from the group consisting of a group, a substituted or unsubstituted amino group, and a substituted or unsubstituted ammonium group. In the formula, R ₁ and R ₂ represent a hydrogen atom,-
SM group (including those having a substituent) a halogen atom, an alkyl group (including those having a substituent) alkoxy group, a hydroxyl group, -COOM group, -SO ₃ M group,
An alkenyl group (including one having a substituent), an amino group (including one having a substituent), a carbamoyl group (including one having a substituent), and a phenyl group (including one having a substituent); R ₁ and R ₂ may form a ring.
The ring that can be formed is a 5- or 6-membered ring, preferably a nitrogen-containing heterocycle. M has the same meaning as M defined in the general formula (1). Preferably, Z 'is a group forming a heterocyclic compound containing two or more nitrogen atoms, and may have a substituent other than the above-described -SM group or thione group. ,
Lower alkyl groups (including those having a substituent, preferably those having 5 or less carbon atoms such as methyl group and ethyl group);
A lower alkoxy group (including those having a substituent; methoxy, ethoxy, butoxy, etc., preferably having 5 or less carbon atoms) and a lower alkenyl group (including those having a substituent; preferably having 5 or less carbon atoms); ), Carbamoyl group, phenyl group and the like. Further, the general formula (1-a)
In the above, compounds represented by the following general formulas A to F are particularly preferred.

[0029]

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In the formula, R ₃ , R ₄ , R ₅ , and R ₆ are each a hydrogen atom, a —SM group, a halogen atom, a lower alkyl group (including those having a substituent; a methyl group, an ethyl group, etc. Those having 5 or less carbon atoms are preferred), lower alkoxy groups (including those having a substituent, and those having 5 or less carbon atoms are preferred), hydroxy groups, -COOM ₁ , -SO ₃ M ₂ groups,
A lower alkenyl group (including a group having a substituent, preferably a group having 5 or less carbon atoms), an amino group, a carbamoyl group and a phenyl group, at least one of which is a -SM group. M, M ₁ and M ₂ each represent a hydrogen atom, an alkali metal atom or an ammonium group. In particular, the substituent other than -SM preferably has a water-soluble group such as a hydroxy group, -COOM ₁ , -SO ₃ M ₂ group, or amino group. R ₃ , R ₄ ,
The amino group represented by R ₅ or R ₆ represents a substituted or unsubstituted amino group, and a preferable substituent is a lower alkyl group. The ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

Specific examples of the compound represented by formula (1) are shown below, but it should not be construed that the invention is limited thereto.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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The amount of the compound represented by the general formula (1) is preferably 10 ^-6 to 10 ^-1 mol, more preferably 10 ^-5 to 10 ^-2 mol, per liter of the stabilizing solution. It is preferred that

As the gelatin hardener, an inorganic or organic hardener can be used. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,
5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.) ), Isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. These curing agents are available from Research Disclosure (Research).
Disclosure) 176 Volume 17643 (197
(Issued in December 2008) on page 26, paragraphs A to C. Among them, a carboxyl group-active hardener is preferable, and among them, compounds represented by the following general formulas (2) to (8) can be mentioned as preferable carboxyl group-active hardeners.

[0040]

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In the formula, R ²¹ and R ²² each have 1 to 10 carbon atoms.
Alkyl group (methyl group, ethyl group, 2-ethylhexyl group, etc.), aryl group having 6 to 15 carbon atoms (phenyl group,
Naphthyl group) or an aralkyl group having 7 to 15 carbon atoms (benzyl group, phenethyl group, etc.). R ²¹ and R ²² may combine with each other to form a heterocyclic ring such as a pyrrolidine ring, a piperazine ring, and a morpholine ring together with the nitrogen atom.

R ²³ is a substituent (hydrogen atom, halogen atom,
Carbamoyl group, a sulfo group, a sulfoxy group, a ureido group, an alkoxy group having 1 to 10 carbon atoms, alkyl group having 1 to 10 carbon atoms, represents a dialkyl-substituted amino group, etc.) having 2 to 20 carbon atoms, R ²³ is an alkoxy group , An alkyl group, a dialkylamino group, or an N-alkylcarbamoyl group, they may further have a substituent such as a halogen atom, a carbamoyl group, a sulfo group, a sulfoxy group, or a ureido group.

[0043] X ^- represents an anion, a counter ion of N- carbamoyl pyridinium salts. When the substituent of R ²³ contains a sulfo group or a sulfoxy group, an internal salt may be formed to eliminate X ⁻ . Preferred anions include halide ions, sulfate ions, sulfonate ions,
ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^{− and the} like.

The carbamoyl ammonium salt hardener represented by the general formula (2) is described in JP-B-56-1285.
No. 3, No. 58-32699, JP-A-49-51945.
And Nos. 51-59623 and 61-9641.

[0045]

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R ³¹ , R ³² , R ³³ and X ⁻ in the general formula (3) are the same as R ²¹ , R ²² , R ²³ and X ⁻ in the general formula (2).
And these compounds are described in detail in Belgian Patent No. 825726.

[0047]

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Wherein R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each
C1-C20 alkyl group (methyl group, ethyl group, butyl group, 2-ethylhexyl group, dodecyl group, etc.), C6-C20 aralkyl group (benzyl group, phenethyl group, 3-pyridylmethyl group, etc.) Or an aryl group having 5 to 20 carbon atoms (phenyl group, naphthyl group, pyridyl group, etc.), which are a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, N, N −
It may have a substituent such as a disubstituted carbamoyl group. Also, any two of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ may combine to form a ring. The ring formed by R ⁴¹ and R ⁴² or R ⁴³ and R ⁴⁴ together with the nitrogen atom includes a pyrrolidine ring,
Examples include a piperazine ring, a perhydroacepine ring, and a morpholine ring. Examples of the ring formed by combining R ⁴¹ and R ⁴³ or R ⁴² and R ⁴⁴ with two nitrogen atoms and a carbon atom interposed therebetween include an imidazoline ring, a tetrahydropyrimidine ring, and a tetrahydroazepine ring.

X represents a group capable of leaving when the compound represented by the general formula (4) reacts with a nucleophile, and is preferably a halogen atom, a sulfonyloxy group, a 1-pyridinium group or the like. Y ^- is represents an anion, halide ions,
Sulfonate ion, sulfate ion, ClO ₄ ⁻ , BF ₄ ⁻ ,
PF _6- ^{and the} like are preferred. Y ^- is to represent a sulfonate ^{ion, X, R 41, R 42} , combined with R ⁴³ or R ⁴⁴ may form an intramolecular salt.

The amidinium salt hardener represented by the general formula (4) is described in detail in JP-A-60-225148.

Formula (5) R ⁵¹ —N ＝ C −N—R ^{52 In the} formula, R ⁵¹ is an alkyl group having 1 to 10 carbon atoms (methyl group,
Ethyl group, 2-ethylhexyl group, etc.), having 3 to 10 carbon atoms
Represents an alkoxyalkyl group (such as a methoxyethyl group) or an aralkyl group having 1 to 15 carbon atoms (such as a benzyl group or a phenethyl group).

R ⁵² is a group defined for R ⁵¹ or

[0053]

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Represents the following. R ⁵³ represents an alkylene group having 2 to 4 carbon atoms (ethylene group, propylene group, trimethylene group, etc.), and R ⁵⁴ and R ⁵⁵ each represent an alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, etc.). And may combine with each other to form a heterocyclic ring such as a pyrrolidine ring, a piperazine ring, and a morpholine ring together with the nitrogen atom. R ⁵⁶ represents an alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, butyl group, etc.);
It may have a substituent (substituted or unsubstituted carbamoyl group, sulfo group, etc.). X ^- represents an anion, halide ions, sulfonate ions, sulfate ion, ClO
_{^{4 -, BF 4 -, PF}} 6 - are preferable. When R ⁵⁶ is substituted with a sulfo group, an internal salt may be formed and X ⁻ may not be present.

The carbodiimide hardeners represented by the general formula (5) are described in JP-A-51-126125 and JP-A-52-126125.
-48311.

[0056]

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In the formula, R ⁶¹ is an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, or a butyl group);
(Phenyl group, naphthyl group, etc.) or an aralkyl group having 7 to 15 carbon atoms (benzyl group, phenethyl group, etc.). These may have a substituent such as a carbamoyl group, a sulfamoyl group, and a sulfo group. R ⁶² and R ⁶³ each represent a substituent (hydrogen atom, halogen atom, acylamide group, nitro group, carbamoyl group, ureido group, alkoxy group, alkyl group, aryl group, aralkyl group, etc.), A condensed ring may be formed together with the skeleton.

X represents a group capable of leaving when the compound represented by the general formula (6) reacts with a nucleophile, and is preferably a halogen atom, a sulfonyloxy group or

[0059]

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[0060] When X is a sulfonyloxy group, X and R ⁶¹ may be bonded.

Y ⁻ represents an anion, and is a halide ion, a sulfonate ion, a sulfate ion, ClO ₄ ⁻ , BF
₄ ^-, PF ₆ ^- are preferable. When R ⁶¹ is substituted with a sulfo group, an inner salt is formed, and Y ⁻ may not be present.

These pyridinium salt hardeners are described in JP-B-58-50699 and JP-A-57-4414.
Nos. 0 and 57-46538.

[0063]

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In the general formula (7), the definitions of R ⁷¹ and R ⁷² are the same as the definitions of R ²¹ and R ²² in the general formula (2), and R ⁷³ is an alkyl group having 1 to 10 carbon atoms (methyl group). , An ethyl group, a butyl group, etc.), an aryl group having 6 to 15 carbon atoms (phenyl group, naphthyl group, etc.) or an aralkyl group having 7 to 15 carbon atoms (benzyl group, phenethyl group, etc.). X
^- represents an anion, halide ions, sulfonate ions, sulfate _{^{ion, ClO 4 -, BF 4 -}} , PF 6 - are preferable.

The pyridinium salt hardener represented by the general formula (7) is described in detail in JP-A-52-54427.

[0066]

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In the formula, R ⁸¹ is an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, 2-ethylhexyl group, etc.), an aryl group having 6 to 15 carbon atoms (phenyl group, naphthyl group, etc.) or 7 to 15 aralkyl groups (benzyl group,
Phenethyl group), a halogen atom, carbamoyl, sulfo, sulfoxy, ureido, carbon number 1-10
Alkoxy, an alkyl group having 1 to 10 carbon atoms, 2 carbon atoms
It may have up to 20 dialkyl-substituted amino groups and other substituents.

Z represents a group of nonmetal atoms necessary to complete the nitrogen-containing heteroaromatic ring, and is preferably a pyridine ring, a pyrimidine ring, a pyrazole ring, an imidazole ring, an oxazole ring, or a benzo-fused ring thereof.

R ⁸² represents a substituent (a hydrogen atom, a halogen atom,
A carbamoyl group, a sulfo group, a sulfoxy group, a ureido group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a dialkyl-substituted amino group having 2 to 20 carbon atoms, etc.), and R ⁸² represents an alkoxy group , An alkyl group, a dialkylamino group, or an N-alkylcarbamoyl group, they may further have a substituent (a halogen atom, a carbamoyl group, a sulfo group, a sulfoxy group, a ureido group, etc.).

[0070] X ^- represents an anion, halide ions, sulfonate ions, sulfate ion, ClO ₄ ^-, BF
₄ ^-, PF ₆ ^- are preferable. When a sulfo group or a sulfooxy group is contained in R ⁸¹ , R ⁸² or a substituent thereof, an internal salt may be formed to eliminate X ⁻ .

In the present invention, besides the compounds represented by the general formulas (2) to (8) as gelatin hardeners, JP-A-50-38540, JP-A-52-93470 and JP-A-56-93470 may be used.
No. 43353, No. 58-113929 and U.S. Pat. No. 3,321,313 can be used.

The following are specific examples of gelatin hardeners, but are not limited thereto.

[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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These gelatin hardeners may be used alone or in combination, and may be used in any amount depending on the processing system. However, it is preferably 10 ^-5 to 1 ^-5 per liter of the stabilized processing solution.
1 mol, and more preferably 10 ^{-4 to} 0.1 mol.

The pH of the stabilizing solution is preferably 4 to 9,
In order to adjust the pH, a compound selected from an organic acid, an inorganic acid and a salt thereof and an alkali agent (a carbonate such as potassium carbonate and sodium carbonate; a bicarbonate such as sodium bicarbonate); Metal hydroxides such as sodium; phosphates such as sodium phosphate, etc.). Among them, it is preferable to use a compound selected from organic acids and salts thereof. Preferred organic acids include acetic acid, citric acid, tartaric acid, malic acid, succinic acid and the like. Examples of salts of acetic acid, citric acid, tartaric acid, malic acid, succinic acid and the like include lithium salts, potassium salts, sodium salts, and ammonium salts thereof, such as lithium hydrogen tartaric acid, potassium hydrogen, sodium hydrogen, ammonium hydrogen, and ammonium potassium tartaric acid. And sodium potassium tartaric acid may be used. Further, these optical isomers and the like are included. Among these, citric acid,
Isocitric acid, malic acid, succinic acid and salts thereof.

In addition to those described above, the stabilizing solution may be a sulfite (sodium sulfite, potassium sulfite, etc.), a halide (sodium chloride, potassium bromide, etc.), or represented by the general formula (1). It may contain a nitrogen-containing heterocyclic compound other than the compound (eg, 1-phenyl-5-mercaptotetrazole, 5-methylbenzotriazole, 5-nitroindazole) and a hardener other than the above (eg, glutaraldehyde, aluminum sulfate). .

In the present invention, it is preferable to perform the processing while replenishing the stabilizing processing solution, but the replenishing amount is preferably 3 liters or less per m ^{2 of the} photographic material from the viewpoints of environment and economy. A part of the replenished stabilizing solution is taken out to the next step such as drying by the photosensitive material, but the rest overflows.

One feature of the present invention is that part or all of the overflow of the stabilizing processing solution is used for the fixing replenisher. Part or all of the overflow of the stabilizing solution is used for diluting the fixing concentrate and dissolving the solid fixing replenisher described below. Even if all of the overflow of the stabilization treatment liquid is used, if the amount of water required for dilution or dissolution is insufficient, water may be further supplied.

<< Fixing Solution >> In the present invention, a water-soluble aluminum salt acting as a hardener is added to the fixing solution. As the water-soluble aluminum salt, it is preferable to use, for example, aluminum chloride, aluminum sulfate, potassium alum and the like. In addition, other compounds having a hardening action, for example, aldehyde compounds (glutaraldehyde, glutaraldehyde sulfite adducts, etc.) can also be added.

In order to carry out the processing with a lower fixing replenishing amount in the present invention, it is preferable that the fixing replenisher is prepared from a solid processing agent, which is also advantageous for speeding up the processing. Here, the solid processing agent refers to a solid formed of two or more components constituting the fixing replenisher. One solid containing all the fixing components, or two or more solids forming the fixing component. It may be something that can be done. In the solid processing agent, at least one type of solid formed from at least two or more compounds may be used, and a single substance other than the formed solid may be used. Preferable solid processing agents include powders prepared by spray-drying, granules formed by extrusion-drying or granulation (extrusion granulation, fluidized-bed granulation, tumbling granulation) (average particle size of 0). 0.1 mm to 10 mm, in particular, the particle size of 90% of the front particles is within ± 40% of the average particle size) and compression-molded tablets. Particularly preferred forms are granules and tablets. The solid processing agent may contain compounds necessary for molding such as a binder and a lubricant.

As the solid treating agent, those in which the treating agent component does not behave as a powder at the time of dissolution are preferable, and for that purpose, a solid treating agent containing a compound represented by the following general formula (9) as a lubricant is preferable.

[0094]

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Wherein X and Y are a halogen atom, a hydroxyl group,
It represents a sulfonic acid group or a carboxyl group, and R ⁹¹ and R ⁹² represent a hydrogen atom or a hydroxyl group. n represents an integer of 3 to 10. As a preferable structure of the general formula (9), the following general formula (9-
a).

[0096]

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Specific examples of the compound represented by the general formula (9-a) are shown below. These compounds have structural isomers and include them.

[0098]

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Of the above compounds, the D of the 9-6 structural isomer
Mannitol and sorbitol are preferred. The addition amount is about 0.2 to 50 g, preferably 0.5 to 20 g, and more preferably 0.5 to 10 g per liter of the fixing replenisher.
g.

In order to reduce the amount of waste liquid, processing is performed while a fixed amount of fixing replenishment proportional to the area of the photosensitive material to be processed is performed. In the present invention, the fixing replenishment amount is 260 cc or less per 1 m ² of the photosensitive material, but is preferably 30 to 250 cc, more preferably 30 to 200 cc. The fixing replenisher is the same as the fixing mother liquor in the tank of the automatic processor,
A liquid prepared from a different liquid or a solid processing agent may be used. The replenishment amount referred to here is the replenishment amount of each solution when replenishing with the same solution as the fixing mother liquor, and the total amount of each concentrated solution and water when replenishing the fixing concentrate with a solution diluted with water. In the case where the solid fixing replenisher is replenished with a solution dissolved in water, it is the total amount of each solid processing agent volume and the volume of water, and when the solid fixing replenisher and water are separately replenished. , The total volume of each solid treatment agent volume and water volume. When replenishing with a solid processing agent, the total volume of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water to be separately added is preferably used.

<< Developer >> A developer usually contains a developing agent (dihydroxybenzene compound, ascorbic acid compound, etc.), a preservative (sulfite such as sodium sulfite, potassium sulfite, ammonium sulfite, etc .; sodium metabisulfite) Meta-bisulfites, etc.), alkaline agents (sodium hydroxide, potassium hydroxide, etc.) and pH buffers (eg carbonates, phosphates, borates, boric acid, acetic acid, citric acid, alkanolamines, etc.) Is done. Carbonates are preferred as pH buffers. 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, Tokiko 47-4
No. 5541), a hardener (glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent can be added. The pH of the developer is preferably adjusted to 8.5 or more and less than 11, and
It is 9.0 or more and 10.7 or less.

<< Automatic Developing Machine >> In the present invention, when processing is performed using an automatic developing machine, the entire processing time (Dryto dry) from the insertion of the leading end of the photosensitive material into the automatic developing machine to the discharge from the drying zone. ~ Time including all steps of development, fixing, bleaching, washing with water, stabilization, drying, etc.)
The time is preferably 80 seconds, more preferably 15 to 60 seconds, in order to meet the demand for shortening the processing time. If the total processing time is less than 10 seconds, satisfactory photographic performance may not be obtained due to desensitization or softening. In order to stably process a large amount of photosensitive material of 100 m ² or more, the development time is 2 to 2.
Preferably, it is 22 seconds.

The temperature of the developing solution, fixing solution and stabilizing solution is 10 to
45 ° C. is preferred, and each may be separately temperature-controlled.

In order to remarkably exert the effects of the present invention,
Heat transfer material at 60 ° C or higher (heat roller at 60 to 130 ° C) or radiant object at 150 ° C or higher (tungsten, carbon, nichrome, zirconium oxide, yttrium oxide,
Drying with a mixture of thorium oxide, silicon carbide, etc., which emits heat by direct current generation, or which transmits thermal energy from a resistance heating element to a radiator such as copper, stainless steel, nickel, various ceramics, etc. to emit infrared rays) An automatic developing machine having a zone in which it is formed is preferred.

It is preferable that the heat roller has an aluminum hollow roller whose outer peripheral portion is covered with silicon rubber, polyurethane or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side walls. Further, it is preferable that a gear is fixed to one end of the heat roller, and the heat roller is rotated in the transport direction by a drive unit and a drive transmission unit. It is preferable that a halogen heater connected to a temperature controller provided in the automatic developing machine be inserted into the roller of the heat roller.

In addition, in the present invention, an automatic developing machine employing the method and mechanism described below can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. (2) upper left column to (3) upper left column (2) Washing water regenerating purifying agent and apparatus: JP-A-6-2503
No. 52, page 3 (0011) to (8), page 0058 (3) Waste liquid treatment method: JP-A-2-64638, lower left column of page (2) to lower left column of page (5) (4) developing bath and fixing Rinse bath during bath: JP-A-4-31
No. 3749, page 18 [0054] to page (21) [00]
65 "(5) Water replenishment method: JP-A-1-281446, page 2 (lower left column to lower right column on page 2) (6) Method of detecting dry air temperature and humidity to control drying air of automatic developing machine: No. 1-315745, lower right column of page (2) to lower right column of page (7), and JP-A-2-108051
No. (2) lower left column to (3) lower left column (7) Silver recovery method of fixing waste liquid: JP-A-6-27623, page (4), "0012" to page (7), "0071".

<< Photosensitive Material >> In the present invention, the effect of the present invention can be more exhibited when the photosensitive material to be processed contains a quaternary onium salt. The quaternary onium compound to be used is a compound having a quaternary cation group of a nitrogen atom or a phosphorus atom in the molecule, and is preferably a compound represented by the general formula (P).

[0109]

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
₇ , R ₈ , R ₉ and R ₁₀ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. R _{7 to} R ₁₀ may be linked to each other to form a ring.

Examples of the substituent represented by R _{7 to} R ₁₀ include an alkyl group (methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, etc.) and an alkenyl group (allyl group, butenyl group, etc.) , Alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (piperidinyl group, piperazinyl group, morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrofuryl group Thienyl group, sulfolanyl group, etc.), amino group and the like.

Examples of the ring which can be formed by connecting R _{7 to} R ₁₀ to each other include a piperidine ring, a morpholine ring, a piperazine ring, a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring and a tetrazole ring. .

The groups represented by R _{7 to} R ₁₀ may have a substituent such as a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group and an aryl group.

R ₇ , R ₈ , R ₉ and R ₁₀ are preferably a hydrogen atom and an alkyl group.

[0115] X ^- include anions represented by the halogen ion, sulfate ion, nitrate ion, acetate ion, and inorganic and organic anions, such as p- toluenesulfonic acid ion.

More preferably, the following general formulas (Pa) and (P
b) or a compound represented by (Pc); and a compound represented by the following general formula [T].

[0117]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetal atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ include a 5- to 6-membered ring (pyridine,
Imidazole, thiozole, oxazole, pyrazine,
Each ring such as pyrimidine), and a more preferred example is a pyridine ring.

_BP represents a divalent linking group, and m represents 0 or 1
Represents Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene group, —SO ₂ —, —SO—, and —O
—, —S—, —CO—, and —N (R ⁶ ) — (R ⁶ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of B _p include an alkylene group and an alkenylene group.

R ¹ , R ² and R ⁵ each have 1 to 20 carbon atoms
Represents an alkyl group. R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and the substituent is the same as the substituents described as the substituents for A ¹ , A ² , A ³ , A ⁴ and A ⁵ .

Preferred examples of R ¹ , R ² and R ⁵ include:
Each is an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0122] X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

[0123]

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The substituent R ¹¹ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T],
R ¹² and R ¹³ are preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.

The Hammett's sigma value for the phenyl group has been described in many literatures, for example, Journal of Medical Chemistry.
Chemistry) 20, vol. 304, p. As a group having a particularly preferable negative sigma value, for example, a methyl group ([sigma] P = -0.17 or less, and any group having a negative sigma value) can be seen in reports by C. Hansch et al.
P value), ethyl group (-0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which has the general formula [T]
Is useful as a substituent of the compound of

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonic acid anions such as toluene sulfonic acid anion; higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl boron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

Hereinafter, specific examples of the quaternary onium compound will be shown below, but it should not be construed that the invention is limited thereto.

[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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The above quaternary onium compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be prepared according to Chemical Reviews 55 p. 3
35-483 can be referred to.

These quaternary onium compounds may be used alone or in an appropriate combination of two or more. About 1 × 10 ^-8 to 1 mol, preferably 1 to 10 mol, per mol of silver halide
It is used in an amount of × 10 ^-7 to 1 × 10 ^-1 mol. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating. It may be added to any of the constituent layers of the light-sensitive material, but is preferably added to at least one of the constituent layers on the side having the silver halide emulsion layer, further to the silver halide emulsion layer and / or a layer adjacent thereto. Added.

[0140]

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

Example 1 << Preparation of Support >> (Syndiotactic Polystyrene Synthesis) Toluene 2
100 parts by weight of styrene, 56 parts of triisobutylaluminum, 234 g of pentamethylcyclopentadienyltitanium trimethoxide at 96 ° C.
A time reaction was performed. After the catalyst was decomposed and removed with a methanol solution of sodium hydroxide, it was washed three times with methanol to obtain 34 parts by weight of syndiotactic polystyrene (SPS).

(Preparation of SPS Film) Obtained SPS
Was melt-extruded from a T-die at 330 ° C. into a film and quenched and solidified on a cooling drum to obtain an uncentrifuged film. At this time, the take-up speed of the cooling drum was performed in two stages, and the unstretched film having a thickness of
After preheating at ℃ and longitudinal stretching (3.1 times), transverse stretching at 130 ° C (3.4 times) and heat fixing at 250 ° C. As a result, the bending elastic modulus of the support was 450 kg / m.
A biaxially stretched film having a thickness of m ² and a thickness of 100 μm was obtained.

(Undercoat of SPS Film) After silica was vapor-deposited on both sides of the SPS film, an undercoat layer containing styrene-glycidyl acrylate and tin oxide fine particles and subjected to antistatic treatment was formed.

<< Preparation of Light-Sensitive Material >> (Preparation of Silver Halide Emulsion A) An average thickness of 70 mol% of silver chloride and the balance of silver bromide was 0.05 by a double jet method.
μm, silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. At the time of mixing the core particles, K ₃ RuCl ₆ was added in an amount of 8 × 10 ⁻⁸ mol per mol of silver. The core particles were shelled using a double jet method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added 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 iodobromide, the remainder being silver bromide). Then, JP-A-2-280139, 287
Desalting was performed using denatured gelatin G-8 (having the amino group in gelatin replaced with phenylcarbamyl) described on page (3).

The EAg after desalting was 190 mV at 50 ° C. 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻³ mol per mol of silver, potassium bromide and citric acid were added to adjust the pH to 5.6 and the EAg to 123 mV. After adding ^10-5 mol, 3 x 1 of inorganic sulfur was added.
0 ^-6 mol added to up sensitivity exits at temperature 60 ° C. chemically ripened.

After completion of ripening, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol per mol of silver, and 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 3. ^-4 moles and gelatin were added.

(Preparation of Silver Halide Emulsion B) Using a double jet method, 60 mol% of silver chloride and 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 / m.
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, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver.

The obtained emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% of silver chloride, silver iodobromide having an average thickness of 0.10 μm and an average diameter of 0.42 μm). 0.5 mol%, the balance consisting of silver bromide). Subsequently, desalting was performed using denatured gelatin G-8 (supra). The EAg after desalting was 180 mV at 50 ° C.

To the resulting 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.
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-
1,3,3a, 7-Tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 ⁻⁴ mol, and gelatin was added.

(Preparation of a silver halide photographic light-sensitive material for a printing plate making scanner for a He-Ne laser and a red semiconductor laser light source) On one undercoat layer of the above support, a gelatin undercoat layer of the following formula 1 was coated. The amount of gelatin is 0.5 g / m ²
The silver halide emulsion layer 1 having the following formula 2 was further provided thereon with a silver content of 1.5 g / m ² and a gelatin content of 0.5 g / m ² as an intermediate protective layer. Formula 3 below
The coating solution as the amount of gelatin is 0.3 g / m ^2, further amount of silver halide emulsion layers 2 formulations 4 thereon 1.
4g / 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 coated with a gelatin amount of 0.6 g / m 2.
² , a hydrophobic polymer layer of the following formulation 7 was further formed thereon, and a backing protective layer of the following formulation 8 was further formed thereon at the same time as the emulsion layer side so that the amount of gelatin became 0.4 g / m ^2. A sample was obtained by coating.

Formulation 1 (Composition of gelatin undercoat layer) 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) Silver halide emulsion A Dye AD so that the silver amount becomes 1.5 g / m ² -8 solid dispersion 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 quaternary onium compound: exemplified compound P-20 30 mg / ² compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener ^{g 5mg / m 2 S-1} 0.7mg / m 2 2- mercapto - - hydroxy purine 5 mg / m ² ethylenediaminetetraacetic acid (EDTA) 30 mg / m ² Colloidal silica (average particle size 0.05 .mu.m) 10 mg / ^{m 2} Formulation 3 (intermediate layer composition) Gelatin 0.3 g / ^{m 2} Redox compound: RE- ^{1 10mg / m 2 S-1} 2mg / m 2 formulation 4 (silver halide emulsion layer 2 composition) silver halide emulsion B silver amount 1.4 g / sensitizing dyes which become ^{m 2 d-1 3mg / m} 2 Sensitizing dye d-2 3 mg / m ² hydrazine derivative: H-1 20 mg / m ² Nucleation promoter Nb-1 40 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 AD-5 (average particle size 0.1 μm) 40 m g / 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 nucleation promoting agent Na-1 40 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 .mu.m) 10 mg / m ² hardener: K-1 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) 1.0 g / m ² Hardener g 6 mg / m ² Formulation 8 (backing protective layer) Gelatin 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 HO (CH ₂ CH ₂ O) ₆₈ H 50 mg / m ² Hardener: K-1 20 mg / m ²

[0153]

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[0154]

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[0156]

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[0157] Note that the surface resistivity of the backing side after coating and drying is 23 ° C., at 6 × ^{10 11} in 20% RH, the film surface pH of the surface of the emulsion side is 5.5, the degree of swelling was 175.

<< Preparation of Processing Agent >> (Preparation of Processing Solution) (1) Development Initiation Solution (1 L of Used Solution) Biodegradable chelating agent: Ch 5 g Diethylenetriaminetetraacetic acid (DTPA) .5Na salt 10.35 g Sodium sulfite 61 g Potassium sulfite 3.8 g Potassium bromide 1.9 g Potassium carbonate 53.3 g Diethylene glycol 38 g 8-mercaptoadenine 0.2 g Hydroquinone 22.8 g Sodium erythorbate 2 g Benzotriazole 0.25 g 1-phenyl-4-hydroxymethyl-4-methyl -3-pyrazolidone (dimesone S) 1.25 g 1-phenyl-5-mercaptotetrazole 0.08 g potassium hydroxide 7.4 g 1 liter by adding water 10.6 after pH adjustment

[0159]

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(2) Preparation of Developing Tablet <Preparation of Granulation A Parts> (for 1 liter of liquid used) Biodegradable chelating agent: Ch 5 g DTPA / 5Na salt 10.35 g Sodium sulfite 61 g Potassium sulfite 3.8 g Potassium carbonate 53.3 g D-mannitol (trade name: manufactured by Kao Corporation) 5 g <Preparation of granulation B parts> (for 1 liter of used solution) Potassium bromide 1.9 g 8-Mercaptoadenine 0.2 g Hydroquinone 22.8 g Sodium erythorbate 2g Benzotriazole 0.25g Dimezone S 1.25g 1-phenyl-5-mercaptotetrazole 0.08g Compound TO-1 0.2g D-sorbitol 5g 1-Sodium 1-octanesulfonate 2g When pH is adjusted 10.6 The above granulation A part material and granulation B part material After mixing for 30 minutes in a commercial bandam mill and further granulating for 10 minutes at room temperature with a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized-bed dryer, and granulated A parts and Granulated B parts were obtained.

The above A parts and B parts were thoroughly mixed for 10 minutes, and the resulting mixture was mixed with a machine UDN DFE30.
Using a 40 tablet press (manufactured by Masina Co., Ltd.), 10 tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² .

When used, 10 tablets were prepared with a capacity of 1
Dissolve in pure water to make liters
Was adjusted.

(3) Fixing start solution (for 1 liter of used solution) Pure water 120 ml Ammonium thiosulfate (70% Na salt: manufactured by Hoechst) 260 g Sodium sulfite 22 g Boric acid 10 g Tartaric acid 3 g Sodium acetate trihydrate 32 g Acetic acid (90% Aqueous solution) 16.5 g Aluminum sulfate / 18-hydrate 18 g Finished to 400 ml using 50% sulfuric acid aqueous solution and pure water. When used, 600 ml of pure water and the above concentrated liquid 40
And 0 ml. The pH at the time of use is 4.7.

(4) Preparation of Fixing Replenishment Tablet <Preparation of Granulation A Parts> (for 1 liter of liquid used) Ammonium thiosulfate 183 g Sodium bisulfite 10 g Sodium acetate 40 g Isoelite P (brine port refined sugar) 5 g Pine flow (trade name) 8g <Preparation of granulation B parts> (1 liter of liquid used) 10 g of boric acid 3 g of tartaric acid 18 g of sodium hydrogen sulfate 18 g of aluminum sulfate 12 hydrate 37 g Pine flow (trade name: manufactured by Matsutani Chemical Co.) 4 g The material of the granulation A part and the material of the granulation B part are mixed in a commercially available bandam mill for 30 minutes, and granulated at room temperature for 10 minutes with a commercially available stirring granulator. The mixture was dried at 40 ° C. for 2 hours to obtain a granulated A part and a granulated B part.

The above A parts and B parts were thoroughly mixed for 10 minutes, and the obtained mixture was used in a machine UD · DFE30 ·
Using a 40 tableting machine (manufactured by Masina Co., Ltd.), 25 tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compressing tablets at a filling amount of 11.0 g per tablet and 1.5 ton / m ² . .

When used, 25 tablets were prepared with a capacity of 1
The solution used was dissolved in water and overflowed with a stabilizing treatment solution so that the volume became 1 liter, and the pH of the working solution was adjusted. The pH at the time of use after dissolution was 4.7.

(5) Stabilization treatment solution (1 liter of working solution) Chelating agent according to the present invention Potassium sulfite shown in Table 1 30 g 8-mercaptoadenine 0.1 g Compound K-1 5 g Citric acid 10 g Used by adding sulfuric acid Adjust the pH to 4.8 and add water to make the total volume 1 liter.

<< Automatic developing machine >> GR-26 manufactured by Konica Corporation
Using the SR washing system modified to a three-stage countercurrent system,
A stabilizing process is performed instead of washing with water, and a stabilizing processing solution overflowing from the processing tank closest to the fixing tank is used for diluting the solid fixing replenisher. Tap water was used as the water short for dilution.

The drying zone of the automatic developing machine has a far-infrared heater and a cover for covering the entire surface of the processing tank so that the processing liquid is difficult to evaporate.

<< Treatment Conditions >> Temperature Time Refill Amount Image 38 ° C. 12 seconds 130 cc / m ² Fixed 38 ° C. 8 seconds 130 cc / m ² Stable 38 ° C. 10 seconds 300 cc / m ² Squeeze 2 seconds Drying 40 10 seconds in total 42 seconds Line speed (conveyance speed) 3300 mm / min In addition, the fixing waste liquid is subjected to silver recovery by using a silver recovery apparatus described in Example 1 of JP-A-6-27623, and the processed liquid is reused. The processing was performed while returning to the fixing tank.

<< Evaluation >> The obtained photosensitive material sample was cut,
Unexposed samples and full-surface exposed samples were alternately and continuously processed 100 m ² one by one so that the blackening ratio of the photosensitive material became 50%.

(Precipitation of Fixing Solution) After the continuous treatment, the precipitation in the fixing tank was visually observed. Assuming that no generation of precipitation was observed as 5, the evaluation was made in five steps according to the degree of turbidity.

(Image preservability) After continuous processing, 3
The sample left for 0 second was processed, stored at 50 ° C. and 80% RH for 2 days, and evaluated by the decrease in the maximum concentration.

(Residual color) After continuous processing, the sample exposed in the same manner as described above was treated with an automatic processor at a line speed of 4620 mm.
/ Min, the total processing time is 30 seconds,
After storing at 80% RH for 1 hour, the color was visually observed. Assuming that there was no coloring at 5, the evaluation was made in five steps according to the degree of coloring.

Table 1 shows the above results.

[0176]

[Table 1]

Example 2 Evaluation was carried out in the same manner as in Example 1 except that the quaternary onium compound in the composition of the silver halide emulsion layer 1 was changed to P-27 and the composition of the stabilizing solution was as described below.

Gelatin hardener according to the present invention Potassium sulfite shown in Table 2 20 g 8-mercaptoadenine 0.1 g Compound K-1 5 g Malic acid 10 g Sulfuric acid was added to adjust the pH at the time of use to 5.2, and water was added. Use the whole volume in 1 liter.

Table 2 shows the results.

[0180]

[Table 2]

<< Preparation of Silver Halide Photographic Material Sample for Turning Back Light Room >> Monodispersion having a silver chloride content of 99 mol% and a silver bromide content of 1 mol% having an average particle size of 0.15 μm by a double jet method. And cubic silver chlorobromide particles were prepared. K ₃ when mixing
Rh (H ₂ O) Br ₅ was added in an amount of 7 × 10 ⁻⁵ mol per mol of silver. Prior to the desalting step of removing soluble salts by a conventional method, 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene (TAI) at 0.6 / mol silver
g (hereinafter referred to as an amount per mole of silver unless otherwise specified).

The temperature of this emulsion was raised to 60 ° C.
mg and 0.75 mg of sodium thiosulfate were added.
60 minutes after adding I, 600 mg of TAI was further added and the temperature was lowered and set.

Then, a coating solution was prepared by adding an additive so as to be in the following amount per 1 m ^{2, and the} following emulsion layer coating solution and protective solution were sequentially coated on one surface of the subbed SPS support of Example 1. The lower layer liquid was simultaneously coated with the following backing coating liquid on the opposite surface.

[0184] <Emulsion Coating Solution> NaOH0.5N solution 4.39 ml / m ² Compound i 6.53mg / m ² 4 quaternary onium compound: T-7 30mg / m ² Quillaja saponin 107 mg / m ² Compound B 18.5 mg / m ² compound c 9.8 mg / m ² of gelatin latex 480 mg / m ² sodium polystyrenesulfonate 52.2 mg / m ² colloidal silica 20 mg / m ² <protective layer infranate> gelatin 0.5 g / m ² dye two solid dispersion body (average particle size 0.1μm) 62.0mg / m ² citric acid 4.1 mg / m ² formalin 1.2 mg / m ² hardener: K-1 0.6mg / m ² sodium polystyrene sulfonate 11.0mg / m ² <upper protective layer solution> gelatin 0.3 g / m ² compound e 18.0 mg / m ² dye d 48.4 mg / m ² compound f 105.0 g / m ² Compound DOO 1.25 mg / m ² amorphous silica (average particle size 1.63μm) 15.0mg / m ² amorphous silica (average particle size 3.5μm) 21.0mg / m ² Citric acid 4. 5 mg / m ² sodium polystyrenesulfonate 11.0 mg / ^{m 2} inline added hardener les 10 mg / m
² <Backing Coating Solution> compound Chi 170 mg / m ² Dye D 30 mg / m ² Compound Li 45 mg / m ² Compound j 10 mg / m ² Quillaja saponin 111 mg / m ² Compound le 200 mg / m ² Colloidal silica 200 mg / m ² Compound O 35 mg / m ² compound follower 31 mg / m ² compound Ca 3.1 mg / m ² of polymethyl methacrylate acid polymer (average particle size 5.6μm) 28.9mg / m ² glyoxal 10.1 mg / m ² citric acid 9.3mg / m ² of sodium polystyrenesulfonate 71.1 mg / m ² additive compound the following in-line Yo 81 mg / m ² compound data 88.2Mg / m ² of calcium acetate 3.0 mg / m ² hardener: K-1 10 mg / M ²

[0185]

Embedded image

[0186]

Embedded image

[0187]

Embedded image

The coating amount was 2.0 g / silver in the emulsion layer.
gelatin amount 1.2 g / m ² m ^{2, and} the amount of gelatin backing layer is uniformly coated so as to be 2.1 g / m ^2.

<< Preparation of Processing Agent >> (6) Preparation of Developing Tablet <Preparation of Granulation A Parts> (for 1 liter of liquid used) Biodegradable chelating agent: Ch 8 g Potassium carbonate 33 g D-mannitol (trade name: Kaosha) 5 g <Preparation of granulation B parts> (for 1 liter of liquid used) Sodium sulfite 16 g Potassium bromide 2.5 g Potassium hydrogen carbonate 65 g 8-mercaptoadenine 0.15 g 5-methylbenzotriazole 0.5 g 1-phenyl- 5-mercaptotetrazole 0.02 g Dimezone S 2.7 g Sodium erythorbate 70 g D-sorbitol 5 g 1-sodium octanesulfonate 2 g pH 9.7 when used as a working solution The above materials for parts A and B were respectively used. Mix in a commercially available bandam mill for 30 minutes, and then use a commercially available stirring granulator. After granulating for 10 minutes at temperature, 40 ° C. The granulation in a fluidized bath dryer, and dried for 2 hours to obtain a granulated A part and granulation B part.

The above parts A and B are thoroughly mixed for 10 minutes, and the resulting mixture is extracted from a machine UDN DFE30.
Using a 40 tableting machine (manufactured by Masina Co., Ltd.), 10 tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² with a filling amount of 21.0 g per tablet.

The starting solution was prepared by dissolving 10 tablets in pure water so as to have a volume of 1 liter and adjusting the pH.

(7) Fixing Processing was carried out using the same one as in Example 1.

(8) Stabilization treatment solution (1 liter of use solution) Compound represented by general formula (1) according to the present invention Potassium sulfite 20 g shown in Table 3 Compound K-1 5 g Citric acid 10 g Add sulfuric acid Adjust the pH at the time of use to 5.1, add water to make the total volume 1 liter, and use.

<< Evaluation >> Development was performed in the same manner as in Example 1, and the evaluation was performed. Table 3 shows the results.

[0195]

[Table 3]

Example 4 A quaternary onium compound having a silver halide emulsion layer 1 composition was prepared using T-
The development processing was carried out in the same manner as in Example 3 except that the stabilizing processing solution was changed to the following composition in place of 6, and evaluated.

(9) Stabilizing solution (for 1 liter of used solution) Antifungal agent according to the present invention Potassium sulfite shown in Table 4 20 g 8-mercaptoadenine 0.1 g Compound K-1 5 g Malic acid 15 g Add sulfuric acid Adjust the pH to 4.9 when used, add water to make the total volume 1 liter, and use.

The results are shown in Table 4.

[0199]

[Table 4]

[0200]

According to the present invention, even if the fixing solution contains a water-soluble aluminum salt as a hardener, it does not cause the problems of precipitation in the fixing solution, deterioration of image storability and residual color. ,
It is possible to reduce the amount of replenishment.

Claims (6)

[Claims] When a black-and-white silver halide photographic material is treated with a stabilizing processing solution after being treated with a fixing solution containing a water-soluble aluminum salt, part or all of the overflow of the stabilizing processing solution is converted into a fixing replenisher. use, and characterized in that supplemented with the following photosensitive material 1 m ² per 260cc processed the fixing replenisher, and chelate stability constant stabilization treatment liquid for ferric ion containing 8 or more chelating agents For processing black-and-white silver halide photographic light-sensitive materials. 2. When a black-and-white silver halide photographic material is treated with a stabilizing processing solution after being processed with a fixing solution containing a water-soluble aluminum salt, part or all of the overflow of the stabilizing processing solution is converted into a fixing replenisher. A black-and-white silver halide photographic light-sensitive material wherein the fixing replenisher is replenished at a rate of 260 cc or less per m ^{2 of the} light-sensitive material to be processed, and the stabilizing processing solution is a processing solution having antifungal properties. Material treatment method. 3. When a black-and-white silver halide photographic light-sensitive material is processed with a stabilizing processing solution after being processed with a fixing solution containing a water-soluble aluminum salt, part or all of the overflow of the stabilizing processing solution is converted into a fixing replenisher. A black-and-white silver halide wherein the fixing replenisher is replenished at a rate of 260 cc or less per m ^{2 of the} light-sensitive material to be processed, and the stabilized processing solution contains a compound represented by the general formula (1). Processing method of photographic photosensitive material. General formula (1) Z-SM [wherein Z is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, a —SO ₃ M ₁ group, a —COOM
_At least one group selected from the group consisting of _one group (where M ₁ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, or a substituted or unsubstituted ammonium group Or
It represents those substituted with at least one substituent selected from this group. M represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate). ] 4. When a black-and-white silver halide photographic material is treated with a stabilizing processing solution after being processed with a fixing solution containing a water-soluble aluminum salt, part or all of the overflow of the stabilizing processing solution is converted into a fixing replenisher. A method for processing a black-and-white silver halide photographic light-sensitive material, wherein the fixing replenisher is replenished at a rate of 260 cc or less per m ^{2 of the} light-sensitive material to be processed, and the stabilizing processing solution contains a gelatin hardener. 5. The fixing replenisher used in the preparation of the fixing replenisher is a solid processing agent.
3. The method for processing a black-and-white silver halide photographic material according to 3 or 4. 6. The method for processing a black-and-white silver halide photographic material according to claim 1, wherein the photographic material to be processed contains a quaternary onium compound.