JPH10325994A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a method for processing a silver halide photographic sensitive material without deteriorations of linearity and maximum density and freed of scattering of a fine powder in preparing processing agents by incorporating a specified developer in a black-and-white developing solution and using a powdery or solid processing agent sealed in a water-soluble film packed material as a replenishing agent for a developing solution or a fixing solution. SOLUTION: This method is for processing a silver halide photographic sensitive material processed by using a powdery or solid processing agent sealed in a water-soluble film packed material as a replenishing agent for a developing solution or a fixing solution and the black-and-white developing solution containing at least one kind of a developer represented by formula in which each of R1 and R2 represents independently a substituted, an unsubstituted alkoxy group or the like and each may combine with each other to form a ring; each of M1 and M2 is an H or an alkali metal atom; (k) is 0 or 1; and X is -CO- or -CS- when (k) is 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly, to an improved method for processing a black-and-white silver halide photographic material for plate-making printing.

[0002]

2. Description of the Related Art In general, black-and-white silver halide photographic materials (hereinafter simply referred to as "photosensitive materials") are continuously processed by an automatic developing machine having processes such as development, fixing, washing (stabilization) and drying after exposure. Usually it is.

For this reason, in order to keep the activity of the developing solution and the fixing solution tired during running constant, a method of replenishing the replenishing solution of the developing solution and the fixing solution is widely used. The replenisher is used for replenishing components consumed by the processing, correcting the liquid by evaporation, or diluting components eluted from the photosensitive material into the processing solution, and is an essential requirement in continuous processing of the photosensitive material. I have.

[0004] In recent years, treatment agents have been supplied in a solid form. However, in the case of a powder treatment agent, fine powder is scattered during preparation, which is environmentally unfavorable for workers. Therefore, there is a tableting method. However, since a tableting step is required, there is a problem that the cost is inevitably increased.

Further, in recent years, as the replenishment of the processing liquid has been progressing, it has been impossible to increase the concentration of the processing liquid with a normal liquid processing agent.
Further, in the case of a conventional developer containing hydroquinone as a main agent, for example, in halftone dot formation, when the exposure amount of a small point is adjusted to the exposure amount of a small point, so-called linearity is deteriorated. It has a serious drawback that a concentration cannot be obtained, and new development has been desired.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a black-and-white silver halide with a developing replenisher and a replenishing fixing agent which do not cause deterioration in linearity or maximum density and do not cause fine powder during preparation of a processing agent. An object of the present invention is to provide a method for processing a photographic light-sensitive material.

[0007]

The object of the present invention has been attained by the following.

(1) In a method for processing a black-and-white silver halide photographic light-sensitive material processed by an automatic developing machine, at least one kind of a developer represented by the following general formula (A) is used in a black-and-white developing solution to be used. A method for processing a silver halide photographic light-sensitive material, wherein the developing replenisher or the fixing replenisher of the developer is a powdery or solid processing agent encapsulated in a water-soluble film packaging material. .

[0009]

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In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, R ₁ and R ₂ may combine with each other to form a ring. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom. k represents 0 or 1, and when k is 1, X is-
Represents CO- or -CS-.

(2) In a method for processing a black-and-white silver halide photographic light-sensitive material processed by an automatic developing machine, a dihydroxybenzene-based developer in a black-and-white developer used: development represented by the above general formula (A) The molar ratio with the agent is 0: 1 to 100
(1) The method for processing a silver halide photographic light-sensitive material as described in (1), wherein the silver halide is contained in a range of 0: 1.

(3) In the method for processing a black-and-white silver halide photographic light-sensitive material according to the above (1) or (2), at least one hydrazine derivative is used as a high contrast agent in the silver halide photographic light-sensitive material constituting layer. A method for processing a silver halide photographic light-sensitive material, characterized by comprising:

(4) In the method for processing a black-and-white silver halide photographic light-sensitive material according to the above (1) or (2), at least one of a tetrazolium compound as a high contrast agent is contained in the silver halide photographic light-sensitive material constituting layer. A method for processing a silver halide photographic light-sensitive material, characterized by comprising:

Hereinafter, the present invention will be described in detail.

The general formula (A) used as the developer of the present invention will be described.

As the compound represented by the general formula (A), a compound represented by the following general formula (Aa) in which R ₁ and R ₂ are bonded to each other to form a ring is particularly preferred.

[0017]

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In the formula, R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, It represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

The alkyl group in the formula (A) or (Aa) is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms. The amino group is preferably an unsubstituted amino group or an amino group substituted with a lower alkyl group, the alkoxy group is preferably a lower alkoxy group, and the aryl group is preferably a phenyl group or a naphthyl group. May have a substituent, and as a group that can be substituted, a hydroxy group, a halogen atom, an alkoxy group, a sulfo group,
Preferred examples of the substituent include a carboxyl group, an amide group, and a sulfonamide group.

Specific examples of the compound represented by formula (A) or (Aa) according to the present invention are shown below.
The present invention is not limited to these.

[0021]

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[0022]

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[0023]

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[0024]

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These compounds are typically ascorbic acid or erythorbic acid or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

In the present invention, the developer containing the compound represented by the general formula (A) or the general formula (A-a) may be used as a powdery or solid process encapsulated in a water-soluble film packaging material. It is characterized by being an agent.

The water-soluble packaging material used in the present invention is formed from a water-soluble film, and various water-soluble polymers are used therefor. The water-soluble polymer includes a natural polymer, a semi-synthetic product, and a synthetic product.

Examples of natural polymers include starchy substances (potato starch, potato starch, tapioca starch, wheat starch, corn starch, etc.), mannan (konjac, etc.), seaweeds (funori, agar, sodium alginate), plant sticky substances (troloaoi) , Tragacanth gum, gum arabic), microbial mucilage (dextran, lepan) and proteins (paste, gelatin, casein, collagen).

Examples of semi-synthetic products include viscose, methylcellulose (MC), ethylcellulose (EC), hydroxyethylcellulose (HEC) and carboxymethylcellulose (CMC), such as cellulose-based soluble starch; Examples include carboxymethyl starch (CMS) and dialdehyde starch.

As synthetic products, polyvinyl alcohol, sodium polyacrylate, polyethylene oxide and the like are known.

The thickness of the water-soluble film may be such that it is completely dissolved or the solid processing agent contained therein can be dissolved in water by permeation of the aqueous solution or tearing of the packaging material. Preferably, the water-soluble film is thin in consideration of solubility, and more preferably completely soluble.

The specific thickness of the water-soluble film considered from the viewpoint of solubility and strength is preferably several μm to 5 mm. For example, those composed of starch or polyvinyl alcohol are preferred. In particular, those partially saponified with polyvinyl alcohol have good solubility, and those made of thermoplastics such as polyvinyl alcohol can be easily subjected to thermal processing such as a bursier, an impulse sealer, and a fusing sealer.

The treatment agent to be included may be a powdery treatment or a granular solid treatment treatment. From the viewpoint of dissolution, a granular solid processing agent is more preferable.

The material of the developer used in the present invention contains at least one of the following (a) and (b).

(A) ascorbic acids, dihydroxybenzenes, 3-pyrazolidones, aminophenols,
1-aryl-3-aminophenols (b) Alkaline compound having an acid dissociation constant (pka) of 9 or more The materials (a) and (b) may be mixed and sealed in a packaging material, It is preferable that each be stored separately in a separate packaging material.

In the present invention, the water-soluble film packaging material may be any as long as the treating agent does not deteriorate or break during storage or handling, and is more preferably easily soluble in water or alkaline water.

The developer (processing agent) to be included may be a powdery solid or a granular solid processing agent, but from the viewpoint of dissolution, a granular solid processing agent is more preferable.

In the present invention, the dihydroxybenzene-based developer used in combination with the compound represented by the above general formula (A) or (Aa) includes the following general formula (I):
Compounds represented by (II) and (III) are preferred.

[0039]

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In the formula, R _{5 to} R ₇ are each independently a hydrogen atom, an alkyl group, an aryl group, a carboxy group or a halogen atom.

Specific examples of the compound include hydroquinone, chlorohydroquinone, bromohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,
Among them, for example, 5-dimethylhydroquinone, the most preferred is hydroquinone.

In the present invention, the molar ratio of the dihydroxybenzene-based developing agent to the compound represented by formula (A) is from 0 to 1,000, preferably from 0 to 100.
And more preferably 0 to 30.

In the present invention, 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone,
-Phenyl-4,4-dimethyl-3-pyrazolidone, 1
-Phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N -Methyl-p-aminophenol, 2,4-diaminophenol, etc.) can be used in combination.

When used in combination, the developing agents such as 3-pyrazolidones and aminophenols are preferably used usually in an amount of 0.01 to 1.4 mol per liter of developer.

The above-mentioned developer of the present invention is packaged in a water-soluble film packaging material together with other development processing materials.

In the processing method of the present invention, not only the developing replenisher but also the fixing replenisher is a processing agent enclosed in a water-soluble film packaging material. The fixing replenisher contains at least one of the following (c) and (d) as a material for the fixing agent.

(C) Thiosulfate, thiocyanate (d) Water-soluble aluminum salt Each of the above materials (c) and (d) may be mixed and sealed in a packaging material. It is preferable from the viewpoint of preservation to divide into packaging materials. Others are the same as in the case of the developer.

In the processing method of the present invention, the processing is performed while replenishing a fixed amount of processing liquid in proportion to the area of the photosensitive material in response to a demand for reducing the amount of waste liquid. The replenishing amount of the developing solution is 200 ml or less per 1 m ² of the photosensitive material. The replenishing amount of the fixing solution is 250 ml or less per 1 m ² of the photosensitive material. Preferably 50 to 190 ml per m ²
It is.

It should be noted that the developer replenishing amount and the fixing solution replenishing amount referred to herein refer to the amount of the replenishing solution. Specifically, it is the replenishment amount of each solution when replenishing the same solution as the developing mother liquor and fixing mother liquor, and the respective replenishing amounts when replenishing the developing concentrated solution and the fixing concentrated solution with a solution diluted with water. It is the total amount of water.

That is, the total amount of the volume of the solid processing agent and the volume of water when the solid processing agent is replenished with a solution in which the solid processing agent is dissolved in water. It is also the total amount of the volume of each solid processing agent and the volume of water when the solid processing agent and water are separately replenished.

In the case of replenishment with a solid processing agent, it is preferable to represent the total amount 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 added separately.

The developing replenisher and the fixing replenisher may be the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, respectively, or may be different liquids or solid processing agents.

In the case of a solid processing agent, the amount of the processing agent to be supplied at one time is preferably 0.1 to 50 g.
To 20 g, preferably 5 to 50 g for a fixing replenisher.
Is preferable. Even when the solid processing agent in this range is directly charged into a processing tank of a general small-sized automatic processor and processed while slowly dissolving, the photographic performance is not adversely affected. Because the solid processing agent does not dissolve rapidly, it dissolves slowly, so even if the amount added at a time is large, the composition is balanced with the amount consumed during processing and shows stable photographic performance It is.

The photographic performance can be made constant by injecting replenishing water in accordance with the dissolution. The temperature of the processing liquid is always adjusted to the processing temperature, and is maintained at a substantially constant temperature. That is, since the dissolution speed of the treating agent is substantially constant, the calculated amount of the solid treating agent and the balance of the components are achieved.

In the processing method of the present invention, development, fixing,
The temperature of the washing tank is preferably between 10 and 45 ° C., and each may be separately temperature-controlled.

In the processing method of the present invention, from the viewpoint of rapid processing, when processing is performed using an automatic developing machine, the total processing time from when the leading end of the photosensitive material is inserted into the automatic developing machine to when it comes out of the drying zone is obtained. (Dry to dry) is 10
~ 60 seconds, more preferably 15 ~
50 seconds. In order to stably process a large amount of photosensitive material of 100 m ² or more, the developing time is 2 to 1
Preferably, it is 8 seconds.

As an automatic developing machine, a heat transfer material (heat roller of 60 to 130 ° C. or more) of 60 ° C. or more or a radiant material of 150 ° C. or more (a mixture of tungsten, carbon, nichrome, zirconium oxide, yttrium oxide, and thorium oxide) , Which emit heat by directly passing current through silicon carbide or the like, or by transferring heat energy from a resistance heating element to a radiator such as copper, stainless steel, nickel, or various ceramics to emit infrared rays. Are preferred.

Further, as the automatic developing machine, those employing the following methods or functions can be preferably used.

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

The silver halide composition of the silver halide photographic light-sensitive material in the processing method of the present invention has a silver chloride content of 60%.
It is preferable to use silver bromochloride or silver chloroiodobromide in an amount of at least mol% for reducing the replenishment amount and for 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.

In the processing method of the present invention, the black-and-white silver halide photographic light-sensitive material to be processed contains a hydrazine derivative represented by the following general formula (H).

[0064]

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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,
Alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, sulfamoyl, sulfinamoyl, alkoxysulfonyl, thioacyl, thiocarbamoyl, oxalyl, or heterocycle Represents a 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 each} represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group or an oxalyl group.

Preferred embodiments of the hydrazine compound represented by the general formula (H) are shown below.

In the formula, the aliphatic group represented by A has 1 to 1 carbon atoms.
It is preferably 30 and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. For example, methyl, ethyl, t-butyl, octyl, cyclohexyl, benzyl group and the like can be mentioned. These are further suitable substituents (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, arylthio group, sulfoxy group, sulfonamide group). Group, acylamino group, ureido group, etc.). The aromatic group represented by A is preferably a monocyclic or condensed-ring aryl group, such as a benzene ring or a naphthalene ring. As the heterocyclic group represented by A, at least nitrogen of a monocyclic or condensed ring,
Sulfur, a hetero ring containing one hetero atom selected from oxygen is preferable, for example, a pyrrolidine ring, an imidazole ring,
Examples include a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, and a furan ring. A
Are particularly preferably an aryl group and a heterocyclic group. The aryl group and heterocyclic group of A 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, the alkyl moiety has 1 to 20 carbon atoms), a substituted amino group (preferably, an amino group substituted with an alkyl group or an alkylidene group having 1 to 20 carbon atoms), an acylamino group (preferably, 1 to 20 carbon atoms) 40), 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) , A hydroxyl group and a phosphoamide group (preferably having 1 to 40 carbon atoms). 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. As the ballast group, an alkyl group or an alkenyl group which is relatively inert to photographic properties having 8 or more carbon atoms is preferable. Alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether, thione, heterocyclic, thioamide heterocyclic,
Examples thereof include a mercapto heterocyclic group and an adsorptive group described in JP-A-64-90439.

B is specifically an acyl group (for example, formyl, acetyl, propionyl, trifluoroacetyl,
Methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl, etc., alkylsulfonyl group (eg, methanesulfonyl, 2-chloroethanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, etc.) ), An alkylsulfinyl group (eg, methanesulfinyl), an arylsulfinyl group (eg, benzenesulfinyl), a carbamoyl group (eg, methylcarbamoyl, phenylcarbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl, methoxyethoxycarbonyl, etc.), aryloxycarbonyl Group (eg, phenoxycarbonyl, etc.), sulfamoyl group (eg, dimethylsulfamoyl, etc.), sulfinamoyl group (eg, Such as tylsulfinamoyl), an alkoxysulfonyl group (eg, methoxysulfonyl), a thioacyl group (eg, methylthiocarbonyl), a thiocarbamoyl group (eg, methylthiocarbamoyl), an oxalyl group), or a heterocyclic group (eg, a pyridine ring, a pyridinium ring) Etc.). B together with A ₂ and the nitrogen atom to which they are attached

[0069]

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May be formed. In the formula, 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. B
Is particularly preferably an acyl group or an oxalyl group.

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

Particularly preferred among the hydrazine compounds used in the present invention are the hydrazine compounds represented by the following formula (Ha).

[0073]

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In the general formula (Ha), R ₁ represents an aryl group or a heterocyclic group, and R ₂ represents

[0075]

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Represents the following. R ₃ and R ₄ are each a hydrogen atom,
Alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, alkynyloxy group, an aryloxy group, or a heterocyclic oxy group, R ₃ and R ₄
May form a ring together with the N atom. R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. A ₁ and A ₂ represent the same meanings groups as A ₁ and A ₂ in the general formula (H).

The general formula (Ha) will be described in more detail.

In the formula, the aryl group represented by R ₁ is preferably a single ring or a condensed ring, and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic group represented by R ₁ is a monocyclic or condensed ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen.
Alternatively, a 6-membered unsaturated hetero ring is preferable, and examples thereof include a pyridine ring, a quinoline ring, a pyrimidine ring, a thiophene ring, a furan ring, a thiazole ring, and a benzothiazole ring. Preferred as R ₁ is a substituted or unsubstituted aryl group. Examples of the substituent include those having the same meaning as the substituent of A in the general formula (H). In the case where the contrast is increased with a developer having a pH of 11.2 or less, it preferably has at least one sulfoamide group. A ₁ and A ₂ represent A ₁ and A ₂ group having the same meaning as in formula (H), in the most preferably both hydrogen atoms. R ₂ is

[0079]

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Wherein R ₃ and R ₄ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, benzyl),
Alkenyl group (allyl, butenyl, etc.), alkynyl group (propargyl, butynyl, etc.), aryl group (phenyl, naphthyl, etc.), heterocyclic group (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidyl) Nyl, quinolidinyl, N, N'-diethylpyrazolidinyl, N-
Benzylpyrrolidinyl, pyridyl, etc.), amino group (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl group, alkoxy group (methoxy, ethoxy, etc.), alkenyloxy group (allyloxy, etc.), alkynyloxy group ( R ₃ and R ₄ may form a ring (piperidine, morpholine, etc.) together with a nitrogen atom, representing a propargyloxy group, an aryloxy group (eg, phenoxy group), or a heterocyclic oxy group (eg, pyridyloxy group). R
₅ is a hydrogen atom, an alkyl group (methyl, ethyl, methoxyethyl, hydroxyethyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl, etc.), an aryl group (phenyl, naphthyl, etc.), a heterocyclic group (2,2,6,6-tetramethylpiperidinyl,
N-methylpiperidinyl, pyridyl, etc.).

Specific examples of the hydrazine compound represented by the general formula (Ha) are shown below. However, the present invention is not limited to these. Besides, specific examples of the hydrazine compound represented by the general formula (Ha) are described in JP-A-5-2412.
No. 64.

[0082]

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The method for synthesizing the hydrazine compound represented by the above general formula (H) used in the present invention is described in JP-A-62-18 / 1987.
No. 0361, No. 62-178246, No. 63-234
No. 245, No. 63-234246, No. 64-9043
9, JP-A-2-37, JP-A-2-841, JP-A-2-94
No. 7, No. 2-120736, No. 2-230233,
No. 3-125134, US Pat. No. 4,686,167
No. 4,988,604 and 4,994,365
No. 253,665 and EP 333,43.
The method described in No. 5, etc. can be referred to.

The amount of the hydrazine compound represented by the general formula (H) of the present invention is 5 × 1 per mol of silver halide.
It is preferably 0 ^{-7 to} 5 × 10 ^-1 mol, particularly 5 × 10 ^-1 mol.
It is preferable to be in the range of 10 ^{-6 to} 5 × 10 ^-2 mol.

In the present invention, when the hydrazine compound represented by the formula (H) is contained in a photographic material, it is contained in a silver halide emulsion layer or a hydrophilic colloid layer adjacent to the silver halide emulsion layer. .

The silver halide photographic light-sensitive material of the present invention preferably contains a tetrazolium compound. Such a tetrazolium compound is represented by the following general formula (T-
1) and tetrazolium compounds represented by (T-2).

[0087]

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Specific examples of the tetrazolium compound other than those described above include, for example, tetrazolium compounds represented by [Chem. 8], [Chem. 9], [Chem. 10], [Chem. 11] and [Chem. 12] of JP-A-1-287557. Can be mentioned. However, the tetrazolium compound used in the present invention is not limited to these. The above tetrazolium compounds are described, for example, in (Chemical Reviews) Vol. 55, No. 3
It can be easily synthesized according to the method described on pages 35 to 483.

The tetrazolium compound of the present invention can be used in an amount of about 1 mg to 10 g, particularly 10 mg to 1 mol per mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention.
It is preferred to use up to 2 g.

The photosensitive material used in the processing method of the present invention preferably has at least one conductive layer on a support. As a typical method of forming the conductive layer,
There are a method using a water-soluble conductive polymer, a hydrophobic polymer, and a curing agent, and a method using a metal oxide. These methods are described in, for example, JP-A-3-2658.
42, pages (5) to (15).

Examples of the silver halide of the silver halide emulsion used in the light-sensitive material include ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride. Can be used, but is preferably silver chlorobromide or silver chloride containing 50 mol% or more of silver chloride.

Further, it was determined from the grain size of silver halide grains measured by electron micrograph (standard deviation of grain size).
/ (Average particle size) × 100 has a variation coefficient of 15
% Or less are preferred. Various photographic additives can be used in the photosensitive material used in the processing method of the present invention before and after physical ripening or chemical ripening.

Compounds used in such a step include, for example, Research Disclosure (RD) N
o. 17643 (December 1978), (RD) No.
18716 (November 1979) and (RD) No. 3
Various compounds described in 08119 (December 1989) can be used. These three (RD)
The types and locations of the compounds described in are described below.

[0094]

[Table 1]

The support usable for the silver halide photographic light-sensitive material includes cellulose acetate, cellulose nitrate, polyesters such as polyethylene terephthalate, polyolefins such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, and glass. , Metal and the like. These supports are subjected to a base treatment as required.

The following techniques are preferably employed for a black-and-white silver halide photographic material to which the processing method of the present invention is applied.

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) Nucleation accelerator JP-A-7-114126, page (32), paragraph "015"
8 ”to (36), paragraph“ 0169 ”7) Pyridinium compound 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

[0098]

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 Silver Halide Emulsion A> Silver chlorobromide core grains having a silver chloride content of 70 mol%, an average thickness of 0.05 μm, and an average diameter of 0.15 μm were prepared by a double-jet method. did. At the time of forming 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 by a simultaneous mixing method. At this time, K ₂ IrCl ₆ was added in an amount of 3 × 10
^-7 mol was added. The resulting emulsion has an average thickness of 0.10 μm.
m, monodispersion with an average diameter of 0.25 μm (coefficient of variation 10%)
This was a silver / chloroiodobromide (90 mol% of silver chloride, 0.2 mol% of silver iodide) tabular grains having a core / shell type (100) plane as a main plane.

This 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% aqueous solution of denatured gelatin thus obtained was added and stirred for 3 minutes. Thereafter, the pH of the emulsion was adjusted to 4.6 by adding a 56% aqueous solution of acetic acid, stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation.

Thereafter, 9.0 liters of distilled water at 40 ° C. was added, and the mixture was allowed to stand with stirring, and the supernatant was drained.
After adding 25 liters and stirring and standing, the supernatant liquid was drained.

Subsequently, an aqueous solution of gelatin and sodium carbonate 1
Adjust the pH to 5.80 by adding 0% aqueous solution,
The mixture was stirred at 50 ° C. for 30 minutes and redispersed. 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 190 mV at 50 ° C.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ⁻³ mol per mol of silver, and potassium bromide and citric acid were further added. After adjusting the pH to 5.6 and an EAg of 123 mV, sodium P-toluenethiosulfonate was added in an amount of 1 × 10 ⁻³ mol per mol of silver, and then chloramine T was added in 350 ml.
mg, 0.6 mg of inorganic sulfur (S8) and 6 mg of trichloroaurate, 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 is 2 × 10 ⁻³ mol per mol of silver, 1 × phenyl-5-mercaptotetrazole is 3 × 10 ⁻⁴ mol, and potassium iodide is 300 mg per mol of silver.
Was added.

<Preparation of Silver Halide Emulsion B> A silver chloride content of 60 mol% and a silver iodide content of 2.5 were obtained by a double jet method.
Mol%, the balance having an average thickness of 0.05 μm made of silver bromide,
Silver chloroiodobromide core grains having an average diameter of 0.15 μm were prepared. At the time of mixing the core particles, 2 × 10 ⁻⁸ mol of K ₃ Rh (H ₂ O) Br ₅ 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.times.10.sup.- ⁷ mol per mol of silver. The obtained emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver iodochlorobromide (0.5 mol% of silver iodide, 90 mol% of silver chloride) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. The remainder was tabular grain emulsions (composed of silver bromide).

Then, the modified gelatin described in JP-A-2-280139 (example in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, exemplified compound G-8 on page 287 (3) of JP-A-2-280139) is used. Use desalted.
The EAg after desalting was 190 mV at 50 ° C.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. The pH was adjusted to 5.6 and the EAg to 123 mV. Then, after adding 2 × 10 ⁻⁵ mol of chloroauric acid per mol of silver, 3 × 10 ⁻⁵ mol of N, N, N′-trimethyl-N′-heptafluoroselenourea was added, and the temperature was increased to 6 ° C.
Chemical ripening was performed at 0 ° C. until the maximum sensitivity was obtained.

After 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 mol. ^-4 moles and gelatin were added.

(Preparation of silver halide photographic light-sensitive material for printing plate making scanner for He-Ne laser light source) A gelatin undercoat layer of the following formula 1 was formed on one surface of a support (polyethylene terephthalate film) subjected to an undercoating treatment. the so-weight gelatin is 0.5 g / m ^2, formulated on the 2
The silver halide emulsion layer 1 was adjusted so that the silver amount was 1.5 g / m ² and the gelatin amount was 0.5 g / m ^2. Formulation 4 is further added to the upper layer so that 0.3 g / m ^2.
The silver halide emulsion layer 2 was prepared so that the silver amount was 1.4 g / m ² and the gelatin amount was 0.4 g / m ² , and the following formulation 5 was further added.
Was applied simultaneously so that the amount of gelatin became 0.6 g / m ² .

On the other side of the undercoat layer, a backing layer of the following formula 6 was further coated with a hydrophobic polymer layer of the following formula 7 so that the amount of gelatin became 0.6 g / m ² , A backing protective layer having the following formulation 8 was simultaneously coated with the emulsion layer so that the amount of gelatin became 0.4 g / m ² to obtain a sample.

Formulation 1 (Gelatin undercoat layer composition) Gelatin 0.5 g / m ² Solid dispersed fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Compound S- 1 0.4 mg / m ² Prescription 2 (Silver halide emulsion layer 1 composition) Silver halide emulsion A (silver content) 1.5 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 derivative HY-1 20 mg / m ² nucleation promoter AM-1 40 mg / 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 5 mg / m ² compound S-1 0.7mg / m ² 2- mercapto - - hydroxy purine 5 mg / m ² ethylenediaminetetraacetic acid 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 Compound S-1 2mg / m ² formulation 4 (silver halide emulsion layer 2 composition) silver halide emulsion B (silver amount) 1.4 g / m ² sensitizing dye d-1 3mg / m ² sensitizing dye d-2 3 mg / m ² hydrazine derivative HY- 2 20 mg / m ² Nucleation promoter AM-1 40 mg / m ² Redox compound RE-1 20 mg / m ² 2-Mercapto-6-hydroxypurine 5 mg / m ² Ethylenediaminetetraacetic acid 20 mg / m ² Latex polymer f 0.5 g / M ² Compound S-1 1.7 mg / m ² Formulation 5 (Emulsion protective layer composition) Gelatin
0.6 g / m ² Dye b solid dispersion (average particle size 0.1 μm) 40 mg / m ² Compound S-1 12 mg / m ² Matting agent: monodisperse silica having an average particle size of 3.5 μm 25 mg / m ² 1 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 Formula 6 (backing layer composition) Gelatin 0.6 mg / m ² Compound 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 (Ba Locking protective layer) Gelatin 0.4 g / m ² Matting agent: monodisperse polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² surfactant h 1 mg / M ² dye k 20 mg / m ² H (OCH ₂ CH ₂ ) ₆₈ OH 50 mg / m ² hardener j
20 mg / m ²

[0113]

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[0114]

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[0115]

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[0116]

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<Starting developer> 1 liter of working solution Pure water 300 ml DTPA / 5Na 1.45 g Sodium sulfite 52 g Potassium carbonate 55 g 8-Mercaptoadenine 0.06 g Diethylene glycol 50 g 5-Methylbenzotriazole 0.21 g 1-phenyl-5 -Mercaptotetrazole 0.03 g Dimezone S 0.87 g Hydroquinone Amount shown in Table 2 A compound shown in Table 2 Amount shown in Table 2 Finished to 400 ml with 55% KOH aqueous solution and pure water (adjusted to pH 10.0).

When used, 600 ml of pure water and 400 ml of the above-mentioned concentrated liquid are mixed and adjusted to pH 10.40.

<Preparation of Developing Replenisher> (Preparation of Part A) 1 liter of working solution 8-mercaptoadenine 0.09 g Dimezone S 1.3 g 5-methylbenzotriazole 0.26 g Sodium sulfite 7.1 g General formula (A) Compound shown in Table 2 Hydroquinone Amount shown in Table 2 D-sorbitol 5.0 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator. The internal pressure was reduced to about 5 mmHg using a batch freeze dryer and then cooled. Then, the mixture was treated at −20 ° C. for 12 hours and dried until the water content became 1% to obtain a granulated A part.

(Preparation of B parts) 1 liter of working solution DTPA · 5Na 4.35 g Sodium carbonate 28.77 g Potassium carbonate 37.5 g Potassium bromide 2.0 g Sodium sulfite 49.5 g LiOH · H ₂ O 8.8 g D -Mannitol (trade name: Kao) 11.7 g D-sorbitol 5 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator, and then batch freeze drying. The internal pressure was reduced to about 5 mmHg using a machine, followed by cooling. Then, the mixture was treated at −20 ° C. for 12 hours and dried until the water content became 1% to obtain a granulated B part.

The thus prepared A. Four liters of each granule of the B part was put in a water-soluble film packaging material (made of polyvinyl alcohol) according to the present invention and sealed. For comparison, a kit not included in the film packaging material was also prepared.

<Starting fixer> 1 liter of working solution Pure water 120 ml Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium sulfite 22 g Boric acid 10 g Tartaric acid 3 g Sodium acetate trihydrate 37.8 g Acetic acid (90% aqueous solution) 13.5 g Aluminum sulfate / 18-hydrate 18 g 333 ml using 50% sulfuric acid aqueous solution and pure water (pH 4.0).
81). When used, 667 ml of pure water
And 333 ml of the above concentrated solution are mixed and used (pH of the starting solution)
4.85).

<Preparation of Fixing Replenisher> (Preparation of Parts A) 1 liter of solution used Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium bisulfite 14 g Sodium sulfite 1.0 g Sodium acetate 18 g Pine flow (product) 9g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator, and then the internal pressure was increased to about 5 mmHg using a batch freeze dryer. After lowering, it was cooled. Then, the mixture was treated at −20 ° C. for 12 hours and dried until the water content became 1% to obtain a granulated A part.

(Preparation of Part B) 1 liter of working solution Boric acid 6 g Tartaric acid 3 g Succinic acid 13.2 g Aluminum sulfate octahydrate 18 g Sodium acetate 10 g D-mannitol 2.5 g D-Sorbit 1.2 g Macrogol PEG # 4000 0.75 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator, and then the internal pressure was reduced to about 5 mmHg using a batch freeze dryer. Cool. Then, the mixture was treated at −20 ° C. for 12 hours and dried until the water content became 1% to obtain a granulated B part.

The thus prepared A. Four liters of each granule of the B part was put in a water-soluble film packaging material (made of polyvinyl alcohol) according to the present invention and sealed. For comparison, a kit not included in the film packaging material was also prepared.

When using the above-mentioned replenisher for development and fixing, it was dissolved in water using a mixer to make up to 4 liters. The pH during finishing was adjusted so that the pH of the developing replenisher was 10.72 and the pH of the fixing replenisher was 4.2.

The above-prepared replenisher was used in an amount of 190 ml / m ² and a replenisher of 190 ml / m ² per large-sized (508 × 610 mm) photosensitive material to be processed.
After replenishment of m ² , 2,000 sheets were processed (one exposed portion of all the sheets was 20% of the entire area). Automatic developing machine is G
R-26SR (manufactured by Konica Corporation) was modified so that a replenishing section of a developing tank and a fixing tank could be used so that a solid processing agent (granules) could be charged.

<Evaluation Method> (Evaluation of Linearity) When linearity is changed by changing the exposure amount in halftone dot formation and adjusting the exposure amount to 2% in theory from what should theoretically be 2%, it is theoretically possible. What percentage of the point that should become 95% was measured. It is desirable that the value be close to 95%. X-Rite361T was used for the measurement.

(Evaluation of Maximum Density) Evaluation was made at the maximum density when a 50% halftone dot document was exposed to a 50% halftone dot area on a film sample. The higher the value, the better.

(Evaluation of dissolution time of kit) A sample of the treatment agent obtained by arbitrarily sampling was used. The kit was placed in 4 liters of warm water at 35 ° C., stirred at a constant speed, and the time until complete dissolution was measured. A preferred level is one in which the dissolution time is within 15 minutes.

(Evaluation of Amount of Fine Powder Generated) A sample arbitrarily sampled from the obtained treating agent kit was used. Give a certain vibration to the kit with a vibration tester,
The weight ratio of the fine powder generated immediately after completion was measured. If the amount of the fine powder exceeds 0.5%, the powder flutters and adheres to the face of the worker, which is not preferable. Table 2 shows the results obtained above.
Shown in

[0132]

[Table 2]

As is evident from the results in Table 2, the sample of the present invention had a high maximum concentration and exhibited excellent linearity. The sample of the present invention was superior when the dissolution time of the treatment agent kit of the present invention and the amount of fine powder generated during preparation were compared with those of a comparative sample.

With respect to the fixing replenisher, the sample with the water-soluble packaging material of the present invention completely dissolved in 12 minutes, and the sample without the water-soluble packaging material completely dissolved in 13 minutes. The sample of the present invention was excellent.

[0135] EXAMPLE _{2 K 3 Os (H 2 O} ) a Cl ₅ per mol of silver 8 × 10 during mixing by using a simultaneous mixing method <Preparation of Silver Halide Emulsion C>
^-5 mol and K ₂ IrCl ₆ × 10 ^-7 mol per mol of silver were added, and desalting was carried out by a conventional method. Silver content 9
An emulsion of cubic grains (9 mol%, the remainder consisting of silver bromide) was obtained.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI), potassium bromide and citric acid were added, and inorganic sulfur was reduced to 3 × per mole of silver. After adding 10 ^-6 mol, chemical ripening was carried out at a temperature of 60 ° C. until the maximum sensitivity was obtained. After aging, TAI
With 2 × 10 ^-3 mole per mole of silver and 1-phenyl-5-
3 × 10 ^-4 mol of mercaptotetrazole and gelatin were added.

(Preparation of a silver halide photographic light-sensitive material for use in a printing plate making room) A subbing layer of gelatin having the following formula 1 was coated on one subbing layer of one of the supports in the same manner as in Example 1 and the amount of gelatin was 0.1%.
5 g / m so that the ^2, amount of silver 2.8 g / m ² of the silver halide emulsion of Formulation 2 thereon, gelatin amount 1.0 g /
m ^2, and a coating solution of the following formula 3 was simultaneously applied thereon as a protective layer so that the amount of gelatin became 0.5 g / m ² . On the opposite undercoat layer, JP-A-5-188518 reports 360 (14) to 361 (15)
After applying the conductive layer of Example 1 described on the page, a backing layer of the following formulation 4 was further coated with a polymer layer of the following formulation 5 so that the amount of gelatin was 0.4 g / m ² , and furthermore, A sample was obtained by simultaneously applying a backing protective layer having the following formulation 6 so that the amount of gelatin became 0.4 g / m ² .

Formulation 1 (Composition of gelatin undercoat layer) Gelatin 0.6 g / m ² Dye b (Dispersed into a powder having a particle size of 0.1 μm by ball mill dispersion) 20 mg / m ² Dye k 10 mg / m ² Dye AD -1 80 mg / m ² hydrophilic polymer of styrene-maleic acid copolymer (thickener) 10 mg / m ² Compound S-1 0.4 mg / m ² Formulation 2 (Silver halide emulsion layer composition) Tetrazolium compound Amount shown in Table 3 Sodium dodecylbenzenesulfonate 10 mg / m ² 5-methylbenzotriazole 10 mg / m ² Compound e 6 mg / m ² Latex polymer f 1.0 g / m ² Hardener g 40 mg / m ² Compound S -1 0.7 mg / m ² styrene - hydrophilic polymer maleic acid copolymer (thickener) 20 mg / m ² formulation 3 (emulsion protective layer composition) gelatin 0.5 g / m ² dye 100 mg / m ² Compound S-1 12mg / m ² Matting agent: average particle size 3μm monodisperse silica 15 mg / m ² Matting agent: monodisperse with an average particle diameter of 8μm silica 20 mg / m ² 1,3-vinylsulfonyl -2 -Propanol 50 mg / m ² surfactant h 1 mg / m
² Colloidal silica (average particle size 0.05 μm) 20 mg / m ² Prescription 4 (backing layer composition) Gelatin 0.4 g / m ² Compound S-1 5 mg / m ² Latex polymer f 0.3 g / m ² Colloidal silica (average 70 mg / m ² hydrophilic polymer of styrene-maleic acid copolymer (thickener) 20 mg / m ² Compound i 100 mg / m ² Formulation 5 (polymer layer composition) Latex n (styrene: butadiene: Acrylic acid = 30: 65: 5) 1.0 g / m ² Hardener g 10 mg / m ² Prescription 6 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: monodisperse polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² Sodium - di - (2-ethylhexyl) - sulfosuccinate 10 mg / m ² surfactant ^{h 1mg / m 2 H (OCH} 2 CH 2) 68 H 50 mg / m ² Hardener j 40 mg / m ² Encyclopedia size of the photosensitive material prepared above (508 × 610
mm) per sheet, 130 ml / m
^2. Replenish the fixing replenisher with 130 ml / m ² to 2000
A large number of sheets were processed (one exposed part of the entire area was 20% of the entire area). The same automatic developing machine as in Example 1 was used, and the solid processing agent (granules) was charged.

<Initiating developer formulation> 1 liter of working solution Pure water 196 g Potassium carbonate 60 g Hydroquinone 16 g Compound of general formula (A) Amount shown in Table 3 1.6 g of dimaison S 3.6 g of DTPA / 5Na (40 wt%) Odor Potassium iodide 2.5 g 5-methylbenzotriazole 0.50 g 1-phenyl-5-mercaptotetrazole 0.02 g 2-mercaptohypoxanthine 0.06 g sodium sulfite 14.66 g potassium sulfite 35.15 g diethylene glycol 50 g Finally, 500 ml with pure water Finished. The pH was adjusted to 10.20 with potassium hydroxide. This concentrated liquid was diluted twice with water to obtain a starting liquid (pH: 9.8).

<Preparation of Development Replenisher> (Preparation of Part A) 1 liter of working solution DTPA / 5Na 4.35 g Sodium sulfite 15.76 g Potassium bromide 5.0 g Potassium carbonate 32.84 g Potassium hydrogen carbonate 16.2 g 8 -Mercaptoadenine 0.06 g Mannit 8 g Sorbit 7 g The above ingredients were mixed in a commercially available bantamul mill for 30 minutes,
Furthermore, after granulating at room temperature for 10 minutes with a commercially available stirring granulator,
Using a batch freeze dryer, the internal pressure was reduced to about 5 mmHg, followed by cooling. Then, the mixture was treated at −20 ° C. for 12 hours and dried until the water content became 1% to obtain a granulated A part.

(Preparation of Part B) 1 liter of used solution 5-methylbenzotriazole 0.50 g Dimezone S 2.50 g 1-phenyl-5-mercaptotetrazole 0.04 g Compound of general formula (A) Amount shown in Table 3 Mannit 7 g Sorbite 8 g Sodium octanesulfonate 1.25 g Hydroquinone The amount shown in the table The above materials were mixed for 30 minutes in a commercially available bantamul mill,
Furthermore, after granulating at room temperature for 10 minutes with a commercially available stirring granulator,
Using a batch freeze dryer, the internal pressure was reduced to about 5 mmHg, followed by cooling. Then, the mixture was treated at -20 ° C for 12 hours and dried until the water content became 1% to obtain a granulated B part.

The thus prepared A. Four liters of each granule of the B part was put in the water-soluble film packaging material (made of starch) according to the present invention and sealed. For comparison, a kit not included in the film packaging material was also prepared.

When the above developer replenisher was used, it was dissolved in water using a mixer to make it up to 4 liters.

<Preparation of fixing replenisher> The same fixing replenisher as in Example 1 was used. However, the same water-soluble film packaging material as that used in the developing replenisher of Example 2 was used.

Processing Step Current image 35 ° C. for 15 seconds Fixing 35 ° C. for 10 seconds Rinse at room temperature 10 seconds Drying 48 ° C. for 10 seconds <Evaluation method> (Evaluation of gradation reproducibility) Dainippon Screen P-627
Was used to expose the film, and the film was processed under the above processing conditions. The exposure amount when 5% of the gray scale of the gray scale of the halftone dot output from the scanner of the exposed photosensitive material is adjusted to 95% on the return photosensitive material, and the exposure on the gray scale is 95%. % Of the halftone dot when the halftone dot was returned on the return photosensitive material was measured. The closer the value is to 5.0, the better the tone reproducibility.

(Evaluation of Draft Characters) When the above-mentioned halftone dot original portion having a halftone dot area ratio of 50% is properly exposed to halftone dots having a halftone dot area ratio of 50%, the character width reproduced is μm.
Expressed in units. Those that can reproduce only characters having a width of 150 μm or more have poor image quality, and those that can reproduce 30 μm are preferable image quality. The smaller the value in the table, the better the blank character performance.

<Evaluation of Maximum Concentration of Actual Technique, Dissolution Time, and Generated Amount of Fine Powder> All were evaluated in the same manner as in Example 1. The above evaluation results are shown in Table 3 below.

[0148]

[Table 3]

As is clear from the table, the sample according to the present invention was excellent in tone reproducibility, blank character quality and maximum density as a return photosensitive material as compared with the comparison. When the dissolution time of the treatment agent kit and the amount of fine powder generated during preparation were compared with the comparative sample, the sample of the present invention was superior.

[0150]

As demonstrated in the examples, according to the present invention, a developing replenisher and a replenishing fixing agent were obtained as a processing agent kit in which fine powder did not flutter during preparation. When processed by the obtained kit, a processing method for a photosensitive material having excellent plate making characteristics such as maximum density, linearity, gradation reproducibility, and blank character quality was obtained.

Claims (4)

[Claims] 1. A method for processing a black-and-white silver halide photographic material processed by an automatic developing machine, wherein a black-and-white developer used contains at least one developer represented by the following general formula (A). A method for processing a silver halide photographic light-sensitive material, wherein the developing replenisher or the fixing replenisher of the developer is a powdery or solid processing agent sealed in a water-soluble film packaging material. Embedded image In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group,
R ₁ and R ₂ may combine with each other to form a ring. M ₁ ,
M ₂ represents a hydrogen atom or an alkali metal atom, respectively. k represents 0 or 1, and when k is 1, X represents -CO- or -CS-. 2. A method for processing a black-and-white silver halide photographic material processed by an automatic developing machine, wherein a dihydroxybenzene-based developer: a developer represented by the above general formula (A) is used in a black-and-white developer used. Is 0: 1 to 100
2. The composition according to claim 1, wherein the content is within a range of 0: 1.
The method for processing a silver halide photographic light-sensitive material described in the above. 3. The method for processing a black-and-white silver halide photographic light-sensitive material according to claim 1, wherein the constituent layer of the silver halide photographic light-sensitive material contains at least one hydrazine derivative as a high contrast agent. A method for processing a silver halide photographic material. 4. The method for processing a black-and-white silver halide photographic light-sensitive material according to claim 1, wherein the constituent layer of the silver halide photographic light-sensitive material contains at least one tetrazolium compound as a high contrast agent. A method for processing a silver halide photographic material.