JPS62210463A - Processing method for silver halide photographic sensitive material by which stable photographic performance is obtainable - Google Patents

Abstract

PURPOSE:To obtain a stable magenta dye image without any change of photographic performance by subjecting a silver halide photographic sensitive material provided with a silver halide emulsion layer contg. a specific magenta coupler and silver chlorobromide emulsion to imagewise exposing then processing the material with a specific color developing soln. CONSTITUTION:The silver halide photographic sensitive material provided with the silver halide emulsion layer contg. the magenta coupler expressed by formula I and the silver chlorobromide emulsion on a base is subjected to the imagewise exposing and is then processed by the color developing soln. contg. bromine ions at <=1X10<-3>mol/l and iron ions at >=0.05ppm concn. A method similar to a method for adding the magenta coupler expressed by formula to the silver halide photographic sensitive material and can be adequately selected according to the chemical structure, etc. of the hydrophobic compds. such as coupler. A high boiling point org. solvent which can be preferably used at the time of dispersing the magenta coupler is more preferably phthalates or phosphates among the high boiling point org. solvents.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing a silver halide photographic material that provides stable photographic performance, and more specifically, to a method for processing a silver halide photographic material that provides stable photographic performance. It has stable sensitivity and gradation,
The present invention also relates to a method for processing a silver halide photographic material, which produces a magenta dye image with little fog.

[Backbone of the invention] In recent years, the development processing speed of silver halide photographic light-sensitive materials has been accelerated, and in order to further improve work efficiency and reduce costs, the so-called low replenishment type reduces the amount of replenisher required by concentrating the developer replenisher. The number of developing solutions has been increasing.

For this reason, the rate of accumulation of compounds that adversely affect photographic performance in color developing solutions tends to increase.

Among these compounds, iron ions are cited as having a large influence on photographic performance.

In the color development process, a bleaching step containing a bleaching agent is provided in order to oxidize the metallic silver produced during development, and a ferric complex salt of aminopolycarboxylic acid is usually used as the bleaching agent. In addition, since the developing (CD') tank and the bleaching (BL) tank are often adjacent to each other, iron ions are likely to be mixed into the color developing solution during dispensing or processing.

Furthermore, in color vapor processing for development, bleach window 1 (BF) processing is widely used, which combines a bleaching step for oxidizing metallic silver and a fixing step for forming and fixing a water-soluble silver complex. Further, since most automatic processors that process color vapor use an endless belt, the bleach-fix solution mixes into the color developer and accumulates due to the endless belt.

Bleach constant@ solution usually contains a ferric complex salt of aminopolycarboxylic acid, which is a bleaching agent, and serves as a source of iron ions.

If iron ions are mixed into the color developer in this way, it will not be a big problem if the iron ion concentration is extremely small, but if the iron ion concentration in the color developer is 0.05 ppm.
When the value exceeds +, changes in sensitivity and gradation and increase in fog are likely to occur, especially in color paper, and photographic characteristics of magenta dye images in particular are likely to be affected.

Increased fog and changes in sensitivity and gradation due to the incorporation of iron ions into color developing solutions significantly deteriorate the finished quality of color prints, and therefore, stabilization of the development process is strongly desired.

For this reason, it has been known to include various additives in photosensitive materials in order to improve processing stability. For example, U.S. Patent Nos. 3,954,474 and 3,982.
These include nitrobenzimidazoles, mercaptothiazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles, etc. described in, .

It is also known to include various additives in the processing liquid for the same purpose. For example, diethylenetriaminepentaacetic acid described in Japanese Patent Publication No. 54-16861.

However, the conventional techniques have drawbacks such as insufficient effects on gradation fluctuations and increased fog, decreased sensitivity, and deteriorated storage stability of the processing solution.

Therefore, there is currently a strong demand for a means for improving the stability of photographic performance when color paper is processed with a color developer containing iron ions.

[Object of the Invention] An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material, which produces a stable magenta dye image with little change in photographic performance such as sensitivity, gradation, fog, etc. .

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic photosensitive material in which a silver halide emulsion layer containing a magenta coupler represented by the following general formula [I] and a silver chlorobromide emulsion is provided on a support. After imagewise exposure of the material, the bromide ion concentration is I x 1
0-3 mol/1 or more, and the iron ion concentration is o,
This can be achieved by including a step of processing with a color developer having an osppm or higher.

General Formula [I] [In the formula, 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by 2 may have an @ exchanger.

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

Further, R represents a hydrogen atom or a substituent. [Specific Structure of the Invention] The silver halide photographic material used in the processing method according to the present invention is a silver halide photographic material containing a magenta coupler represented by the general formula [I] and a silver chlorobromide emulsion on a support. It has a silver emulsion layer.

The magenta coupler represented by the general formula [I] will be explained.

In the magenta coupler represented by the general formula (1) and general formula CI) according to the present invention, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and The ring may have a substituent.

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom, a furkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a 71-nol group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, Carbamoyl group, 77 moyl group, cyano group,
Spiro compound residue, 4% iR hydrogen compound residue, flukoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acyl 7 group, sulfonamide group, imide group,
ureido group, 7 sul 7 moyl amine groups, 7 flukoxy luponyl 7 groups, 7 aryloxy carbonyl amide groups,
Examples thereof include a flukoxycarbonyl group, an aryloxycarbonyl group, a furkylthio group, a 71-northio group, and a heterocyclic thio group.

Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

The furkyl group represented by R'1' has 1 to 32 carbon atoms.
, alkenyl group, alkynyl group has 2 carbon atoms
-32, dichlorofurkyl group, and cycloalkenyl group preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl group, alkenyl group, and alkynyl group may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cya/, halogen atom, heterocycle, cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon In addition to compound residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and 7lyloxycarbonyl, and those substituted via a hetero atom (specifically, hydroxy, alkoxy, aryloxy, heterocyclic oxy,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, 7mino (including dialkylamino 7, etc.), sul7amoylamino, alfukidicarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, Those substituted through the nitrogen atom such as imide and ureido, furkylthio, 7lylthio, heterocyclic thio, sulfonyl, sulfinyl,
Those substituted via a sulfur atom such as sulf7moyl, and those substituted via a phosphorus atom such as phosphonyl may have J.

Specifically, for example, methyl group, ethyl group, isopropyl group, butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1'-noventylnonyl group,
2-chloro-t-butyl group, tri7fluoromethyl group, 1
-Ditoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl i, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonami77e/xypropyl group , 3-4'-1α-(4”(p-hydroxybenzenesulfonyl)7e/xy)dodecanoylamino 1
Phenylpropyl group, 3-14'-CQ-(2", 4"
-di-t-amylphenoxy)butanamido]phenyl)-propyl group, 4-(α-(0-chlorophenoxy)
Examples include tetradecanamide 7e/xy]propyl group, allyl group, cyclopentyl group, and cyclohexyl group.

The 7-aryl group represented by R'c is preferably a phenyl group, which may have a substituent (for example, an alkyl group, an alkoxy group, a 7-sylami 7 group, etc.).

Specifically, phenyl group, 4-t-butyl 7-enyl group,
2,4-sheet t-7 milphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-L-butylphenoquine)tetradecanamidophenyl group and the like.

R'? The heterocyclic group represented is preferably a 5 to 7 ring group, which may be substituted (or may be integrated, specifically 2-furyl group, 2-chenyl group, 2-biriminonyl group). group, 2-benzothiazolyl group, and the like.

Examples of the acyl group represented by R″t′ include 7 cetyl group, phenylacetyl group, dodecanoyl group, a-2,4-
Examples thereof include a furkylcarbonyl group such as a 2-t-7 milphenoquinptanoyl group, a 7-aryl carbonyl group such as a benzoyl group, a 3-pentadecyloxybenzoyl group, and a p-chlorobenzoyl group.

Examples of the sulfonyl group represented by R include a methylsulfonyl group, an alkylsulfonyl group such as a dodecylsulfonyl group, and an alkylsulfonyl group such as a benzenesulfonyl i, p-)luenesulfonyl group.

T2n Rejoice angler 1 Ruanonyl Examples include arylsulfinyl groups such as a furkylsulfinyl group, phenylsulfinyl fr, and m-pentadecylphenylsulfinyl group.

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and a phenylphosphonyl group. Examples include 87-arylphosphonyl group and the like.

The carbamoyl group represented by R″C may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, an N,N-7butylcarpamoyl group, an N-( 2-pentadecyl octylethyl)carbamoyl group, N-x 4-ruN-1'
f' dylcarbamoyl i, N-[3-(2,4-not
-7milphenoxy)propyl)carbamoyl group and the like.

The sulfamoyl group represented by the margin R below may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-pro and rusul 7 amoyl i, NtN-noethyl sul 7 amoyl i, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group, etc. can be mentioned.

Examples of spiro compound residues represented by R include spiro [
3,3]hebutan-1-yl and the like.

Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2,1]hebutan-1-yl, tricyclo[3
, 3,1,1co°7]decane-1-yl, 7,7-nomethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as methoxy group, propoxy group/2-ethoxyethoxy group, pentadenyloxy group, 2-ethoxy group, etc. Examples include dodecyloxyethoxy group and 7enethyloxyethoxy group.

The 7-aryloxy group represented by R is preferably 7-enyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group,
For example, phenoxy group, p- is -butylphenoxy group, l
-pentadecylphenoxy group and the like.

The heterocyclic oxy group represented by R preferably has 5 to 7 heterocycles, and the heterocycle may further have a substituent, for example, 3゜4.5.6-tetrahydro. Examples include pyranyl-2-oxy group and 1-phenyltetrazol-5-oxy group.

The siloxy group represented by R may be further @-substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like.

The 7-syloxy group represented by R includes, for example, an alkylcarbonyloxy group, a 7-arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, a-chloroacetyl group, etc. Examples include oxy group and benzoyloxy group.

The carbamoyloxy group to be oxidized may be substituted with an alkyl group, an aryl group, etc., such as N-ethylcarbamoyloxy group, N,N-noethylcarbamoyloxy group, N-phenylcarbamoyloxy group, etc. .

The amine group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethyl amine group, anilino group, m-chloroanily group, 3-pentadecyl group, etc. Oxycarbonylanilino group, 2-
Examples include 7 chloro-5-hexadecaneamide aniline groups.

Examples of the acylamine 7 groups represented by R include alkylcarbonylamino groups, arylcarbonylamino 7 groups (preferably phenylcarbonylamino 7 groups), and may further have a substituent (specifically, acetamide 7 groups). group, a-ethylpropanamide group, N-phenylacetamide group,
Examples include dodecanamide group, 2,4-monoamylphenoxyacetamide group, and α-3-L-butyl 4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group represented by R include alkylsulfonyl groups, arylsulfonyl groups, and the like, and may further have a substituent.

Specifically, 7 methylsulfonylamide groups, 7 pentadecylsulfonylamide groups, benzenesulfonylamine PM, p-)
Examples include a luenesulfonamide group and a 2-methoxy-5-t-7 milbenzenesulfonamide group.

The imide group represented by R may be open-chain or cyclic (and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a 7-talimide group, etc.). , glutarimide group, and the like.

The ureido group represented by R may be substituted with an alkyl group, a 71J-l group (preferably a phenyl group), etc., such as N-ethylureido group, N-methyl-N-decylureido group, N- Examples include 7enylureido group and N-9-silylureido group.

The sul77moylamide7 group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N,N-butylsul77moyl77moyl7 group, N-methylsulfTmoyl777 group, N-72nylsul7Tmoyl777 group etc.

As the alfkhidicarbonylamino group represented by R,
It may further have a substituent, for example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group,
Examples include 7 octadecyloxycarbonylamide groups.

The 7 aryloxycarbonylamide groups to be reduced by R″C are:
It may have a substituent, and examples thereof include phenoxycarbonylamine 7 groups and 4-methylphenoquine carbonyl 7 groups.

The phenoxycarbonyl group represented by R″c2! may further have a substituent, such as methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benoloxy Examples include carbonyl group.

The 7-aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group,
Examples include p-chlorophenoxycarbonyl group, and pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R may further have a substituent (for example, an ethylthio group, a dodecylthio group, an octadecylthio group, a 7enethylthio group, a 3-phenoxypropylthio group).

The 7-arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
Examples include p-methoxyphenylthio group, 2-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, p-7ceto7minophenylthio group, and the like.

The heterocyclic thio group represented by R is preferably a 5- to 7-shell heterocyclic thio group, which may further have a condensed ring or a substituent. Examples include pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-)lyazole-6-thio group. Examples of the substituent which can be separated by a friendly reaction with the oxidized product of the color developing agent represented by 'X' include a laxative atom of a halogen atom (chlorine atom, bromine atom, fan atom, etc.), an oxygen atom, a sulfur atom, or a nitrogen atom. Groups that substitute via atoms are expedited.

Groups substituted via a carbon atom include, in addition to carboxyl groups, for example, those of the general formula (R3' is the same as the above R, Z' is the same as the above Z, 1 (2j and R3' are hydrogen atoms, aryl group, a group represented by ) representing an alkyl group or a heterocyclic group, a hydroxymethyl group, and a triphenylmethyl group.

Examples of groups substituted via an oxygen atom include an alkoxy group, a 7-aryloxy group, a heterocyclic oxy group, a 7-syloxy group, a sulfonyloxy group, a flukoxyluponyloxy group, a 7-aryloxycarponyloxy group, a flukyloxalyloxy group, Alkoxyoxalyloxy radical r
Can be mentioned.

The alkoxy group may further have a substituent, for example,
Examples include ethoxy group, 2-7e/xyethoxy group, 2-one7noethoxy group, 7enethyloxy group, p-chlorobenzyloxy group, and the like.

The 7-aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent.
Physically, phenoxy group, 3-notyl 7-functional/oxy group, 3-
Dodecylphenoxy group, 4-notanesulfone 7midophenoxy! , 4-(ff-(3'-pentadecylphenoxy)butane7mido]phenoxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-notanesulfonylphenoxy group, 1-su7tyloxy group, p
-methoxyphenoxy group and the like.

The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a condensed ring or may have a substituent, specifically, l-phenyl Examples include a tetrazolyloxy group and a 2-benzothiazolyloxy group.

Examples of the acyloxy group include acetoxy group, fulkylcarbonyloxy group such as butanoloxy group, alkenylcarbonyloxy group such as cinnamoyloxy group,
Examples include arylcarbonyloxy groups such as benzoyloxy groups.

Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group.

Examples of the flukoxyluponyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group.

Examples of the aryloxycarbonyl group include a 7-enoxycarponyloxy group.

Examples of the alkyloxalyloxy group include methyloxalyloxy.

Examples of the flukoxyoxalyloxy group include an ethoxyoxalyloxy group.

Examples of the group substituting through the sulfur atom include an alkylthio group, an arylthio group, a convex heterocyclic thio group, and a fulkyloxythiocarbonylthio group.

Examples of the furkylthio group include a butylthio group, a 2-cyanoethylthio group, a 7enethylthio group, a pennorthio group, and the like.

The arylthio group includes a phenylthio group, a 4-7thanesulfonemidophenylthio group, a 4-dodecyl7enethylthio group, a 4-7fluoropentane7midophenylthio group, a 4-carboxyphenylthio group, a 2-ethoxy-5-t -butylphenylthio group and the like.

Examples of the heterocyclic thio group include 1-722-1.
Examples include 2.3.4-nato2zolyl-5-thio group and 2-benzothiazolylthio group.

Examples of the fulkyloxythiocarbonylthio group include dodecyloxythiocarbonylthio group.

For example, those represented by the general formula -N represent an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and R4' and R5' are bonded. may form a heterocycle, provided that R1' and RS
' cannot both be hydrogen atoms.

The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, fulkylamino group, arylami 7 group, acylami/group, sulfonamido group, imino group, 7-syl group, alkylsulfonyl-711-luzuronyl carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Examples include seven fluoryloxycarbonylamide groups, seven aryloxycarbonylamide groups, a hydroxyl group, a carboxyl group, a cyano group, and a halogen atom.

Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-chloroethyl group.

The aryl group represented by R4' or R5' preferably has 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group,
The aryl group may have a substituent (substituents include those listed above as substituents for the alkyl group represented by R4' or R1' and an alkyl group.The 7-aryl group includes Specific examples include phenyl group, 1-su7tyl group, and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R and/or R5' is 5 to 6
Shellfish are preferred, and may be fused rings and may have substituents. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, 2- Examples include bilinol group.

The sul77moyl group represented by R4' or R5' includes N-furkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-7'7-dialkylsul7amoyl group, N,N-diaryl Examples include sul77 moyl group,
These alkyl groups and aryl groups may have the substituents listed above for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N,N-diethylsul77moyl group, N-methylsulfamoyl group, etc. group, N-dodecylsulfamoyl group, and N-p-tolylsul77moyl group.

The carbamoyl group represented by R4' or Rs' is
N-furkylcarbamoyl group, N,N-nofurkylcarbamoyl group, N-7ylcarbamoyl group, N,N-
Examples of carbamoyl groups include noarylcarbamoyl groups, and these furkyl groups and aryl groups may have the substituents listed for the alkyl groups and 7-aryl groups. Specific examples of carbamoyl groups include N,N-diethyl, etc. Carbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-9-cyanophenylcarbamoyl i,
N-p-)lylcarbamoyl group is mentioned.

Examples of the 7-syl group represented by R4' or Rs' include an alkylcarbonyl group and an arylcarbonyl group.

group, heterocyclic carbonyl group, and the alkyl group,
The 7-aryl group and the heterocyclic group may have a substituent. Specific examples of the acyl group include hexafluorobutanoyl group, 2゜3.4.5.6-pentafluorobenzoyl group, 7-cetyl group, benzoyl group, naphthonyl group, 2-7lylcarbonyl group, and the like.

Examples of the sulfonyl group represented by R4' or R%' include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group. , a benzenesulfonyl group, an oftane sulfonyl group, a naphthalenesulfonyl group, a p-chlorobenzenesulfonyl group, and the like.

The aryloxycarbonyl group represented by R, J or Rs' may have any of the substituents listed above for the aryl group, and specific examples thereof include a 7-ethyloxycarbonyl group and the like.

The alkoxycarbonyl group represented by R1' or R, 7 may have a substituent listed for the furkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, etc. can be mentioned.

The heterocycle formed by combining R1' and R5' is preferably one with 5 to 6 shells, and may be saturated or unsaturated, and may or may not have aromaticity, or,
Examples of the heterocycle, which may be a condensed ring, include N-7 talimide group, N-cohelyl imide group, 4-N-urazolyl group, 1-N-hyguntoynyl,! , 3-N-2,4-dioxoxasilicnyl group, 2-N-1,1-quoxo 3-(2H)-oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolidinyl group , 1-pyrazolyl group, 1-pyrazolidinyl group, 1-piperidinyl group, 1
-pyrrolinyl group, 1-imidazolyl group, 1-indolyl group, 1-indolyl group, 1-isoindolinyl group, 2-
Isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-pencyimigzolyl group, 1-(
1,2,4-)su7zolyl) group, 1-(1,2,3-)
(7zolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3.4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2
-IH-pyridone group, 7-talathion group, 2-oxo-1
-piperidinyl group, etc., and these heterocyclic groups include furkyl group, aryl group, furkyloxy group, 7lyloxy group, acyl group, sulfonyl group, furkyl 7mi7 group,
7 lylami 7 groups, 7syl 7mino group, sulfonami 7 groups, carbamoyl group, sulfo 1 moyl group, alkylthio group, 71J-ruthio group, ureido group, alkoxycarbonyl group, 7lyloxycarbonyl group, imido group, nitro group, It may be substituted with a cyano group, carboxyl group, halogen atom, etc.

Examples of the nitrogen-containing heterocycle formed by 2 or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. 6 Also, general formula (1) and general formula (II) to [■] described below
Substituents on the heterocycle (e.g., R1R1 to RS)
has a moiety (here, R'', X and Z II have the same meanings as R, X and Z in general formula [1)), it forms a so-called screw-type coupler, but of course it is included in the present invention. Further, the ring formed by z, z', z'' and Z described below may be further fused with another ring (for example, 5 to 7 dichloroflukenes). For example, in general formula [V], R5 and R6 are R7, and in general formula (Vl), R7 is
and R8 may be combined with each other to form a ring (for example, a 5- to 7-shell cycloalkene, benzene).

What is represented by the general formula (1) below is more specifically represented by, for example, the following general formulas (11) to [■].

General formula [11] General formula (II[) N -N -N General formula [IV] N -N -N)I General formula (V) General formula (Wl General formula [■] General formula (II) - [ ■] in R1~R, and C/
X has the same meaning as R and c/X above.

Also, among the general formula CI), the following general formula [
■].

General formula [■] In the formula, R, , X and VZ1 have the same meanings as R9X and Z in the general formula (1).

Particularly preferred among the magenta couplers represented by the general formulas (II) to [■] is the magenta coupler represented by the general formula (III).

Also, general formula (1) ~ [)! Regarding the substituents on the heterocycle in ], it is preferable that R in general formula (1) and R1 in general formulas (n) to [■] satisfy the following condition 1. It is preferable that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1 and 2 are satisfied.
, 2 and 3 are satisfied.

Condition 1: The root atom directly connected to the heterocycle is a carbon atom.

Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom.

Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.

The most preferred substituents R and R on the heterocycle are those represented by the following general formula (■). .

General formula (ff) s R,, -C- R1 In the formula, R,,R,. and RII are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkyl group, an alkynyl group, a 7-aryl group, a heterocyclic group, a 7-syl group, a sulfonyl group, a sulfinyl group,
Phosphonyl group, carbamoyl group, sul77 moyl group, cyano group, spiro compound residue, endowed hydrocarbon compound residue,
alkoxy group, 7-aryloxy group, heterocyclic oxy group,
Siloxy group, acyloxy group, carbamoyloxy group,
ami7 group, 7sil7mi7 group, sulfonamide group, imide group, ureido group, sul77moylamino group, flukoxyluponylamine7 group, 7lyloxycarponyl7mino group, alkoxycarbonyl group, aryloxycarbonyl group, furkylthio group, arylthio group, heterocyclic thio group, at least two of R0R2° and R51 are not hydrogen atoms +11°, and two of the RItRIO and VR+ +, for example, R1 and R8°, are bonded and saturated Alternatively, an unsaturated ring (eg, cycloflucane, dichloroflukene, heterocycle) may be formed, and R1 may be further bonded to the ring to constitute a bridged hydrocarbon compound residue.

The group represented by Rs -R may have a substituent, and specific examples of the group represented by R-R11 and the substituents that the group may have include the above-mentioned general formula (I ) Specific examples of the group represented by R and substituents are listed.

Also, for example, the ring formed by combining R9 and R8゜ and R1
Specific examples of the bridged hydrocarbon compound residue formed by -R11 and its optional substituents include dichlorofurkyl, cycloalkyl, heterocycle s bridged carbonized Specific examples of hydrogen compound residues and their substituents are listed.

Among the general formulas (IK), (i) R17R
When two of 1 are alkyl groups, (ii) R*-R
When one of II, for example RIl, is a hydrogen atom, and the other 2 R9 and R1° combine to form dichlorofurkyl with the root carbon atom, the following is true.

Furthermore, among (i), it is preferable that two of %R9 to R11 are furkyl groups and the other one is a hydrogen atom or an alkyl group.

Here, the furkyl and the cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the furkyl, cycloalkyl, and its substitution represented by R in the general formula (1). Specific examples of the group are listed below.

In addition, substituents which the ring formed by Z in general formula [1] and the ring formed by Z in general formula [■] may have, and R2- in general formulas (II) to (VI) R1 is preferably represented by the following general formula (X).

General formula (X) -R1-3Q, -R2 In the formula, R' represents alkylene and R'' represents alkyl, dichlorofurkyl or aryl.

The fullkylene represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and has 9 straight chain carbon atoms.
This alkylene may have any substituents.

Examples of the substituent include R in the above-mentioned general formula (1)
When is an alkyl group, the substituents that the alkyl group may have include those shown below.

Preferred substituents include phenyl.

Preferred specific examples of alkylene represented by R1 are shown below.

The alkyl group represented by R2 may be a linear or branched alkyl group.

Specific examples include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, oftagyl, 2-hexyldecyl, and the like.

The cycloalkyl group represented by R2 is preferably one with 5 to 6 shells, such as cyclohexyl.

The alkyl and cycloalkyl represented by R2 may have a substituent, and examples thereof include those exemplified as the substituent for R1 above.

Specific examples of the aryl represented by R2 include phenyl and naphthyl. The aryl group may have a substituent, and examples of the substituent include a straight chain or branched furkyl group, and those exemplified as the substituent for R1 described above.

Moreover, when there are two or more substituents, those substituents may be the same or different.

Among the compounds represented by the general formula CI), those represented by the following general formula [revised] are most preferred.

General formula []] In the formula, R and X have the same meanings as R and X in the general formula [I], and R' and R have the same meanings as R1tR2 in the general formula (X).

Specific examples of compounds used in the present invention are shown below.

Margin below 12H25 l CH.

CH3 CH.

CH2 CH.

, 14 CH.

C2O.

Margin below C41(.

C.I.

H3 C? H1s 3H7 Js CI(3 CI(.

" C8゜ CH1 CdLs - CH.

■ ceI(+3 1;H! Cl.

QC) tzcONflcHzcfhOcHi0CII2
C1I□SO□Cl5 C2H.

CHi CH.

shi2n5 6H13 H3 H3 C2H5 C.I.

Hi 1;aH+y(t) C.I.

C too 12 feet CH3 CH3L@l’1t7(tJ CH.

Sweet 7Hts H3CCH3 0(CH2)zU[;Hllzs 1F9 N 192C2Hs ■ L;SH+ + (t) The turnip 2- is Sharnall turnip the chemical.
Society 4 (Journal of theC
hemical SocieLy) *Parkin (
Perkin) 1 (1977), 2047~
No. 2052, U.S. Pat.
No. 162548, No. 59-171956, No. 60-3
No. 3552, No. 80-43859, No. 80-1729
It can be synthesized by referring to No. 82 and No. 60-190779.

The couplers of the present invention are usually halogenated! lX per 11 moles
It can be used in a range of 10'-' mol to 1 mol, preferably 1X10-' mol to 8X10-' mol.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

The magenta coupler represented by the general formula [I] (hereinafter referred to as the magenta coupler according to the present invention unless otherwise specified) is added to a silver halide photographic material using a general hydrophobic method. Similar to the method of compound addition,
Various methods can be used, such as a solid dispersion method, a latex dispersion method, and an oil-in-water emulsion dispersion method, which can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method can be applied to various methods for dispersing hydrophobic compounds such as couplers. Usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is used, and if necessary, a low boiling point and/or water-soluble compound is used. Dissolve using an organic solvent and emulsify and disperse using a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, 70-jit mixer, or ultrasonic device. After that, it may be added to the desired hydrophilic colloid layer. Low boiling point # at the same time as dispersion or dispersion! 1. A step of removing the solvent may be included.

Examples of high-boiling organic solvents include phenol derivatives, phthalates, phosphates, citric esters, benzoic esters, alkylamides, fatty acid esters, trimesic esters, etc., which have a boiling point of 150°C and do not react with the oxidized form of the developing agent. The above organic solvents are used.

In the present invention, the high boiling point organic solvent that can be preferably used when dispersing the magenta coupler according to the present invention is l! These are compounds with a dielectric constant of 6.0 or less, such as esters such as phthalates and phosphates, all amides, ketones, and hydrocarbon compounds with a dielectric constant of 6.0 or less.

Preferably, it is a high boiling point organic solvent having a dielectric constant of 6.0 or less and 1.9 or more and a vapor pressure at 100° C. of 0.5 mo+1-1 g or less. Even more preferred are heptatarates or phosphoric acid esters in the high-boiling organic solvent.

Furthermore, the high boiling point organic solvent may be a mixture of two or more kinds.

Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C.

Examples of phthalic acid esters advantageously used in the present invention include those represented by the following general formula [a].

General Formula [a] In the formula, Rls and R17 each represent an alkyl group, an alkenyl group, or an aryl group. However, the total number of carbon atoms in the groups represented by Rls and R17 is 8 to 32. More preferably, the total number of carbon atoms is 1
6 to 24.

In the present invention, R16 and R1 of the general formula [a]
The alkyl group represented by 7 may be linear or branched, such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group. , pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. The aryl group represented by Rlg and R17 is, for example, a phenyl group, a naphthyl group, etc.
Alkenyl groups include, for example, hexenyl group, heptenyl group,
Such as octadecenyl group. These alkyl groups, alkenyl groups, and aryl groups may have single or multiple substituents, and examples of substituents for alkyl groups and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, and aryloxy groups. groups, alkenyl groups, alkoxycarbonyl groups, etc., and examples of substituents for aryl groups include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups,
Examples include an alkoxycarbonyl group.

Phosphate esters advantageously used in the present invention include those represented by the following general formula [b].

General formula [b] Overseas R,,0-P-OR,.

0 Rt s In the formula, R+a, R+s and R20 each represent an alkyl group, an alkenyl group or an aryl group.

However, the total number of carbon atoms represented by R+a, R+s and R20 is 24 to 54.

The alkyl groups represented by R+a, R+s and R20 in the general formula [bl are, for example, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group,
Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, etc., and examples of the aryl group include phenyl group, naphthyl group, etc.
Examples of the alkenyl group include hexenyl group, heptenyl group, and octadecenyl group.

These alkyl groups, alkenyl groups and aryl groups are
Those having single or multiple substituents are also included. Preferably R+a, R+s and R20 are alkyl groups, such as 2-edylhexyl group, n-octyl group,
3.5.5-trimedhexyl group, n-nonyl group, n
-decyl group, sec-decyl group, 5ec-dodecyl group, [-octyl group and the like.

Typical specific examples of the detectable solvent used in the present invention are shown below, but the present invention is not limited thereto.

Margin below Exemplary organic solvent S-2C2H.

〇 2 Hs S-13 0-Clo H21(n) 0-C1, H23 (These organic solvents are generally used in a proportion of 10 to 150% by weight with respect to the magenta coupler according to the present invention,
Preferably it is 20 to 100% by weight.

Anionic surfactants, nonionic surfactants are used as dispersion aids when hydrophobic compounds such as couplers are dissolved in a high boiling point solvent alone or in combination with a low boiling point solvent and dispersed in water using mechanical or ultrasonic waves. Active agents and cationic surfactants can be used.

A silver chlorobromide emulsion is used as the silver halide emulsion in the silver halide emulsion layer containing the 7 zenta coupler according to the present invention.

The silver chlorobromide grains contained in the silver chlorobromide emulsion may have any composition as long as it is silver chlorobromide, but preferably silver bromide is 10 to 99 mol%, more preferably silver bromide is 30 to 99 mol%. ~90
silver chlorobromide containing mole %.

There is no particular restriction on the particle size distribution of the silver chlorobromide grains contained in the silver chlorobromide emulsion, but monodispersity is preferred. Here, monodisperse means the standard deviation S of the particle size distribution of silver chlorobromide particles (see below).
divided by the average particle diameter T (hereinafter referred to as the coefficient of variation) is 0.
．． 20 or less, preferably this value is 0.15
These are as follows.

The average grain size here refers to the diameter of spherical silver halide grains, or the diameter when the projected image is converted to a circular image of the same area in the case of grains with shapes other than cubic or spherical. The average value is defined by the following formula, where the individual grain size is ri and the number is ni.

Note that the particle size can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Loveround's [Particle Size Analysis Method JA.

S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122 or [The Theory of the Copy Process] by Mies and James, 3rd edition, published by Macmillan (1966), No. 29. Are listed. The particle size can be measured using the projected area or approximate diameter of the particle.

If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size of the silver chlorobromide grains contained in the silver chlorobromide emulsion is not particularly limited, but from the viewpoint of developability and sensitivity, the average grain size is 0.2.
μg is preferably in the range of 1 to 1.5 μm, particularly 0.2 μI
A range of 11 to 0.8 μm is preferred. The average particle diameter and its measuring method here are the same as those described above.

The silver chlorobromide grains contained in the silver chlorobromide emulsion may have any crystal shape, and any ratio of the (100) plane to the (iiB plane) can be used. particles of various crystal shapes may be mixed.In the present invention, octahedral, tetradecahedral, and cubic particles having regular crystal shapes are particularly preferred, and more preferably Cubic particles and/or tetradecahedral particles, more preferably measured by X-ray diffraction analysis - [intensity of diffraction lines attributed to (200) plane]
/[Intensity of diffraction line attributed to (222) plane] Cubic grains and/or tetradecahedral silver chlorobromide grains satisfying 5≦K≦5000.

Here, the above values are measured as follows.

That is, in X-ray diffraction analysis, α
Using a line, (
(222) corresponding to the (200) and (111) planes
) The diffraction angle 2θ of each diffraction line attributed to the surface is approximately 30
．． The above value is determined by measuring the intensities observed at 9° and 55.0'') and taking their ratio.

In the present invention, silver chlorobromide grains having the preferable silver halide composition, average grain size, grain size distribution, and crystal habit as explained above are the silver chlorobromide grains contained in the magenta coupler-containing layer according to the present invention. It is preferably 50% by weight or more,
In particular, it is preferably 75% by weight.

The silver chlorobromide emulsion used in the present invention is, for example,
It can be manufactured by applying the method described in JP-A-48521. For example, it is produced by a method in which a potassium chlorobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. At this time, a highly monodisperse silver chlorobromide emulsion can be obtained by appropriately selecting the time function of addition rate, pAg, temperature, etc.

The silver chlorobromide emulsion used in the present invention can be prepared by an acid method, a neutral method,
It may be obtained from any ammonia method.

Furthermore, by using a silver chlorobromide solvent as necessary when producing a silver chlorobromide emulsion, it is possible to control the grain size, grain shape, grain size distribution, and grain growth rate of silver chlorobromide grains. can. The silver chlorobromide grains contained in the silver chlorobromide emulsion used in the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, or lead salt in the process of forming and/or growing grains. , rhodium salts or complex salts, iron salts or complex salts can be used to incorporate metal ions into the interior of the particles and/or on the surface of the particles, and by placing them in an appropriate reducing atmosphere, metal ions can be added into the interior of the particles and/or on the surface of the particles.
Alternatively, reduction sensitizing nuclei can be added to the particle surface.

In the silver chlorobromide emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of silver chlorobromide grains is completed, or the salts may be left in the emulsion. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver chlorobromide grains of the silver chlorobromide emulsion used in the present invention may consist of uniform layers inside and on the surface, or may consist of one layer from different layers.

The silver chlorobromide grains of the silver chlorobromide emulsion used in the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver chlorobromide emulsion used in the present invention consists of two
More than one type of silver chlorobromide emulsion may be mixed and used.

The silver chlorobromide emulsion used in the present invention is chemically sensitized by a conventional method. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

Silver halide photographic material used in the present invention (hereinafter referred to as
It is simply called a silver halide photographic light-sensitive material. ) may be for a single color or for multiple colors. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-photosensitive silver halide emulsion layer are usually used. 81 layers with an appropriate number and order of layers on the support.
Although it has a H structure, the number and order of layers may be changed as appropriate depending on the important performance and purpose of use.

When the silver halide photographic light-sensitive material is a light-sensitive material for multicolor photographic paper, the specific layer structure includes a yellow dye image-forming layer, an intermediate layer, and a magenta dye image-forming layer on the support, sequentially from the support side. , an intermediate layer, a cyan dye image forming layer, an intermediate layer, and an arrangement of Ili is particularly preferred.

The silver halide emulsion used in the magenta coupler-containing layer according to the present invention is a silver chlorobromide emulsion, as described above, but the silver halide emulsion (hereinafter referred to as (simply referred to as silver halide emulsion) include silver halide used in conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. You can use anything you like.

The silver halide grains used in the silver halide emulsion may be obtained by any one of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be simultaneously flooded, or one may be present and the other may be mixed. In addition, taking into account the critical growth rate of silver halide crystals, we added halide ions and silver ions to one part in a mixing pot.
) Hl pAo may be produced by sequentially and simultaneously adding them while controlling the pAo. After growth, a conversion method may be used to change the halogen composition of the particles.

By using a silver halide solvent as necessary during the production of a silver halide emulsion, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled.

Silver halide grains used in silver halide emulsions are produced by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Metal ions can be added to the inside of the particles and/or on the surface of the particles using complex salts, and reduction-sensitized nuclei can be formed inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. can be given.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left as they are contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion may consist of uniform layers inside and on the surface, or may consist of different layers.

The silver halide grains used in the silver halide emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion may be a mixture of two or more silver halide emulsions formed separately.

The silver halide emulsion is chemically sensitized by conventional methods. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods can be used alone or in combination.

The silver chlorobromide emulsion used in the magenta coupler-containing layer and the silver halide emulsion used in the other silver halide emulsion layers according to the present invention are prepared using dyes known in the photographic industry as sensitizing dyes. Can be optically sensitized to the wavelength range of The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The above-mentioned silver chlorobromide emulsions and silver halide emulsions contain additives for the purpose of preventing fog and/or maintaining stable photographic performance during the manufacturing process, storage, or photographic processing of light-sensitive materials.
Addition of compounds known in the photographic industry as antifoggants or stabilizers during chemical ripening and/or at the end of chemical ripening and/or after the end of chemical ripening and before coating the silver halide emulsion. I can do it.

Although it is advantageous to use gelatin as a binder (or protective colloid) for silver halide photographic materials,
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

Photographic emulsion layers and other hydrophilic colloid layers of silver halide photographic light-sensitive materials are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. The hardening agent is used to harden the photosensitive material to such an extent that it is not necessary to add a hardening agent to the processing solution. Although it is desirable to add a hardening agent as soon as a film is formed, it is also possible to add a hardening agent to the processing solution.

Silver halide emulsion layer and/or silver halide photographic material
Alternatively, a plasticizer can be added for the purpose of increasing the flexibility of the hydrophilic colloid layer.

A dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer can be included in the photographic emulsion layer or other hydrophilic colloid layer of a silver halide photographic light-sensitive material for the purpose of improving dimensional stability.

In the emulsion layer of a silver halide photographic light-sensitive material, a dye is produced by a coupling reaction with an oxidized form of an aromatic primary amine phenomenon agent (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color-forming waste acid treatment. A dye-forming coupler is used that forms . The dye-forming coupler is
Typically, each emulsion layer is selected to form a dye that absorbs light in the emulsion layer's photosensitive spectrum, with a yellow dye-forming puller in the blue-light sensitive emulsion layer and a yellow dye-forming puller in the blue-light sensitive emulsion layer; A magenta dye-forming coupler is used in the photosensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

The cyan dye-forming couplers used in the present invention include:
Phenol-based and naphthol-based 4-equivalent or 2-equivalent type cyan dye-forming couplers are typical, and specific examples thereof include U.S. Pat. Nos. 2,306,410 and 2.356,4.
No. 75, No. 2.362.598, No. 2.367.
No. 531, No. 2,369.929@, No. 2,423
．． No. 730, No. 2,474,293, No. 2.47
No. 6,008, No. 2,498.466, No. 2,5
No. 45,687, No. 2.728.660, No. 2.
No. 772.162, No. 2.895.826, No. 2
．． 976.146, 3.002.836, 3,419,390, 3,446,622, 3.476, 563, 3,737.316,
British Patent No. 3,758,308, British Patent No. 3.839.044, British Patent No. 478,991, British Patent No. 945,542, British Patent No. 1.084,480, British Patent No. 1,377, 23
No. 3, No. 1,388,024 and No. 1,543,
Each specification of No. 040, as well as JP-A Nos. 47-37425, 50-10135, 50-25228, and 5
No. 0-112038, No. 50-111422, No. 50
-130441, 51-6551, 51-37
No. 647, No. 51-52828, No. 51-1088
No. 41, No. 53-109630, No. 54-4823
No. 7, No. 54-66129, No. 54-131931, and No. 55-32071.

Furthermore, as the cyan dye-forming coupler used in the present invention, the following general formulas [CG-1] and [CG-2] are preferable.

General Formula [CC-1] In the formula Otsu, R1 represents an alkyl group or an aryl group. R
2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Also, R3 is R1
It may be combined with to form a ring. 2 represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

General Formula [CG-2] In the formula, R4 represents a linear or branched alkyl group having 1 to 4 carbon atoms, and R5 represents a ballast group.

2 has the same meaning as 2 in the general formula [CG-11]. Particularly preferred R is a straight-chain or branched alkyl group having 2 to 4 carbon atoms.

In the present invention, the alkyl group represented by R1 in the general formula [CG-11] is a linear or branched one, such as a methyl group, an ethyl group, a 1so-propyl group, a butyl group, a pentyl group, an octyl group, Examples of the aryl group include a nonyl group and a tridecyl group, and examples of the aryl group include a phenyl group and a naphthyl group.

These groups represented by R1 include those having single or multiple substituents. For example, substituents introduced into the phenyl group include halogen atoms (e.g., fluorine, chlorine, bromine, etc.). each atom), furkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, Siam L nitro group, alkoxy group (e.g., methoxy group, ethoxy group), alkylsulfonamide groups (e.g., methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide groups (e.g., phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl groups (e.g., butylsulfamoyl group, etc.) ), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.), aminosulfonamide group (For example, N,N-dimethylaminosulfone amide group, etc.), acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfooxy group, sulfo group, aryloxy group, alkoxy group, carboxyl group, and alkylcarbonyl group.

Two or more of these substituents may be introduced into the phenyl group.

The halogen atom represented by R3 is, for example, each atom such as fluorine, chlorine, or bromine, and the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group, or an alkoxy group. is, for example, a methoxy group,
These include ethoxy group, propyloxy group, butoxy group, etc.

R3 may combine with R1 to form a ring.

In the present invention, the alkyl group represented by R2 in the general formula [CC-1] is, for example, a methyl group, an ethyl group, a butyl group, a hexyl group, a tridecyl group, a pentadecyl group, a heptadecyl group, or a so-called fluorine substituted group. These include polyfluoroalkyl groups.

The aryl group represented by R2 is, for example, a phenyl group or a naphthyl group, preferably a phenyl group. The heterocyclic group represented by R2 is, for example, a pyridyl group or a 7-ran group. The cycloalkyl group represented by R2 is, for example, a cyclopropyl group or a cyclohexyl group. These groups represented by R2 include those having single or multiple substituents. For example, typical substituents introduced into phenyl groups include halogen atoms (e.g. fluorine, chlorine, bromine). each atom), alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy M (e.g. methoxy group, ethoxy group, etc.), alkyl sulfonamide groups (e.g. methylsulfonamide group,
octylsulfonamide group, etc.), arylsulfonamide group (e.g., phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), sulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.), aminosulfonamide group, acylamino group, carbamoyl group, sulfonyl group, sulfinyl group Examples include a sulfooxy group, a sulfo group, an aryloxy group, an alkoxy group, a carboxylalkylcarbonyl group, an arylcarbonyl group, and the like. Two or more of these substituents may be introduced into the phenyl group.

Preferred groups represented by R2 include polyfluoroalkyl groups, phenyl groups or halogen atoms, alkyl groups, alkoxy groups, alkylsulfonamide groups, arylsulfonamide groups, alkylsulfamoyl groups, arylsulfamoyl groups, and alkylsulfonyl groups. It is a phenyl group having one or more substituents of a group, an aryl sulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, or a cyano group.

In the present invention, the cyan dye-forming coupler represented by the general formula [CC-1 1 is preferably the following general formula [CG-
3].

General Formula [CC-3] In General Formula [CC-3], R6 represents a phenyl group. This phenyl group includes those having single or multiple substituents, and typical substituents to be introduced include halogen atoms (e.g., fluorine, chlorine, bromine, etc. atoms), alkyl N (e.g., methyl group), , ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (e.g. phenylsulfonamide group, naphthylsulfonamide group, etc.),
Alkylsulfamoyl groups (e.g. butylsulfamoyl groups, etc.), arylsulfamoyl groups (e.g. phenylsulfamoyl groups, etc.), alkyloxycarbonyl groups (
For example, methyloxycarbonylcyclocarbonyl group (eg, phenyloxycarbonyl group, etc.) can be mentioned. Two or more of these substituents may be substituted with a phenyl group. Preferred groups represented by R6 include phenyl group, halogen atom (preferably fluorine, chlorine, and bromine atoms), alkylsulfonamide group (preferably 0-methylsulfonamide group, p-octylsulfonamide group, O -doacylsulfonamide group), arylsulfonamide group (preferably phenylsulfonamide group), alkylsulfamoyl group (preferably butylsulfamoyl M), arylsulfamoyl M (preferably phenylsulfamoyl group), It is a phenyl group having one or more substituents of an alkyl group (preferably a methyl group or a trifluoromethyl group) or an alkoxy group (preferably a methoxy group or an ethoxy group).

R7 is an alkyl group or an aryl group. Alkyl groups or aryl groups include those having single or multiple substituents, and typical examples of these substituents include halogen atoms (e.g., fluorine, chlorine, bromine, etc.), human O-oxyl groups, etc. , carboxyl group, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), aralkyl group, cyano group, nidool
, alkoxy group (e.g. methoxy group, ethoxy group), aryloxy group, alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.)
, arylsulfonamide group (e.g. phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g. butylsulfamoyl group, etc.),
Arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.), aminosulfonamide group (e.g., dimethylaminosulfone group, etc.) amido group, etc.), an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, an aminocarbonylamide group, a carbamoyl group, a sulfinyl group, and the like. Two or more types of these substituents may be introduced.

Preferred groups represented by R7 are an alkyl group when n1 is 0, and an aryl group when nl-1 or more. More preferable groups represented by R7 include n
When l-o, it is an alkyl group having 1 to 22 carbon atoms (preferably a methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group), and when nl-1 or more, it is a phenyl group, or Alkyl group (preferably t-butyl group, t-amyl group, octyl group), alkylsulfonamide group (preferably butylsulfonamide group, octylsulfonamide group, dodecylsulfonamide group), arylsulfonamide group (preferably phenyl sulfonamide group), an aminosulfonamide group (preferably a dimethylaminosulfonamide group), or an alkyloxycarbonyl group (preferably a methyloxycarbonyl group or a butyloxycarbonyl group) as a substituent. be.

R8 represents an alkylene group. It represents a straight chain or branched alkylene group having 1 to 20 carbon atoms, and further having 1 to 12 carbon atoms.

R9 represents a hydrogen atom or a halogen atom (fluorine, chlorine, bromine, iodine, etc.). Preferably it is a hydrogen atom.

nl is O or a positive integer, preferably O or 1
It is.

X is 10-, -CO-, -COO-, -OCO-, -SO2 NR-, -NR' 802NR
“21i of -, -S-, -SO- or -SO2-!
Represents the i group. Here, R1 and RJI represent an alkyl group, and R' and R'' each include those having a substituent. X is preferably -0-, -S-, -SO-, -
SO2 -1.

Z has the same meaning as Z in general formula [00-1].

In the present invention, the linear or branched alkyl group having 1 to 4 carbon atoms represented by R4 in the general formula [CG-21] is, for example, an ethyl group, a 1-copyl group, a butyl group, a 1-so
-propyl group, 1so-butyl group, 5ec-butyl group,
Alternatively, it is a tert-butyl group, and these also include those having a substituent. Examples of the substituent include an acylamino group (eg, acetylamino group), an alkoxy group (eg, methoxy group), and the like.

R4 is preferably an alkyl group having 2 to 4 carbon atoms.

The ballast group represented by R5 is an organic group having a size and shape that imparts sufficient bulk to the coupler molecule to substantially prevent the coupler from diffusing from the layer to which it is applied to other layers. .

Typical ballast groups include alkyl or aryl groups having 8 to 32 total carbon atoms.

These alkyl groups or aryl groups also include those having substituents. Substituents for aryl groups include, for example, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, carboxy groups, acyl groups, ester groups, hydroxy groups, cyano groups, nitro groups, carbamoyl groups, carbonamide groups, alkylthio groups, etc. group, arylthio group, sulfonyl group, sulfonamide group, sulfamoyl group, and halogen atom. Furthermore, examples of substituents for the alkyl group include the substituents listed for the Tateki aryl group excluding the alkyl group.

Particularly preferred as the ballast group is one represented by the following general formula [CG-4].

General formula [CC-4] -CH-0-Ar R+.

R1o represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and A' represents an aryl group such as a phenyl group, and this aryl group also includes those having a substituent. +i
Examples of the substituent include an alkyl group, a hydroxy group, an alkylsulfonamide group, and the most preferred one is t.
-A branched alkyl group such as a butyl group.

General formulas [CC-1], [CG-2] and [CG-3]
The groups which can be separated by reaction with the oxidized product of the aromatic primary amine color developing agent, each represented by 2, are well known to those skilled in the art, and are used to modify the reactivity of the coupler. It acts advantageously by separating from the coupler and performing functions such as development inhibition, bleaching inhibition, and color correction in the coating layer or other layers containing the coupler in the silver halide color photographic light-sensitive material. be. Typical examples include halogen atoms such as chlorine and fluorine, substituted and unsubstituted alkoxy groups, aryloxy groups, arylthio groups, carbamoyloxy groups, acyloxy groups, sulfonyloxy groups, sulfonamide groups, and heteroylthio groups. group, heteroyloxy group, etc.

Particularly preferred Z is a hydrogen atom or a chlorine atom.

More specifically, JP-A-50-10135, JP-A No. 50-10135;
No. 120334, No. 50-130441, No. 54-4
No. 8237, No. 51-146828, No. 54-14
No. 736, No. 47-37425, No. 50-1233
No. 41, No. 58-95346, Special Publication No. 48-3689
No. 4, U.S. Pat. No. 3.476, 563, U.S. Pat. No. 3.737.
No. 316, 3.227551 of the same publication.

Below, in the margin, there is a general 2℃ ko C-1].
Typical specific examples are shown below, but they are not limited to (n) However, it is not limited to these.

As the yellow dye-forming coupler used in the present invention, compounds represented by the following general formula [Yl] are preferred.

General formula [Yl In the formula, R11 represents an alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, etc.) or an aryl group (e.g. phenyl group, p-methoxyphenyl etc.), and R+
2 represents an aryl group, and Yl represents a hydrogen atom or a group that leaves during the color development reaction process.

Furthermore, particularly preferred yellow dye-forming couplers are compounds represented by the following general formula [Y'].

General formula [Y'] In the formula, R+3 represents a halogen atom, an alkoxy group, or an aryloxy group, and R++, R+s, and R+6 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, respectively. carbonyl group, sulfonyl group, carboxyl group, flukoxycarbonyl group, carbamyl group, sulfone group, sulfamyl group, sulfonamide group, acylamide group,
It represents a ureido group or an amino group, and Yl has the above-mentioned meaning.

These include, for example, U.S. Patent Nos. 2.778.658, 2,875,057, 2,908,573
Same No. 3.227゜155, Same No. 3,227,550, Same No. 3.253.924, Same No. 3,285,508
No. 3.277, No. 155, No. 3,341.33
No. 1, No. 3.369.895, No. 3,384,6
No. 57, No. 3.408.194, No. 3.415.
No. 652, No. 3,447, No. 928, No. 3.551
．． No. 155, No. 3,582,322, No. 3.72
5.072, 3.894.875, etc., German Patent Office 1,547,868, 2.
o57゜941 No. 1. 2.1!32.899, 2.163.812, 2,213,461,
No. 2,219,917, No. 2,261,361, No. 2,263,875, Special Publication No. 13576/1976
No. 48-29432, 48-66834, 49-10736, 49-122335, 50-28834, and 50-132926.

Typical specific examples of the yellow dye-forming coupler represented by the general formula [Y] are shown below, but the invention is not limited thereto.

Below Margin Below Margin The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of a silver halide photographic light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity. Color antifogging agents are used to prevent deterioration of sharpness and noticeable graininess.

The color antifoggant may be used in the emulsion layer itself, or
An intermediate layer may be provided between adjacent emulsion layers and used as the intermediate layer.

The silver halide photographic material of the present invention may contain an image stabilizer that prevents deterioration of the dye image.

As the image stabilizer preferably used in the present invention, the general formula [A]
Compounds represented by (specifically, pages 109 to 11 of the same)
Examples A-1 to 8-32 shown on page 6), patent application No. 1983
No. 0-117493, page 117 Compounds represented by the general formula [81 (specifically, examples B-1 to B-55 shown on pages 123 to 127), Japanese Patent Application No. 117-1982
No. 493, page 128 Compounds represented by the general formula [C] (specifically, examples C-1 to G-17 shown on pages M733 to M134 of the same), Patent Application No. 1174934/1982, page 128 Compounds represented by general formula [D] (specifically,
Examples D-1 shown on pages M135 to 736 of the same
D-11), Japanese Patent Application No. 117493/1983, page 137 of the compound represented by the general formula [E] (specifically, the compound represented by the general formula [E]
Examples E-1 to E-42 shown on pages 147 to 147)
, Japanese Patent Application No. 117493/1983, page 148 General formula [F]
Compounds represented by (specifically, pages 155 to 15 of the same)
Examples F-1 to F-47 shown on page 9), patent application No. 6
No. 0-117493, page 160 Compounds represented by the general formula [G] (specifically, examples G-1 to G-45 shown on pages 164 to 166 of the same), Japanese Patent Application No. 1983- 117
No. 493, page 167, compounds represented by the general formula [H] (specifically, examples H-1 to H-36 shown on pages 111 to 174 of the same), Japanese Patent Application No. 117493/1983 Page 175 Compounds represented by general formula [J] (specifically,
Examples J-1 to 1 shown on pages 178 to 183 of the same
J-74), Japanese Patent Application No. 117493/1988, page 188 Compounds represented by the general formula [K] (specifically, compounds represented by the general formula [K]
Examples shown on pages ~197-1~-41)
, Japanese Patent Application No. 117493/1983, page 198 General formula [L]
and the compound represented by [M] (specifically, the same No. 20
Examples L-1 to L-20 shown on pages 4 to 210
and Examples M-1 to M-3 shown on page 211 of the same
), Tokugan Sho [30-117493@Page 212 General formula [
N] (specifically, examples N-1 to N-107 shown on pages 223 to 249 of the same).

These image stabilizer additives are optional but preferably the silver halide emulsion layer of the present invention containing a magenta coupler of general formula [I] according to the present invention.

The amount added is not particularly limited, but is preferably 2 to 161
11 (J/ (h' ter.

Ultraviolet absorbers are added to hydrophilic colloid layers such as the 4L intermediate layer of silver halide photographic light-sensitive materials to prevent fogging due to discharge caused by charging of the light-sensitive material due to friction, etc., and to prevent image deterioration due to U light. May contain.

The silver halide photographic light-sensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is intended to reduce the gloss of the light-sensitive material, increase the ease of writing, and prevent mutual sticking of the light-sensitive materials. A matting agent can be added.

A lubricant can be added to reduce the sliding friction of the silver halide photographic material of the present invention.

Ultraviolet absorbers are added to hydrophilic colloid layers such as protective layers and intermediate layers of silver halide photographic light-sensitive materials to prevent fogging caused by discharge caused by charging of the light-sensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

The silver halide photographic material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

A matting agent is added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photographic light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, increasing the ease of writing, and preventing mutual scratching of the light-sensitive materials. I can do it.

A lubricant can be added to reduce the sliding friction of silver halide photographic materials.

Antistatic agents can be added to silver halide photographic materials for the purpose of preventing static electricity. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of a silver halide photographic light-sensitive material is used to improve coating properties, prevent static electricity, improve slipperiness, emulsification and dispersion, prevent adhesion, and (promote development, harden the film, and sensitize it. Various surfactants are used for the purpose of improving photographic properties (such as).

The silver halide photographic light-sensitive material is a photographic emulsion layer, and the other layers are flexible reflective supports such as baryta paper, paper laminated with α-olephne polymer, etc., synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, polychloride, etc. vinyl,
Films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate, polycarbonate, polyamide,
It can be applied to rigid bodies such as glass, metal, and ceramics.

Silver halide photographic light-sensitive materials can be prepared directly or (adhesiveness, antistatic property, dimensional stability, resistance The coating may be applied via one or more subbing layers to improve abrasion, hardness, antihalation, friction properties, and/or other properties.

When coating the silver halide photographic light-sensitive material, a thickener may be used to improve coating properties. As for the application method,
Particularly useful are extrusion coatings and curtain coatings in which two or more layers can be applied simultaneously.

A silver halide photographic light-sensitive material can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material is sensitive. Light sources include natural light (sunlight), tungsten lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser beams, light emitting diode lights, electron beams, and Xm.

Any known light source can be used, such as light emitted from a phosphor excited by γ rays, α rays, etc.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

In the processing method according to the present invention, the silver halide photographic light-sensitive material is imagewise exposed and then processed with a color developer having a bromide ion concentration of 1X10-3E/l or more and an iron ion concentration of 0.05 ppm or more. be done.

The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known ones that are widely used in various color photographic processes.

These color developing agents include aminephenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Further, these compounds are generally used in a concentration of 0.2 g to 30 g for the color developer 12, preferably 2 g to 20 g for the color developer 111.
Use at a concentration of

Examples of aminophenol-based developers include 0-aminephenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-〇-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride z, N
, N/-dimethyl-〇-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 -aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-〇-
Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal binitites,
Alkali metal thiocyanates, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of this color developer is usually 7 or more,
Most commonly from about 10 to about 13.

Further, an anti-capri agent is generally used in the color developing solution. Potassium bromide is a typical anti-capri agent, and bromide ions in the developer have an anti-fogging effect.

In the present invention, the stability of photographic properties is obtained by processing the silver halide photographic material according to the present invention described above with a color developer having a bromide ion concentration within a specific range.

The color developing solution used in the present invention has a bromide ion concentration of 1X.
10" E Schiff 1 or more, preferably 2 x 10-
In the range from 3 to 4 X 10-2 mol/1, more preferably from 3 X 10-3 to 2.5X 10-2 mol/1! is within the range of

Although this color developing solution does not normally contain iron ions when prepared, when it is continuously processed in an automatic processor etc., as mentioned above, bleaching agents such as ferric complex salts of aminopolycarboxylic acids contain iron ions. Iron ions become a source of ions, and iron ions are mixed into the color developer and gradually accumulate. In the present invention, the iron ion concentration of the color developer is O.05pp.
The effect is particularly exhibited when the pH is 0.1 ppm or more, especially 0.1 ppm to 3 ElpIS, and even 0.31) l) m to 31) pH 1. The iron ion concentration in the color developing solution can be measured by a generally known quantitative analysis method. It is also possible to use a method of measuring the iron ion concentration by developing color in the presence of an ion coloring reagent and comparing the resulting color density with a color standard prepared in advance in correspondence to the iron ion concentration.

The above color development process is generally carried out at a density of 25°C to 45°C and 30°C.
It is carried out for 10 seconds to 10 minutes. Particularly preferably in the present invention, the heating time is 1 minute 30 seconds to 3 minutes 30 seconds at a concentration of 33°C to 38°C.

After the above-mentioned color development process, the film is usually processed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching process is performed before that. There are 11 bleaching agents used in this bleaching process! A metal complex salt of an acid is used, and the metal complex salt has the effect of oxidizing the metallic silver produced by development and converting it into silver halide, and at the same time coloring the uncolored part of the coloring agent. Iron, cobalt,
It is coordinated with metal ions such as copper. For example, ferric complex salts of aminopolycarboxylic acids are commonly used as bleaching agents. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] ]Nitrilotriacetic acid sodium salt The bleaching agent used is as described above. It contains the metal complex salt of II as a bleaching agent and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

IIM again! pH buffering agents such as salts, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and the like which are known to be commonly added to bleaching solutions can be appropriately added.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid It may contain one or more types of l)H buffers consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.

When processing is carried out while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the replenisher to replenish the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank (or an appropriate oxidation Agents such as hydrogen peroxide, bromates, persulfates, etc. may be added as appropriate.

The pH value of the bleach-fixing solution is usually 4 to 9, and the bleach-fixing process is generally carried out at a temperature of 20 DEG C. to 45 DEG C. for 30 seconds to 3 minutes.

[Effects of the Invention] According to the method for processing silver halide photographic materials according to the present invention, even if iron ions are mixed into the color developing solution during processing and gradually accumulate, causing fluctuations in the iron ion concentration, the resulting There are few changes in photographic properties such as sensitivity, gradation, and fog of magenta dye images, and stable photographic properties can be obtained.

[Example-11 A silver nitrate aqueous solution and a potassium chlorbromide aqueous solution were simultaneously added to an aqueous gelatin solution to produce a salt consisting of irregularly shaped particles containing 70 mol% silver bromide and having an average particle size of 0.4 μm and a coefficient of variation of 0.17. A silver bromide emulsion was prepared. (referred to as Emulsion A) Furthermore, in the same manner, 5 mol% of silver iodide and 70 mol% of silver bromide were prepared.
A silver iodochlorobromide emulsion consisting of irregularly shaped grains having an average grain size of 0.4 μm and a coefficient of variation of 0.17 was prepared. (referred to as emulsion B) Emulsion A and emulsion B were further chemically sensitized by adding sodium thiosulfate as a sulfur sensitizer according to the conventional method, and 5 minutes before the end of chemical sensitization, a green sensitizing dye was added. 4-hydroxy-6-methyl-1,3,38 as a stabilizer at the end of chemical sensitization.

7-tetrazaindene was added to prepare a green sensitized emulsion.

Next, a magenta coupler dispersion was prepared using the magenta coupler according to the present invention and the following comparative magenta coupler MC-1.

That is, 40 g of each magenta coupler, 1 g of dioctyl hydroquinone as a color stain preventive agent, dibutyl phthalate 40142 as a high boiling point organic solvent, and ethyl acetate ioo, I2 as a low boiling point organic solvent are dissolved in a mixed solvent, and this solution is dissolved in dodecylbenzenesulfone. After adding 300 g of a 5% aqueous gelatin solution containing sodium acid, the mixture was dispersed using an ultrasonic homogenizer to prepare a coupler dispersion.

Next, a green-sensitive silver chlorobromide emulsion (emulsion A) or a green-sensitive silver iodochlorobromide emulsion (emulsion A) was deposited on a polyethylene-coated paper support.
Mix emulsion B) and each magenta coupler, coat silver m
2. Omg/dyd ((11, 4.0mg/σ in combination with MC-1), magenta coupler coating amount 4, omO/dgo, gelatin coating amount 30mg/dm
An emulsion layer was provided so that the emulsion layer was formed, and a protective layer was coated on top of the emulsion layer so that the gelatin coating amount was 120 vg/dTd, and the sample shown in Table 1 was obtained by drying.

The sample prepared in this way was heated at 40°C and 60%RH for 2 hours.
After controlling the temperature and humidity for 4 hours, the sample was exposed to white light through a light wedge using a sensitometer (Model KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.), and then processed according to the following processing steps. However, the following A to H were used as color developing solutions.

Standard processing steps (!2!1 Processing temperature and processing time) [1] Color development 38°C 3 minutes 30 seconds [2] Bleach-fixing 3
3℃ 1 minute 30 seconds [3] Water washing treatment 25-30℃
3 minutes [4] Drying 75-80℃ for about 2 minutes Processing solution composition [Color developer A Cobenzyl alcohol 151g Ethylene glycol 15i12 Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
30. OQ Hydroxylamine Sulfate
3.0g polyphosphoric acid (TPPS) 2
．． 5(+3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g optical brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1. Add 2.0 g of Oa potassium hydroxide water to bring the total m to 12, and adjust the pH to 10.20.

[Color developer B] ... Color developer A contains ferric ammonium hydrate of ethylenediaminetetraacetate (iron ions o, o
Same as color developer A except that it contains 3 opm (equivalent to 3 opm).

[Color developer C]...Ethylenediaminetetraacetic acid ferric ammonium dihydrate (iron ion 0.0%) is added to color developer A.
061) I) Color developer A except that it contains +11 equivalent)
Same as.

[Color developer D]...Ethylenediaminetetraacetic acid ferric ammonium dihydrate (iron ion 0.
Same as color developer A except that it contains 15 ppm (equivalent to 15 ppm).

[Color developer E]...Ethylenediaminetetraacetic acid ferric ammonium dihydrate (iron ion 0.0%) is added to color developer A.
Same as color developer A except that it contains 35 ppm (equivalent to 35 ppm).

[Color developer F]...Ethylenediaminetetraacetic acid ferric ammonium dihydrate (iron ion 1.
Same as color developer A except that it contains 5 ppm (equivalent to 5 ppm).

[Color developer G]...Color developer A contains ethylene diamine diamine and ferric ammonium acetate dihydrate (iron ion 2.
Same as color developer A except that it contains 8 ppm (equivalent to 8 ppm).

[Color developer H]...Ethylenediaminetetraacetic acid ferric ammonium dihydrate (iron ion 3.
Same as color developer A except that it contains 2ppH equivalent).

Color developers A-H all have a bromide ion concentration of 5.9X.
It is 10-3 mol/l.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetate dihydrate 60σ ethylenediaminetetraacetic acid M 3g Ammonium thiosulfate (70% solution) 100. Q Ammonium sulfite (40% solution) 27.5mff1 W! to pH 7.1 with potassium carbonate or glacial acetic acid! Jnt, add water to make a total volume of 1 ft.

[Comparative magenta coupler MG-1] The sensitivity, gamma, and capri of each sample obtained by processing were measured using an optical densitometer (PDA-65 manufactured by Konishiroku Photo Industry Co., Ltd.).
(type). As for gamma, a gamma value of density 0.8 to 1.8 was determined. Sensitivity was determined by the reciprocal of the exposure amount required to obtain an optical density of 0.8. The results are shown in Table-1.

From the margin table-1 below, the iron ion concentration in the color developer is 0.05p.
When processed with color developing solutions [A] and [B] that are less than pm, there is no difference in sensitivity, gamma, and fog in both the comparison sample and the sample of the present invention even if the iron ion concentration in the color developer changes. I understand.

On the other hand, when treated with color developers [C] to [H] with an iron ion concentration of 0.051)I)m or more, comparative samples 1 to 3 had iron ion concentrations in the color developer Sensitivity, gamma, and fog increase with increasing
Although the influence of the iron ion concentration in the color developing solution is large, Samples 4 to 8 of the present invention in which the magenta coupler of the present invention was changed
It can be seen that even if the iron ion concentration in the color developing solution increases, the sensitivity, gamma, and fog hardly change, and the object of the present invention is achieved.

[Example-2] Sample N006 prepared in Example-1 was evaluated in the same manner as in Example-1.

However, the color developer had the same composition as the color developer [A] used in Example 1, except that the iron ion concentration and bromide ion concentration were changed as shown in Table 2. There are 35 types. The results obtained are shown in Table-2.

Table 2 shows that when the bromide ion concentration is within the range of the present invention, the treatment performance is stable against changes in the iron ion concentration. Furthermore, the bromide ion concentration is 3.5
It can be seen that when X 10-'' mol/ffi and 1X 10-2 mol/ffi, the fog was particularly low, showing favorable results.

The following margin [Example-3] In the same manner as in Example-1, a silver chlorobromide emulsion (silver chlorobromide emulsion) consisting of amorphous grains containing 70 mol% of silver bromide and having an average grain size of 0.5 μm and a coefficient of variation of 0.17 was prepared. Emulsion C) was prepared.

Further, in the same manner as in Example 1, a silver nitrate aqueous solution and a potassium chlorbromide aqueous solution were simultaneously added to an aqueous gelatin solution containing silver chlorobromide seed particles while changing the addition rate as a function of time. average particle size 0.5 μm, containing 70 mol%;
A silver chlorobromide emulsion (referred to as emulsion) consisting of amorphous grains with a coefficient of variation of 0.12 was prepared.

In addition, according to the method described in JP-A No. 54-48521,
An aqueous solution of silver nitrate and an aqueous solution of potassium chlorobromide were simultaneously added to an aqueous gelatin solution containing silver chlorobromide seed particles by varying the addition rate as a function of time, and 70 mol of silver bromide was added while controlling DA(). Average particle size including % 0.5μm1
Silver chlorobromide emulsions consisting of octahedral, tetradecahedral and cubic grains with a coefficient of variation of 0.12 (emulsions E, F and G, respectively)
) was prepared.

Furthermore, regarding emulsions E, F and G, JP-A-59-29
The values were measured according to the method described in No. 243, and the results were as follows: Emulsion E: Octahedral grains with K = 0.05, Emulsion F: Tedecahedral grains with -95 Emulsion G: K -12
There were 50 cubic particles.

These emulsions C-G were chemically sensitized in the same manner as in Example 1, and a green-sensitive sensitizing dye was added to obtain a green-sensitized silver chlorobromide emulsion.

Exemplary magenta coupler 59 was dispersed in the same manner as in Example-1 to prepare a magenta coupler dispersion liquid, and mixed with these emulsions C-G.
No. 16 was prepared and evaluated.

The results obtained are shown in Table 3.

From Table 3 below, samples 11 to 15 in which the crystal habits and coefficients of variation of silver chlorobromide were varied also achieved the object of the present invention in the same manner as in Example 1, and among them, the monodisperse tetradecahedral structure was achieved. It can be seen that Samples 14 and 15 using particles and monodisperse cubic particles have high sensitivity and gamma, and low fog, and have particularly favorable performance in color paper.

[Example-4] With the configuration shown in Table-4, multilayer samples 21 to 24 were prepared, treated in the same manner as in Example-1, and the magenta coloring layer was measured. The obtained results are shown in Table-5. .

From Table 5, it can be seen that even when multilayered, Samples 21 to 23 have stable performance even when the iron ion concentration changes, indicating that the object of the present invention has been achieved.

Furthermore, the dielectric constant is 6 as a high boiling point solvent for the magenta coupler.
．． It can be seen that when a high boiling point solvent of 0 or less is used, the fog is particularly low and the performance is favorable.

Picture 4L Anni Liu B-35 UV absorber anti-stain agent Rih

Claims (1)

[Scope of Claims] (1) A silver halide photographic light-sensitive material in which a silver halide emulsion layer containing a magenta coupler represented by the following general formula [I] and a silver chlorobromide emulsion is provided on a support, After imagewise exposure, the bromide ion concentration is 1×10^-^3 mol/
1. A method for processing a silver halide photographic material, comprising the step of processing with a color developing solution having an iron ion concentration of 0.05 ppm or more and an iron ion concentration of 0.05 ppm or more. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. It's okay. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ] (2) The magenta coupler represented by the general formula [I] has a dielectric constant of 6.0.
A method for processing a silver halide photographic light-sensitive material according to claim (1), characterized in that the silver halide photographic material is dispersed in a silver halide emulsion layer using the following high-boiling organic solvent. (3) Silver bromide content of silver chlorobromide emulsion is 10 to 99 mol%
A method for processing a silver halide photographic material according to claim (1). (4) The method for processing a silver halide photographic material according to claim (1), wherein the silver chlorobromide emulsion is a monodisperse emulsion. (5) A silver halide photograph according to claim (1), wherein the silver chlorobromide grains contained in the silver chlorobromide emulsion have an average grain size of 0.2 μm to 1.5 μm. How to process photosensitive materials. (6) The silver chlorobromide grains contained in the silver chlorobromide emulsion are measured by X-ray diffraction analysis: K = [Intensity of diffraction line attributed to (200) plane]/[(222) plane Claim (1) characterized in that the particle is a cubic particle and/or a tetradecahedral particle satisfying 5≦K≦5000 when expressed by the intensity of the diffraction line attributed to A method for processing a silver halide photographic material as described in . (7) The bromide ion concentration of the color developer is 2×10^-^
The method for processing a silver halide photographic material according to claim 1, wherein the amount is 3 to 4 x 100^-^2 mol/l.