JPH0731388B2 - Dye image forming method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dye image forming method, and more specifically, it has a stable sensitivity and gradation with respect to a composition change of a color developer, particularly a change in bromine ion concentration. And a method for forming an excellent dye image with less fog.

BACKGROUND OF THE INVENTION In recent years, development of silver halide color photographic light-sensitive materials (hereinafter simply referred to as color light-sensitive materials) has been accelerated, and
Further, so-called low replenishment type developing solutions, in which the amount of the replenishing solution is reduced by concentrating the developing replenishing solution for the purpose of improving work efficiency and cost reduction, are increasing. In response to such trends in the industry, there is a strong demand for silver halide photographic light-sensitive materials having rapid processing properties and low replenishment type suitability. However, in the low replenishment type developer, halogen ions are accumulated in the developer at a higher concentration than in the conventional type.

In general, halogen ions have a development inhibitory effect, and iodine ions are particularly strong, followed by bromine ions and chlorine ions in this order, and the chlorine ion inhibitory power is very weak compared to the other two ions. Therefore, to meet the above needs,
Studies have been conducted using a silver chlorobromide emulsion having a relatively high chlorine content, but it is difficult to significantly increase the chlorine content because the sensitivity decreases as the silver chloride content increases. However, the current situation is.

Further, it is well known that bromine ion is also effective as an antifoggant, and it is preferable to make it exist in an appropriate amount in a developing solution, but in general, the photographic performance is changed by the fluctuation of the bromine ion concentration in the developing solution, In particular, in the case of a color light-sensitive material using silver chlorobromide, there is a drawback that sensitivity and gradation, which are very important among photographic performances, greatly change.

Normally, in the general market, color photographic materials are continuously processed by an automatic processor, and efforts are made to keep the bromine ion concentration in their developers constant, but the replenisher excess Fluctuations in bromine ion concentration, which are thought to be due to shortages and evaporation of liquid, occur. Such changes in sensitivity and gradation given to the color light-sensitive material when the bromine ion concentration fluctuates significantly impairs the quality of a color print for direct viewing.

For the above reasons, it is difficult to prevent the fluctuation of the bromine ion concentration in the developer, and therefore, there is a strong demand for a method of preventing the gradation fluctuation even when the bromine ion concentration changes.

On the other hand, in order to form a dye image by using a color light-sensitive material, usually, the aromatic primary amine type color developing agent is oxidized by itself when reducing the silver halide grains in the exposed color light-sensitive material. This oxidant is formed by reacting with a coupler previously contained in the color light-sensitive material to form a dye. Usually, as the coupler, three types of couplers that form three dyes of yellow, magenta and cyan are used in order to perform color reproduction by the subtractive color method.

Of these, to form a magenta dye image,
Generally, 5-pyrazolone, cyanoacetophenone, isodazolone coupler and the like are used.

Most of the practically used magenta dye image forming couplers have been 5-pyrazolone type couplers. The dye image formed from this 5-pyrazolone-based coupler has some advantages, but on the other hand, the color tone is not sufficient, there is a side absorption having a yellow component around 430 nm, and the skirt on the long wave side is sharp. There was a defect in the spectral absorption characteristics such that it was not broken and the color was turbid, and the coloring dye image was lacking in vividness.

In particular, it was an important problem in a color print for direct viewing in which an image is carried on a reflective support.

As a coupler without this side absorption, U.S. Pat. No. 3,725,067
No. 59-99437, 59-162548, 59-171956
Issue, Research Disclosure Magazines 24220, 24230
The pyrazolotriazole couplers described in JP-A No. 24531 and JP-A No. 24531 are particularly excellent.

Further, the change in photographic performance due to the fluctuation of the bromine ion concentration in the developing solution depends on the type of coupler, and it is desired to select a coupler having a small performance change. The inventors of the present invention have found that the magenta coupler described in Japanese Patent Application No. 59-276725 is preferable in terms of color reproduction, and has a relatively small change in performance with respect to variations in the bromine ion concentration in the developer (hereinafter referred to as Br variation resistance). However, it has been found that the resistance to Br fluctuation is not sufficient yet, and that these couplers are apt to cause fog, and further improvement is required for practical use.

[Object of the Invention] A first object of the present invention is to provide excellent rapid processing suitability, stability of development processing, and particularly to fluctuations in the bromine ion concentration of the developer.
It is an object of the present invention to provide a dye image forming method capable of obtaining stable sensitivity and gradation.

A second object of the present invention is to provide a dye image forming method having excellent color reproducibility and low fog.

[Structure of the Invention] As a result of intensive studies conducted by the present inventors, the above object of the present invention is to provide a silver halide photographic light-sensitive material having a photographic constituent layer containing at least one silver halide emulsion layer on a reflective support. In at least one of the silver halide emulsion layers, at least one of magenta couplers represented by the following general formulas [II] and [III] and a silver chlorobromide emulsion are contained, and After imagewise exposing a silver halide color photographic light-sensitive material containing a mercapto heterocyclic compound in at least one layer thereof, at least a bromine ion concentration of 7 × 10 ^-3 mol / l or more and hydroxylamines of 0.
It has been found that this can be achieved by a dye image forming method characterized by processing with a color developing solution containing 02 mol / l to 0.15 mol / l.

General formula (II) General formula (III) [In the formula, X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidation product of a color developing agent. Moreover, R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent. [Specific Configuration of the Invention] Next, the present invention will be specifically described.

The general formula [II] and [III] general formula [II] according to the present invention General formula (III) In the magenta coupler represented by, X represents a hydrogen atom or a substituent capable of splitting off upon reaction with the oxidation product of the color developing agent. Moreover, R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent.

As the substituent represented by R ₁ , R ₂ and R ₃ , for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group,
Heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, Siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group,
Examples thereof include imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group and heterocyclic thio group.

Examples of the halogen atom include a chlorine atom and a bromine atom, and a chlorine atom is particularly preferable.

The alkyl group represented by R ₁ , R ₂ and R _{3 has 1 to} 32 carbon atoms, an alkenyl group and an alkynyl group have 2 to 32 carbon atoms, and a cycloalkyl group and a cycloalkenyl group have carbon atoms. The number 3 to 12, especially 5 to 7, is preferable, and the alkyl group, alkenyl group and alkynyl group may be linear or branched.

Further, these alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group are substituents [for example, aryl, cyano, halogen atom, heterocycle,
In addition to cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, those substituted through carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, and further through hetero atom Substituents (specifically those substituted through an oxygen atom such as hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulfa Substituted through a nitrogen atom such as moylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide and ureido, alkylthio, arylthio, heterocyclic thio, sulfonyl,
Those substituted through a sulfur atom such as sulfinyl and sulfamoyl, those substituted through a phosphorus atom such as phosphonyl, and the like}].

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group,
1-hexylnonyl group, 1,1′-dipentylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4 ′-{α- [4 ″ (p-hydroxybenzenesulfonyl) phenoxy] dodecanoylamino}
Phenylpropyl group, 3- {4 '-[α- (2 ", 4"-
Di-t-amylphenoxy) butanamide] phenyl}
-Propyl group, 4- [α- (o-chlorophenoxy) tetradecanamidophenoxy] propyl group, allyl group,
Examples thereof include a cyclopentyl group and a cyclohexyl group.

The aryl group represented by R ₁ , R ₂ and R ₃ is preferably a phenyl group and may have a substituent (for example, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, a phenyl group, a 4-t-butylphenyl group,
2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'-
[Α- (4 ″ -t-butylphenoxy) tetradecanamide] phenyl group and the like.

The heterocyclic group represented by R ₁ , R ₂ and R ₃ is preferably a 5- to 7-membered heterocyclic group, which may be substituted or may be condensed. Specific examples thereof include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group.

Examples of the acyl group represented by R ₁ , R ₂ and R ₃ include acetyl group, phenylacetyl group, dodecanoyl group and α-
Examples thereof include an alkylcarbonyl group such as a 2,4-di-t-amylphenoxybutanoyl group, a benzoyl group, a 3-pentadecyloxybenzoyl group, and an arylcarbonyl group such as a p-chlorobenzoyl group.

Examples of the sulfonyl group represented by R ₁ , R ₂ and R ₃ include an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group, an benzenesulfonyl group, and an arylsulfonyl group such as a p-toluenesulfonyl group.

Examples of the sulfinyl group represented by R ₁ , R ₂ and R ₃ include an alkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group and a 3-phenoxybutylsulfinyl group, a phenylsulfinyl group and a m-pentadecylphenylsulfinyl group. Examples thereof include an arylsulfinyl group.

The phosphonyl group represented by R ₁ , R ₂ and R ₃ is an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl such as a phenoxyphosphonyl group. Group, and an arylphosphonyl group such as a phenylphosphonyl group.

The carbamoyl group represented by R ₁ , R ₂ and R ₃ may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like. For example, an N-methylcarbamoyl group, N, N-
Dibutylcarbamoyl group, N- (2-pentadecyloctylethyl) carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl group, etc. Can be mentioned.

The sulfamoyl group represented by R ₁ , R ₂ and R ₃ may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include N-propylsulfamoyl group, N,
N-diethylsulfamoyl group, N- (2-pentadecyloxyethyl) sulfamoyl group, N-ethyl-N-
Examples thereof include dodecylsulfamoyl group and N-phenylsulfamoyl group.

Examples of the spiro compound residue represented by R ₁ , R ₂ and R ₃ include spiro [3.3] heptan-1-yl and the like.

Examples of the bridged carbonized compound residue represented by R ₁ , R ₂ and R ₃ include bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.1 ^3′7 ] decan-1-yl, 7, 7-Dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

The alkoxy group represented by R ₁ , R ₂ and R ₃ may be further substituted with those mentioned as the substituent for the alkyl group, for example, methoxy group, propoxy group, 2-ethoxyethoxy group, penta Examples thereof include a decyloxy group, a 2-dodecyloxyethoxy group and a phenethyloxyethoxy group.

The aryloxy group represented by R ₁ , R ₂ and R ₃ is preferably phenyloxy, and the aryl nucleus may be further substituted with a substituent or an atom mentioned for the aryl group, for example, a phenoxy group. , P-t-butylphenoxy group, m-pentadecylphenoxy group and the like.

The heterocyclic oxy group represented by R ₁ , R ₂ and R ₃ is 5
To 7-membered heterocycle are preferable, and the heterocycle may further have a substituent, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole- A 5-oxy group is mentioned.

The siloxy group represented by R ₁ , R ₂ and R ₃ may be further substituted with an alkyl group and the like, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group and a dimethylbutylsiloxy group.

Examples of the acyloxy group represented by R ₁ , R ₂ and R ₃ include an alkylcarbonyloxy group and an arylcarbonyloxy group, which may further have a substituent, specifically, an acetyloxy group. , Α-chloroacetyloxy group, benzoyloxy group and the like.

The carbamoyloxy group represented by R ₁ , R ₂ and R ₃ may be substituted with an alkyl group, an aryl group or the like, and examples thereof include N-ethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group and N- Examples thereof include a phenylcarbamoyloxy group.

The amino group represented by R ₁ , R ₂ and R ₃ may be substituted with an alkyl group, an aryl group (preferably a phenyl group) and the like, and examples thereof include an ethylamino group, anilino group, m-chloroanilino group and 3- Examples thereof include a pentadecyloxycarbonylanilino group and a 2-chloro-5-hexadecanamide anilino group.

Examples of the acylamino group represented by R ₁ , R ₂ and R ₃ include an alkylcarbonylamino group and an arylcarbonylamino group (preferably a phenylcarbonylamino group), which may further have a substituent. Include acetamide group, α-ethylpropanamide group, N-phenylacetamide group, dodecane amide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group, etc. Is mentioned.

As the sulfonamide group represented by R ₁ , R ₂ and R ₃ ,
Examples thereof include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specific examples thereof include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by R ₁ , R ₂ and R ₃ may be an open chain type, a cyclic type, or may have a substituent,
For example, succinimide group, 3-heptadecyl succinimide group, phthalimide group, glutarimide group and the like can be mentioned.

The ureido group represented by R ₁ , R ₂ and R ₃ is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group) and the like, for example, N-ethylureido group, N-
Examples thereof include a methyl-N-decylureido group, an N-phenylureido group and an Np-tolylureido group.

The sulfamoylamino group represented by R ₁ , R ₂ and R ₃ is
It may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., for example, an N, N-dibutylsulfamoylamino group, an N-methylsulfamoylamino group,
Examples thereof include N-phenylsulfamoylamino group.

The alkoxycarbonylamino group represented by R ₁ , R ₂ and R ₃ may further have a substituent, and examples thereof include a methoxycarbonylamino group, a methoxyethoxycarbonylamino group and an octadecyloxycarbonylamino group. To be

The aryloxycarbonylamino group represented by R ₁ , R ₂ and R ₃ may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R ₁ , R ₂ and R ₃ may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, ethoxymethoxycarbonyl. Examples thereof include an oxy group and a benzyloxycarbonyl group.

The aryloxycarbonyl group represented by R ₁ , R ₂ and R ₃ may further have a substituent, for example, a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, a m-
Examples include a pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R ₁ , R ₂ and R ₃ may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group and 3
A phenoxypropylthio group.

The arylthio group represented by R ₁ , R ₂ and R ₃ is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group, p-methoxyphenylthio group, 2-t-octylphenylthio group, 3 Examples include -octadecylphenylthio group, 2-carboxyphenylthio group and p-acetaminophenylthio group.

The heterocyclic thio group represented by R ₁ , R ₂ and R ₃ is 5
A ~ 7-membered heterocyclic thio group is preferable, and it may further have a condensed ring or may have a substituent. Examples thereof include a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Examples of the substituent which can be removed by the reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), carbon atom, oxygen atom, sulfur atom or nitrogen atom. Groups which substitute by

Examples of the group substituting through a carbon atom include a carboxyl group and other general formulas. R _'1, R' ₂ and R _'3 has the same meaning as the R _1, R ₂ and R _3, R _"2 and R" ₃ represents a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group. ), A hydroxymethyl group, and a triphenylmethyl group.

Examples of the group substituting through an oxygen atom include an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy group, an alkoxyoxalyloxy group. Is mentioned.

The alkoxy group may further have a substituent, for example,
Examples thereof include an ethoxy group, a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a phenethyloxy group and a p-chlorobenzyloxy group.

The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent.
Specifically, phenoxy group, 3-methylphenoxy group, 3
-Dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4- [α- (3'-pentadecylphenoxy) butanamide] phenoxy group, hexadecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p
-Methoxyphenoxy group and the like.

The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples thereof include a 1-phenyltetrazolyloxy group and a 2-benzothiazolyloxy group.

Examples of the acyloxy group include an acetoxy group, an alkylcarbonyloxy group such as a butanoloxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
An arylcarbonyloxy group such as a benzoyloxy group can be mentioned.

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

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

Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group and the like.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group and the like.

Examples of the group substituting via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group and an alkyloxythiocarbonylthio group.

Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a phenethylthio group and a benzylthio group.

Examples of the arylthio group include phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butyl. Examples thereof include a phenylthio group.

Examples of the heterocyclic thio group include 1-phenyl-1,2,
Examples thereof include a 3,4-tetrazolyl-5-thio group and a 2-benzothiazolylthio group.

Examples of the alkyloxythiocarbonylthio group include dodecyloxythiocarbonylthio group.

Examples of the group substituting through the nitrogen atom include those represented by the general formula The items shown in are listed. Where R _4'and R _{5 '}
Represents a hydrogen atom, an alkyl group, 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 R _{4 ′} and R _{5 ′} are bonded to each other to form a heterocyclic ring. May be formed. However never _{R 4 'and R 5'} are both 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,
Alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylamino group, arylamino group,
Acylamino group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group,
Examples thereof include a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkyloxycarbonylamino group, an aryloxycarbonylamino group, a hydroxyl group, a carboxyl group, a cyano group and a halogen atom. Specific examples of the alkyl group include an ethyl group, an octyl group, a 2-ethylhexyl group, and a 2-chloroethyl group.

The aryl group represented by R _{4 ′} or R _{5 ′} is preferably a carbon number of 6 to 32, especially a phenyl group or a naphthyl group, and the aryl group may have a substituent and the substituent may be the above-mentioned R. Examples of the substituent to the alkyl group represented by _{4 ′} or R _{5 ′} and the alkyl group are mentioned. Specific examples of the aryl group include a phenyl group,
Examples thereof include a 1-naphthyl group and a 4-methylsulfonylphenyl group.

The heterocyclic group represented by R _{4 ′} or R _{5 ′} is 5 to 6
Preferred is a member, which may be a condensed ring or may have a substituent. Specific examples thereof include a 2-furyl group, a 2-quinolyl group, a 2-pyrimidyl group, a 2-benzothiazolyl group, and a 2-pyridyl group.

Examples of the sulfamoyl group represented by R _{4 ′} or R _{5 ′} include N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,
Examples thereof include N-diaryl sulfamoyl groups, and these alkyl groups and aryl groups may have the substituents described above for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N, N-diethylsulfamoyl group, N-methylsulfamoyl group, N-dodecylsulfamoyl group, and Np-tolylsulfamoyl group.

As the carbamoyl group represented by R _{4 ′} or R _{5 ′} ,
N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group and the like can be mentioned, and these alkyl groups and aryl groups can be substituted by the alkyl groups and aryl groups mentioned above. It may have a group. Specific examples of the carbamoyl group include, for example, N, N-diethylcarbamoyl group,
N-methylcarbamoyl group, N-dodecylcarbamoyl group, Np-cyanophenylcarbamoyl group, Np-
A trilylcarbamoyl group may be mentioned.

Examples of the acyl group represented by R _{4 ′} or R _{5 ′} include an alkylcarbonyl group, an arylcarbonyl group and a heterocyclic carbonyl group, and the alkyl group, the aryl group and the heterocyclic group have a substituent. You may have. Specific examples of the acyl group include a hexafluorobutanoyl group, a 2,3,4,5,6-pentafluorobenzoyl group, an acetyl group, a benzoyl group, a naphthoyl group, and a 2-furylcarbonyl group. .

Examples of the sulfonyl group represented by R _{4 ′} or R _{5 ′} include an alkylsulfonyl group, an arylsulfonyl group and a heterocyclic sulfonyl group, which may have a substituent, and specific examples thereof include ethanesulfonyl group. Group, benzenesulfonyl group, octanesulfonyl group, naphthalenesulfonyl group, p-chlorobenzenesulfonyl group and the like.

The aryloxycarbonyl group represented by R _{4 ′} or R _{5 ′} may have the substituents described above for the aryl group, and specific examples thereof include a phenoxycarbonyl group.

The alkoxycarbonyl group represented by R _{4 ′} or R _{5 ′} may have the substituents described above for the alkyl group, and specific examples thereof include a methoxycarbonyl group, a dodecyloxycarbonyl group and a benzyloxycarbonyl group. Etc.

The hetero ring formed by combining R _{4 ′} and R _{5 ′} is preferably a 5- or 6-membered hetero ring, which may be saturated or unsaturated, and may or may not have aromaticity. Often,
It may also be a condensed ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxooxazolidinyl group, 2- N-1,1-dioxo-
3- (2H) -oxo-1,2-benzthiazolyl group, 1-
A pyrrolyl group, a 1-pyrrolidinyl group, a 1-pyrazolyl group,
1-pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group, 1-isoindolinyl group, 2-
Isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl group, 1-
(1,2,4-triazolyl) group, 1- (1,2,3-triazolyl) group, 1- (1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3, 4-tetrahydroquinolyl group, 2-
Oxo-1-pyrrolidinyl group, 2-1H-pyridone group, phthalazinone group, 2-oxo-1-piperidinyl group and the like, these heterocyclic groups are alkyl groups, aryl groups,
Alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkylamino group, arylamino group, acylamino group, sulfoneamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxy It may be substituted with a carbonyl group, an imide group, a nitro group, a cyano group, a carboxyl group, a halogen atom or the like.

The nitrogen-containing heterocycle formed by Z or Z'includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, and the like, and the substituent which the ring may have is the same as those described above for R. Is mentioned.

In addition, a substituent on the heterocycle in the general formula [II] (for example,
R ₁ , R ₂ and R ₃ ) are When it has a moiety (wherein R ₁ ″, R ₂ ″, R ₃ ″ and X have the same meanings as R ₁ , R ₂ , R ₃ and X in the general formula [II]), a so-called bis type coupler is formed. However, it is of course included in the present invention.

Among the magenta couplers represented by the general formulas [II] to [III], the magenta coupler represented by the general formula [II] is particularly preferable.

Regarding the substituents on the heterocycle in the general formulas [II] and [III], it is preferable that R1 satisfies the following condition 1, and it is more preferable that R1 satisfies the following conditions 1 and 2. Especially preferred is when the following conditions 1, 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 is bonded to the carbon atom or none is bonded.

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

The most preferable substituent R ₁ on the heterocycle is represented by the following general formula [IX].

General formula [IX] In the formula, R ₉ , R ₁₀ and R ₁₁ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group. , Phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group , An acylamino group, a sulfonamide group, an imide group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
It represents an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and at least two of R ₉ , R ₁₀ and R ₁₁ are not hydrogen atoms.

Two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ may combine to form a saturated or unsaturated ring (eg cycloalkane, cycloalkene, heterocycle), Further, R ₁₁ may be bonded to the ring to form a bridged hydrocarbon compound residue.

The group represented by R _{9 to} R ₁₁ may have a substituent, and R ₉
~ As specific examples of the group represented by R ₁₁ and the substituent which the group may have, specific examples and substituents of the group represented by R ₁ in the general formula [II] and general formula [III] described above. Is mentioned.

Further, for example, specific examples of the ring formed by combining R ₉ and R ₁₀ and the bridged hydrocarbon compound residue formed by R _{9 to} R ₁₁ and the substituent which it may have are as described above. Cycloalkyl represented by R ₁ in formula [II] and general formula [III],
Specific examples of the cycloalkenyl and heterocyclic bridged hydrocarbon compound residues and the substituents thereof are given.

Among the general formula [IX], it is preferable that (i) when two of R _{9 to} R ₁₁ are alkyl groups, (ii) one of R _{9 to} R ₁₁ is, for example, R ₁₁ is a hydrogen atom. And when the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom.

Further preferred among (i) is when two of R _{9 to} R ₁₁ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl and the cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl and the substituent thereof include the general formula [II] and the general formula [II
Specific examples of the alkyl, cycloalkyl and the substituent thereof represented by R ₁ in I] are mentioned. As R ₁ , R ₂ and R _{3 in the} general formulas [II] and [III], those represented by the following general formula [X] are preferable.

The general formula (X) -R ¹ -SO ^₂ -R ₂ Formula wherein R ¹ is alkylene, R ² represents alkyl, cycloalkyl or aryl.

The alkylene represented by R ¹ preferably has a straight chain portion having 2 or more carbon atoms, more preferably 3 to 6, and may be straight chain or branched. Further, this alkylene may have a substituent.

Examples of the substituent include those shown as the substituents that the alkyl group may have when R ₁ in the above general formula [II] and general formula [III] is an alkyl group.

Preferred as the substituent is phenyl.

Preferred specific examples of the alkylene represented by R ¹ are shown below.

The alkyl group represented by R ² may be linear or branched.

Specifically, methyl, ethyl, propyl, iso-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadacil, 2-
Hexyldecyl and the like can be mentioned.

The cycloalkyl group represented by R ² is preferably a 5- or 6-membered cycloalkyl group, and examples thereof include cyclohexyl.

The alkyl and cycloalkyl represented by R ² may have a substituent, and examples thereof include those exemplified as the substituent for R ¹ described above.

Specific examples of the aryl represented by R ² include phenyl,
Examples include naphthyl. The aryl group may have a substituent. Examples of the substituent include straight-chain or branched alkyl, and those exemplified as the substituent for R ¹ described above.

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

Among the compounds represented by the general formula [II] and the general formula [III], particularly preferable are those represented by the following general formula [XI].

General formula (XI) In the formula, R and X are in the general formula [II] and the general formula [III].
R ^1, R ² have the same meanings as R _1, X is, R ¹ in the general formula (X), R ²
Is synonymous with.

Also, the synthesis of the coupler is described in the Journal of the Chemical Societ.
y), Perkin I (1977), 2047-2052, US Pat. No. 3,725,067, JP-A-59-99437, JP-A-58-42045.
No. 59-162548, 59-171956, 60-3
The synthesis was carried out with reference to 3552 and JP-A-60-43659.

The coupler of the present invention usually contains 1 × 10 5 mol / mol of silver halide.
^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10
It can be used in the range of ^-1 mol.

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

In the color developing solution used in the dye image forming method of the present invention, the bromine ion concentration in the color developing solution is 7 × 10 ⁻³ mol / l.
If it is at least the above, the upper limit is not particularly limited, but is preferably 5 ×
It is 10 ^-2 mol / l or less, more preferably 2.5 x 10 ^-2 mol / l or less.

As described above, the presence of bromine ion as a fog inhibitor in a color developing solution has been conventionally made, but this variation in bromine ion concentration is a major cause of variation in photographic performance, particularly in sensitivity and variation in gradation. ing. However, in the development processing of the color light-sensitive material of the present invention, if the bromine ion concentration is 7 × 10 ⁻³ mol / l or more, even if the bromine ion concentration varies, variations in sensitivity and gradation are extremely small, and stable quality is obtained. A color print can be obtained.

Further, in the color developer used in the dye image forming method of the present invention, hydroxylamines are added together with the bromine ion.
It is contained in an amount of 0.02 mol / l to 0.15 mol / l (hereinafter referred to as a color developer according to the invention, preferably in a range of 0.03 mol / l to 0.12 mol / l).

The hydroxylamines used in the present invention are preferably represented by the following general formula [XII].

General formula [XII] In the general formula [XII], R ₁₀ and R ₁₁ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic residue, and R ₁₀ and R ₁₁ May combine with each other to form a ring,
R ₁₀ and R ₁₁ may be further substituted with a hydroxylamino group to form a bis form or tris form. Y represents a hydrogen atom or a hydrolyzable group. The term "hydrolyzable group" as used herein means a group that forms a hydroxylamino group by hydrolysis during development, and is a hydroxylamino group.

R ₁₀ and R ₁₁ are more preferably a hydrogen atom, an alkyl group having 1 to 16 carbon atoms and an aryl group having 6 to 26 carbon atoms, and the alkyl group and the aryl group may have other substituents. Well, R ₁₀ and R ₁₁ may have a 5- or 6-membered ring.

When a hydroxylamine represented by the general formula [XII] is used by adding a treatment liquid, Y is a hydrogen atom, and R ₁₀ and R ₁₁ are each a hydrogen atom and a carbon number of 1 to 5 in terms of solubility.
It is preferable that the alkyl group and R ₁₀ and R ₁₁ form a pyrrolidine, piperidine, or morpholine ring, and more preferably, R ₁₀ and R ₁₁ are each a hydrogen atom, a methyl group, an ethyl group, or a 2-ethoxyethyl group. , Tetrahydro-
It is a 2-furfuryl group.

The hydroxylamines represented by the general formula [XII] may form a salt with an acid.

Next, specific compounds of the hydroxylamines represented by the general formula [XII] will be shown, but the invention is not limited thereto.

Exemplified hydroxylamines _{(21) (nC 8 H 17} ) 2 N-OH · HClO 4 (22) (nC 18 H 37) 2 N-OH · 1 / 2H 2 SO 4 (24) nC ₁₈ H ₃₇ NHOH ・ HCl Some of the hydroxylamines represented by the general formula [XII] are easily available as reagents, and can be easily synthesized according to the general synthetic method described in the following documents. For example, oxidation of amines [BCChallis and AR
Butler)], The Chemistry of the Amino
Group (The Chemistry of the Amino Group) 320-3
35, Interscience Publishers, New York, 1968, Reduction of oximes [H. Feuer and BF Vincent, Journal of American Chemical Society (H.Feuer and BFVincent, Journal of A
merican Chemical Society)] 84, 3771 , 1962 years, of amine oxide Kope (Cope) reaction [er Sea Kope and E. R. Trumbull (ACCope and ERTrumb
ull)] Organic Reactio
ns) 11 , 317-493, 1960), addition reaction of hydroxylamine to olefins [MS Gibson, The Chemistry of the Amino Group (KSGibso
n, The Chemistry of the Amino Group)] 61-65, InterScience Publishers New York (In
terscience Publishers, New York) 1968, substitution reaction of active halides with hydroxylamines (US Pat. No. 3,493)
1,151) and the like are well known.

Also, U.S. Pat.Nos. 3,864,131, 3,287,124, and 3,28
No. 7,125, No. 3,293,034, No. 3,405,034, No. 3,455,916
The specification describes specific compounds of hydroxylamines.

Conventionally, it is known that hydroxylamines are used as a preservative of a developing solution, but in the development processing of the color light-sensitive material used in the present invention, the Br variation resistance depends on the amount of hydroxylamines, that is, hydroxylamines. It was unpredictable and unpublished that there was no document that suggested or suggested that Br variation tolerance improvement was achieved in the optimum amount range of the class.

The aromatic primary amine type color developing agents used in the color developing solution according to the present invention include known ones which are widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Also, these compounds are generally used at a concentration of about 0.1 g to about 30 g for color developer 1, preferably at a concentration of about 1 g to about 15 g for color developer 1.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-Oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful primary aromatic amine color developing agents are N, N'-
A dialkyl-p-phenylenediamine compound,
The alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include
N, N'-diethyl-p-phenylenediamine hydrochloride, N
-Methyl-p-phenylenediamine hydrochloride, N, N'-dimethyl-p-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-
Examples thereof include N- (2-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate.

In the color developing solution according to the present invention, in addition to the primary aromatic amine-based color developing agent, various components usually added to the color developing solution, such as sodium hydroxide, sodium carbonate, potassium carbonate, etc. The above-mentioned alkali agent, alkali metal sulfite, alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol, water softener, thickener and the like can be optionally contained. The pH value of this color developer is usually 7 or more, preferably about 9 to about 13, and more preferably
9.5 to 11.

In the dye image forming method of the present invention, the processing temperature with the color developing solution is selected from 20 ° C to 70 ° C, but preferably 30
It is ℃ ~ 50 ℃.

The color development processing time is usually 1 to 20 minutes,
It is more preferably 1 minute to 10 minutes.

The color light-sensitive material used in the present invention may be a single color or a multicolor one as long as it has a silver halide emulsion layer containing a magenta coupler represented by the above general formula [I] and a silver chlorobromide emulsion. But good. In the case of a multicolor color light-sensitive material, a silver halide emulsion layer and a non-light-sensitive layer containing magenta, yellow, and cyan couplers are usually used as photographic couplers in order to perform color reduction subtraction. Although it has a structure in which the support is laminated in an appropriate number of layers and layer order, the number of layers and layer order may be appropriately changed depending on the priority performance and the purpose of use.

A silver chlorobromide emulsion is used for the silver halide emulsion layer containing the magenta coupler represented by the above general formula [I] of the present invention, and the emulsion used may be substantially a silver chlorobromide emulsion. . The term "substantially silver chlorobromide emulsion" as used herein means that the halogen composition of the silver halide emulsion may contain a small amount of iodine, as long as the effect of the present invention is not impaired.
It is less than mol% and the balance consists of chlorine and bromine, preferably 5 mol% or more, more preferably 15 mol%.
It is at least mol%.

When the color light-sensitive material used in the present invention is for multicolor, there is no particular limitation on the halogen composition of the silver halide grains used in the other silver halide emulsion layers, but it is suitable for rapid processing and low replenishment type. Chlorine is 5 from the viewpoint of suitability
It is preferably a silver halide substantially consisting of mol% or more of silver chlorobromide.

The silver halide grains used in the silver halide emulsion of the color light-sensitive material used in the present invention (hereinafter referred to as the silver halide emulsion of the present invention) are those obtained by any of the acidic method, the neutral method and the ammonia method. But it's okay. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or one of them may be present while the other is mixed. In addition, while considering the critical growth rate of silver halide crystals, the halide ion and silver ion are mixed in the p
It may be generated by sequentially adding simultaneously while controlling H and pAg. After the growth, the conversion method may be used to change the halogen composition of the grains.

The grain size, grain shape, grain size distribution and grain growth rate of the silver halide grains can be controlled by using a silver halide solvent, if necessary, during the production of the silver halide emulsion of the present invention.

The average grain size of silver halide grains contained in the silver chlorobromide emulsion used in the silver halide emulsion layer containing the magenta coupler according to the present invention is preferably about 0.2 μm to 2 μm, and particularly preferably Is 0.4 μm to 1.5 μm.

The average particle size is defined by the following formula.

Here, ri represents the particle size of each particle, and ni represents the number thereof. The term "particle size" as used herein means the diameter of spherical silver halide grains, and the diameter of a cubic image or a non-spherical grain obtained by converting the projected image into a circular image of the same area.

The color light-sensitive material used in the present invention is a blue-sensitive emulsion layer,
In the case of multicolor having a green-sensitive emulsion layer and a red-sensitive emulsion layer, the grain size of silver halide grains used in the blue-sensitive emulsion layer is larger than that of silver halide grains used in other emulsion layers. It is preferably a silver halide grain.

In general, a silver halide emulsion has blue sensitivity in addition to the desired spectral sensitivity even if it is optically sensitized with green or red sensitization. Therefore, when exposed to blue light, it is inevitable that not only the blue-sensitive emulsion but also the green-sensitive emulsion and the red-sensitive emulsion which should not be exposed to light are exposed to some extent.

Therefore, if the blue sensitivity of the blue-sensitive emulsion is close to the blue sensitivity of the green-sensitive emulsion or the red-sensitive emulsion, after blue exposure,
During color development processing, in addition to the dye formed by the reaction of the coupler combined with the blue-sensitive emulsion, a part of the dye is formed from the coupler combined with the red-sensitive emulsion and the green-sensitive emulsion to cause color turbidity. And the color reproducibility deteriorates.

Various efforts have been made to prevent such deterioration of color reproducibility, but no effective means has been found. For example, yellow filter dyes have been used to attempt to reduce the blue sensitivity of green and red sensitive emulsions. However, in the case of multi-color color photographic paper, the above-mentioned method is not suitable because the blue-sensitive emulsion layer is usually on the support side of the other emulsion layers, and if the blue-sensitive emulsion layer is above the other emulsion layers. Even if it is provided and a yellow filter dye layer is arranged below it, in the case of color photographic paper in which multiple reflected light greatly contributes to sensitivity, in this case the blue sensitivity of the blue-sensitive emulsion is greatly reduced, and it is suitable for practical use. Have difficulty. Therefore, when the color reproducibility is improved by using the magenta coupler according to the present invention having the above good characteristics, it is absolutely necessary to avoid that the color reproducibility is largely deteriorated by the above factors. . For this reason, it is necessary to design the blue sensitivity of the blue-sensitive emulsion to be significantly higher than that of the green-sensitive emulsion and the red-sensitive emulsion. The grain size of silver halide grains used for the blue-sensitive emulsion is the green-sensitive emulsion. And preferably larger than the grain size of the silver halide grains used in the red-sensitive emulsion. More specifically, in order to obtain the sensitivity required for a blue-sensitive emulsion so that it can be practically used as a color photographic paper, it is preferable that the silver halide average grain used for the blue-sensitive emulsion is 0.6 μm or more.

When the silver halide photographic light-sensitive material used in the present invention is a multicolor color light-sensitive material, the specific layer constitution is as follows: on the support, from the side of the support, the yellow dye image forming layer, the intermediate layer, It is particularly preferable to arrange a magenta dye image-forming layer, an ultraviolet absorber-containing intermediate layer, a cyan dye image-forming layer, an ultraviolet absorber-containing intermediate layer, and a protective layer.

The silver halide grains used in the silver halide emulsion of the present invention have a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt in the step of forming and / or growing the grain. , Iron salt or complex salt,
It is possible to add a metal ion to the inside of the particle and / or to incorporate it into the surface of the particle by placing it in a suitable reducing atmosphere, and to impart a reduction sensitizing nucleus to the inside of the particle and / or the surface of the particle. .

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained therein. When removing the salts, the method described in Research Disclosure 17643 can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be composed of a layer having a uniform inside and surface,
It may consist of different layers.

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

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal form, or may have an irregular crystal form such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The gold halide emulsion of the present invention may be a mixture of two or more kinds of silver halide emulsions which are separately formed.

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

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Is also good.

The silver halide emulsion of the present invention includes a light-sensitive material manufacturing process,
Silver halide during chemical ripening and / or at the end of chemical ripening for the purpose of preventing fogging during storage or during photographic processing and / or for maintaining stable photographic performance, and / or after the end of chemical ripening By the time the emulsion is coated, compounds known in the photographic industry as antifoggants or stabilizers can be added.

By incorporating a mercapto heterocyclic compound in the color light-sensitive material used in the present invention, the effects of the present invention can be further improved.

A preferred mercapto heterocyclic compound is represented by the following general formula [XII
I].

General formula [XIII] In the formula, Zo is an imidazoline ring, an imidazole ring, an imidazolone ring, a pyrazoline ring, a pyrazole ring, a pyrazolone ring,
Oxazoline ring, oxazole ring, oxazolone ring, thiazoline ring, thiazole ring, thiazolone ring, selenazoline ring, selenazole ring, selenazolone ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, benzimidazole ring, benztriazole ring, indazole Ring, benzoxazole ring, benzthiazole ring, benzselenazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, oxazine ring, thiazine ring, tetrazine ring, quinazoline ring, phthalazine ring and polyazaindene ring (for example triazain Den ring, tetrazaindene ring, pentazaindene ring, etc.)
Represents a group of atoms necessary to form a heterocycle such as.

Of general formula [XIII] The heterocyclic residue represented by may have a substituent, and examples of these substituents include an alkyl group, an aryl group,
Examples thereof include an alkenyl group, a sulfamoyl group, a carbamoyl group and an acyl group.

The mercapto heterocyclic compound represented by the general formula [XIII] is more preferably a mercaptotriazole compound having a triazole ring.

Specific examples of the compound represented by the general formula [XIII] used in the present invention are shown below, but the invention is not limited thereto.

Exemplified mercapto heterocyclic compound Examples of the mercapto heterocyclic compound represented by the general formula [XIII] used in the present invention include those disclosed in JP-B-48-42974 and 57-516.
66, JP-A-48-102621, French Patent No. 701,053,
No. 701,301, No. 1,563,019, U.S. Pat. No. 3,457,078 and The Journal of Photographic Science 19 ,
p83-87 etc.

The addition amount of the mercapto heterocyclic compound used in the present invention may vary widely depending on the use conditions, but it is 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, and more preferably 1 × 10 ⁶ mol per mol of silver halide.
^-5 to 1 × 10 ^-3 mol shows good results. Further, as the addition method, a conventional photographic additive addition method, for example, water, or an acid or alkaline aqueous solution having a suitable pH value, or dissolved in an organic solvent such as methanol or ethanol, the silver halide of the present invention Added to emulsion.

The mercapto heterocyclic compound used in the present invention may be used alone or in combination of two or more kinds thereof, and further, other compounds known as antifoggants or stabilizers in the photographic industry may be additionally added.

As the addition position of the mercapto heterocyclic compound used in the present invention, the effect of the present invention can be achieved in any of silver chlorobromide emulsion layers and / or other photographic constituent layers containing the magenta coupler of the present invention. Particularly, it is preferably used in the silver chlorobromide emulsion layer containing the magenta coupler of the present invention. The timing of addition to the silver chlorobromide emulsion layer containing a magenta coupler is not particularly limited, but it is preferably from after the completion of chemical sensitization to immediately before the coating of the silver chlorobromide emulsion containing a magenta coupler. It does not matter if they are added all at once or in portions.

In the present invention, it is preferable to use image stabilizers represented by the following general formulas [A] to [H] and [J], [K] for the purpose of preventing the deterioration of the dye image, particularly the magenta dye image.

General formula [A] In the formula, R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, R ₂ , R ₃ , R ₅ , and R ₆ are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, It represents an alkenyl group, an aryl group, an alkoxy group or an acylamino group, and R ₄ represents an alkyl group, a hydroxy group, an aryl group or an alkoxy group.

R ₁ and R ₂ may be ring-closed to each other to form a 5-membered or 6-membered ring, and R ₄ at that time represents a hydroxy group or an alkoxy group. Further, R ₃ and R ₄ may be closed to form a 5-membered hydrocarbon ring, and R _{1 at} that time represents an alkyl group, an aryl group or a heterocyclic group. However, the case where R ₁ is a hydrogen atom and R ₄ is a hydroxy group is excluded.

In the above general formula [A], R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. Among them, examples of the alkyl group include a methyl group, an ethyl group, a propyl group and n- Examples thereof include linear or branched alkyl groups such as octyl group, tert-octyl group, and hexadecyl group. Examples of the alkenyl group represented by R ₁ include allyl, hexenyl and octenyl groups. Furthermore, examples of the aryl group of R ₁ include phenyl and naphthyl groups. Specific examples of the heterocyclic group represented by R ₁ include a tetrahydropyranyl group and a pyrimidyl group. Each of these groups can have a substituent, for example, a benzyl group as an alkyl group having a substituent, an ethoxymethyl group, a methoxyphenyl group as an aryl group having a substituent, a chlorophenyl group, 4-hydroxy-3, Examples thereof include a 5-dibutylphenyl group.

In the general formula [A], R ₂ , R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an acylamino group. Examples of the group, alkenyl group and aryl group are the same as the alkyl group, alkenyl group and aryl group described for R ₁ . Examples of the halogen atom include fluorine,
Examples thereof include chlorine and bromine. Further, examples of the alkoxy group include a methoxy group and an ethoxy group. Further, the acylamino group is represented by R'CONH-, wherein R'is an alkyl group (for example, methyl, ethyl, n-propyl, n-butyl,
n-octyl, tert-octyl, benzyl, etc.), alkenyl group (eg, allyl, octynyl, oleyl, etc.), aryl group (eg, phenyl, methoxyphenyl, naphthyl, etc.), or heterocyclic group (For example, each group of pyridyl and pyrimidyl) can be mentioned.

In the general formula [A], R ₄ represents an alkyl group, a hydroxy group, an aryl group or an alkoxy group. Among them, the alkyl group and the aryl group are the same as the alkyl group and the aryl group represented by R _1. The following can be specifically mentioned. The alkenyl group for R ₄ may be the same as the alkoxy group described for R ₂ , R ₃ , R ₅ and R ₆ .

Examples of the ring formed by ring-closing R ₁ and R ₂ together with the benzene ring include chroman, coumaran, and methylenedioxybenzene.

In addition, examples of the ring formed by R ₃ and R ₄ closed together with the benzene ring include indane. These rings have substituents (eg alkyl, alkoxy, aryl)
May have.

Further, R ₁ and R ₂ , or R ₃ and R ₄ may be closed to form a spiro compound with an atom in the ring formed as a spiro atom, or R ₂ , R ₄ or the like as a linking group, and bis. It may form a body.

Of the phenol compounds or phenyl ether compounds represented by the general formula [A], preferred ones are RO
A biindane compound having four groups (R represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group), and particularly preferably can be represented by the following general formula [A-1].

General formula [A-1] In the formula, R is an alkyl group (eg, methyl, ethyl, propyl, n-octyl, tert-octyl, benzyl, hexadecyl), an alkenyl group (eg, allyl, octenyl, oleyl), an aryl group (eg, phenyl, naphthyl) or hetero. It represents a group represented by a cyclic group (eg, tetrahydropyranyl, pyrimidyl). R ₉ and R
₁₀ is a hydrogen atom, a halogen atom, (for example, fluorine,
Chlorine, bromine), alkyl groups (eg methyl, ethyl, n
-Butyl, benzyl), alkenyl groups (eg allyl,
Hexenyl, octenyl) or an alkoxy group (eg methoxy, ethoxy, benzyloxy), R ₁₁
Is a hydrogen atom, an alkyl group (for example, methyl, ethyl, n-
Butyl, benzyl), an alkenyl group (eg, 2-propenyl, hexenyl, octenyl), or an aryl group (eg, phenyl, methoxyphenyl, chlorophenyl, naphthyl).

The compound represented by the general formula [A] is described in US Pat.
5,016, 3,982,944, 4,254,216, JP-A-5
5-21004, 54-145530, British Patent Publication 2,077,455
No. 2,062,888, U.S. Pat.Nos. 3,764,337, 3,43
2300, 3,574,627, 3,573,050, JP-A-52
-152225, 53-20327, 53-17729, 55-6321
Nos. 1,347,556, 2,066,975, JP-B 54-12337, 48-31625, and U.S. Pat. No. 3,700,455.

The amount of the compound represented by the general formula [A] used is preferably 5 to 300 mol% and more preferably 10 to 200 mol% with respect to the magenta coupler.

Typical specific examples of the compound represented by the above general formula [A] are shown below.

General formula [B] (In the formula, R ₁ and R ₄ are each a hydrogen atom, a halogen atom,
Represents an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl or an alkoxycarbonyl group, and R ₂ is a hydrogen atom. Represents an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group, and R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acyloxy group. , A sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, alkyl group, alkenyl group, alkoxy group,
Examples thereof include an aryl group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, an acyloxy group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group.

R ₂ and R ₃ may be ring-closed to each other to form a 5- or 6-membered ring. Examples of the ring formed by R ₂ and R ₃ closed together with the benzene ring include a chroman ring and a methylenedioxybenzene ring.

Y represents a group of atoms necessary for forming a chroman or coumaran ring.

The chroman or coumaran ring has a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
It may be substituted with an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, or a heterocycle,
Further, a spiro ring may be formed.

Among the compounds represented by the general formula [B], the compounds particularly useful in the present invention include the compounds represented by the general formulas [B-1], [B-2], [B-3], and [B-
4] and compounds represented by [B-5].

General formula [B-1] General formula [B-2] General formula [B-3] General formula [B-4] General formula [B-5] General formulas [B-1], [B-2], [B-3], [B-4] and [B-
R ₁ , R ₂ , R ₃ and R ₄ in 5] have the same meanings as in the above general formula [B], and R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and
R ₁₀ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group or a heterocyclic group.

Furthermore, R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ and R ₉ and R ₁₀
And may form a carbocycle by cyclizing each other, and the carbocycle may be further substituted with an alkyl group.

In the general formulas [B-1], [B-2], [B-3], [B-4] and [B-5], R ₁ and R ₄ are a hydrogen atom, an alkyl group,
An alkoxy group, a hydroxy group or a cycloalkyl group,
Particularly useful are compounds in which R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are hydrogen atoms, alkyl groups, or cycloalkyl groups.

The compound represented by the general formula [B] is tetrahedron (Tetr
ahedron), 1970, vo126, 4743-4751, Journal of the Chemical Society of Japan,
1972, No10, 1987-1990, Chemistry Letters (ch
em. Lett.), 1972 (4) pages 315 to 316, and compounds described and described in JP-A-55-139383, and can be synthesized according to the methods described therein.

The amount of the compound represented by the general formula [B] used is 5 to 300 mol% with respect to the magenta coupler of the present invention, and more preferably 10 to 200 mol%.

Representative specific examples of these compounds are shown below.

General formula [C] General formula [D] In the formula, R ₁ and R ₂ are hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, alkenyloxy group, hydroxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group or Represents an alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, halogen atom, alkyl group, alkenyl group,
Examples thereof include an alkoxy group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonamide group and a sulfamoyl group.

Y represents a group of atoms necessary for forming a dichroman or dicoumaran ring together with a benzene ring.

The chroman or coumaran ring has a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
It may be substituted with an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group,
Further, a spiro ring may be formed.

Of the compounds represented by the general formulas [C] and [D], the compounds particularly useful in the present invention are represented by the general formulas [C-1], [C-2],
Included in the compounds represented by [D-1] and [D-2].

General formula [C-1] General formula [C-2] General formula [D-1] General formula [D-2] R ₁ and R ₂ in the general formulas [C-1], [C-2], [D-1] and [D-2] have the same meanings as in the general formulas [C] and [D], R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are hydrogen atom, halogen atom, alkyl group, alkoxy group, hydroxy group, alkenyl group, alkenyloxy group, aryl group, aryloxy group or heterocyclic group. Represents In addition, R ₃ and R ₄ , R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ and R ₇
R ₈ may cyclize with each other to form a carbocycle, and the carbocycle may be substituted with an alkyl group.

In the above general formulas [C-1], [C-2], [D-1] and [D-2], R ₁ and R ₂ are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups or cycloalkyl. Group, R ₃ , R ₄ ,
Compounds in which R ₅ , R ₆ , R ₇ and R ₈ are hydrogen atoms, alkyl groups, or cycloalkyl groups are particularly useful.

The compounds represented by the general formulas [C] and [D] are journals
Of the Chemical Society (J.Chem.So
cC) 1968 (14), pp. 1837-1843, Journal of Synthetic Organic Chemistry, 19
70, 28 (1), pp. 60-65, tetrahedron (Tetrahedro
n) Compounds described in 1973. (29), pp. 2707 to 2710, and can be synthesized according to the methods described therein.

The amount of the compounds represented by the general formulas [C] and [D] used is 5 to 30 with respect to the magenta coupler according to the present invention.
0 mol% is preferable, and 10 to 200 mol% is more preferable.

Specific representative examples of these compounds are shown below.

General formula [E] In the formula, R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group, and R ³ represents a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group.

R ² and R ⁴ are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an acylamino group,
It represents a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group,
Acylamino group, carbamoyl group, sulfonamide group,
Examples thereof include a sulfamoyl group.

R ¹ and R ² may be ring-closed to each other to form a 5- or 6-membered ring.

At that time, R ³ and R ⁴ are hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, alkenyloxy group, hydroxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group or alkoxy. Represents a carbonyl group.

Y represents an atomic group necessary for forming a chroman or coumaran ring.

The chroman or coumaran ring has a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
It may be substituted with an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group, and may further form a spiro ring.

Among the compounds represented by the general formula [E], the compounds particularly useful in the present invention are represented by the general formulas [E-1], [E-2], [E-3], [E-
4] and [E-5] are included in the compound.

General formula [E-1] General formula (E-2) General formula (E-3) General formula (E-4) General formula (E-5) R ¹ , R ² , R ³ and R ⁴ in the general formulas [E-1] to [E-5] have the same meanings as in the general formula [E], and R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are hydrogen atom, halogen atom,
It represents an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group or a heterocyclic group. Further R ⁵ and R ⁶ , R ⁶ and
R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ and R ⁹ and R ¹⁰ may cyclize with each other to form a carbocycle, and the carbocycle may be substituted with an alkyl group.

In the general formulas [E-1] to [E-5], R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, an alkyl group or a cycloalkyl group, and in the general formula [E-5], R ³ and R ⁴ are a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group or a cycloalkyl group, and in the above general formulas [E-1] to [E-5], R ⁵ , R ⁶ , R ⁷ , R ⁸ , Compounds in which R ⁹ and R ¹⁰ are hydrogen atoms, alkyl groups, or cycloalkyl groups are especially useful.

The compound represented by the general formula [E] is tetrahedron.
Letters (Tetrahedron Letters) 1965. (8), 457-46
0 pages, Journal of the Chemical Society (J.Chem.Soc.C) 1966. (22), 2013-2016,
Zh.OrR.Khi
m) Compounds described in 1970, (6), pages 1230 to 1237, and can be synthesized according to the methods described therein.

The amount of the compound represented by the general formula [E] used is preferably 5 to 300 mol% and more preferably 10 to 200 mol% with respect to the magenta coupler according to the present invention.

Specific representative examples of these compounds are shown below.

General formula [F] In the formula, R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group, and R ₂ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy. Represents a group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an acylamino group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group.

R ₄ is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, or an alkoxycarbonyl group. Represent.

Each of the groups listed above may be substituted with other substituents. For example, alkyl group, alkenyl group, alkoxy group,
Examples thereof include an aryl group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonamide group and a sulfamoyl group.

R ₁ and R ₂ may be ring-closed to each other to form a 5- or 6-membered ring. At that time, R ₃ and R ₄ are a hydrogen atom, a halogen atom,
It represents an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, or an alkoxycarbonyl group.

Y represents a group of atoms necessary for forming a chroman or coumaran ring.

The chroman or coumaran ring has a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
It may be substituted with an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group, and may further form a spiro ring.

Among the compounds represented by the general formula [F], the compounds particularly useful in the present invention are represented by the general formulas [F-1], [F-2], [F-3], [F-
4] and [F-5] are included in the compound.

General formula (F-1) General formula (F-2) General formula (F-3) General formula (F-4) General formula (F-5) R ₁ , R ₂ , R _{3 in the} general formulas [F-1] and [F-5] and
R ₄ has the same meaning as in the above general formula [F],
R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are hydrogen atom, halogen atom, alkyl group, alkoxy group, hydroxy group, alkenyl group, alkenyloxy group, aryl group, aryloxy group or heterocyclic group. Represents

Furthermore, R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ and R ₉ and R ₁₀
And may form a carbocycle by cyclizing each other, and the carbocycle may be further substituted with an alkyl group.

Two R _{1 in} [F-3], [F-4] and [F-5]
~ R ₁₀ may be the same or different.

In the general formulas [F-1], [F-2], [F-3], [F-4] and [F-5], R ₁ , R ₂ and R ₃ are each a hydrogen atom, an alkyl group or a cyclo group. An alkyl group, R ₄ is a hydrogen atom, an alkyl group,
An alkoxy group, a hydroxy group or a cycloalkyl group,
Furthermore, compounds in which R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are hydrogen atoms, alkyl groups or cycloalkyl groups are particularly useful.

The compound represented by the general formula [F] is tetrahedron (Tetrahedron) 1970, Vol 26, 4743-4751, Journal of the Chemical Society of Japan 1972, No. 10, 1987-1990, Synthesis (Synthes).
is) 1975, Vol 6, 392-393, Buretin de la
Socette Simic de Belgic (Bul Soc, Chi
m, Belg) 1975, Vol 84 (7), pages 747-759, and can be synthesized according to the methods described therein.

The amount of the compound represented by the general formula [F] used is preferably 5 to 300 mol% and more preferably 10 to 200 mol% with respect to the magenta coupler according to the present invention.

Specific representative examples of the compound represented by formula [F] are shown below.

General formula [G] In the formula, R ¹ and R ³ are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group. Represents a group or an alkoxycarbonyl group.

R ² represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. As a substituent, for example, an alkyl group, an alkenyl group,
Examples thereof include an alkoxy group, an aryl group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonamide group and a sulfamoyl group.

R ² and R ³ may be ring-closed to each other to form a 5- or 6-membered hydrocarbon ring. The 5- or 6-membered hydrocarbon ring has a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, a hydroxy group, an aryl group,
It may be substituted with an aryloxy group or a heterocyclic group.

Y represents an atomic group necessary for forming an indane ring. Indane ring has a halogen atom, an alkyl group, an alkenyl group,
It may be substituted with an alkoxy group, a cycloalkyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group or the like, and may further form a spiro ring.

Among the compounds represented by the general formula [G], the compounds particularly useful in the present invention are included in the compounds represented by the general formulas [G-1] to [G-3].

General formula (G-1) General formula (G-2) General formula (G-3) R ¹ , R ² and R ³ in the general formulas [G-1] to [G-3] have the same meanings as in the general formula [G], and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸
And R ⁹ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group. R ⁴
And R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ and R ⁸ and R ⁹ may be ring-closed to each other to form a hydrocarbon ring, and the hydrocarbon ring is an alkyl group. May be replaced with.

In the general formulas [G-1] to [G-3], R ¹ and R ³ are a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group or a cycloalkyl group, and R ² is a hydrogen atom, an alkyl group, a hydroxy group or A compound in which a cycloalkyl group, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen atoms, an alkyl group or a cycloalkyl group is particularly useful.

The amount of the compound represented by the general formula [G] used is preferably 5 to 300 mol% and more preferably 10 to 200 mol% with respect to the magenta coupler.

Typical specific examples of the compound represented by the general formula [G] are shown below.

General formula [H] In the formula, R ¹ and R ² each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group.

R ³ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group. .

The above-mentioned groups may be substituted with other substituents, for example, an alkyl group, an alkenyl group, an alkoxy group,
Examples thereof include an aryl group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group.

R ¹ and R ² and R ² and R ³ may be ring-closed with each other to form a 5- or 6-membered hydrocarbon ring, which hydrocarbon ring is a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group. It may be substituted with an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group or the like.

Y represents an atomic group necessary for forming an indane ring, and the indane ring may be substituted with a substituent capable of substituting the hydrocarbon ring, and may further form a spiro ring.

Among the compounds represented by the general formula [H], the compounds particularly useful in the present invention are included in the compounds represented by the general formulas [H-1] to [H-2].

General formula [H-1] General formula [H-2] General formula [H-3] R ¹ , R ² and R ³ in the general formulas [H-1] to [H-3] have the same meanings as in the general formula [H], and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸
And R ⁹ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an aryl group, an aryloxy group or a heterocyclic group. R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ and R ⁸ and R ⁹ may be ring-closed to each other to form a hydrocarbon ring. May be substituted with an alkyl group.

In the general formulas [H-1] to [H-3], R ¹ and R ² are each a hydrogen atom, an alkyl group or a cycloalkyl group, R ³
Is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group or a cycloalkyl group, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R
Compounds in which ⁹ is a hydrogen atom, an alkyl group or a cycloalkyl group respectively are particularly useful.

The method for synthesizing the compound represented by the general formula [H] is known, and is disclosed in US Pat.・ American Chemical Society (JA
m. Chem. Soc.) 1973, 95 (5), 1673 to 1674, Chemistry Letters 1980, 739 to 742.

The compound represented by the general formula [H] is preferably 5 to 300 mol%, and more preferably 10 to 2 mol% with respect to the magenta coupler.
It is 00 mol%.

Specific representative examples represented by the general formula [H] are shown below.

General formula [J] [In the formula, R ¹ represents an aliphatic group, a cycloalkyl group or an aryl group, and Y represents a non-metal atom group necessary for forming a 5- to 7-membered heterocycle with a nitrogen atom. However, when there are two or more heteroatoms among the non-metal atoms including the nitrogen atom forming the heterocycle, at least two heteroatoms are not adjacent to each other. Examples of the aliphatic group represented by R include a saturated alkyl group which may have a substituent and an unsaturated alkyl group which may have a substituent. Examples of the saturated alkyl group include a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group, and examples of the unsaturated alkyl group include an ethenyl group,
Examples thereof include a propenyl group.

The cycloalkyl group represented by R ¹ is a 5- to 7-membered cycloalkyl group which may have a substituent, and examples thereof include a cyclopentyl group and a cyclohexyl group.

The aryl group represented by R ¹ represents a phenyl group or a naphthyl group, each of which may have a substituent.

Examples of the substituent of the aliphatic group, cycloalkyl group, and aryl group represented by R ¹ include an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbamoyl group, an acylamino group, a sulfamoyl group, a sulfonamide group, and a carbonyloxy group. , An alkylsulfonyl group, an arylsulfonyl group, a hydroxy group, a heterocyclic group, an alkylthio group, an arylthio group, and the like, and these substituents may further have a substituent.

In the general formula [J], Y is 5 to 7 together with a nitrogen atom.
Represents a non-metal atom necessary to form a heterocycle of a member ring, but at least two of the non-metal atoms containing a nitrogen atom forming the heterocycle must be a heteroatom, and
The at least two heteroatoms must not be adjacent to each other. In the heterocycle of the compound represented by the general formula [J], it is not preferable that all the heteroatoms are adjacent to each other because the function as a magenta dye image stabilizer cannot be exhibited.

The 5- to 7-membered heterocycle of the compound represented by the general formula [J] may have a substituent, and the substituent is an alkyl group, an aryl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group. Group, sulfonyl group, sulfamoyl group and the like, which may further have a substituent. Also, the 5 to 7
The membered heterocycle may be saturated, but a saturated heterocycle is preferred. Further, a benzene ring or the like may be condensed with the heterocycle, and a spiro ring may be formed.

The amount of the compound represented by the general formula [J] of the present invention to be used is preferably 5 to 300 mol%, more preferably 10 to 10% with respect to the magenta coupler represented by the general formula [I] of the present invention. It is 200 mol%.

Typical specific examples represented by the general formula [J] are shown below.

Among the compounds represented by the general formula [J], a piperazine compound and a homopiperazine compound are particularly preferable,
More preferably, it is a compound represented by the following general formula [J-1] or [J-2].

General formula [J-1] General formula (J-2) In the formula, R ² and R ³ each represent a hydrogen atom, an alkyl group or an aryl group. However, R ² and R ³ are not hydrogen at the same time. R ^{4 to} R ¹³ each represent a hydrogen atom, an alkyl group or an aryl group.

In the general formulas [J-1] and [J-2], R ² and R ³ each represent a hydrogen atom, an alkyl group or an aryl group, and examples of the alkyl group represented by R ² or R ³ include , Methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like. Examples of the aryl group represented by R ² or R ³ include a phenyl group and the like. The alkyl group and aryl group represented by R ² or R ³ may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and a heterocyclic group. Can be mentioned.

The total number of carbon atoms of R ² and R ³ (including a substituent) is preferably 6 to 40.

In the general formula [J-1] or [J-2], R ^{4 to} R
Each ¹³ represents a hydrogen atom, an alkyl group or an aryl group, and examples of the alkyl group represented by R ^{4 to} R ¹³ include a methyl group and an ethyl group. Examples of the aryl group represented by R ^{4 to} R ¹³ include a phenyl group and the like.

Specific examples of the compound represented by the general formula [J-1] or [J-2] include the exemplified piperazine compounds (J-1) to (J
-30) and exemplified homopiperazine compounds (J-51) to (J-6
As described in 2).

Next, a synthesis example of a typical magenta dye image stabilizer of the present invention represented by the general formula [J] will be shown.

Synthesis Example-1 (Synthesis of Compound J-2) 15 g of anhydrous potassium carbonate was added to 100 ml of acetone in which 9.0 g of piperazine and 55 g of myristyl bromide were dissolved.
The mixture was reacted by boiling under reflux for 10 hours. After the reaction, the reaction solution is 500m
After pouring in 1 l of water, it was extracted with 500 ml of ethyl acetate. The ethyl acetate layer was dried over magnesium sulfate, and then ethyl acetate was distilled off to obtain a desired product as white crystals. 300 ml of acetone
The crystals were recrystallized from to give 34 g of white scale-like crystals (yield 70%).

Melting point 55-58 ° C. Synthesis example-2 (Synthesis of compound J-34) 4-morpholinoaniline 18 g was dissolved in 100 ml of ethyl acetate, and the mixture was stirred while keeping the reaction solution at 20 ° C.
ml was added little by little. After addition of acetic anhydride, the mixture was cooled with ice and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate to obtain 16.5 g of white powdery crystals (yield 75%).

Melting point 207-210 ℃ General formula [K] In the formula, R ¹ represents an aliphatic group, a cycloalkyl group or an aryl group, and Y represents a mere bond or a divalent hydrocarbon group necessary for forming a 5- to 7-membered heterocycle with a nitrogen atom. Represent ^{R 2, R 3, R 4} , R 5, R 6, R 7 are each a hydrogen atom, an aliphatic group, a cycloalkyl group or an aryl group. However, R ² and R ⁴ and R ³ and R ⁶ may combine with each other to form a simple bond to form an unsaturated 5- to 7-membered heterocyclic ring together with the nitrogen atom and Y. When Y is a mere bond, R ⁵ and R ⁷ may bond to each other to form a mere bond to form an unsaturated 5-membered heterocycle with the nitrogen atom and Y. When Y is not a simple bond, R ⁵ and Y, R ⁷ and Y or Y itself form an unsaturated bond to form an unsaturated 6-membered or 7-membered heterocyclic ring together with the nitrogen atom and Y. May be.

Examples of the aliphatic group represented by R ¹ include a saturated alkyl group which may have a substituent and an unsaturated alkyl group which may have a substituent. Examples of the saturated alkyl group include a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group, and examples of the unsaturated alkyl group include an ethenyl group,
Examples thereof include a propenyl group.

The cycloalkyl group represented by R ¹ is a 5- to 7-membered cycloalkyl group which may have a substituent, and examples thereof include a cyclopentyl group and a cyclohexyl group.

The aryl group represented by R ¹ represents a phenyl group or a naphthyl group which may have a substituent.

Examples of the substituent of the aliphatic group, cycloalkyl group, and aryl group represented by R ¹ include an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbamoyl group, an acylamino group, a sulfamoyl group, a sulfonamide group, and a carbonyloxy group. , An alkylsulfonyl group, an arylsulfonyl group, a hydroxy group, a heterocyclic group, an alkylthio group, an arylthio group, and the like, and these substituents may further have a substituent.

In the general formula [K], Y is 5 to 7 together with a nitrogen atom.
Represents a mere bond or a divalent hydrocarbon group necessary for forming a heterocycle of a member ring. When Y is a mere bond, R ⁵ and R ⁷ are further bonded to each other to form a mere bond. To form an unsaturated 5-membered heterocyclic ring, and Y
Is a divalent monovalent hydrogen group, that is, when it is a methylene group, R ⁵ and Y or R ⁷ and Y form an unsaturated bond to form an unsaturated 6-membered heterocycle. In the case of an ethylene group, R ⁵ and Y, R ⁷ and Y or Y itself may form an unsaturated bond to form an unsaturated 7-membered heterocycle.
Further, the divalent hydrocarbon group represented by Y may have a substituent, and the substituent includes an alkyl group, a carbamoyl group, an alkyloxycarbonyl group, an acylamino group, a sulfonamide group, a sulfamoyl group and an aryl group. Groups, heterocyclic groups and the like.

In the above general formula [K], R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷
Each represents a hydrogen atom, an aliphatic group, a cycloalkyl group or an aryl group, and the aliphatic group represented by R ^{2 to} R ⁷ may be a saturated alkyl group which may have a substituent and a substituent. The unsaturated alkyl group which may have is mentioned. Examples of the saturated alkyl group include a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group.Examples of the unsaturated alkyl group include an ethenyl group and a propenyl group. To be

The cycloalkyl group represented by R ^{2 to} R ⁷ is a 5- to 7-membered cycloalkyl group which may have a substituent, and examples thereof include a cyclopentyl group and a cyclohexyl group.

Examples of the aryl group represented by R ^{2 to} R ⁷ include a phenyl group which may have a substituent and a naphthyl group.

As the aliphatic group represented by R ^{2 to} R ⁷ , a cycloalkyl group, and a substituent of the aryl group, an alkyl group, an aryl group,
Examples thereof include an alkoxy group, a carbonyl group, a carbamoyl group, an acylamino group, a sulfamoyl group, a sulfonamide group, a carbonyloxy group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy group, a heterocyclic group and an alkylthio group.

The compound represented by the general formula [K] preferably has a saturated 5- to 7-membered heterocycle rather than being unsaturated.

The amount of the compound represented by the general formula [K] used is as follows.
It is preferably 5 to 300 mol%, more preferably 10
~ 200 mol%.

Representative specific examples of the compound represented by the general formula [K] are shown below.

Next, typical synthetic examples of the compound represented by the above general formula [K] are shown.

Synthesis Example-1 (Synthesis of Compound K-14) 6.0 g of anhydrous potassium carbonate was added to 60 ml of acetone in which 9.0 g of piperazine and 28 g of myristyl bromide were dissolved,
The mixture was reacted by boiling under reflux for 20 hours. After the reaction, the reaction solution is 300m
It was poured into 1 l of water and then extracted with 300 ml of ethyl acetate. The ethyl acetate layer was dried over magnesium sulfate, and then ethyl acetate was distilled off to obtain a desired product as white crystals. Acetone 10
Recrystallization from 0 ml gave 12 g of white scale-like crystals (yield 43%).

Melting point 175 to 180 ° C. As the binder (or protective colloid) of the silver halide emulsion of the present invention, it is advantageous to use gelatin,
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 homopolymers or copolymers can also be used.

In the photographic emulsion layer of the color light-sensitive material using the silver halide emulsion of the present invention and other hydrophilic colloid layers, a hardener which crosslinks a binder (or protective colloid) molecule and enhances the film strength is used alone or in combination. Is hardened by. The hardener is preferably added in an amount capable of hardening the photosensitive material to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

A plasticizer may be added for the purpose of enhancing the flexibility of the silver halide emulsion layer and / or other hydrophilic colloid layer of the color light-sensitive material using the silver halide emulsion of the present invention.

A photographic emulsion layer or other hydrophilic colloid layer of a color light-sensitive material using the silver halide emulsion of the present invention contains a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. I can do things.

In the color development processing, the emulsion layer of the color light-sensitive material used in the present invention is subjected to a coupling reaction with an oxidant of an aromatic primary amine developer (for example, p-phenylenediamine derivative or aminophenol derivative). Dye-forming couplers are used that form dyes. The dye-forming coupler is usually selected so that a dye that absorbs light in the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer, and a yellow dye-forming coupler is formed in the blue-light-sensitive emulsion layer. A coupler, a magenta dye-forming coupler is used for the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used for the red light-sensitive emulsion layer. However, the color light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

Yellow dye-forming couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), and magenta dye-forming couplers include 5-pyrazolone couplers and open-chain acylacetonitrile couplers in addition to the couplers of the present invention.
Examples of cyan dye-forming couplers include naphthol couplers and phenol couplers.

It is desirable that these dye-forming couplers have a group having a carbon number of 8 or more, which makes a coupler called a ballast group non-diffusible in the molecule. Also, these dye-forming couplers need only reduce two silver ions even if they are four-equivalent in which four silver ions need to be reduced in order to form one molecule of dye. Either of two equivalents may be used.

A typical yellow dye image-forming coupler is an acylacetamide type benzoylmethane type 4-equivalent or 2-equivalent coupler. For example, US Pat. No. 2,186,849.
No. 2, No. 2,322,027, No. 2,728,658, No. 2,875,05
No. 7, No. 3,265,506, No. 3,277,155, No. 3,408,1
No. 94, No. 3,415,652, No. 3,447,928, No. 3,664,
No. 841, No. 3,770,446, No. 3,778,277, No. 3,84
No. 9,140, No. 3,894,875, British Patent No. 778,089, No. 808,276, No. 875,476, No. 1,402,511, No.
1,421,126 and 1,513,832, respective specifications and Japanese Patent Publication No. 49-13576, JP-A-48-29432, 48-66834, 49
-10736, 49-122335, 50-28834, 50-132926
No. 50, No. 50-138832, No. 51-3631, No. 51-17438, No. 51
-26038, 51-26039, 51-50734, 51-53825
No. 51, No. 51-75521, No. 51-89728, No. 51-102636, No. 5
1-107137, 51-117031, 51-122439, 51-143
No. 319, No. 53-9529, No. 53-82332, No. 53-135625,
53-145619, 54-23528, 54-48541, 54-65
No. 035, No. 54-133329, No. 55-598.

Cyan dye image forming couplers include phenolic compounds,
A naphthol-based 4-equivalent or 2-equivalent cyan dye image-forming coupler is typical, and US Pat. No. 2,306,410,
No. 2,356,475, No. 2,362,598, No. 2,367,531
No. 2,369,929, 2,423,730, 2,474,29
No. 3, No. 2,476,008, No. 2,498,466, No. 2,545,6
No. 87, No. 2,728,660, No. 2,772,162, No. 2,895,
No. 826, No. 2,976,146, No. 3,002,836, No. 3,41
No. 9,390, No. 3,446,622, No. 3,476,563, No. 3,7
Nos. 37,316, 3,758,308, 3,839,044, British Patents 478,991, 945,542, 1,084,480, 1,377,233, 1,388,024, and 1,543,040, and special specifications. Kaisho 47-37425, 50-10135,
50-25228, 50-112038, 50-117422, 50-1
No. 30441, No. 51-6551, No. 51-37647, No. 51-52828,
51-108841, 53-109630, 54-48237, 54-6
No. 6129, No. 54-131931, and No. 55-32071.

For the hydrophobic compound such as a dye-forming coupler which does not need to be adsorbed on the silver halide crystal surface, various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water emulsion dispersion method can be used. Can be appropriately selected according to the chemical structure of the hydrophobic compound such as The oil-in-water emulsion dispersion method can be applied to a method in which a hydrophobic additive such as a coupler is dispersed, and is usually used in a high-boiling organic solvent having a boiling point of about 150 ° C. or higher and, if necessary, a low-boiling and / or water-soluble organic solvent. Dissolve in combination with a solvent, using a dispersing agent such as a stirrer, a homogenizer, a colloid mill, a flowgit mixer, and an ultrasonic device with a surfactant in a hydrophilic binder such as an aqueous gelatin solution, after emulsifying and dispersing, It may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

As the high-boiling organic solvent, the boiling point of a phenol derivative, a phthalic acid ester, a phosphoric acid ester, a citric acid ester, a benzoic acid ester, an alkylamide, a fatty acid ester, a trimesic acid ester, etc., which does not react with an oxidized product of a developing agent.
An organic solvent of 150 ° C or higher is used.

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, A cationic surfactant can be used.

Between the emulsion layers of the color light-sensitive material used in the present invention (same color-sensitive layers and / or different color-sensitive layers), an oxidant of a developing agent or an electron transfer agent moves to cause color turbidity,
An antifoggant is used to prevent deterioration of sharpness and conspicuous graininess.

The color antifoggant may be used in the emulsion layer itself, or may be used in the intermediate layer by providing an intermediate layer between adjacent emulsion layers.

An image stabilizer which prevents deterioration of a dye image can be used in a color light-sensitive material using the silver halide emulsion of the present invention.

The protective layer of the color light-sensitive material used in the present invention, to prevent fog due to discharge caused by charging of the hydrophilic colloid layer such as an intermediate layer due to friction of the light-sensitive material, ultraviolet rays for preventing deterioration of the image by UV light It may contain an absorbent.

The color photographic light-sensitive material using the silver halide emulsion of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer and / or an antiirradiation layer.
In these layers and / or in the emulsion layer, a dye which flows out from the color photographic paper or is bleached during the developing process may be contained.

In the silver halide emulsion layer and / or other hydrophilic colloid layer of the color light-sensitive material using the silver halide emulsion of the present invention, the gloss of the light-sensitive material is reduced, the writing property is enhanced, and sticking of the light-sensitive materials to each other is prevented. A matting agent can be added as a target.

Further, a lubricant can be added to reduce sliding friction.

The color light-sensitive material using the silver halide emulsion of the present invention,
An antistatic agent for the purpose of antistatic can be added. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used to protect the emulsion layer and / or the emulsion layer on the side of the support other than the emulsion layer. It may be used for the colloid layer.

The photographic emulsion layer and / or other hydrophilic colloid layer of the color light-sensitive material using the silver halide emulsion of the present invention can be improved in coating property, antistatic property, slip property improvement, emulsion dispersion, adhesion prevention and (development acceleration, Various surfactants are used for the purpose of improving photographic characteristics (such as increasing contrast and sensitization).

Examples of the reflective support used in the present invention include plastic films, that is, polyester (for example, polyethylene terephthalate), vinyl alcohol, vinyl chloride,
Homopolymers and copolymers such as fluorinated vinyl and vinyl acetate, cellulose acetate, acrylonitrile, alkyl ethesyl acrylate, methacrylic acid alkyl ester, methacrylonitrile, alkyl vinyl ester, alkyl vinyl ether, polyamide and other homopolymers and copolymers. be able to. Further, a laminated body of two or more kinds of substrates such as a laminated body of paper or synthetic paper and polyolefin (polyethylene, polypropylene, etc.) and the like are used.

The reflective support according to the present invention may contain a white pigment for imparting reflectivity, or a hydrophilic colloid layer containing a white pigment may be coated on the transparent support.

The white pigment used is an inorganic and / or organic white pigment, preferably an inorganic white pigment,
Examples thereof include sulfates of alkali metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, finely divided silicic acid, silicas of synthetic silicates, calcium silicate, alumina, hydrated alumina, titanium oxide. , Zinc oxide, talc, clay and the like.

The color light-sensitive material used in the present invention is directly or after (corresponding to the adhesiveness of the support surface, antistatic property, dimensional stability) after subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc. , To improve abrasion resistance, hardness, antihalation, frictional properties and / or other properties)).

At the time of coating a color light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

The color light-sensitive material used in the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As a light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam, X ray, γ ray Any of known light sources such as light emitted from a phosphor excited by α-rays or the like can be used.

The exposure time is not limited to 1 millisecond to 1 second which is usually used in a camera, but is shorter than 1 microsecond, for example, a cathode ray tube or a xenon arc lamp can be used for 100 microsecond to 1 microsecond. Exposures longer than 1 second or longer are possible. The exposure may be performed continuously or intermittently.

In the present invention, after color development processing, processing is carried out with a processing solution having fixing ability. When the processing solution having fixing ability is a fixing solution, bleaching processing is carried out before that. As the bleaching agent used in the bleaching step, a metal complex salt of an organic acid is used, and the metal complex salt oxidizes the metal silver produced by development to convert it to silver halide, and at the same time, acts to color the uncolored part of the color former. And has a structure in which a metal ion such as iron, cobalt or copper is coordinated with an aminopolycarboxylic acid or an organic acid such as an acid or citric acid. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The following can be mentioned as specific representative examples of these.

[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] Nitrilotritri Sodium acetate salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent and can also contain various additives. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide, a metal salt or a chelating agent. In addition, borate, acid salt, acetate, carbonate, phosphate and other pH buffering agents, alkylamines, polyethylene oxides and the like, which are known to be added to ordinary bleaching solutions, can be appropriately added. .

Further, the fixer and the bleach-fixer are 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 A single pH buffer or two or more pH buffers composed of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained.

When the processing of the present invention 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 or the like, The bleach-fixing replenisher may contain these salts and be replenished to the processing bath.

In the present invention, in order to increase the activity of the bleach-fixing solution, air may be blown or oxygen may be blown in the bleach-fixing bath and the storage tank for the bleach-fixing replenisher, if desired, or a suitable oxidizing agent is used. For example, hydrogen peroxide, bromate, persulfate or the like may be added as appropriate.

Reference Example The present invention will be described in more detail with reference to specific reference examples below.

Reference Example-1 The following emulsions EM-1 to 4 were prepared by a conventional method.

EM-1 ... Silver halide emulsion containing silver chlorobromide grains having an average particle size of 0.30 μm containing 25 mol% chlorine EM-2 ... Salt bromide having an average particle size of 0.55 μm containing 25 mol% chlorine Silver halide emulsion having silver particles EM-3 ... Silver halide emulsion containing silver chlorobromide grains having an average particle size of 0.75 μm containing 25 mol% chlorine EM-4 ... Average containing 2 mol% iodine Silver halide emulsion having silver iodobromide grains having a grain size of 0.31 μm. Then, EM-1 to 4 were subjected to sulfur sensitization to obtain the following sensitizing dye [A].
After the spectral sensitization with ## STR1 ## and after completion of the sensitization, 1 g of the following stabilizer [B] was added per 1 mol of silver halide to prepare EM-ad.

Magenta couplers shown in Table 1 were added to EM-a and d, and then coated on a polyethylene-coated paper support and dried to prepare Sample Nos. 1 to 6.

The obtained sample was wedge-exposed and then processed according to the following processing steps to perform sensitometric measurement and fog measurement. The results are shown in Table-1.

Table 1 shows the measured values of fog and the relative sensitivity (S) of each sample. Here, the following color developing solutions [A] to [D]
When processed with the color developing solution [D], the sensitivity when processed with the color developing solution [D] is set to 100, and the following color developing solutions [E] to [H] are used.
The relative sensitivity of each of the color developing solutions [E] was expressed as 100 when the processing was performed with the color developing solution [E].

Further, it is a value that expresses gradation, and Δ is a value that represents the range of variation, and when processed with color developing solutions [A] to [D], it is based on the time when processed with color developing solution [D]. When the color developing solutions [E] to [H] are used for processing, the fluctuation values are shown with respect to the time when the color developing solution [E] is used for the processing. The smaller the absolute value of Δ, the better the Br fluctuation resistance. There is.

Standard processing steps (processing temperature and processing time) [1] Color development 38 ° C 3 minutes 30 seconds [2] Bleach fixing 33 ° C 1 minute 30 seconds [3] Washing treatment 25-30 ° C 3 minutes [4] Drying 75- 80 ℃ Approx. 2 minutes Processing solution composition (color developer) Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 4.1g [Exemplified hydroxyamines (2)] (0.05mol) Polyphosphoric acid (TPPS) 2.5g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbenz sulfonic acid Derivative) 1.0g potassium hydroxide 2.0g Add water to make the total amount 1 and adjust to pH 10.20.

Potassium bromide (denoted by Br concentration) in the color developer of the above composition
Was added in the amounts shown in Table 1 to prepare color developing solutions [A] to [H].

(Bleach fixer) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Water adjusted to pH 7.1 with potassium carbonate or glacial acetic acid Is added to bring the total amount to 1.

Sensitizing dye [A] used in Sample Nos. 1 to 6,
The structural formulas of the stabilizer [B], the comparative couplers [C] and [D] are shown below.

Sensitizing dye [A] Stabilizer [B] Comparison coupler [C] Comparison coupler [D] As is clear from Table 1, when using the sample Nos. 1 and 2 in which the comparative coupler was combined with the silver chlorobromide emulsion of the present invention,
Even when processed with the color developing solutions [E] to [H] according to the present invention, the sensitivity and gradation vary greatly due to Br concentration fluctuations, resulting in image quality that is too soft or too hard, and also causes a large color balance deviation. Since it invites, it is not put to practical use.

Also in the case of using the sample Nos. 3, 4 and 5 in which the coupler of the present invention was combined with the silver chlorobromide emulsion of the present invention, the sensitivity when processed with the color developing solutions [A] to [D], Gradient variation is large and resistance to Br variation is still poor, and fog is high. On the other hand, when the sample Nos. 3, 4, and 5 were treated with the color developing solutions [E] to [H] according to the present invention, the Br concentration ratio varied to the same extent as [A] to [D]. However, the fluctuations in sensitivity and gradation are small, and sample Nos. 1 and 2 are [E] ~
Changes in sensitivity and gradation are about 1/2 compared to when processed with [H]
The resistance to Br fluctuation is improved, and the fluctuation is within a practically acceptable range. As for fog, [A]
It is suppressed to a low level and stable as compared with the case of the treatment of [D].

Further, in Sample No. 6 using a silver iodobromide emulsion other than the present invention, any color developing solution could not be evaluated at 3 minutes and 30 seconds in the middle of development and remarkably inferior in rapid processing suitability.

Reference Example-2 After the sample No. 3 produced in Reference Example-1 was wedge-exposed,
It processed according to the same process as the said reference example-1. However, the color developers are [I-1] to [N-4] shown in Table-2.
It was used. The color developing solutions [I-1] to [N-4] contain hydroxylamines and KBr shown in the table, and the other compositions are the same as those of the color developing solution. Table 2 shows Δ of the dye image obtained by processing with each color developing solution of sample No. 3. Here, Δ is a variation value based on the case of processing with the No. 1 developing solution for each of I to N.

As is clear from Table-2, when the type and amount of hydroxylamines are within the range of the present invention, gradation variation with respect to Br concentration variation is small and is not a practical problem, but when the amount of hydroxylamine is outside the range of the present invention. However, the gradation variation becomes large, which causes a color balance shift as described above, which is a problem.

Example-1 EM-a to c prepared in Reference Example-1 were applied in the same manner as in Reference Example-1 to prepare color photosensitive material samples Nos. 7 to 10. At this time, when the sample No. 9 was prepared, the exemplified mercapto heterocyclic compound 13 was added so as to be 40 mg per mol of silver halide. The obtained sample was subjected to wedge exposure and then processed according to the same processing steps as in Reference Example-1.

Table 3 shows the relative sensitivities S of the respective color light-sensitive material samples Nos. 7 to 10 when they were processed with the color developer [E].
And Δ.

As is clear from Table 3, when the average grain size of the silver halide grains contained in the silver chlorobromide emulsion used in the present invention is large to some extent, the Br fluctuation resistance is more excellent. However, no difference is observed between = 0.55 μm and 0.75 μm. In addition, the coexistence of a mercapto heterocyclic compound makes it possible to achieve even more excellent Br fluctuation resistance.
At o.9, the four types of processed samples processed with the color developing solutions [E] to [H] had stable image quality with almost no visible change.

Example-2 A multilayer color light-sensitive material sample No. 11 was prepared by sequentially coating the following layers on a polyethylene-coated paper support. Here, the addition amount of each compound is the color photosensitive material dm ²
It is a hit.

Layer 1 ... Yellow coupler [E] (8.0 mg) below and blue-sensitive silver chlorobromide emulsion (average particle size 0.75 μm 3.5 m in terms of metallic silver)
g) and a blue-sensitive emulsion layer containing gelatin 20 mg Layer 2 ... Dioctylhydroquinone 0.3 mg and gelatin 1
Intermediate layer having 0 mg Layer 3: Exemplified magenta coupler [127] (4.0 mg) and EM-b (1.7 mg in terms of metallic silver) prepared in Example-1, Exemplified mercapto heterocyclic compound 13 (6 × 10 6) ^-4 mg), and a green-sensitive emulsion layer having 20 mg of gelatin Layer 4 ... 0.3 mg of dioctylhydroquinone and 8 mg of the following UV absorber [F] and 15 mg of gelatin Layer 5 ... The following cyan coupler [G] (3.0 mg) And red-sensitive silver chlorobromide emulsion (2.5 mg in terms of average particle size 0.4 μm metallic silver)
And a red-sensitive emulsion layer containing 15 mg of gelatin Layer 6 ... Intermediate layer containing 4.0 mg of the following UV absorber [F] and 10 mg of gelatin Layer 7 ... Protective layer containing 10 mg of gelatin Yellow coupler [E] UV absorber [F] Cyan coupler [G] The obtained multicolor color light-sensitive material sample No. 11 was exposed through a negative film, baked, and developed with the same color developers [E] to [H] as used in Example-1, and bleach-fixed according to the above processing steps. It was washed with water and dried.

As a result, the magenta dye image obtained by processing with any of the color developing solutions [E] to [H] has little fog and is excellent in stable tone reproduction and color reproduction. It can be seen that the formation method has excellent Br fluctuation resistance.

Example-3 In the sample 11 of Example-2, instead of the addition of the exemplified mercapto heterocyclic compound 13 (6 × 10 ⁻⁴ mg) of the layer 3, 1 × 10 ⁻ of the exemplified mercapto heterocyclic compound 12 was added to the layer 2. Add ³ mg, layer 3
Sample 12 was prepared in the same manner as Sample 11 except that the exemplified magenta coupler [151] was used instead of the exemplified magenta coupler [127] (4.0 mg). When this sample 12 was treated in the same manner as in Example 2, the same good result as in Example 2 was obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having a photographic constituent layer containing at least one silver halide emulsion layer on a reflective support, wherein at least one of the silver halide emulsion layers has the following general formula [II ] And at least one magenta coupler represented by the following general formula [III] and a silver chlorobromide emulsion, and at least one of the above-mentioned photographic constituent layers.
After imagewise exposing a silver halide color photographic light-sensitive material containing a mercapto heterocyclic compound in a layer, at least a bromine ion concentration of 7 × 10 ^-3 mol / l or more and hydroxylamines of 0.02 mol / l to 0.15 mol It has been found that this can be achieved by a dye image forming method characterized by processing with a color developer containing / l. General formula (II) General formula (III) [In the formula, X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidation product of a color developing agent. Moreover, R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent. ]