JP2000292891A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method a silver halide photographic sensitive material by which the dot quality of a processed film is not deteriorated even is water-waving processing is carried out by incorporating 2-(p-hydroxyphenyl) glyoxylohydroxymoyl chloride and a specified compound into a fixing solution or the like. SOLUTION: A silver halide photographic sensitive material is developed, fixed and washed or stabilized using an automatic processing machine. At this time, a fixing solution or a washing or stabilizing solution used contains 2-(p-hydroxyphenyl)glyoxylohydroxymoyl chloride and at least one compound selected out of the group comprising 4,5-dichloro-2-n-octylisothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, α-chlorobenzaldoxime acetate, 5-chloro-2,4,6-trifluoroisophthalonitrile, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material which enables water saving processing.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter also referred to as a "light-sensitive material") used in the field of printing and plate making is subjected to processes such as development, desilvering, washing with water and stabilization after exposure. Processing is usually performed in an automatic processor, and a method is generally used in which a replenisher is replenished to maintain the activity of the processing solution at a constant level, to dilute the eluate from the photosensitive material, correct the amount of evaporation, and replenish the consumed components. Widely used. In the water washing step, ordinary tap water is usually supplied to wash out and remove the fixing components remaining inside the processed photosensitive material.

[0003] Since a large amount of washing water is used, there is a problem that scale is generated in the washing water when water is to be saved. To prevent such scaling, a filter is removed or a disinfectant is added. Is not enough.

There is also a need for a rinse system that can save water. The waste liquid of the rinsing liquid is used as dilution water of the fixing liquid, and has an advantage of reducing the waste liquid. However, there is a problem that the treated film is discolored with time. .

On the other hand, in order to improve the working environment, the odor may be reduced by increasing the pH of the fixing solution. However, in order to increase the pH of the fixing solution, it is necessary to remove the water-soluble aluminum salt from the fixing solution. Yes, the dot quality of the processed film is degraded. It is known that ascorbic acids can be used as a developing agent to improve this.
There is a problem that the sensitivity and the maximum density decrease.

[0006]

With the recent rise in environmental awareness, there is a demand for reducing the amount of waste liquid even in processing using an automatic developing machine for photosensitive materials. In order to reduce the amount of waste liquid, it is necessary to reduce the replenishment amount of the processing solution.However, especially when the replenishment amount of the fixing solution is reduced, the fixing solution becomes contaminated with gelatin or other eluted substances from the photosensitive material, and these are washed with water. Or it is brought into a stabilization tank, and there is a problem that bacteria are propagated and scale is generated.

[0007] In addition, there is a serious problem that dirt adheres to the crossover roller, and the resulting deposits deteriorate the halftone dot quality of the treated film and cause dry roller dirt.

Accordingly, it is a first object of the present invention to provide a washing or stabilizing tank which does not produce dirt or scale even when a water saving treatment is performed, thereby deteriorating the halftone dot quality of the treated film, or making the drying roller dirty. It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material in which no silver halide occurs.

On the other hand, due to the rapid processing that has become mainstream in recent years, carry-over from the washing tank increases, and the drying property of the film is remarkably deteriorated. became. In addition, ascorbic acid-based developers that are advantageous for rapid processing are liable to undergo oxidative deterioration, so there is a difficulty in reducing replenishment. When a high-pH fixing solution is used, there is a problem that a processed film is stained with blue.

Accordingly, a second object of the present invention is to improve the water-saving and working environment, to obtain an image having excellent halftone dot quality and maximum density even after rapid processing, to reduce drying property and to reduce the quality of a processed film. An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which does not cause blue stains.

[0011]

A first object of the present invention is to develop, fix, wash or stabilize a silver halide photographic light-sensitive material using an automatic developing machine. The chemical solution contains 2- (p-hydroxyphenyl) glyoxylohydroxymoyl chloride and at least one selected from the following compound group: (compound group) 4,5-dichloro-2-n-octylisothiazoline-
3-one 1,2-benzisothiazolin-3-one 2-bromo-2-nitropropane-1,3-diol α-chlorobenzaldoxime acetate 5-chloro-2,4,6-trifluoroisophthalonitrile o -Phthaldehyde 5-chloro-2-methyl-4-isothiazolin-3-one In developing, fixing, washing or stabilizing a silver halide photographic light-sensitive material using an automatic developing machine, a fixing solution or washing or stabilization. The developing solution contains 2-n-octyl-4-isothiazolin-3-one and polyhexamethylene biguanidine hydrochloride, and the silver halide photographic material is developed, fixed, washed or stabilized using an automatic developing machine. In processing, the fixing solution or the washing or stabilizing solution is at least selected from sucrose fatty acid ester and sodium dehydroacetate. And at least one of which contains 0.0003 to 0.3% by weight of hydrogen peroxide in a washing or stabilizing solution, and contains 2 to 35% by weight of hydrogen peroxide. This can be achieved by supplying a kit concentrate of a chemical solution using a kit concentrate, directly charging the kit concentrate in a washing or stabilizing tank, and washing the inside of the washing tank with water or a stabilizing solution after the treatment. .

A second object of the present invention is to provide a washing or stabilizing tank for a silver halide photographic material.
When developing, fixing, washing or stabilizing using the automatic developing machine having the above, the compound represented by the general formula (1) and the compound represented by the general formula (2) substantially containing no dihydroxybenzene-based compound are used. Washing or stabilizing treatment is carried out by a multi-stage AC method using a developer containing the compound to be treated, and the treating solution used for the treatment contains a propylene glycol compound or an ethylene glycol compound, and the sulfite ion concentration is 0. A fixing solution containing 15 mol / L or more and containing substantially no aluminum is used, and the surface tension of the processing solution used for washing or stabilizing treatment is 8 to 78 dyn / c.
m, and the photosensitive material to be processed is represented by the general formula (3)
Wherein the film has a film swelling degree of 100 to 25 upon development, fixing, washing with water or stabilization treatment.
0%, and wash the silver halide photographic material with water or stabilize
When developing, fixing, washing or stabilizing using the automatic developing machine having the above, the compound represented by the general formula (1) and the compound represented by the general formula (2) substantially containing no dihydroxybenzene-based compound are used. This is achieved by using a developing solution containing the compound to be prepared, adding a recovery / regenerating solution for overflow of the developing solution to a replenishing solution, and performing washing or stabilizing treatment in a multi-stage AC system.

Hereinafter, the present invention will be described in detail.

The invention according to the above has found an effective combination of a bactericide to be added to a fixing solution or a washing or stabilizing solution. That is, a bactericide group-a 2- (p-hydroxyphenyl) glyoxylohydroxymoyl chloride-b 4,5-dichloro-2-n-octylisothiazolin-3-one-c1,2-benzoisothiazolin-3-one -D 2-bromo-2-nitropropane-1,3-diol -e α-chlorobenzaldoxime acetate -f 5-chloro-2,4,6-trifluoroisophthalonitrile -go-phthalaldehyde -h 5-chloro-2-methyl-4-isothiazolin-3-one-1 2-n-octyl-4-isothiazoline-3-
In the -2 polyhexamethylene biguanidine hydrochloride, the effect is thin when used alone, -a is a fungicide selected from -b to -h, -1 is a fungicide of -2, The synergistic effect of using each of them together has the effect of increasing bactericidal power and improving photographic performance. The bactericide selected from -b to -h with respect to -a is -a: -b to -h = 9 by weight ratio.
It is preferably used in a ratio of 0:10 to 30:70.
Particularly preferred in the latter are -e and -g. Further, -1: -2 is used in a weight ratio of 20: 1 to 1:20, preferably 5: 1 to 1: 5.

According to the invention described above, at least one selected from sucrose fatty acid esters and sodium dehydroacetate is added to a fixing solution or a washing or stabilizing solution.

Examples of the sucrose fatty acid ester include, but are not limited to, -a sucrose acetate ester -b sucrose propionate ester -c sucrose laurate ester -d sucrose stearate ester -e sucrose linoleate.

These sucrose fatty acid esters and sodium dehydroacetate also function as fungicides. Their content is about 0.001 to 100 g / L, preferably 0.01 to 50 g / L, and more preferably 0.1 to 30 g / L.

The fixer preferably also contains a bactericide to prevent the growth of bacteria in the washing or stabilizing bath.

When the fixing solution or the replenisher of the stabilizing solution is prepared using a solid processing agent, a non-liquid germicide may be employed, or the solid processing agent may be washed with a germicide or a waste solution of the stabilizing solution. Or disinfectant is added separately.

When these disinfectants are used, it is more preferable that the washing or stabilizing solution contains 0.0003 to 0.3% by weight of hydrogen peroxide. Thus, scale can be effectively prevented without inducing generation of silver sludge. Specifically, hydrogen peroxide is added to the concentrated solution of the stabilizing solution in a concentration of 2 to 35% by weight.
It is preferable to add the kit concentrate directly to a washing or stabilizing tank.

In this case, it is preferable to provide a supply means for automatically supplying hydrogen peroxide to the washing or stabilizing tank of the automatic developing machine for processing the photosensitive material, based on the photosensitive material processing area information. Hydrogen peroxide is added to decompose hypos introduced into the washing or stabilization tanks.However, when the concentration of contaminants reaches a certain level due to accumulation of eluting components from the photosensitive material, water must be replaced. It has 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 the specification is such that hydrogen peroxide is sent when a certain concentration of contamination, that is, a certain treatment area is reached. Is preferred.

It is also effective to wash the inside of the washing or stabilizing tank with water or a stabilizing solution after the treatment is completed.

The stabilizing solution may contain the following chelating agent. That is, ethylenediamine orthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilo3
Acetic acid, hydroxyethylethylenediamine triacetic acid, dihydroxyethylglycine, ethylenediamine diacetic acid, ethylenediamine dipropionic acid, imino diacetic acid, diethylene triamine pentaacetic acid, hydroxyethyl imino diacetic acid, 1,3-diaminopropanol tetraacetic acid, triethylene tetramine hexaacetic acid, Transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphono -2-carboxylic acid, 2-phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,3,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. And particularly preferably diethylenetriamine 5
Acetic acid, triethylenetetramine hexaacetic acid, 1,3-diaminopropanol tetraacetic acid, glycol ether diamine 4
Acetic acid, hydroxyethylethylenediamine triacetic acid, 2-
Phosphonobutane-1,2,4-tricarboxylic acid, 1,1
-Diphosphono-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof.

The invention according to the present invention relates to a water-saving system in which washing or stabilizing treatment is carried out by a multi-stage AC system, which contains substantially no dihydroxybenzene-based compound and which is represented by the general formula (1) and the general formula (2) ), Wherein a propylene glycol-based compound or an ethylene glycol-based compound is contained in a processing solution used for washing or stabilizing treatment.

In the compound represented by formula (1), it is preferable to use a developing agent represented by formula (1-a) in which R ₁₁ and R ₁₂ are bonded to each other to form a ring.

[0026]

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In the general formula (1-a), R ₁₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an amino group, an alkoxy group, or a sulfo group, a carboxyl group, an amide group or a sulfonamide group. Y ₁₁ represents O or S, and Y ₁₂ represents O, S or NR ₁₄ . R ₁₄ represents a substituted or unsubstituted alkyl group or aryl group.

The general formula (1) or the general formula (1-a)
Specific examples of preferred compounds represented by are shown below, but are not limited thereto.

[0029]

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[0030]

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[0031]

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[0032]

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These compounds are typically ascorbic acid or erythorbic acid and their derivatives,
It is available as a commercial product or can be easily synthesized by a known synthesis method.

The compounds represented by the general formula (2) are typically phenidones and aminophenols. Examples of phenidones include 1-phenyl-3-pyrazolidones. Examples of the compound represented by the general formula (2) are shown below. However, the present invention is not limited to these.

2-a 1-phenyl-3-pyrazolidone (phenidone) 2-b 1-phenyl-4-methyl-3-pyrazolidone 2-c 1-phenyl-4-dimethyl-3-pyrazolidone 2-d 1-phenyl -5-methyl-3-pyrazolidone 2-e 1-phenyl-4-methyl-4'hydroxymethyl-3-pyrazolidone 2-f 1-phenyl-4,4-dihydroxymethyl-
Methyl-3-pyrazolidone 2-g 1-phenyl-4,4-di-n-propyl-3
-Pyrazolidone 2-h 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone 2-io-aminophenol 2-j p-aminophenol 2-k N-methyl-o-aminophenol 2-l N-methyl-p-aminophenol (methol) 2-m 2.4-diaminophenol 2-n M-methyl-p-aminophenol 2-o N- (β-hydroxyethyl) -p-aminophenol 2-p N- (4-hydroxyphenyl) glycine 2-q 2-methyl-p-aminophenol 2-rp-benzylaminophenol These compounds are used in an amount of about 0.01 to 50 g, preferably 0.01 to 20 g, per liter of the developer. , More preferably 0.
Use between 03 and 15 g.

In the present invention, a sulfite such as sodium sulfite, potassium sulfite, ammonium sulfite or sodium metabisulfite, or metabisulfite may be used as a preservative in the developer. The sulfite is used in an amount of 0.25 mol / L or more, particularly preferably 0.4 mol / L or more.

It is preferable that an alkali agent (such as sodium hydroxide or potassium hydroxide) and a pH buffer (such as carbonate or alkanolamine) are added to the developer. As the pH buffering agent, carbonate is preferable, and the amount of addition is preferably 0.25 to 2.5 mol, more preferably 0.40 to 1.5 mol per liter.

If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.),
Surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (Eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and a development accelerator (eg, US Pat. No. 2,30)
No. 4,025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent can be added.

The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, pH8.
5 or more and 10.4 or less.

The developing waste liquid can be regenerated by energizing.

Since the developer to be regenerated contains materials eluted from the photosensitive material by the processing, it is necessary to remove these first. Specifically, the overflow liquid as waste liquid is passed through a commercially available filter to remove silver sludge, dirt, dust and the like.

A cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in the waste developing solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum and titanium) is placed in the electrolyte solution. The developing waste liquid tank and the electrolyte solution tank are brought into contact with each other through an ion exchange resin (anion exchange resin), and both electrodes are energized for regeneration. The ion-exchanged developing waste liquid is used by being mixed with a new developing replenisher.

The photosensitive material can be processed while energizing. At that time, various additives added to the developer, for example, a preservative that can be added to the developer, an alkali agent,
A pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor and the like can be additionally added. 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.

Specific examples of the propylene glycol compound or ethylene glycol compound include polypropylene glycol, dipropylene glycol, propylene glycol, polyethylene glycol, diethylene glycol, ethylene glycol and the like. The molecular weight is not particularly limited, but those having good water solubility are preferred. As those having different molecular weights, polyethylene glycol (PEG # 4000, PE
G # 6000 and PEG # 400... # Indicate the molecular weight).

These compounds are used in an amount of 0.1 to 1 L of the processing solution.
The amount is about 01 to 100 g, preferably 0.01 to 50 g, and more preferably 0.03 g to 15 g.

The surface tension of the treatment solution containing a propylene glycol compound or an ethylene glycol compound is 8
It is preferably from 78 dyn / cm, more preferably from 8 to 60 dyn / cm. Here, it is assumed that the surface tension is obtained by using a Cenco tension system (manufactured by Central Scientific) attached to a glass plate with which a liquid is brought into contact.

In the invention according to the invention, it is preferable to use a fixing solution having a sulfite ion concentration of 0.15 mol / L or more and containing substantially no aluminum.

The fixing solution is an aqueous solution containing a thiosulfate such as sodium thiosulfate and ammonium thiosulfate as a fixing agent, and the pH of the fixing initiating solution is 4.0 or more, preferably 4.2 to 5.5. Preferably, 4.6 to 5.3
It is. As the thiosulfate, sodium thiosulfate is particularly preferred for the purpose of preventing generation of odor. The amount of the fixing agent to be used can be appropriately changed, and is generally 0.1 to about 6 mol / L.

The fixing solution contains a preservative (for example, sulfite,
Bisulfite), a pH adjuster (eg, sulfuric acid, sodium hydroxide), a chelating agent having a curing softening agent,
-78551.

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.

In the invention according to the invention, the effect is particularly exhibited when the photosensitive material to be processed contains the hydrazine compound represented by the general formula (3). Also, development,
It is preferable that the film swelling degree of the photosensitive material at the time of fixing, washing or stabilizing treatment is 100 to 250%.

In the general formula (3), the aliphatic group represented by A preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
To 20 linear, branched or cyclic alkyl groups, such as methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group, and benzyl group. For example, it may be substituted with an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfoxy group, a sulfonamide group, an acylamino group, a ureido group, and the like. The aromatic group represented by A is preferably a monocyclic or condensed-ring aryl group, and examples thereof include a benzene ring and a naphthalene ring. As the heterocyclic group represented by A, a monocyclic or condensed ring, preferably containing at least a heteroatom selected from nitrogen, sulfur and oxygen, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, Examples include a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, and a furan ring. A is particularly preferably an aryl group or a heterocyclic group, which may have a substituent. Representative substituents in this case are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or condensed ring having an alkyl moiety having 1 to 3 carbon atoms), an alkoxy group (Preferably those having 1 to 20 carbon atoms in the alkyl portion), substituted amino groups (preferably substituted with an alkyl group or alkylidene group having 1 to 20 carbon atoms), and acylamino groups (preferably having 1 to 40 carbon atoms). ), A sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having 1 to 40 carbon atoms), a hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms),
Hydroxyl group, sulfoamide group (preferably having 1 carbon atom)
To 40). A preferably contains at least one diffusion-resistant group or silver halide adsorption promoting group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and as the ballast group, an alkyl group or an alkenyl group which is relatively inert to photographic properties having 8 or more carbon atoms, Examples thereof include an alkoxy group, a phenyl group, a phenoxy group, and an alkylphenoxy group. Examples of the silver halide adsorption accelerating group include thiourea, thiourethane, mercapto, thioether, thione, heterocyclic, thioamide heterocyclic, mercapto heterocyclic, and those described in JP-A-64-90439. Adsorbing groups and the like can be mentioned.

B is an acyl group (formyl, acetyl, propionyl, trifluoroacetyl, methoxyacetyl, phenoxyacetyl, methylthioacetyl,
Chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl, etc.), alkylsulfonyl group (methanesulfonyl group, 2-chloroethanesulfonyl group, etc.), arylsulfonyl group (benzenesulfonyl group, etc.), alkylsulfinyl group (Such as methanesulfinyl group), arylsulfinyl group (such as benzenesulfinyl group), carbamoyl group (such as methylcarbamoyl group and phenylcarbamoyl group), alkoxycarbonyl group (such as methoxycarbonyl group and methoxyethoxycarbonyl group), and aryloxycarbonyl group (such as Phenoxycarbonyl group, etc.), sulfamoyl group (dimethylsulfamoyl group, etc.), alkoxysulfonyl group (methoxysulfonyl group, etc.), thioacyl group (methylthiocarbonyl group), thiocal Sulfamoyl group (such as methyl thio carbamoyl group), represents a oxalyl group or a Hajime Tamaki (pyridine ring, pyridinium ring, etc.). B together with A ₂ and the nitrogen atom to which they are attached

[0054]

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May be formed. R ₉ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. As B, an acyl group or an oxalyl group is particularly preferred.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.), a sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.) or Represents an oxalyl group (such as an ethoxyl group).

Particularly preferred among the hydrazine compounds according to the present invention are represented by the following general formula (4).

[0058]

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Here, R ₄₁ represents an aryl group or a heterocyclic group, and R ₄₂ is

[0060]

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Represents the following. R ₄₃ and R ₄₄ each represent a hydrogen atom, an alkyl group (methyl group, ethyl group, benzyl group, etc.), an alkenyl group (allyl group, butenyl group, etc.), an alkynyl group (propargyl group, butynyl group, etc.), an aryl group (phenyl, Group, naphthyl group, etc.), heterocyclic group (2,2,6,6,-
Tetramethylpiperidinyl, N-benzylpiperidinyl, quinolidinyl, N, N'-diethylpyrazolinyl,
N-benzylpyrrolidinyl, pyridyl, etc.), amino group (amino group, methylamino group, dimethylamino group, dibenzylamino group, etc.), hydroxyl group, alkoxy group (methoxy group, ethoxy group, etc.), alkenyloxy group ( Allyloxy group, etc.), alkynyloxy group (propargyloxy group, etc.), aryloxy group (phenoxy group)
Or a heterocyclic oxy group (pyridyloxy group);
₄₃ and R ₄₄ may form a ring (piperidine, morpholine, etc.) together with the N atom. R ₄₅ is a hydrogen atom, an alkyl group (methyl group, ethyl group, methoxyethyl group, hydroxyethyl group), an alkenyl group (allyl group, butenyl group),
Alkynyl group (propargyl group, butynyl group), aryl group (phenyl group, naphthyl group) or heterocyclic group (2,
2,6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl, etc.). A ₁ and A ₂ have the same meanings as those in formula (3).

In formula (4), the aryl group represented by R ₄₁ is preferably a monocyclic or condensed ring.
Examples thereof include a benzene ring and a naphthalene ring. As the heterocyclic group represented by R ₄₁ , a 5- or 6-membered unsaturated heterocyclic ring containing at least a heteroatom selected from nitrogen, sulfur and oxygen in a single ring or a condensed ring is preferable, and a pyridine ring, a quinoline ring and a pyrimidine are preferable. Ring, thiophene ring, furan ring, thiazole ring or benzothiazole ring. R ₄₁
Is a substituted or unsubstituted aryl group, and examples of the substituent include those having the same meaning as the substituent of A in the general formula (3). It is preferable to have Most preferably, both A ₁ and A ₂ are hydrogen atoms.

Specific examples of the hydrazine compound represented by the general formula (4) are shown below, but it should not be construed that the invention is limited thereto. Another example is described in, for example, JP-A-5-241264.

[0064]

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It is preferable to use a nucleation accelerator as exemplified below in combination with the above hydrazine compound.

[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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In the present invention, the degree of swelling of the light-sensitive material is determined by measuring the thickness (swelled film thickness) of the emulsion layer at the time when the light-sensitive material is immersed in a developer adjusted to 35 ° C. Divided by the value of the dry film thickness to obtain 1
The value is multiplied by 00. The thickness of the photosensitive material is measured by observing the cross section of the photosensitive material with a microscope capable of measuring in water. A preferred value of the degree of swelling is from 100 to 250%, more preferably from 150 to 220%.

The invention according to the present invention uses a developing solution containing substantially no dihydroxybenzene compound and containing the compound represented by the general formula (1) and the compound represented by the general formula (2). The recovery / regeneration solution of the overflow of the developing solution is used in addition to the replenishing solution, and the washing or stabilizing treatment is performed in a multi-stage AC system. The individual techniques are as described above.

The treating agent used in the present invention may be supplied in any form such as a powder, a paste, a granule, a tablet, a concentrated solution, and a working 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.

The solid processing agent is composed of two components constituting the processing solution.
One or more types are preferable, and a single solid containing all the components of the processing liquid or a solid that can constitute the components of the processing liquid by two or more types may be used. As a method of preparing a solid processing agent, a method of adding water, granulating and then drying to obtain granules, and a method of granulating with a small amount of water, or adding water at all. Without directly drying step. 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 a raw material is directly compression-molded without performing granulation to form a granular solid processing agent. As the granulation means, there is a method using a generally used stirring granulator or Henschel mixer.

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 solution and the fixing mother solution. 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.

The replenishing amount of the silver halide of 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:
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) Tetrazolium compound JP-A-6-208188, page (8), paragraph "0059"
To page (10), paragraph "0067" 7) Pyridinium compounds JP-A-7-110556, page (5), paragraph "0028"
8) Redox compounds JP-A-4-245243, 235 (7) to 250
(22) 9) 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).

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

As the automatic developing machine, 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".

In the present invention, two or more stabilizing tanks are provided in principle, and a multistage countercurrent system is used as a means for reducing the amount of replenisher for washing water. If this multi-stage countercurrent method is used, the photosensitive material after fixing is gradually contacted in a clean direction, that is, a processing solution which is not contaminated with the fixing solution, and is processed, so that efficient water washing is performed.

[0088]

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

Example 1 <Preparation of silver halide photographic light-sensitive material for printing plate making scanner for He-Ne laser light source> (Preparation of silver halide emulsion A) 70 mol% of silver chloride was obtained by a double jet method, and the rest was odor. Average thickness of silver halide 0.05
μm, silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. At the time of mixing the core particles, 8 × 10 ⁻⁸ mol of K ₃ 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 the redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C. After desalting, the EAg of this emulsion was 50 ° C.
Was 190 mv.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a7-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, the EAg was adjusted to 123 mv, and sodium P-toluenethiosulfonate was adjusted to 1 × 10 ^−3.
After the addition of mol, chloramine T was added at 350 m per mol of silver.
g, 0.6 mg of inorganic sulfur (S ₈ ) and 6 mg of trichloroaurate were added, and chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained.

After 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 simultaneous mixing method, 60 mol% of silver chloride and 2.5 mol% of silver iodide, and the balance was made 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 resulting emulsion was a core / shell monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% silver chloride, 0.5 mol% silver iodide) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. , The remainder being silver bromide). Then, JP-A-2-280139
No. 287 (3), modified gelatin G-8 (in which the amino group in gelatin is substituted with phenylcarbamyl)
It was desalted using. EAg after desalting is 190 mv at 50 ° C.
Met.

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. 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-1,3,3a, 7-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 support, the following formulation 1
Gelatin undercoat layer, a silver halide emulsion layer 1-1 of formula 2-1 thereon, an intermediate protective layer thereon having the following formula 3, and a silver halide emulsion layer 2 of formula 4-1 further thereon. -1, Further, the respective coating liquids of the emulsion protective layer of the following formula 5 are coated simultaneously and in layers, the backing layer of the following formula 6 on the opposite undercoat layer, the hydrophobic polymer layer of the following formula 7 thereon, Sample 1 was obtained by simultaneously applying the respective coating solutions of the backing protective layer having the following formula 8 on the emulsion layer side. Sample 2 was obtained by formulating 1-2 in place of the silver halide emulsion layer 1-1 and 2-2 in place of the silver halide emulsion layer 2-1.

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 Formulation 2-1 (Composition of silver halide emulsion layer 1-1) Silver halide emulsion A Silver amount becomes 1.5 g / m ² Gelatin amount 0.5 g / m ² Solid dispersed fine particles 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 compound 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 Polymer f 0.5 g / m ² hardener ^{g 5mg / m 2 S-1} 0.7mg / m 2 2- mercapto-6-hydroxy purine ^{5mg / m 2 EDTA 30mg / m} 2 Colloidal silica (average particle diameter 0. 05 μm) 10 mg / m ² Formula 2-2 (Composition of silver halide emulsion layer 1-2) Formula 2-1 in which the hydrazine compound is changed to that shown in Table 2.

Formula 3 (intermediate layer composition) Gelatin 0.3 g / m ² S-1 2 mg / m ² Formula 4-1 (silver halide emulsion layer 2-1 composition) Silver halide emulsion B Silver content 1.4 g / ² sensitized gelatin 0.4 g / m so that m ² dye d-1 6 mg / m ² hydrazine derivative HY-2 20 mg / m ² nucleation accelerator AM-1 40 mg / m ² redox compound RE-1 20 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 20 mg / m ² latex polymer f 0.5 g / m ² S-1 1.7 mg / m ² Formula 4-2 (silver halide emulsion layer 2-2) Composition) A composition obtained by changing the hydrazine compound in Formula 4-1 to the composition shown in Table 2.

Formulation 5 (Emulsion protective layer composition) Gelatin 0.6 g / 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: average particle size 3 0.5 μm monodisperse silica 25 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² surfactant h 1 mg / m ² colloidal silica (average particle size 0.05 μm) 10 mg / m ² hardener j 30 mg / m ² Prescription 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 polystyrene sulfone sodium 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 polymethylmethacrylate 50 mg / m ² Sodium an average particle diameter of 5 [mu] m - 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 used solution)
Min) >> (Pretreatment of material) Sodium erythorbate and hydroquinone were each added to MIKRO- manufactured by Hosokawa Micron Corporation.
Pulverizer AP-B crusher, mesh 8
mm, and crushed at a rotation speed of 25 Hz. 8-Mercaptoadenine was meshed with the above-mentioned pulverizer at a mesh of 8 mm and a rotation speed of 50.
Milled at Hz. KBr was crushed with the same crusher at a mesh of 8 mm and 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.

Mixture-1 Sodium Erythorbate (Pulverized Material) 163 kg Dimezone S 3.5 kg 8-Mercaptoadenine (Pulverized Material) 0.3 kg Diethylenetriaminepentaacetic acid 11 kg KBr (Pulverized Material) 6.5 kg Sorbitol 5 kg Mixture-2 In the mixture-1, 65 kg of hydroquinone (the above-mentioned pulverized product) was used in place of sodium erythorbate.

Mixture-3 Sodium Erythorbate (Pulverized Material) 163 kg Compound represented by Formula (2) 8-mercaptoadenine (Pulverized Product) 0.3 kg Diethylenetriaminepentaacetic acid 11 kg KBr (Pulverized material) 6.5 kg Sorbitol 5 kg Mixture-4 In mixture-3, 65 kg of hydroquinone (the above-mentioned pulverized material) instead of sodium erythorbate and 3.5 kg of dimazone S instead of the compound represented by the general formula (2)
Was used.

When the obtained mixture was sampled at 50 g points from arbitrary points (5 places) and analyzed, it was found that the concentration of each component was within ± 5% of the above prescribed value and was sufficiently uniform. Had been mixed.

(Molding) Using a compression granulator Briquetter BSS-IV manufactured by Shinto Kogyo Co., Ltd., each of the above mixtures 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. The obtained granules are each designated as DA.

(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 78 g of benzotriazole in 400 ml of ethyl alcohol
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. When 10 g of each sample was sampled from arbitrary points (5 places) of the obtained mixture and analyzed, 1-phenyl-5-mercaptotetrazole and benzotriazole were sufficiently homogeneously mixed. Let the obtained mixture be M-1.

Mixing of potassium carbonate / sodium carbonate / anhydrous / lithium hydroxide / 1H ₂ O or hydroquinone Using a commercially available V-type mixer (200 L capacity), 56 kg of potassium carbonate, 42 kg of sodium carbonate, 1H _{2 of} lithium hydroxide / 1H ₂ 2 kg of O (22 kg when using hydroquinone) was mixed for 10 minutes. The resulting mixture is
Let it be 2.

(Packaging (10 L kit for use solution)) A raw material mixture and a molded product were filled in the form of 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. PH = 10.70 when using hydroquinone
Met.

<< Preparation of Solid Fixing Agent Kit (Liquid 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.

Sodium thiosulfate 15 kg Sodium sulfite 2.2 kg 8-mercaptoadenine (silver sludge inhibitor) 50 g To the obtained mixture, 1 kg of sodium 1-octanesulfonate (the above ground product) was added and mixed for further 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 rotation. It was molded at a number of 67 rpm. 1. The obtained plate-like molded product was crushed by a classifier, and
It was divided into granules of 4-7.0 mm and fine powder of 2.4 mm or less (things of 7.0 mm or more were 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, granule FA-1 was obtained.

The granules formed by adjusting the amount of sodium sulfite to the sulfite ion concentration shown in Table 2 are collectively referred to as FA.

(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 mixed with a compression granulator Briquetta BSS-IV manufactured by Shinto Kogyo Co., Ltd. , Pocket shape 5.0mm
Φ × 1.2mm (Depth), roller rotation speed 30r
pm and a feeder rotation speed of 67 rpm. The obtained plate-like molded product was crushed by a classifier, and 2.4 to 7.0 m was obtained.
m and granules of 2.4 mm or less (7.0 mm
The above 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) Granules FB and FA-1 (or FA) were filled in this order in the form of a standing pouch.

The 100 L portion was packaged in a 10 L kit.

The pH after dissolving in 10 L of finished product is 4.5 to 4.5.
It was between 7.0 and adjusted to pH = 5.60 with 50% sulfuric acid or 50% KOH.

Stabilizing Solution Formulation-1 35 wt% Hydrogen Peroxide Aqueous Salicylic Acid 1.0 g Fungicide added to have the concentration shown in Table 1 Disinfectant Finished to 1 L using pure water shown in Table 1. The kit configuration was 10 L. When used, it is added to tap water to a predetermined concentration and used as washing water.

Stabilizing solution formulation-2 (1 L for common use of starting solution and replenishing solution) Diethylenetriaminepentasodium pentasodium 1.0 g 5-Chloro-2-methyl-4isothiazoline-3one 0.1 g Propylene glycol-based compound or Ethylene glycol-based compound 5.85 g of NaCl shown in the table was dissolved in pure water to prepare a 100 L portion.

The black-and-white silver halide photographic material sample 1 prepared according to the above formula was exposed so as to have a blackening ratio of 10%, and was modified to increase the line speed by 1.5 times. The washing tank of the developing machine GR-960 was remodeled into a two-stage multi-stage countercurrent tank, and a mixer SM-10 manufactured by Konica Corporation was remodeled so that granules could be charged.
Or 130 ml of a developing replenisher and 1 ml of a fixing replenisher per 1 m ^{2 of a} silver halide photographic light-sensitive material, using a developer using No. 2 and a fixing agent using a granule FA-1 and a stabilizing solution-1. The solution was replenished in an amount, and 500 sheets were treated per day for 4 months, and the resulting solution was used as a running solution. In the experiments according to the present invention, the inside of the washing tank was washed with water or a stabilizing solution after these treatments were completed every day.

Each time a sheet film of large overall size (508 mm × 610 mm) was inserted, the stabilizing solution kit was replenished to the washing tank so that the hydrogen peroxide concentration was as shown in Table 1, and the concentration in the washing tank was changed. Adjustments were made.

For dissolving the fixing solid processing agent, an overflow solution containing a bactericide was diluted and used.

(Processing conditions) Temperature Time Development 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 following evaluation was performed.

(Evaluation of Silver Sludge Stain Generated in Washing or Stabilizing Tank) The degree of the stain generated in the developing tank after running was visually evaluated according to the following criteria in five steps.

A: No precipitate at all, and the solution is clear. B: No precipitate at all. C: No precipitate occurs, but there is dirt. Peasable D: Slight precipitation E: Precipitation accumulates at the bottom.

(Evaluation of dot quality) Using FYR3050Q manufactured by Dainippon Screen Co., Ltd., 175 lpi (24
00dpi) (the target 5)
0%) was evaluated for halftone dot quality (clearness) using a 100-fold loupe. The highest rank is 5, and depending on the dot quality,
The rank was lowered to 2, 1 and evaluated. Ranks 1 and 2 are levels that are not practically desirable.

(Precipitation / Draining in Rinse or Stabilize Tank) The degree of precipitation generated in the rinse tank after running was visually evaluated according to the following criteria in five steps.

A: No sedimentation, no sedimentation / scale, and the liquid is clear. B: No sedimentation, sedimentation, and almost no scale. Adhesion. Practical possible D: Slight precipitation occurs and scale is partially generated E: Precipitation accumulates at the bottom and scale is generated as a whole.

(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: No dirt at all B: Little dirt, but some dirt on the edge C: Partially dirt, but no problem with film D: Dirt on roller as a whole There is a case where it adheres to the film. E: Dirt accumulates on the roller as a whole, and the treated film becomes a level that cannot be used practically.

The above results are shown in Tables 1 and 2.

[0139]

[Table 1]

[0140]

[Table 2]

The black-and-white silver halide photographic light-sensitive material sample 2 was similarly exposed, and replenished with a developing agent using the mixture-3 or 4, a fixing agent using the granule FA, and a stabilizing solution-2. 100ml / m ² , fixing replenishment amount 130m
l / m ^2, in stabilizing solution replenishment rate 130 ml / m ^2, the developing machine and processing 500 sheets per day for 20 days was used to the liquid and the running solution.

(Processing conditions) Temperature Time Developing 38 ° C. 12 seconds Fixing 38 ° C. 7 seconds Stabilizing 1 Room temperature 5 seconds Stabilizing 2 Room temperature 5 seconds Drying 48 ° C. 8 seconds Regenerating overflow developing waste liquid and replenishing new liquid development Experiments added to the liquid were also performed.

The following evaluation was performed.

(Evaluation of halftone dot quality) Same as above (Evaluation of maximum density of practical technique) The maximum density when an original having a blackening rate of 50% was exposed to a film sample so as to have an area of 50% was evaluated. 4.7 or more is a preferable value.

(Coloring of Dye) After completion of the running, 10 sheets of large-sized films which were not exposed were processed, and blue stains generated on the 10 samples were visually evaluated.

A: The film has no blue stains, and no blue stains are found even when viewed carefully. B: A blue pigment sometimes adheres to one of the films, but is too thin to be found without care. C: A blue pigment adheres to one or two sheets of the film, but the color is light and there is no problem. D: A blue stain adheres to 3 to 8 sheets of the film, and the blue stain is clearly seen. E: All films have a level. A level where blue stains are clearly visible.

(Evaluation of Film Drying Property) The film drying property after drying and the degree of drying unevenness were visually evaluated as follows.
It was evaluated on a scale.

A: The film is completely dry, has no drying unevenness, and is smoothly discharged from the drying section. B: The film is completely dry, has no drying unevenness, but is slightly unusual than the drying section. C: The film is almost dry, but adheres to other films after discharge. D: The film does not dry and is discharged. E: The film does not dry and is not entangled with the drying roller and discharged.

Tables 3 and 4 show the results.

[0150]

[Table 3]

[0151]

[Table 4]

Example 2 The experiment and evaluation using the photosensitive material sample 1 of Example 1 were carried out, except that the developer and the fixing agent were changed to liquids as shown below.

(Developer Formulation) 1 L of Working Solution Pure Water 300 ml Diethylenetriaminepentasodium pentasodium 1.45 g Sodium sulfite 52 g Potassium carbonate 55 g 8-Mercaptoadenine 0.06 g Diethylene glycol 50 g 5-Methylbenzotriazole 0.21 g 1-phenyl- 5-mercaptotetrazole 0.03 g dimezone S 0.87 g hydroquinone 20 g KOH (55% aqueous solution) and pure water 400 mL (p
H10.45). When using pure water 60
0 mL and 400 mL of the above concentrated solution are mixed and used. (Use solution pH 10.40) (Fixing solution formulation) 1 L of use solution Purified water 120 ml Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium sulfite 22 g Boric acid 10 g Tartaric acid 3 g Sodium acetate trihydrate 37.8 g Acetic acid ( 90% aqueous solution) 13.5 g Aluminum sulfate / 18-hydrate 18 g Fungicide Compounds and amounts shown in Table 5 333 ml (50% aqueous solution) using 50% sulfuric acid aqueous solution and pure water.
81). When used, 667 ml of pure water and 333 ml of the above concentrated liquid are mixed and used (pH of the used liquid).
4.85).

Tables 5 and 6 show the results.

[0155]

[Table 5]

[0156]

[Table 6]

Example 3 The experiment and evaluation were conducted in the same manner as in Example 1 except that the developer and the fixing agent were changed from granules to tablets as shown below.

<< Preparation of Developer >> Preparation of Developer A Part (for 1 L of used solution) 8-mercaptoadenine 0.09 g Compound of general formula (2) Amount shown in table 5-methylbenzotriazole 0.26 g Sodium sulfite 7 0.1 g sodium erythorbate 60 g (24 g in the case of hydroquinone) D-sorbitol 5.0 g Preparation of developer B part (for 1 L of used solution) diethylenetriaminepentaacetic acid pentasodium 4.35 g sodium carbonate 28.77 g potassium carbonate 37.5 g odor Potassium chloride 2.0 g Sodium sulfite 49.5 g LiOH.H ₂ O 2.2 g (8.8 g for hydroquinone) D-mannitol (trade name: Kao) 11.7 g D-sorbitol (trade name: Towa Chemical Industry) 5 g << Preparation of Fixing Agent >> Preparation of Fixing Agent A Part (Liquid 1 L) Sodium thiosulfate 170 g Sodium sulfite Trisodium citrate dihydrate 19.4 g Pine flow (trade name: Matsutani Chemical) 9 g Preparation of fixing agent B part so that the sulfite ion concentration shown in Table 7 is obtained (1 L of used solution) Min) Sodium gluconate 5 g Succinic acid 11.9 g Trisodium citrate dihydrate 10 g D-mannitol 2.5 g D-sorbitol 1.2 g Macrogol PEG # 4000 (trade name: manufactured by NOF CORPORATION) 0.75 g Developer, 0.5% by weight of water was added to each material of the fixing agent for each part using a commercially available Henschel mixer, and the mixture was added at room temperature for 10 parts.
Granulation was performed for minutes to obtain each granulated material.

Sodium 1-octanesulfonate was added in an amount of 2% by weight to each of the developed granulated product A parts and B parts and the fixed granulated product A parts and B parts, and each A.B. The B part was thoroughly mixed, and the resulting mixture was compressed to 1.5 tons / m ² using a Macina UD · DFE30 / 40 tableting machine manufactured by Masina Co., Ltd. to form a tablet having a diameter of 30 mm, a thickness of 10 mm, and a weight of 10 g. Tablets were obtained.

Each of the prepared developer and fixing agent was placed in an aluminum bag at a rate of 4 liters each and stored at 50 ° C. and 70% in an environment.
Saved for a week. When used, it was dissolved in water using a mixer SM-10 manufactured by Konica Corporation and finished to 4 L.

The pH when the developer was dissolved was 9.8.
0 (pH when using hydroquinone is 10.70), pH when dissolving the fixing agent is between 4.5 and 7.0,
PH = 5.60 using 50% sulfuric acid or 50% KOH
Was adjusted.

Tables 7 and 8 show the results.

[0163]

[Table 7]

[0164]

[Table 8]

[0165]

As demonstrated in the examples, according to the treatment method of the present invention, even if water saving treatment is performed, no dirt or scale is generated in the washing or stabilizing tank, and the dot quality of the treated film is reduced. Excellent, does not cause drying roller stains, saves water and improves the working environment, and has excellent halftone dot quality and maximum density of images obtained even after rapid processing. Do not invite.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/305 G03C 5/305 5/31 5/31 5/395 5/395 11/00 11/00

Claims (13)

[Claims] In developing, fixing, washing or stabilizing a silver halide photographic light-sensitive material using an automatic processor, a fixing solution or a washing or stabilizing solution contains 2- (p-hydroxyphenyl) glyoxyl. A method for processing a silver halide photographic light-sensitive material, comprising hydroxymoyl chloride and at least one member selected from the group consisting of the following compounds. (Compound group) 4,5-dichloro-2-n-octylisothiazoline-
3-one 1,2-benzisothiazolin-3-one 2-bromo-2-nitropropane-1,3-diol α-chlorobenzaldoxime acetate 5-chloro-2,4,6-trifluoroisophthalonitrile o -Phthalaldehyde 5-chloro-2-methyl-4-isothiazolin-3-one 2. A method for developing, fixing, washing or stabilizing a silver halide photographic light-sensitive material using an automatic developing machine, wherein a fixing solution or a washing or stabilizing solution comprises 2-n-octyl-4-isothiazoline. A method for processing a silver halide photographic light-sensitive material, comprising 3-one and polyhexamethylene biguanidine hydrochloride. 3. A process for developing, fixing, washing or stabilizing a silver halide photographic material using an automatic processor, wherein a fixing solution or a washing or stabilizing solution is selected from sucrose fatty acid esters and sodium dehydroacetate. A method for processing a silver halide photographic light-sensitive material, characterized by containing at least one kind. 4. A water-washing or stabilizing solution containing 0.0003 to 0.
4. The method for processing a silver halide photographic material according to claim 1, wherein hydrogen peroxide is contained at 3% by weight. 5. The method for processing a silver halide photographic light-sensitive material according to claim 4, wherein the solution is supplied as a concentrated solution of a stabilizing solution containing 2 to 35% by weight of hydrogen peroxide. 6. The method for processing a silver halide photographic material according to claim 5, wherein the concentrated solution of the kit is directly poured into a washing or stabilizing tank. 7. The method according to claim 1, wherein after the treatment is completed, the inside of the washing tank is washed with water or a stabilizing solution.
7. The method for processing a silver halide photographic light-sensitive material according to 5 or 6. 8. Developing and fixing the silver halide photographic material using an automatic developing machine having two or more washing or stabilizing tanks.
In the washing or stabilizing treatment, a developer containing substantially no dihydroxybenzene-based compound and containing a compound represented by the following general formula (1) and a compound represented by the following general formula (2) is used. Alternatively, a method for processing a silver halide photographic light-sensitive material, wherein the stabilization processing is performed by a multi-stage AC method, and a processing solution used for the processing contains a propylene glycol compound or an ethylene glycol compound. Embedded image [In the formula, R ₁₁ and R ₁₂ each represent an alkyl group, an amino group, an alkoxy group, or an alkylthio group, which may have a substituent or may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. [Chemical formula 2] [In the formula, R ₁ represents hydrogen or an acetyl group, and R ₂ , R ₃ , and R ₄ each represent hydrogen or a substituted or unsubstituted alkyl group. ] 9. The method for processing a silver halide photographic material according to claim 8, wherein a fixing solution having a sulfite ion concentration of 0.15 mol / L or more and containing substantially no aluminum is used. 10. The method for processing a silver halide photographic light-sensitive material according to claim 8, wherein the surface tension of the processing solution used for washing or stabilizing processing is 8 to 78 dyn / cm. 11. The method for processing a silver halide photographic light-sensitive material according to claim 8, wherein the light-sensitive material to be processed contains a compound represented by the following general formula (3). Embedded image [In the formula, A represents an aliphatic group, an aromatic group, or a heterocyclic group, and may have a substituent. B is an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Represents a sulfamoyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, an oxalyl group, or a heterocyclic group. B may form a heterocyclic ring together with A ₂ and the nitrogen atom to which they are bonded. A ₁ and A ₂ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group or an oxalyl group. ] 12. The silver halide according to claim 8, wherein the photosensitive material has a film swelling degree of 100 to 250% during development, fixing, washing or stabilization. Processing method of photographic photosensitive material. 13. When the silver halide photographic material is developed, fixed, rinsed or stabilized using an automatic developing machine having two or more washing or stabilizing tanks, the silver halide photographic material contains substantially no dihydroxybenzene-based compound. A developer containing the compound represented by the general formula (1) and the compound represented by the general formula (2) is used, and a recovery / regeneration solution for overflow of the developer is added to a replenisher, and used for washing or A method for processing a silver halide photographic light-sensitive material, wherein the stabilization processing is performed by a multi-stage AC method.