JPH0954400A - Development processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the development processing method for the silver halide black-and-white sensitive material capable of obtaining a sufficiently high- contrast negative image with a stable developing solution low in pH of <=11.0 and reducing fluctuation of photographic performance and silver stains even in a small rate of replenishing the developing solution and obtaining always stable performances. SOLUTION: The silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer and at least one protective layer on the same side of a support and it contains at least one kind of hydrazine derivative in the emulsion layer or another hydrophilic colloidal layer, and the total amount of a coated gelatin on the side of the emulsion layers is <=2.8g/m<2> and the swelling rate of the total coated layers on the side of the emulsion layers is <=120%. This photosensitive material is exposed and processed by using the developing solution containing a hydroxybenzene type developing agent and its assistant agent and having an initial pH of 9.5-11.0, and when 0.1mol of acetic acid is added to 1l of the developing solution, having a pH drop of <=0.3, and by replenishing the developing solution in an amount of <=180ml/m<2> .

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a development processing method using a silver halide photographic light-sensitive material to form an ultrahigh contrast image at a pH of less than 11.0. The present invention relates to a less developing method.

[0002]

2. Description of the Related Art In the field of graphic arts, photographic characteristics of ultra-high contrast (especially gamma of 10 or more) are required in order to improve the reproduction of continuous tone images or line images using halftone dots. Is required. As a method for obtaining high-contrast photographic characteristics, a lith development method utilizing an infectious development effect has been used for a long time, but it has a drawback that the developer is unstable and difficult to use.

The addition of hydrazine compounds to silver halide photographic emulsions and developers is described in US Pat. No. 3,730,7.
No. 27 (developer combining ascorbic acid and hydrazine), No. 3,227,552 (using hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,
No. 386,831 (containing β-mono-phenylhydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitizers), No. 2,419,975 and by Mees.
The Theory of Photographic Process
Theory of Photographic Process) 3rd Edition (1966)
Year) 281 pages, etc. Among these, in particular,
U.S. Pat. No. 2,419,975 discloses the addition of a hydrazine compound to obtain a hard negative image. According to the patent specification, when a hydrazine compound is added to a silver chlorobromide emulsion and developed with a developer having a high pH of 12.8, a gamma (γ) of more than 10 and extremely high photographic characteristics are obtained. Is listed. However, a strong alkaline developer having a pH close to 13 is easily oxidized by air and is unstable, and cannot withstand long-term storage and use. Attempts have been made to develop a high-contrast image by developing a silver halide light-sensitive material containing a hydrazine compound with a developer having a lower pH. JP-A-1-179939 and JP-A-1-179940 disclose a photographic material containing a nucleation development accelerator having an adsorptive group for silver halide emulsion grains and a nucleator having the same adsorptive group, and a pH of 11 or more. A processing method of developing with a developer of 0.0 or less is described. However, when a compound having an adsorptive group is added to a silver halide emulsion, if it exceeds a certain limit, the photosensitivity may be impaired, the development may be suppressed, or the action of other useful adsorptive additives may be hindered. Therefore, the amount used is limited, and sufficient hardness cannot be achieved. JP-A-60-1403
No. 40 discloses that the addition of amines to a silver halide photographic light-sensitive material improves the contrast. However, when developing with a developer having a pH of less than 11.0, sufficient high contrast cannot be exhibited. JP 56
-106244 discloses that an amino compound is added to a developer having a pH of 10 to 12 to promote contrast. However, when amines are used by adding them to a developing solution, there are problems such as odor of the solution and stains due to adhesion to equipment used, or environmental pollution due to waste solution, and it is desired to incorporate it into a light-sensitive material. It has not yet been found that it can be added to a light-sensitive material to obtain sufficient performance.

US4998604 and US499
No. 4365 discloses a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, as is clear from these examples, the contrast is not sufficient,
It is difficult to obtain the high contrast and the required Dmax under practical development processing conditions.

In order to obtain a super-high contrast image by using a stable developing solution having a pH of less than 11.0, various investigations have been carried out and a specific hydrazine nucleating agent and a specific quaternary onium salt nucleation promoting agent are contained in a light-sensitive material. It has been found that a super-high contrast image can be obtained by using the agent together. However, even in this method, the replenishing amount of the developing solution is required to be about 320 to 450 ml when processing 1 square meter of the silver halide photographic light-sensitive material, and a further replenishing amount reducing method and a stable processing method are desired. When the replenishment amount is reduced, there is a problem that silver sludge in the developing tank increases and adheres to the photosensitive material.

It is known to reduce the change in photographic performance by reducing the change in pH value of the developer,
Stabilizing photographic performance by increasing the buffering capacity of a developing solution is disclosed in Japanese Patent Publication No. 3730/1993.

[0007]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to obtain a sufficiently hard negative image with a stable developing solution having a pH of less than 11.0 and to improve the photographic performance with a small replenishing amount of the developing solution. It is an object of the present invention to provide a development processing method for a silver halide black and white photographic light-sensitive material, which has a small fluctuation and a small amount of silver stain, and can always obtain stable performance.

[0008]

The object of the present invention is to have at least one photosensitive silver halide emulsion layer and at least one protective layer on the same surface of a support, and the emulsion layer or other 1. The hydrophilic colloid layer of No. 1 contains at least one hydrazine derivative, and the total gelatin coating amount on the emulsion layer side is 2.
A silver halide photographic light-sensitive material having a swelling ratio of 8 g / m ² or less and a total coating layer on the emulsion layer side of 120% or less is exposed, and then a dihydroxybenzene-based developing agent and an auxiliary developing agent are contained in the developer. When 0.1 mol of acetic acid was added to 1 liter, the pH decrease was 0.3 or less, and the initial pH of the developer was
It was achieved by a method of developing a silver halide photographic light-sensitive material, which comprises developing the developer with a replenishing amount of 180 ml / m ² or less using a developer of 9.5 to 11.0.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The silver halide photographic light-sensitive material of the present invention contains a hydrazine derivative. As the hydrazine derivative, any known compound can be used, but a compound represented by the following general formula (I) is preferable.

[0010]

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In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group, Or represents a hydrazino group, G ₁ is a —CO— group,
-SO ₂ group, -SO- group,

[0012]

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A --CO--CO-- group, a thiocarbonyl group,
Or an iminomethylene group, A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted Represents a substituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

The general formula (I) will be described in more detail. In the general formula (I), the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent. In the general formula (I), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group. The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group-containing group, a pyridinium group and a hydroxy group. Group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, group having a hydrazide structure A group having a quaternary ammonium structure, an alkyl or aryl thio group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carboxyl group, a sulfo group, an acyl group, an alkoxy or aryloxy carbonyl group, a carbamoyl group, a sulfamoyl group, Examples include a rogen atom, a cyano group, a phosphoric acid amide group, a diacylamino group, an imide group, a group having an acylurea structure, a group containing a selenium atom or a tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure, and the like. As a preferred substituent, a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 20),
An aralkyl group (preferably having 1 to 4 carbon atoms in the alkyl moiety)
3 monocyclic or bicyclic), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms),
Acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (Preferably having 1 to 3 carbon atoms
0) and so on.

In the general formula (I), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
5- and 6-membered compounds containing oxygen and sulfur atoms, for example, imidazolyl, pyrazolyl, triazolyl,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. Pyridyl or pyridinium groups are particularly preferred. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, aryl Amino groups are preferred. R ₂ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₁ . Preferred among the groups represented by R ₂ is when G ₁ is a —CO— group,
A hydrogen atom, an alkyl group (eg, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group, etc.), an aralkyl group (eg, an o-hydroxybenzyl group, etc.), Aryl group (for example, phenyl group, 3,5
-Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom and a trifluoromethyl group. Also, G ₁ is -S
In the case of an O ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, , Dimethylamino group, etc.) are preferred. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and an amino group are preferred.
As G in the general formula (I), a -CO- group and a -COCO- group are preferable, and a -CO- group is most preferable. R ₂ is G
The part of _1- R ₂ is split from the residual molecule, and -G ₁ -R ₂
It may be one that causes a cyclization reaction to form a cyclic structure containing a partial atom, and examples thereof include those described in JP-A-63-29751.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
A phenylsulfonyl group substituted so as to have a value of 0.5 or more; an acyl group having 20 or less carbon atoms (preferably a benzoyl group or a substituent having a sum of Hammett's substituent constants of -0.5 or more); A benzoyl group or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group; ))). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (I) may be further substituted, and preferable examples thereof include those exemplified as the substituents of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ...
, Etc. may be substituted multiple times, and preferred examples also include those exemplified as the substituent of R ₁ .

R ₁ or R ₂ of the general formula (I) may have a ballast group or polymer commonly used in a non-moving photographic additive such as a coupler incorporated therein. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (I) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of such an adsorbing group include U.S. Pat. Nos. 4,385,108 and 4,459,34 such as an alkylthio group, an arylthio group, a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

Preferred hydrazine derivatives in the present invention are those in which R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of silver halide grains, a group having a quaternary ammonium structure or an alkylthio group. A phenyl group having a group, G
Is a —CO— group, and R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is preferably an electron-withdrawing group or a hydroxymethyl group at the 2-position). It should be noted that any combination of the above-mentioned options of R ₁ and R ₂ is possible and preferable.

In the present invention, a hydrazine derivative characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the hydrazine group is particularly preferably used.

Specific examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. The nonionic group that forms an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and has at least an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. A group having one. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group, and an acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred. Preferred nucleating agents used in the present invention are those represented by the following general formulas (1) to (3). General formula (1)

[0023]

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(Wherein R ¹ represents an alkyl group, an aryl group or a heterocyclic group, L ¹ represents a divalent linking group having an electron-withdrawing group, Y ¹ represents an anionic group or a hydrogen atom of hydrazine). Represents a nonionic group that forms an intramolecular hydrogen bond.) General formula (2)

[0025]

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(In the formula, R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, and Y
² represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. ) General formula (3)

[0027]

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(In the formula, X ³ represents a group capable of substituting on a benzene ring, R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group or an amino group, and Y ³ represents An anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine, m ³ is an integer of 0 to 4, n ³ is 1 or 2. When n ³ is 1, R ³ is It has an electron-withdrawing group.)

The general formulas (1) to (3) will be described in more detail. The alkyl group of R ¹ and R ² is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, such as methyl, ethyl,
Propyl, isopropyl, t-butyl, allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl, 4-methylbenzyl,
2-methoxyethyl, cyclopentyl and 2-acetamidoethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, for example, phenyl, naphthyl, p-alkoxyphenyl, p-sulfonamidophenyl, p-ureidophenyl, p-amidophenyl. Is. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocycle containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The type of the element may be one or plural, and examples thereof include 2-furyl, 2-thienyl, and 4-pyridyl.

An aryl group is preferred as R ¹ and R ² .
An aromatic heterocyclic group or an aryl-substituted methyl group,
More preferably, it is an aryl group (eg phenyl, naphthyl). R ¹ and R ² may be substituted with a substituent, and examples of the substituent include an alkyl group, an aralkyl group,
An alkoxy group, an alkyl- or aryl-substituted amino group,
Amide group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group,
A sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphorus amide group. These groups may be further substituted. Of these, a sulfonamide group, a ureido group, an amide group, an alkoxy group, and a urethane group are preferable, and a sulfonamide group and a ureido group are more preferable. When possible, these groups may be linked to each other to form a ring.

The alkyl group of R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethynyl and phenylethynyl. The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms.
Linear, branched or cyclic alkoxy group such as methoxy, isopropoxy and benzyloxy.
The amino group has 0 to 16 carbon atoms, preferably 1 carbon atom.
-10, and are ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group, or an alkynyl group. n ³ =
In the case of 2, R ³ is preferably an amino group or an alkoxy group.

The electron-withdrawing group possessed by R ³ has a Hammett's σ _m of 0.2 or more, preferably 0.3
As described above, for example, a halogen atom (fluorine, chlorine, bromine), a cyano group, a sulfonyl group (methanesulfonyl, benzenesulfonyl), a sulfinyl group (methanesulfinyl), an acyl group (acetyl, benzoyl), an oxycarbonyl group (methoxycarbonyl) ), Carbamoyl group (N-methylcarbamoyl), sulfamoyl group (methylsulfamoyl), halogen-substituted alkyl group (trifluoromethyl), heterocyclic group (2-benzoxazolyl, pyrrolo), quaternary onium group (tri Phenylphosphonium, trialkylammonium, pyridinium). Examples of R ³ having an electron-withdrawing group include trifluoromethyl, difluoromethyl, pentafluoroethyl, cyanomethyl, methanesulfonylmethyl, acetylethyl, trifluoromethylethynyl and ethoxycarbonylmethyl.

L ¹ and L ² each represent a divalent linking group, and include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, and those represented by —O—, —S—,
It is a group in which groups such as —NH—, —CO—, and —SO ₂ — are used alone or in combination. L ¹ and L ² are R
^It may be substituted with the group described as the substituent of ¹ . Examples of the alkylene group include methylene, ethylene, trimethylene, pentamethylene, octamethylene, propylene, 2-butene-1,4-yl, 2-butyne-1,4-.
And p-xylylene. The alkenylene group is, for example, vinylene. The alkynylene group is ethynylene. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ¹ is an alkylene group,
An alkenylene group, an alkynylene group and an arylene group are preferable, and an alkylene group is more preferable. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L ² is an alkylene group, an arylene group, —NH-alkylene-,
-O-alkylene- and -NH-arylene- are preferable, and -NH-alkylene- and -O-alkylene- are more preferable.

The electron-withdrawing group of L ¹ is R ³
Examples of the electron-withdrawing group of the above include.
Examples of L ¹ include tetrafluoroethylene, fluoromethylene, hexafluorotrimethylene, perfluorophenylene, difluorovinylene, cyanomethylene, and methanesulfonylethylene.

Y ¹ to Y ^{3 are} as described above, and are anionic groups or nonionic groups in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring. More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid, and salts thereof. Examples of the salt include alkali metal ions (sodium and potassium), alkaline earth metal ions (calcium and magnesium), ammonium (ammonium, triethylammonium, tetrabutylammonium, pyridinium) and phosphonium (tetraphenylphosphonium). As the nonionic group, an oxygen atom, a nitrogen atom, a group having at least one of a sulfur atom and a phosphorus atom, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group,
Examples thereof include an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. Y ¹ to Y ³ are preferably anionic groups, and more preferably carboxylic acids and salts thereof.

Examples of the group capable of substituting on the benzene ring of X ³ and its preferable groups include those mentioned as the substituents of R ^{1 in the} general formula (1). When m ³ is 2 or more, they may be the same or different.

R ¹ to R ³ or X ³ may have a diffusion-resistant group used in photographic couplers or may have a group promoting adsorption to silver halide. The diffusion-resistant group has 8 to 30 carbon atoms, and preferably has 12 to 25 carbon atoms. As the adsorption-promoting group for silver halide, thioamides (eg, thiourethane,
Thioureido, thioamide), mercaptos (eg 5
-Mercaptotetrazole, 3-mercapto-1,2,2
Heterocyclic mercapto such as 4-triazole, 2-mercapto-1,3,4-thiadiazole, and 2-mercapto-1,3,4-oxadiazole, alkylmercapto,
Aryl mercapto) and a 5- or 6-membered nitrogen-containing heterocycle (eg benzotriazole) which produces silver imino
It is. Examples of those having a silver halide adsorption promoting group include those having a structure in which the adsorptive group is protected and the protective group is removed at the time of development to increase the adsorptivity to silver halide.

In the general formulas (1) to (3), the radicals of each of the two compounds from which the hydrogen atoms have been removed may combine to form a bis-type. In the general formulas (1) to (3), the general formulas (1) and (2) are preferable, and the general formula (1) is more preferable. Furthermore, in the general formulas (1) to (3), the following general formulas (4) to (6) are more preferable, and the general formula (4) is most preferable. General formula (4)

[0040]

[Chemical 6]

(Wherein R ⁴ , X ⁴ and m ⁴ have the same meanings as R ³ , X ³ and m ^{3 in the} general formula (3), respectively, and L ⁴ , Y ^{4 and}
Is synonymous with L ¹ and Y ^{1 in} the general formula (1). ) General formula (5)

[0042]

[Chemical 7]

(In the formula, R ⁵ , X ⁵ and m ⁵ have the same meanings as R ³ , X ³ and m ^{3 in the} general formula (3), respectively, and L ⁵ and Y ⁵
Is synonymous with L ² and Y ^{2 in} the general formula (2). ) General formula (6)

[0044]

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(In the formula, R ⁶¹ , R ⁶² , X ⁶ , m ⁶ and n ⁶ have the same meanings as R ³ , R ³ , X ³ , m ³ and n ^{3 in} formula (3).)

Specific examples of the hydrazine derivative used in the present invention are shown below, but the present invention is not limited thereto.

[0047]

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[0048]

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[0049]

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[0050]

[Chemical 12]

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

[Chemical 21]

[0060]

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[0061]

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[0062]

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[0063]

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As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
No. 3516 (November 1983, P. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, 4,269,929, 4,276,364
Nos. 4,278,748, 4,385,108
No. 4,459,347 and 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
No. 4,994,365, No. 5,041,355
No. 5,104,769, British Patent 2,011,
391B, EP 217,310, EP 301,310,
No. 799, No. 356, 898, JP-A-60-1797.
No. 34, No. 61-170733, No. 61-27074
No. 4, 62-178246, 62-270948
Nos. 63-29751, 63-32538, 63-110407, 63-121838, and 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
No. 234246, No. 63-294552, No. 63-3
Nos. 06438 and 64-10233, JP-A-1-90
No. 439, No. 1-100530, No. 1-1095941
No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2
No. 83549, No. 1-285940, No. 2-2541
No. 2, No. 2-77057, No. 2-139538, No. 2
196234, 2-196235, 2-19
No. 8440, 2-198441, 2-198442
Nos. 2-220042, 2-221953, 2-221954, 2-285342, and 2-2
No. 85343, No. 2-289843, No. 2-3027
No. 50, No. 2-304550, No. 3-37642,
3-54549, 3-125134, 3-1
No. 84039, No. 3-240036, No. 3-2400
No. 37, No. 3-259240, No. 3-280038.
Nos. 3-282536, 4-51143, and 4
-56842, 4-84134, 2-2302
No. 33, No. 4-96053, No. 4-216544,
5-45761, 5-45762, 5-45
No. 763, No. 5-45764, No. 5-45765,
Those described in Japanese Patent Application No. 5-94925 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, and particularly 1 × 1 mol per mol of silver halide.
The preferable addition amount is in the range of 0 ^-5 mol to 2 × 10 ^-2 mol.

The hydrazine derivative of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve. It can be used by dissolving it in Also, by an already well-known emulsification dispersion method, dissolution using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsifying and dispersing. An object can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used. Further, as described in JP-A-2-948, it can be used by being contained in polymer fine particles.

In the present invention, it is preferable to add a nucleation accelerator together with the hydrazine derivative to the silver halide emulsion layer and / or the non-photosensitive layer on the silver halide emulsion layer side on the support. In particular, in the case of processing with the developing solution of the present invention having a pH of less than 11, it is particularly preferable to use a nucleation accelerator together. As the nucleation accelerator, various compounds are known and, for example, amine derivatives, onium salts, disulfide derivatives, and hydroxylamine derivatives can be used. Among them, the following general formulas (II), (III) and (IV ), (V) or amine compounds that function as nucleation accelerators are preferably used.

[0068]

[Chemical formula 26]

In the formula, R ₁ , R ₂ and R ₃ are alkyl groups,
It represents a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, or a heterocyclic residue, which may further have a substituent. m represents an integer of 1 to 4,
L represents an m-valent organic group which is bonded to the P atom by its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X may be linked to L.

[0070]

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In the formula, A represents an organic group for completing the heterocycle. B and C each represent a divalent group. R
₁ and R ₂ each represent an alkyl group or an aryl group, and R ₃ and R ₄ each represent a hydrogen atom or a substituent. X
Represents an anion group, but is not necessary when forming an intramolecular salt.

[0072]

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In the formula, Z represents an atomic group necessary for forming a nitrogen-containing heteroaromatic ring, R represents an alkyl group,
X ⁻ represents a counter anion.

The general formula (II) will be described in detail.
In the formula, R ₁ , R ₂ and R ₃ are an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group,
It represents a heterocyclic residue, which may further have a substituent. m represents an integer, L represents an m-valent organic group which is bonded to the P atom by its carbon atom, and n is 1 to 3
Represents an integer, X represents an n-valent anion, and X represents L
May be connected. Examples of the groups represented by R ₁ , R ₂ and R ₃ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, octyl group, 2- Linear or branched alkyl groups such as ethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, aralkyl groups such as substituted or unsubstituted benzyl group; cycloalkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group Group, phenyl group, naphthyl group, aryl group such as phenanthryl group; allyl group, vinyl group, 5-hexenyl group,
And other alkenyl groups; cyclopentenyl, cyclohexenyl and other cycloalkenyl groups; pyridyl, quinolyl, furyl, imidazolyl, thiazolyl, thiadiazolyl, benzotriazolyl, benzothiazolyl, morpholyl, pyrimidyl And heterocyclic residues such as pyrrolidyl group. Examples of the substituents on these groups include, in addition to the groups represented by R ₁ , R ₂ and R ₃ , a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a nitro group, and a nitro group. 2, secondary or tertiary amino group, alkyl or aryl ether group, alkyl or aryl thioether group, carbonamide group, carbamoyl group, sulfonamide group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group, carboxyl group, sulfonic acid group, A cyano group or a carbonyl group. Examples of the group represented by L are R ₁ , R ₂ and R
_In addition to the groups synonymous with ₃ , trimethylene group, tetramethylene group, hexamethylene group, pentamethylene group, octamethylene group, polymethylene group such as dodecamethylene group, divalent aromatic group such as phenylene group, biphenylene group and naphthylene group. , A polyvalent aliphatic group such as a trimethylenemethyl group and a tetramethylenemethyl group, a polyvalent aromatic group such as a phenylene-1,3,5-toluyl group and a phenylene-1,2,4,5-tetrayl group. Can be mentioned. Examples of the anion represented by X include a chloride ion, a bromine ion, a halogen ion such as an iodine ion, a carboxylate ion such as an acetate ion, an oxalate ion, a fumarate ion, and a benzoate ion, p-toluenesulfonate, and methanesulfonate. , Butanesulfonate, benzenesulfonate and the like, sulfate, perchlorate, carbonate, and nitrate. In the general formula (II), R ₁ , R ₂ and R ₃ are preferably groups having 20 or less carbon atoms, and aryl groups having 15 or less carbon atoms are particularly preferred. m is preferably 1 or 2, and when m represents 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group or an aryl group having 15 or less total carbon atoms. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group or a divalent group formed by combining these groups,
Furthermore, these groups and -CO- group, -O- group, -NR ₄
A group (wherein R ₄ represents a hydrogen atom or a group having the same meaning as R ₁ , R ₂ and R ₃ and when a plurality of R _4's are present in the molecule,
These may be the same or different, and may be bonded to each other), -S- group, -SO- group,
It is a divalent group formed by combining a —SO ₂ — group. When m represents 2, L is particularly preferably a divalent group having a total carbon number of 20 or less, which is bonded to a P atom at that carbon atom. When m represents an integer of 2 or more, R ₁ , R in the molecule
₂ and R ₃ are present in plural, respectively, and the plural R ₁ ,
R ₂ and R ₃ may be the same or different. n is preferably 1 or 2 and m is preferably 1 or 2. X may combine with R ₁ , R ₂ , R ₃ or L to form an inner salt. Many of the compounds represented by the general formula (II) of the present invention are known and commercially available as reagents. As a general synthesis method, there is a method in which a phosphinic acid is reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester, or a method in which a counter anion of a phosphonium salt is exchanged by a conventional method. Specific examples of the compound represented by the general formula (II) are shown below. However, the present invention is not limited to the following compounds.

[0075]

[Chemical 29]

[0076]

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[0077]

[Chemical 31]

[0078]

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[0079]

[Chemical 33]

[0080]

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[0081]

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[0082]

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[0083]

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General formulas (III) and (IV) will be described in more detail. In the formula, A represents an organic group for completing the heterocycle, and may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. As a preferred example, A can be a 5- or 6-membered ring, and a more preferred example is a pyridine ring. B, 2 divalent group represented by C is an alkylene, arylene, alkenylene, -SO ₂
-, - SO -, - O -, - S -, - N (R 5) - those constituted alone or in combination are preferred. Where R
₅ represents an alkyl group, an aryl group, or a hydrogen atom. As particularly preferable examples, B and C are alkylene, arylene,
The thing comprised by combining -O- and -S- individually or in combination can be mentioned. R ₁ and R ₂ are preferably an alkyl group having 1 to 20 carbon atoms, and may be the same or different. The alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom),
A substituted or unsubstituted alkyl group (eg, methyl group,
Hydroxyethyl group), substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group) Etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (for example, methoxy group, ethoxy group, etc.),
It represents an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group and an arylthio group. Particularly preferred examples are R ₁ and R
₂ represents an alkyl group having 1 to 10 carbon atoms. Preferred examples of the substituent include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. R ₃ , R ₄
Represents a hydrogen atom or a substituent, and examples of the substituent are selected from the above-mentioned substituents of the alkyl group of R ₁ and R ₂ . As preferred examples, R ₃ and R ₄ have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. X represents an anionic group, but X is not necessary in the case of an inner salt. Examples of X include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate. Next, specific compounds of the present invention are described, but are not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (See Quart. Rev., 16, 163.
(1962). ) Specific compounds of the general formulas (III) and (IV) are shown below, but the present invention is not limited thereto.

[0085]

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[0086]

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[0087]

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The general formula (V) will be described in more detail. The nitrogen-containing heteroaromatic ring represented by Z may contain a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom in addition to the nitrogen atom,
Further, the benzene ring may be condensed. The heteroaromatic ring formed is preferably a 5- or 6-membered ring, more preferably a pyridine ring, a quinoline ring, or an isoquinoline ring. R has 1 to 1 carbon atoms
The alkyl group of 20 is preferable, and it may be a straight-chain, branched or cyclic alkyl group. 1 to 1 carbon atoms
Alkyl groups of 2 are more preferred, with 1 to 8 carbons being most preferred. X ⁻ represents an anion group, but in the case of an intramolecular salt, X ⁻ is not necessary. Examples of X ^- are chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-
Represents toluene sulfonate ion, oxalate.

The groups represented by Z and R may be substituted and preferable substituents include a halogen atom (eg chlorine atom, bromine atom), a substituted or unsubstituted aryl group (eg phenyl group, tolyl group). Group, p-chlorophenyl group, etc.), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, Ethoxy group),
It represents an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group and an arylthio group. Examples of particularly preferred substituents include
Examples include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. In addition, as the substituent of Z, a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), a substituted or unsubstituted aralkyl group (eg, benzyl group, p-methoxyphenethyl group, etc.) can also be used. preferable. Next, specific compounds of the present invention are described, but are not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (Reference, Quart. Rev., 16, 163 (1962).) Specific compounds of the general formula (V) are shown below, but the present invention is not limited thereto.

[0090]

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[0091]

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[0092]

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The amino compound that functions as a built-in nucleation accelerator will be described in detail. Effective amino compounds are described in US Pat. No. 4,975,354,
(1) contains at least one secondary or tertiary amino group, and (2) at least 3 in their structure.
A group consisting of one repeating ethyleneoxy unit and (3) exhibiting at least one, preferably at least three, most preferably at least four partition coefficients,
It is an amino compound.

The range of amino compounds used as built-in nucleation accelerators includes monoamines, diamines and polyamines. These amines may contain aliphatic amines or aromatic or heterocyclic moieties. The aliphatic, aromatic and heterocyclic groups present in the amine can be substituted or unsubstituted groups. The amino compounds of the present invention are compounds of at least 20 carbon atoms. The amino compound used as a built-in nucleation accelerator is a bis-tertiary amine having a distribution coefficient of at least 3 represented by the following formula.

[0095]

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In the above formula, n is an integer value of 3 to 50, more preferably 10 to 50, and R ₁ , R ₂ , R ₃ and R
₄ is independently an alkyl group having 1 to 8 carbon atoms, or R ₁ and R ₂ together represent an atom necessary for completing a heterocyclic ring, or R ₃ and R ₃ R ₄ represents an atom necessary to complete a heterocyclic ring together.

The amino compound used as a built-in nucleation accelerator has a structure represented by the following formula and has at least 3
Bis secondary amines having a partition coefficient of

[0098]

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In the above formula, n is an integer value of 3 to 50, more preferably 10 to 50, and each R is independently a straight chain or branched chain substituted or unsubstituted group having at least 4 carbon atoms. It is a substituted alkyl group. Preferably, the group consisting of at least 3 repeating ethyleneoxy units is directly attached to a tertiary amino nitrogen atom, and most preferably the group consisting of at least 3 repeating ethyleneoxy units is a bis-tertiary amino compound. Is linked to the tertiary amino nitrogen atom of. The most preferred amino compound is a compound represented by the following formula. Pr represents n-propyl.

[0100]

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Another amino compound useful as a built-in nucleation accelerator is the amino compound described in US Pat. No. 4,914,003 and is represented by the following formula.

[0102]

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In the above formula, R ₂ and R ₃ may be substituted or unsubstituted alkyl groups or may be linked to each other to form a ring, and R ₄ is a substituted or unsubstituted alkyl, aryl or heterocyclic ring. the stands, a represents a divalent linking group, X is _{-CONR 5 -, - O-CONR} 5, -NR 5
CONR ₅ , -NR ₅ COO-, -COO-, -OCO
-, - CO -, - NR 5 CO -, - SO 2 NR 5 -, -
NR ₅ SO ₂ —, —SO ₂ —, —S— or —O— group, R ₅ in these groups represents a hydrogen atom or a lower alkyl group, and n represents 0 or 1, provided that The total number of carbon atoms contained in R ₂ , R ₃ , R ₄ and A is 20 or more.

Further, another amino compound useful as a built-in nucleation accelerator is the amino compound described in US Pat. No. 5,030,547 and represented by the following formula. Y ₀ [(A ₀ ) _n B] _{m In the} above formula, Y ₀ represents a group that promotes adsorption to silver halide, A ₀ represents a divalent linking group, B represents an amino group, an ammonium group or nitrogen. Represents a heterocyclic group containing, m is 1, 2 or 3, and n is 1 or 2.

General formula (II), general formula (III), general formula (I
The addition amount of V), the compound represented by the general formula (V) and the amino compound useful as a nucleation accelerator is not particularly limited as long as it is added in a necessary amount depending on the characteristics of the photosensitive material. When used in the present invention, the preferable addition amount is 1 ×
10 ^{−5 to} 2 × 10 ⁻² mol / molAg, more preferably 2
It is x10 ^-5 to 1 x 10 ^-2 mol / molAg.

The compounds of the general formula (II), general formula (III), general formula (IV) and general formula (V) of the present invention and the amino compound useful as a nucleation accelerator are suitable water-miscible organic solvents. , For example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like can be used. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, a fine dispersion can be used by a method known as a solid dispersion method.

The total coating amount of gelatin on the side where the silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention is provided is 2.8 g / m ² or less, preferably 0.5 to 2.8.
g / m, particularly preferably 1.0 to 2.5 g / m ² or less. The swelling ratio of the entire coating layer on the side where the emulsion layer of the silver halide photographic light-sensitive material of the present invention is provided is 120% or less. Here, the swelling rate is a well-known concept in this field, and the value obtained by subtracting the dry film thickness from the swollen film thickness (swelling thickness) is divided by the dry film thickness, that is, (swelling thickness / dry film thickness) × 10.
It is calculated by 0 (%). In the present invention, it is particularly preferable that the swelling rate is 100% or less. A method for controlling the swelling ratio is known, and it can be achieved by, for example, adjusting the addition amount of the hardener used on the emulsion layer side.

The halogen composition of the silver halide emulsion used in the present invention is such that silver chloride having a silver chloride content of 50 mol% or more, silver chlorobromide, and chloroiodo are more effective in achieving the object of the present invention. Silver bromide is preferred. The content of silver iodide is preferably less than 5 mol%, particularly preferably less than 2 mol%.

In the present invention, the light-sensitive material suitable for high-illuminance exposure such as scanner exposure and the light-sensitive material for line drawing are
Rhodium compounds are included to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaaminerhodium ( III) Complex salt, trisalathodium (II
I) Complex salts and the like can be mentioned. These rhodium compounds are
It is used by dissolving it in water or an appropriate solvent, but it is generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.), or halogenation. A method of adding an alkali (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide. The addition amount is 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver in the silver halide emulsion.

In the present invention, the light-sensitive material suitable for high-illuminance exposure such as scanner exposure and the light-sensitive material for line drawing are
The silver halide photographic light-sensitive material can contain an iridium compound in order to achieve high sensitivity and high contrast. As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like. These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). etc),
Alternatively, an alkali halide (eg KCl, NaC
1, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide. The total amount of the iridium compound added is 1 × 10 ^{−8 to} 5 × 10 5 per mol of the finally formed silver halide.
^-6 mol is suitable, preferably 5 × 10 ^-8 to 1 × 10
^-8 mol. The addition of these compounds can be appropriately carried out at the time of producing silver halide emulsion grains and at each stage before coating the emulsion.
It is preferably incorporated into silver halide grains. The photographic emulsion used in the present invention is described by P. Glafkides Chimie.
et Physique Photographique (published by Paul Montel, 1
967), by GFDufin Photographic Emulsion Che
mistry (published by The Focal Press, 1966), VLZeli
By kman et al Making and Coating Photographic Emulsi
on (The Focal Press, 1964) and the like.

As the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinthione. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016, JP-B-48-3689.
No. 5,163,364, a method in which the addition rate of silver nitrate or alkali halide is changed in accordance with the grain growth rate, or a method disclosed in British Patent No. 4,242,44.
No. 5, JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 2
It is 0% or less, particularly preferably 15% or less. Average grain size of grains in monodisperse silver halide emulsion is 0.5 μm
It is below, and particularly preferably 0.1 μm to 0.4 μm.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination,
For example, a sulfur sensitization method and a gold sensitization method, a sulfur sensitization method, a selenium sensitization method and a gold sensitization method, a sulfur sensitization method, a tellurium sensitization method, and a gold sensitization method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748 and 43-13489,
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
Compounds described in JP-A-121798 can be used. Especially, the general formula (VIII) in Japanese Patent Application No. 3-121798.
It is preferable to use the compounds represented by and (IX).

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in No. 146739.
Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33.
No. 3819, No. 3-53693, No. 3-131598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1,191 (1980), edited by S. Patai, The Chemistry of O, The Chemistry of Organic Selenium and Tellurium Company
rganic Serenium and Tellunium Compounds), Vol 1
(1986) and the compounds described in Vol. 2 (1987) can be used. In particular, the compounds represented by the general formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but is generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to. It is 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide.
About 10 ^-7 to 10 ^-2 mol per mol can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. To the silver halide emulsion of the present invention, a thiosulfonic acid compound may be added according to the method disclosed in European Patent Publication (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes,
Those having different halogen compositions, those having different crystal habits, and those having different conditions of chemical sensitization) may be used in combination.

In the present invention, a silver halide emulsion particularly suitable as a reversal light-sensitive material is a silver halide containing 90 mol% or more, more preferably 95 mol% or more, and a silver bromide of 0 to 10%. It is silver chlorobromide or silver chloroiodobromide containing mol%. If the ratio of silver bromide or silver iodide increases, the safety of safelight in a bright room deteriorates, or γ
Is lowered, which is not preferable.

The silver halide emulsion used in the reversal light-sensitive material of the present invention preferably contains a transition metal complex. As transition metals, Rh, Ru, Re, Os, I
r, Cr, and the like. The ligands include nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenoate ligand Cyanate, tellurocyanate, acid and aquo ligands. When an aco ligand is present, it preferably occupies one or two of the ligands.

Specifically, in order to contain a rhodium atom, a metal salt in any form such as a single salt or a complex salt can be added and added at the time of grain preparation. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium complex compound such as hexachlororhodium (III) acid or a salt thereof ( Ammonium salts, sodium salts, potassium salts, etc.). The amount of these water-soluble rhodium salts added is in the range of 1.0 × 10 ⁻⁶ mol to 1.0 × 10 ⁻³ mol per mol of silver halide. Preferably 1.0 × 10 ⁻⁵ mol to 1.0
× 10 ⁻³ mol, particularly preferably 5.0 × 10 ⁻⁵ mol
It is 5.0 × 10 ⁻⁴ mol.

The following transition metal complexes are also preferable. 1 [Ru (NO) Cl ₅ ] ^-2 2 [Ru (NO) ₂ Cl ₄ ] ^-1 3 [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 4 [Ru (NO) Cl ₅ ] ^-2 5 [Rh (NO) Cl _5] ^-2 6 [Re (NO) CN _5] ^-2 7 [Re (NO) ClCN _4] ^-2 8 [Rh (NO) ₂ Cl _4] ^-1 9 [Rh (NO ) (H ₂ O) Cl _4] ^-1 10 [Ru (NO) CN _5] ^-2 11 [Ru (NO) Br _5] ^-2 12 [Rh (NS) Cl _5] ^-2 13 [Os (NO) Cl ₅ ] ^-2 14 [Cr (NO) Cl ₅ ] ^-2 15 [Re (NO) Cl ₅ ] ^-1 16 [Os (NS) Cl ₄ (TeCN)] ^-2 17 [Ru (NS) I ₅ ] ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

The spectral sensitizing dye used in the present invention is not particularly limited. The addition amount of the sensitizing dye used in the present invention varies depending on the shape, size, etc. of the silver halide grains, but it is used in the range of 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount range of 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol is preferable per 1 m ² of the surface area of the silver halide grain. , Especially 6.5 × 10 ^{−7 to} 2.0 ×
The addition amount range of 10 ⁻⁶ mol is preferable.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized with a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holoholer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643 IV-
Item A (p.23, December 1978), Item 183
It is described in the literature described or cited in Section 1X (p.437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, as for A) an argon laser light source, JP-A-60-1
No. 62247, JP-A-2-48653, US Pat.
No. 161,331, West German Patent 936,071, Simple Merocyanines described in Japanese Patent Application No. 3-189532,
B) For a helium-neon laser light source, see JP-A-50-62425, JP-A-54-18726, and JP-A-59-62426.
No. 102229, trinuclear cyanine dyes, C) L
Japanese Patent Publication No. 48 for ED light source and red semiconductor laser
-42172, 51-9609, 55-398
No. 18, JP-A-62-284343, JP-A-2-10
JP-A-59-1910 for thiacarbocyanines described in 5135 and D) infrared semiconductor laser light source.
No. 32, tricarbocyanines described in JP-A-60-80841, JP-A-59-192242 and JP-A-3-67242, and general formula (IIIa) and general formula (IIIb). -Dicarbocyanines and the like containing a quinoline nucleus are advantageously selected. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Resear
ch Disclosure) Volume 176 17643 (December 1978)
(Published monthly), page 23, IV, J.

For the helium-neon light source, in addition to the above, it is represented by the general formula (I) described in Japanese Patent Application No. 4-228745, page 8, line 1 to page 13, line 4 to line 13. Particularly preferred are sensitizing dyes. In addition to these, Japanese Patent Application No. 4-2
Any of those described in General Formula (I) of 28745 are preferably used.

The sensitizing dye of the general formula (IV) described in Japanese Patent Application No. 5-201254 (page 14, line 14 to page 22, line 23) is preferably used for white light sources such as those photographed by a camera. .

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item This section 1) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, lower left column 13 From line 4 to page 4, lower right column, line 18. 2) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further JP-A 1-237538. Thiosulfinic acid compounds described in the public notice. 3) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 4) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 5) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 7) Dyes Dyes in the lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-187573. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Black spot inhibitor The compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Monomethine compound Compounds of general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 11) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to category 12, page 12, lower left column, and EP452772A.

The developing solution used in the development processing method of the present invention contains a dihydroxybenzene type developing agent and an auxiliary developing agent, and the pH drop is 0 when 0.1 mol of acetic acid is added to 1 liter of the developing solution. Below 0.3, the initial pH of the developer =
It has a property of 9.5 to 11.0. This developer contains additives usually used in the developer (for example,
Alkaline agent, pH buffering agent, preservative, chelating agent) can be contained.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
There are hydroquinone monosulfonate, etc., but hydroquinone is particularly preferable. The auxiliary developing agent used in the present invention is preferably one which exhibits superadditivity with respect to the dihydroxybenzene developing agent, and 1-phenyl-3-pyrazolidone or its derivative and p-aminophenols are particularly useful. 1-phenyl-3-pyrazolidone-based auxiliary developing agents include 1-phenyl-3-pyrazolidone and 1-
Phenyl-4,4-dimethyl-3-pyrazolidone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. Examples of p-aminophenol-based auxiliary developing agents used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl). ) Glycine etc., but among them N-
Methyl-p-aminophenol is preferred. The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter. Particularly preferably, it is in the range of 0.2 to 0.6 mol / liter. The auxiliary developing agent such as 1-phenyl-3-pyrazolidone or p-aminophenol is preferably used in an amount of 0.06 mol / liter or less, more preferably 0.03 mol / liter or less.

Examples of the preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite.
The sulfite is used in an amount of 0.20 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is 1.2 mol / liter. Is desirable. Particularly preferably, 0.
It is 35 to 0.7 mol / liter. As a preservative for a dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Examples of the ascorbic acid derivative include ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof, and sodium erysorbate is preferably used from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably 0.05 to 0.10. In molar ratio to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

As used in the present invention, "the developer 1
The pH decrease when 0.1 mol of acetic acid is added to 1 liter is 0.3 or less. ”Will be described in detail. In the case of the developing solution having a pH of 10.5, for example, p of the case where 0.1 mol of acetic acid is added to 1 liter of the developing solution is used.
A developer having an H value of 10.2 or more. More preferably, the pH drop is 0.25 or less.

As the alkaline agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (eg sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used. Additives other than those described above include development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; alkanolamines such as diethanolamine and triethanolamine; A development accelerator such as imidazole or a derivative thereof; a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound as an antifoggant or black pep
per) may be included as an inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-
Nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-[(2-mercapto-1,3,4-
Sodium thiadiazol-2-yl) thio] butanesulfonate, 5-amino-1,3,4-thiadiazole-
Examples thereof include 2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these antifoggants is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of developer.

Further, various organic / inorganic chelating agents can be used in combination in the developer of the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate or the like can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used. Examples of the organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acelineic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. , Itaconic acid, malic acid, citric acid, tartaric acid and the like, but are not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, and others, JP-A-52-25632, and JP-A-55-67
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Organic phosphonocarboxylic acids include those disclosed in JP-A Nos. 52-102726, 53-42730 and 54.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol per liter of developer.
It is 10 ^-3 to 1 × 10 ^-2 mol.

Further, as a silver stain preventing agent in the developing solution, JP-A-56-24347, JP-B-56-46585,
The compounds described in JP-B-62-2849 and JP-A-4-362942 can be used. Further, a compound described in JP-A-62-212651 can be used as a development unevenness inhibitor, and a compound described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a color toning agent, a surfactant, an antifoaming agent, a hardener and the like may be contained.

The developer used in the present invention contains a carbonate as a buffer, boric acid described in JP-A-62-186259, saccharides (for example, saccharose) and oximes described in JP-A-60-93433. (Eg acetoxime),
Phenols (for example, 5-sulfosalicylic acid), tertiary phosphates (for example, sodium salt, potassium salt) and the like are used, and carbonate and boric acid are preferably used. The pH of the developer is 9.5 to 11.0, particularly preferably 9.
It is in the range of 8 to 10.7. The developing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the developing temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C, and the developing time is 5 seconds to 2 seconds. Minutes, preferably 7
Second to 1 minute and 30 seconds. In the present invention, the photosensitive material 1
When processing a square meter, 180 ml or less of developer is replenished. A preferable range of the developer replenishing amount is 50 to 180 ml, and particularly preferably 100 to 160 ml per square meter of the light-sensitive material. It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / l. The fixing solution may optionally contain a hardener (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), and a pH adjuster (eg, ammonia, sulfuric acid). ), Chelating agents, surfactants, wetting agents, fixing promoters. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754 and 58-122535.
No. 58-122536, alcohols having a triple bond in the molecule, U.S. Pat.
A thioether compound described in JP-A-126449;
The mesoionic compounds described in JP-A No. 229860 and the like may be mentioned, and the compounds described in JP-A-2-44355 may be used. As the pH buffer, for example, acetic acid, malic acid, succinic acid, tartaric acid, oxalic acid citric acid, maleic acid, glycolic acid, organic acids such as adipic acid, boric acid,
Inorganic buffers such as phosphates and sulfites can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffer is used for the purpose of preventing the pH of the fixing agent from rising due to bringing in a developing solution, and is 0.01 to 1.0 mol / liter, more preferably 0.02 to 0.6 mol / l.
Use about 1 liter. The pH of the fixing solution is preferably 4.0 to 6.5, particularly preferably 4.5 to 6.0. Further, as a dye elution accelerator, JP-A-64-473 is used.
The compound described in No. 9 can also be used.

As the hardening agent in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The preferable addition amount is 0.01 to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. Fixing temperature is
The fixing time is 5 seconds to 1 minute, preferably 7 seconds to 50 seconds at about 20 ° C to about 50 ° C, preferably 25 to 45 ° C. The replenishing amount of the fixing solution is 100 to 4 with respect to the processing amount of the light-sensitive material.
The amount is 00 ml / m ² or less, and particularly preferably 200 to 300 ml / m ² or less.

The light-sensitive material that has been developed and fixed is then washed with water or stabilized. In the washing or stabilizing treatment, the washing water amount is usually ² m ² per m ^{2 of the} silver halide photosensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
In other words, it can also be carried out by washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of washing water, a multi-stage countercurrent method (for example, 2
Stage, three stage, etc.) are known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not stained with the fixing solution is sequentially contacted, so that the efficiency is further improved. Washing is performed. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in JP-A Nos. 350 and 62-287252. Alternatively, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in 23
As described in JP-A No. 5133, it can be used for a processing solution having a fixing ability which is a preceding processing step. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when washing with a small amount of water and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. Good. Further, in order to prevent contamination by the dye eluted from the photosensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in a washing tank. In addition, a stabilization process may be performed following the water washing process,
Examples thereof include JP-A-2-201357 and JP-A-2-132.
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as a final bath of the light-sensitive material. If necessary, this stabilizing bath may also contain a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, various chelating agents, a membrane pH regulator, a hardening agent, a bactericide, a fungicide, an alkanolamine, or a surfactant. Agents can also be added. The water used in the washing step or the stabilization step includes tap water, deionized water, halogen, ultraviolet sterilizing lamp, and water sterilized by various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time are 0-5
0 ° C. and 5 seconds to 2 minutes are preferred.

The processing liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971, and is referred to simply as a roller-conveying type processor in this specification. The roller conveyance type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. . Four steps of a stabilization step may be used instead of the washing step.

The developing solution used in the present invention may be prepared from a solid processing agent, and the solid processing agent may be powder, tablets, granules, powders, lumps or pastes. It is in the form or tablet described in Kaisho 61-259921. The method for producing tablets is described in, for example, Japanese Patent Laid-Open No.
Nos. 1-61837, 54-155038 and 52-
No. 88025, British Patent No. 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-109042 and 2-109043.
And JP-A-3-39735, JP-A-3-39939, and the like. Furthermore, powder treating agents are disclosed in, for example, JP-A-54-133332 and British Patent 7
It can be produced by a general method as described in JP-A Nos. 25,892 and 729,862 and German Patent 3,733,861.

The bulk density of the solid processing agent of the present invention depends on its dissolution.
From the viewpoint of sex and the effect of the object of the present invention, 0.5 to
6.0 g / cm^ThreeThose of 1.0 to 5.0 are particularly preferable.
g / cm ^ThreeAre preferred.

[0143]

The present invention will be described in more detail with reference to the following examples. Example 1 Emulsion Preparation Emulsion A was prepared by the following method. [Emulsion A] An aqueous solution of silver nitrate, potassium bromide, sodium chloride and K corresponding to 3.5 × 10 ^-7 mol per mol of silver.
₃ IrCl ₆ and K ₂ Rh equivalent to 2.0 × 10 ⁻⁷ mol
A halogen salt aqueous solution containing (H ₂ O) Cl ₅ , sodium chloride, and a gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinthione were added by stirring by a double jet method to give an average particle size of 0.25 μm. Silver chlorobromide grains having a silver chloride content of 70 mol% were prepared.

After that, the product was washed with water by the flocculation method according to a conventional method, and an appropriate amount of gelatin was added per 1 mol of silver (the gelatin amount is shown in Table 1).
After adding 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid per mol, pH 6.0, pA
It was adjusted to g 7.5, and 2 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per 1 mol of silver, and chemical sensitization was performed at 60 ° C. for optimum sensitivity. After that, as a stabilizer 4-
150 mg of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and further 100 mg of proxel was added as a preservative. The obtained particles were silver chlorobromide cubic particles each having an average particle size of 0.25 μm and a silver chloride content of 70 mol%. (Variation coefficient 10%)

Preparation of Coating Sample On a polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride, from the support side,
Samples were prepared by applying the layers sequentially to form a UL layer, an EM layer, a PC layer, and an OC layer. The preparation method and application amount of each layer are shown below.

(UL layer) A dispersion of 30 wt% of polyethyl acrylate to gelatin was added to an aqueous gelatin solution and coated. The amount of gelatin is shown in Table 1.

[0147] in (EM layer) above emulsions A, the following compound as a sensitizing dye (S-1) per mole of silver 5 × 10 ^-4 mol, the 5 × 10 ^-4 mol was added (S-2), further 3 × 10 ^-4 mol of mercapto compound represented by the following (a), 4 × 10 ^-4 mol of mercapto compound represented by (b), and 4 × 10 ^-4 mol of (c) per 1 mol of silver Triazine compound, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline, 5 × 10 ⁻⁴ mol of the following compound (p), and 4 × 10 ⁻⁴ mol of the following compound (A) as a nucleation accelerator. Was added. Further, 100 mg of hydroquinone and sodium salt of N-oleyl-N-methyltaurine were added so as to be applied at 30 mg / m ² . As the nucleating agent (hydrazine derivative), the following compound (B) is 1 × 10 ⁻⁵ mol / m ² , the water-soluble latex represented by (d) is 200 mg / m ² , and the polyethyl acrylate dispersion is 200 mg / m ² . m ² , Methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate latex copolymer (weight ratio 88: 5: 7)
The 200 mg / m ^2, an average particle diameter of the colloidal silica 200 mg / m ² of 0.02 [mu] m, the more 1,3-vinylsulfonyl-2-propanol as a hardening agent was added, the addition amount is the swelling ratio of Table 1 Was adjusted. The pH of the solution was adjusted to 5.65 using acetic acid. The amount of silver coated on them 3.
It was applied so as to be 5 g / m ² .

(PC layer) A dispersion of 50 wt% of ethyl acrylate in gelatin aqueous solution, and
The following surfactant (w) was added in an amount of 5 mg / m ² , and 1,5-dihydroxy-2-benzaldoxime was added so as to be applied in an amount of 10 mg / m ^{2 and} applied. The amount of gelatin is shown in Table 1.

[0149] (OC layer) Average particle size of about 3.5μm of an amorphous SiO ₂ matting agent 40 mg / m ^2, methanol silica 0.1 g / m ^2, polyacrylamides 100 mg / m ² and the silicone oil 20 mg / m ² and As a coating aid, 5 mg / m ^{2 of} a fluorosurfactant represented by the following structural formula (e), 100 mg / m ^{2 of} sodium dodecylbenzenesulfonate and gelatin (the amount of gelatin was as shown in Table 1) were coated.

[0150]

Embedded image

These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ²

[0152]

Embedded image

SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² Dye Mixture of dye [a], dye [b], dye [c] Dye [a] 70 mg / m ² Dyes [b] 70 mg / m ² Dyes [c] 90 mg / m ²

[0154]

Embedded image

[Back protective layer] Gelatin 0.8 g / m ² Polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

Using the sample thus prepared, 488
It was exposed to xenon flash light with an emission time of 10 ^-5 sec through an interference filter having a peak at nm and a step wedge. Next, these samples are used as FG manufactured by Fuji Photo Film Co., Ltd.
A running test was performed using -520AG. The running conditions were 16 samples of a large paper size (50.8 x 61.0 cm) half-exposed (blackening rate = 50%) per day.
1 run for processing 5 sheets, operating for 5 days and resting for 2 days
Six rounds were performed. The developer described in Table 2 was used. The replenishment amount of the developing solution is shown in Table 1. The fixer used had the following formulation. The replenishing amount of the fixing solution was 1.5 times the replenishing amount of the developing solution. The processing was carried out at a developing temperature of 35 ° C. for 30 seconds.

<Fixer Solution Formulation> Ammonium thiosulfate 360 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.1 g Sodium thiosulfate pentahydrate 33.0 g Sodium sulfite 75.0 g Sodium hydroxide 37.0 g Glacial acetic acid 87.0 g Tartaric acid 8.8 g Sodium gluconate 6.6 g Aluminum sulphate 25.0 g Water to add 3 liter pH (adjusted with sulfuric acid or sodium hydroxide) 4.85

[0158]

[Table 1]

[0159]

[Table 2]

The evaluation of photographic properties was carried out as follows. The gradation is a value obtained by dividing the difference between density 3.0 and density 0.1 by the logarithm of the exposure amount giving density 3.0 and the logarithm of the exposure amount giving density 0.1. The reciprocal of the exposure amount required to obtain a density of 1.5 when treated with a fresh running solution was set as 100 and shown as a relative value. It is necessary for the change in sensitivity to be within the range of 95 to 105 for practical purposes. Using an argon light source color scanner SG708 manufactured by Dainippon Screen Co., Ltd., 95% flat mesh was output to the sample with 500 lines, and the sample was processed after running to evaluate the unevenness of the process. The treated film was visually evaluated for processing unevenness.
Mura was sensory-evaluated by a 5-point method of (good) 5 to 1 (bad). Silver stain was visually evaluated on a five-point scale. A state in which no silver stain is generated on the film, the developing tank, and the roller is “5”, and a state in which silver is generated on the entire surface of the film and a large amount of silver is generated on the developing tank and the roller is “1”. " “4” is not generated in the film, but is slightly generated in the developing tank and the roller, but it is a practically acceptable level. "3" and below are practically problematic or impossible levels.

From the results shown in Table 1, even when the replenishment amount of the developing solution is reduced by the combination of the present invention, the stability is good, the processing unevenness is good, and the silver stain is small.

Example 2 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion B was prepared by the following method. [Emulsion B] Emulsion except that 1 mg of a selenium sensitizer having the following structural formula, 1 mg of sodium thiosulfate and 4 mg of chloroauric acid are added per 1 mol of silver and chemically sensitized to obtain optimum sensitivity at 60 ° C. It adjusted like A.

[0163]

[Chemical 51]

Preparation of Coating Sample Instead of the sensitizing dye in the EM layer of Example 1, 2.1 × 10 ⁻⁴ mol of the following compound (S-3) was added per 1 mol of silver to prepare an emulsion for the EM layer. A sample was prepared in the same manner as in Example 1 except that Emulsion B was used.

[0165]

Embedded image

Using the sample thus prepared, 633
It was exposed to xenon flash light with an emission time of 10 ^-6 sec through an interference filter having a peak at nm and a step wedge. Then, running was performed in the same manner as in Example 1. The running conditions are the same as in Example 1.

[0167]

[Table 3]

From Table 3, it can be seen that the combination of the present invention is a treatment in which the decrease in the liquid activity due to running is small and the silver stain is small.

Example 3 A sample was prepared in the same manner as in Example 2 except that the following compound (S-4) was used instead of the sensitizing dye in the EM layer of Example 2.

[0170]

Embedded image

Using the sample thus prepared, 780
It was exposed to xenon flash light with an emission time of 10 ^-6 sec through an interference filter having a peak at nm and a step wedge. Then, running was performed in the same manner as in Example 1. The running conditions are the same as in Example 1.

[0172]

[Table 4]

From Table 4, it can be seen that the combination of the present invention is a treatment in which the decrease in the liquid activity due to running is small and the silver stain is small.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 5/31 G03C 5/31 // G03C 1/06 501 1/06 501

Claims (7)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer and at least one protective layer on the same surface, and at least one hydrazine derivative in the emulsion layer or other hydrophilic colloid layer. After exposure of a silver halide photographic light-sensitive material containing one of them, the total coating amount of gelatin on the emulsion layer side is 2.8 g / m ² or less, and the swelling ratio of all coating layers on the emulsion layer side is 120% or less, A dihydroxybenzene-based developing agent and an auxiliary developing agent are contained, and 1 liter of the developing solution contains 0.
The pH drop when adding 1 mol of acetic acid is 0.3 or less,
Development processing of a silver halide photographic light-sensitive material, characterized in that development processing is performed using a development solution having an initial pH of 9.5 to 11.0 and a replenishment rate of the development solution of 180 ml / m ² or less. Method. 2. The development processing method according to claim 1, wherein a nucleation accelerator is contained in the constituent layer on the emulsion layer side of the silver halide photographic light-sensitive material. 3. The development processing method according to claim 1, wherein the developer contains a carbonate in an amount of 0.5 M or more. 4. A developer containing a dihydroxybenzene-based developing agent in an amount of 0.3 M or more.
4. The development processing method according to any one of 3 above. 5. A 1-phenyl-3-pyrazolidone compound and // as an auxiliary developing agent exhibiting superadditivity to a developing solution.
Alternatively, the development processing method according to any one of claims 1 to 4, further comprising a p-aminophenol compound. 6. The developer contains 0.3 to 1.2 mol / liter of free sulfite ion and ascorbic acid derivative, and the concentration ratio of ascorbic acid derivative / dihydroxybenzene type developing agent is 0.03 to 0. The developing treatment method according to any one of claims 1 to 5, wherein the developing treatment is carried out with a developing solution of No. 12. 7. The development processing method according to claim 1, wherein the developing solution is prepared from a solid processing agent.