JPS6259953A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility and the light resistance of a magenta dye image and to prevent the generation of Y-stain by incorporating two kinds of specific magenta dye image stabilizers in combination with a specific magenta dye image forming coupler into a titled material. CONSTITUTION:The magenta dye image stabilizers expressed by the formula II (R<1>, R<4> are respectively H, alkyl, alkenyl, alkoxy, etc., R<2> is H, alkyl, aryl, etc., R<3> is H, halogen, acyl, etc., R<2> and R<3> may form 5-6-membered rings and Y is a cumarone ring, etc.) and the formula III (R<11>, R<13> are respectively, H, halogen, alkyl, alkenyl, etc., R<12> is H, halogen, alkyl, acyl, etc., R<12> and R<13> may form 5-6-membered rings Y2 is an indan ring) are incorporated in combination with the magenta color image forming coupler expressed by the formula I [Z is an (non)substd. N-contg. heterocycle, X is H or a group which can be desorbed by reaction with the oxidant of a color developing agent, R is H or substituent] into the titled material. The stabilizer expressed by the formula II is combined with the magenta color coupler expressed by the formula I and is added to the material in the above-mentioned manner, by which the color reproducibility is improved, the generation of the Y-stain is decreased and the light resistance is improved.

Description

[Detailed Description of the Invention] [Industrial Field of Application J] The present invention relates to a silver halide photographic light-sensitive material.
This invention relates to a silver halide color photographic light-sensitive material in which a dye image is stable against heat and light, and staining is prevented.

[Backbone of the invention] Conventionally, a coupling reaction between an oxidized product of an aromatic primary amine color developing agent and a color forming agent is carried out by imagewise exposing a silver halide color photographic light-sensitive material and performing color development. It is well known that, for example, indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine, and similar pigments are produced and color images are formed. In this type of photography, the color reproduction method usually uses the subtractive color method,
A silver halide color photographic light-sensitive material is provided, in which blue-sensitive, green-sensitive and red-sensitive light-sensitive silver halide emulsion layers each contain a color former having an extra color relationship, that is, a coupler that produces colors of yellow, magenta and cyan. used.

Examples of couplers used to form the above-mentioned yellow image include acylacetanilide-based couplers, and examples of couplers used to form magenta images include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, and indacilone-based couplers. Furthermore, as a coupler for forming a cyan image, for example, a phenol or naphthol coupler is generally used.

It is desired that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity. Furthermore, it is desired that the uncolored areas of silver halide color photographic light-sensitive materials do not turn yellow (hereinafter referred to as Y-stain) when exposed to light or moist heat.

However, in the case of magenta couplers, Y-staining due to moist heat in uncolored areas and fading due to light in dye image areas are extremely large compared to yellow couplers and cyan couplers, and often pose a problem.

Couplers commonly used to form magenta dyes are 1,2-pyrazolo-5-ones. This one
．． In addition to the main absorption near 550 nm, the dye formed from magenta couplers of 2-pyrazolo-5-ones has an absorption wavelength of 430 nm.
Having sub-absorption in the vicinity of nm is a major problem, and various studies have been conducted to solve this problem.

A magenta coupler having an anilino group at the 3-position of a 1.2-pyrazolo-5-one has a small side absorption and is particularly useful for obtaining a color image for printing. Regarding these techniques, see, for example, U.S. Patent No. 2.343.703;
It is described in British Patent No. 1.059.994 and the like.

However, the above-mentioned magenta coupler has the disadvantage that the image storage property, particularly the fastness of the dye image to light, is extremely poor, and the Y-stain in the uncolored area is large.

As another means for reducing the n1 absorption near 430 nm of the magenta coupler, British Patent No. 1.047,
Pyrazolobenzimidazoles described in U.S. Pat. No. 612, indasilones described in U.S. Pat. No. 3,770,447, and U.S. Pat.
2.418, 1 day described in 1,334,515-
Pyrazolo[5,1-C]-]1,2,4-triazole type coupler 1H- described in JP-A-59-171956, Research Disclosure No. 24,531
Pyrazolo[1,5-b]-1,2,44 lyazole coupler, Research Disclosure NO, 24
, 626-pyrazolo[1,5-C]-]1
．． 2.3-triazole type coupler JP-A-59-162
No. 548, Research Disclosure No. 24
1H-imidazo[1,2-b]-pyrazole type couplers described in JP-A-60-43659, Research Disclosure No. 24,230; type coupler, 1 day-pyrazolo [described in JP-A-60-33552, Research Disclosure No. 24.220]
Magenta couplers such as 1°5-d]tetrazole type couplers have been proposed. Among these, 1H-pyrazolo [
5,1-c]-]1.2.4-triazole coupler 1H-pyrazolo[1,5-b]-1,2,4-triazole coupler, 1-pyrazolo[1,5-c]
-]1.2.3-t-lyazole-type couplers 1H-imidazo[1,2-b]pyrazole-type couplers, 1-pyrazolo[1,5-d]pyrazole-type couplers and 1-day-pyrazolo[1,5 -d ] The dye formed from the tetrazole type coupler has a sub-absorption near 430 nm, and color reproduction is significantly smaller than that of the dye formed from the 1,2-pyrazol-5-ones having an anilino group at the 3-position. Preferably, the Y-
The generation of stains is also extremely small, which is a desirable advantage.

However, the light fastness of azomethine dyes formed from these couplers is extremely low, and furthermore, the dyes are easily discolored by light, making them difficult to use in silver halide color photographic materials, especially printed silver halide color photographic materials. It has not been put to practical use in printing-type silver halide color photographic materials because it significantly impairs the performance of the color photographic material.

Furthermore, JP-A No. 59-125732 discloses that a 1H-pyrazolo[5,1-c]-]1.2.4-triazole type Zentacoupler is used in combination with a phenol compound or a phenyl ether compound. proposed a technique for improving the light fastness of a magenta dye image obtained from a 1H-pyrazolo[5,1-c]-1,2°4-triazole type magenta coupler. However, it has been recognized that even the above techniques are not yet effective in preventing the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light.

[Object of the Invention] The present invention has been made in view of the above-mentioned problems, and the first object of the present invention is to provide a halogenated image with excellent color reproducibility and significantly improved light fastness of magenta dye images. Our objective is to provide silver photographic materials.

A second object of the present invention is to provide a silver halide photographic material having a magenta dye image with little discoloration due to light.

The third object of the present invention is to reduce Y in uncolored areas against light and moist heat.
- It is an object of the present invention to provide a silver halide color photographic material in which staining is prevented.

[Structure of the Invention] The above object of the present invention is to provide at least one magenta color image forming coupler represented by the following general formula [I], at least one compound represented by the following general formula [Xn], and the following general formula [ This is achieved by a silver halide photographic material containing at least one compound represented by X1.

General Formula [I] [In the formula, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have an exchange group.

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

Further, R represents a hydrogen atom or a substituent. ] General formula [X
II] [In the formula, R and R" each represent 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, and an acyl group. R2 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R3 represents a hydrogen atom or a halogen atom. , an alkyl group, 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 and R3 are ring-closed with each other to form a 5- or 6-membered group. May form a membered ring.ZaraniR
and R may form a medilenedioxy ring. Yl represents an atomic group necessary to form a taloman or coumaran ring. ] General formula [XVII] Scale I+ In the formula, R and R 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, represents a sulfonamide group, cycloalkyl group or alkoxycarbonyl group, R'
3 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.

Further, R and R may be ring-closed with each other to form a 5- or 6-membered hydrocarbon ring.

Y2 represents an atomic group necessary to form an indane ring. ] [Specific structure of the invention] Next, the present invention will be specifically explained.

General formula [1] General formula CI) according to the present invention! In the magenta coupler represented by N-J=/, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. .

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

Moreover, R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a 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, peterocyclic oxy group, siloxy group, Acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamido group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, Examples include an alkylthio group, an arylthio group, and a heterocyclic thio group.

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

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

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted through a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted through a heteroatom (specifically, hydroxy, alkoxy, and aryloxy , heterocyclic oxy,
Those substituted through an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido Substituents via the nitrogen atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl,
(e.g., those substituted via a sulfur atom such as sulfamoyl, those substituted via a phosphorus atom such as phosphonyl)].

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, l
-hexylnonyl group, 1.1-dipentylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group, L
-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)phenoxyfudodecanoylamino)phenylpropyl group, 3-(4·-[α-(2··,
Examples include 4...-di-t-amylphenoxy)butanamido]phenyl)-propyl group, 4-[α-(0-chlorophenoxy)tetradecanamidephenoxypropyl group, allyl group, cyclopentyl group, and cyclohexyl group.

The aryl group represented by R is preferably a phenyl group, and may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, phenyl group, 4-t-butylphenyl group,
2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4.
-[α-(4...-t-butylphenoxy)tetradecanamidophenyl group and the like.

The heterocyclic group represented by R is preferably 5- to 7-membered, and may be substituted or fused.

Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

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

The sulfonyl group represented by R includes an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group,
Examples include arylsulfonyl groups such as benzenesulfonyl group and p-toluenesulfonyl group.

Examples of the sulfinyl group represented by R include alkylsulfinyl groups such as ethylsulfinyl group, octylsulfinyl group, and 3-phenoxybutylsulfinyl group, and arylsulfinyl groups such as phenylsulfinyl JE and l11-pentadecylphenylsulfinyl group. .

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

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

The sulfamoyl group represented by the margin R below may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, I-phenylsulfamoyl group, Examples include moyl group.

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

Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2,1cohebutan-1-yl, tricyclo[3
,3,1,1'']]decan-1-yl7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group, a propoxy group, a 2-ethoxyethoxy group,
Examples include pentadecyloxy group, 2-dodecyloxyethoxy group, phenethyloxyethoxy group, and the like.

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

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

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

The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-chloroacetyloxy group, etc. , benzoyloxy group, etc.

The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, an N-phenylcarbamoyloxy group, etc. It will be done.

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

Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent, specifically an acetamido group, an α- Ethylpropanamide group, N-phenylacetamide group,
Examples include dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, and α-3-t-butyl 4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent.

Specifically, methylsulfonylamino group, pentadecylsulfonylamino group, benzenesulfonamide group, I)-
) A luenesulfonamide group, a 2-methoxy-5-t-amylbenzenesulfonamide group, and the like.

The imide group represented by R may be open-chain or cyclic, and may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutaric acid group. Examples include imide groups.

The ureido group represented by R is an alkyl group, an aryl group (
Preferably, it may be substituted with a phenyl group), and examples thereof include an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group, and an Np-tolylureido group.

The sulfamoylamino group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, N-phenylsulfamoylamino group, etc. .

As the alkoxycarbonylamino group represented by R,
It may further have a substituent, for example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group,
Examples include octadecyloxycarbonylamino group.

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

The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc.

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

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

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

The heterocyclic thio group represented by R is preferably a 5- to 7-shell heterocyclic thio group, which may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine, bromine, fluorine, etc.), as well as substituents that and substituent groups.

In addition to the carboxyl group, examples of the group substituted via a carbon atom include the general formula % (R,. is the same as the above R, Z. is the same as the above Z, R2. and R1. are hydrogen (representing an atom, an aryl group, an alkyl group, or a heterocyclic group), a hydroxymethyl group, and a triphenylmethyl group.

Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkoxyoxalyloxy groups. can be mentioned.

The alkoxy group may further have a substituent, for example,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, phenethyloxy group, and 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, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group group, 1-naphthyloxy group, p-
Examples include methoxyphenoxy group.

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

The acyloxy group includes, for example, an acetoxy group, an alkylcarbonyloxy group such as a butazuroxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
Examples include arylcarbonyloxy groups such as benzoyloxy groups.

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

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

Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

Examples of the group substituted 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, a benzylthio group, and the like.

The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butyl Examples include phenylthio group.

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

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group.

Examples of the group substituting via the nitrogen atom include those represented by the general formula -N. Here, R4 and Rs' are hydrogen atoms, alkyl groups,
Represents an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and R4 and R
8. may be combined to form a heterocycle. However, R4・
and R6. are never 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, an alkoxy group, an aryloxy group, an 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 alkyloxycarbonyl 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 ethyl group, oxytyl group, 2-ethylhexyl group, and 2-chloroethyl group.

The aryl group represented by R4 or R3 has preferably 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group,
The nucleol group may have a substituent, and examples of the substituent include those listed above as a substituent for the alkyl group represented by R4 or Rs', and an alkyl group. Specific examples of the aryl group include phenyl group, -naphthyl group, and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R4 or R6 is 5 to 6
It is preferable that the ring is a membered ring, and it may be a condensed ring or have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, and 2-pyridyl group.

Examples of the sulfamoyl group represented by R4 or R6 include N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-arylsulfamoyl group,
, N-diarylsulfamoyl group, etc., and these alkyl groups and aryl groups may have the substituents listed 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 N-p-tolylsulfamoyl group.

The carbamoyl group represented by R4 or R5 is,
Examples include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and aryl groups can be substituted with the substituents listed above for the alkyl group and aryl group. It may have a group. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-1)-cyanophenylcarbamoyl group,
N-p-tolylcarbamoyl group is mentioned.

Examples of the acyl group represented by R4 or R6 include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. It's okay. Specific examples of the acyl group include hexafluorobutanoyl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-furylcarbonyl group, etc. .

Examples of the sulfonyl group represented by R4 or R2 include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group and a benzene group. Examples include a sulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, and a p-chlorobenzenesulfonyl group.

The aryloxycarbonyl group represented by R4. or R6. may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like.

The alkoxycarbonyl group represented by R4 or R6 may have the substituents listed above for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, etc. Can be mentioned.

The heterocycle formed by combining R4 and R1 is preferably a 5- to 6-membered ring, and may be saturated or unsaturated, and may or may not have aromaticity, or,
It may 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-dioxoxazolidinyl group, 2- N-1,1-dioxo-
3-(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, l-pyrrolidinyl group, l-pyrazolyl group, l-pyrazolidinyl group, 1-biperidinyl group, 1-
Pyrrolinyl group, l-imidazolyl group, 1-imidazolinyl group, ■-indolyl group, l-isoindolinyl group, 2
-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl group, 1-
(1,2,4-triazolyl) group, 1-(1,2,3-
) riazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1.2.3.4-tetrahydroquinolyl group, 2-oxo-I-pyrrolidinyl group,
2-IH-pyridone group, phthaladione group, 2-oxo-
1-piperidinyl group, etc., and these heterocyclic groups include alkyl groups, aryl groups, alkyloxy groups, aryloxy groups, acyl groups, sulfonyl groups, alkylamino groups, arylamino groups, acylamino groups, sulfonamino groups, It may be substituted with a carbamoyl group, a sulfamoyl group, an alkylthio group, an arylthio group, a ureido group, an alkoxycarbonyl group, an aryloxycarbonyl group, an imido group, a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like.

Examples of the nitrogen-containing heterocycle formed by Z or Z include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

Also, substituents (for example, R9R1 to R,) on the heterocycle in general formula (1) and general formulas (II) to [■] described below! The moieties (herein, R. ), it forms a so-called screw-type coupler, which is, of course, included in the present invention. Further, the ring formed by Z, Z., Z... and 28 described below may be further fused with another ring (for example, a 5- to 7-membered cycloalkene). For example, in general formula (V), R6 and R8 are R7 and R8 are in general formula (Vl).
, and may be bonded to each other to form a ring (eg, 5- to 7-membered cycloalkene, benzene).

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

General formula (II) General formula [III) N N -N General formula (■) N N -Nll General formula (V) General formula [VI) N -N -NH General formula [■] General formula (ff) ~ In [■] R, ~R, and X
has the same meaning as R and X above.

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

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

Among the magenta couplers represented by the general formulas (n) to [■], the magenta coupler represented by the general formula (II) is particularly preferred.

Regarding the substituents on the heterocycle in general formulas (1) to [■], R in general formula CI) and R8 in general formulas (II) to [■] satisfy the following condition l. The following conditions 1 and 2 are more preferable and more preferable.
The following conditions 1 and 1 are particularly preferred.
This is a case where conditions 2 and 3 are satisfied.

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

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

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

The most preferred substituents R and R8 on the heterocycle are those represented by the following general formula (IX).

General formula (IX) Rs R3゜-C- In the formula, R-, R1o and R11 are each a hydrogen atom, a halogenine atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a 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, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group, R1°R,. and at least 2 of RlI
One is not a hydrogen atom.

Furthermore, two of the above Rs, R1° and R11, for example, Rs and RIO, may be combined to form a saturated or unsaturated ring (for example, a cycloalkane, a cycloalkene, a heterocycle), and furthermore, R11 may be bonded to form a bridged hydrocarbon compound residue.

The group represented by R, to R11 may have a substituent, and specific examples of the group represented by R1 to RII and the substituent that the group may have include the above-mentioned general formula CI) Specific examples of the group represented by R and substituents are listed.

Also, for example, a ring formed by combining R1 and R1゜ and R8
Specific examples of the bridged hydrocarbon compound residue formed by ~R++ and its optional substituents include the cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the above general formula (1); Specific examples of hydrocarbon compound residues and their substituents are listed.

Among the general formulas (IX), (r)rts-
When two of R, , are alkyl groups, (ii) Re~
When one of R1I, for example R11, is a hydrogen atom and the other two R- and RIG combine to form a cycloalkyl together with the root carbon atom, the following is true.

Furthermore, in (i), it is preferable that two of R and ~R1 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

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

Below, in the margins, the substituents that the ring formed by Z in general formula (1) and the ring formed by Z in general formula [■] may have, and the substituents in general formulas (n) to (Vl) R
2-R6 is preferably represented by the following general formula (X).

General formula (X) -R'-Sow-R'' In the formula, R' represents alkylene, and R1 represents alkyl, cycloalkyl or aryl.

The alkylene represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and has 9 straight chain carbon atoms.
Regardless of branching. Moreover, this alkylene may have a substituent.

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

Preferred substituent groups include phenyl.

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

The alkyl group represented by R2 may be a linear, monobranched group.

Specifically, methyl, ethyl, b) Lt, tso
-propyl, butyl, 2-ethylhexyl, octyl,
Examples include dodecyl, tetradecyl, hexadecyl, octadacil, 2-hexyldecyl, and the like.

The cycloalkyl group represented by RR is preferably a 5- to 6-membered one, such as cyclohexyl.

The alkyl and cycloalkyl represented by R8 may have a substituent, and examples thereof include those exemplified as the substituent for R1 above.

Specific examples of the aryl represented by R8 include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched furkyl, as well as those exemplified as the substituent for R1 described above.

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

Among the compounds represented by the general formula (1), particularly preferred are those represented by the following general formula (XI).

General formula [sword] In the formula, R and X have the same meanings as R and X in general formula (1), and RI and nt are R1゜R in general formula (X)
It is synonymous with R.

Below margin C21+.

IJ2I Js xHS Below margin xHS C,H.

ll HICH1 C, 11,.

CIO1h! 12H2S C411 tragedy CIJ25 Below margin C2M.

Js ゝC1! +1111 CJ+y(t) IHIs C1I11. (t) C3B.

C.II.

CJl* C.II.

Below margin ■ CaBr2 Js C,l11 0CII2CONHCH,CH,OCH.

ocH2cn, so, cHm C21t.

C2+1゜ C,M.

2R5 Js CJ deaf C2M.

C Yi H.

CM.

Below margin C, H5 1CaH C41(.

l2H2J C, lI.

Below margin CH.

CH.

CJg NHSO2CtaHii CH.

CJ++(t) CJ++(t) CH5 ■ CH.

■ CM.

c,, C*I+++(t)CL
CJth (1) CH.

C.R.

C, H Tsu 7HIS 11, c CM.

C,H.

Below margin o(cu,)2oc,2n,.

N -N -N 5O N N N
C, J□H-N□N (mountain 06, N -N NH-HN N N 8M N -8811 N N NH CJs cn, N N N1
1N N Ml (C, Hl C, Hg N -H- between H-H- N N NHCJs N N M N N 811 +91 N -N N 8N N -N -N CrHICiH+ N"-" The following margins and the coupler The synthesis was published in the Journal of the °Chemical Society.
he Chemical 5ociety), Perkin (197γ), 2047
~2052, U.S. Patent No. 3,725,067, JP-A-5
9-99437, JP 58-42045, JP 59-162548, JP 59-171956,
JP-A-60-33552 and JP-A-60-43659
Synthesis was performed with reference to No.

The couplers of this invention typically contain 1X per mole of silver halide.
10-3 mol to 1 mol, preferably i x io-
It can be used in a range of 2 mol to 8 x 10-' mol.

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

Japanese Patent Application No. 59-280486 and Japanese Patent Application No. 60-851
No. 95 discloses that the general formula [XII] of the present invention is used to stabilize magenta dye images obtained from the magenta coupler of the present invention.
It has been described that coumaran or chroman compounds represented by are effective. On the other hand, the patent application 1986-2
No. 5793 and Japanese Patent Application No. 60-85193 disclose that the hydroxyindan-based compound represented by the general formula [XVII] of the present invention is effective in stabilizing magenta dye images obtained from the magenta coupler of the present invention. Are listed.

However, in each of the above specifications, regarding the stabilization of magenta dye images obtained from the magenta coupler of the present invention, the compound represented by the general formula [X[] of the present invention and the compound represented by the general formula [XVII] are described. There is no description of the effects when the compounds are used together.

As a result of intensive studies, the present inventors have determined that the general formula [I] of the present invention
At least two types of at least one compound represented by the general formula [XI[] of the present invention and at least one compound represented by the general formula [XVII] of the present invention are used in combination with the magenta coupler represented by It has been found that when this is done, the stability against light of the magenta dye image obtained from the magenta coupler of the present invention is dramatically improved.

Hereinafter, unless otherwise specified, the general formula [
XII] and -. The compound represented by the general formula [XVII] is referred to as a magenta dye image stabilizer according to the present invention.

The magenta dye image stabilizer according to the present invention used in conjunction with the magenta coupler of the present invention not only has an effect of preventing browning of a magenta dye image due to light, but also has an effect of preventing discoloration due to light. One of them is a chroman or coumaran compound represented by the following general formula [XII].

General formula [XII] [wherein R1 and R'' are each 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, represents an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group, R is a hydrogen atom, an alkyl group,
Represents an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, or a sulfone group. Represents an amide group, cycloalkyl group or alkoxycarbonyl group.

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

Further, R2 and R3 may be ring-closed with each other to form a 5- or 6-membered ring. Further, R and R may be ring-closed to form a methylenedioxy ring.

Yl represents an atomic group necessary to form a chroman or coumaran ring.

This chroman or coumaran ring is a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, a hydroxy group, an aryl group,
It may be substituted with an aryloxy group or a heterocyclic group, or may even form a spiro ring.

Among the compounds represented by the general formula [XII], compounds particularly useful in the present invention are those represented by the general formula [XI[I], [XIV][X
V], [XVI] and [XVI]r are included in the compounds shown.

1418[XNJ General formula [XI[[ko, [XrVko,
R', R, R3 and R4 in [XV], [XVI] and [XVI] have the same meaning as in the general formula [XII], and R, R, R7, R, R' and R
each represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group or a hetero m group.

Furthermore, R and R, R and R, R and R2, R2 and R', and R and R may be cyclized with each other to form a carbocycle, and furthermore, the carbocycle may be substituted with an alkyl group. .

The above general formula [X], [XrV], [XV].

In [XVI] and [XVI], R' and R'' are a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a cycloalkyl group, and R and R3 are a hydrogen atom, an alkyl group, a cycloalkyl group, and R.

Particularly useful are compounds in which R, R, R, R, and R are hydrogen atoms, alkyl groups, or cycloalkyl groups.

Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

Margin below CH-1) CH Yo Cl-1-2> C) 13 CH-3) C)! 3 CI-1-4) CH-5) CH3 C'A -6) C)l -7) CI-(-8) CI-1-9) C14-11) C)13 C)l -12) CI -1-13) CI-1-14) CI-15) Day 0-16) (,1-1-17) CI-18) CI-1-19) CI-1-20) Day 0-21 ) C) (-22) (,) (-23) CI-24) 0 days-25) C) l-26) CI4-27) CI-1-28) C) I-29) 0@-30) CH-31) (, l-1-33) C) (-34) CI-1-37) CI-1-40) C) l-41) Shii3 LJI3 Cl-1-48) CI-47) II cH-48) CI-1-49) CI-1-51) cl-1-52) cH Cl-1-53) C3117 Cl-1-54) Magenta dye image stability represented by the general formula fX]I] The oxidizing agent is Tetrahedron, 1970
．． vol 26. pp. 4743-4754, Journal of the Chemical Society of Japan, 1972. No. 10, 1987~
1990 pages, 'y Mikaroo L/Ivy (Chem,
Lett), 1972 (4) pp. 315-316, JP-A-55-139383, and can be synthesized according to the methods described therein.

On the other hand, a hydroxyindan compound represented by the following general formula [XVII], which is a magenta dye image stabilizer used in conjunction with the magenta coupler of the present invention, will be described.

General formula [XVII] R1+R1 co[In the formula, R 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 acylamine L acyloxy group, a sulfone Represents an amide group, cycloalkyl group or alkoxycarbonyl group.

A halogen atom, an alkyl group represented by R1 and R,
alkenyl group, alkoxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group,
Specific examples of the sulfonamide group, cycloalkyl group, or alkoxycarbonyl group include the groups detailed for R in general formula [I].

R12 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.

Specific examples of the halogen atom, alkyl group, alkenyl group, aryl group, acyl group, acylamimum L acyloxy group, sulfonamide group, cycloalkyl group, or alkoxycarbonyl group represented by R include those detailed in R of the general formula CIJ. The following groups can be mentioned.

Each of the groups listed above may be substituted with other substituents. Examples of the substituent include an alkyl group, an alkenyl group, 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. .

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

Y2 represents an atomic group necessary to form an indane ring. This indane ring may be substituted with a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, etc., and may also form a spiro ring. good.

Among the compounds represented by the general formula [XVII], compounds particularly useful in the present invention are included in the compounds represented by the general formulas [XrX] to [XXI].

General formula [XIX] General formula [XX] General formula [XXI] R in general formulas [XIX] to [XXI].

R11 and R13 are represented by the general formula [I
Cow Ita 16 IQ
+R definition, and R, R, R, R, R and RI9 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 heteroya group. R
and R, R and R, R and R'', R'' and R'', and R'' and R'' may be closed to each other to form a hydrocarbon ring, and the hydrocarbon ring is further substituted with an alkyl group. It's okay.

In the general formulas [XIX] to [XXI], R1+
and R is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group or a cycloalkyl group, R11 is a hydrogen atom, an alkyl group, a hydroxy group or a cycloalkyl group, R,
R, R, R.

Particularly useful are compounds in which R18 and R19 are hydrogen atoms, alkyl groups or cycloalkyl groups.

Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

r-i HI-2 Below margin HT-3 HI-4 HT-5 113 I-6 I-7 I-a I-9 I-10 H-11 l-12 l-14 l-15 ) (E -16 l-17 l-18 I-21 HI-22 CH3 l-23 l-24 rI!5 CI+3 l-25 l-26 1-II-27 l-28 l-29 T-31 l-32 l- 33 l-35 ) (I-36 HI-37 HI-38 HI-39 l-40 l-41 ) 1i-42 l-43 l-44 r-45 The following margins are the above general formulas [XVII], [XIX] ~ The method for synthesizing the magenta dye image stabilizer of the present invention represented by [XXI] is known and is described in Journal of Chemistry-'/Cyati (J, Chem, 3oc, ).

1962, pp. 415-417, Special Publication No. 59-3278
No. 5, Piurethane of Chemical Society of Japan (3ull, Chem, So
c, Japan).

1980, 53. 555-556.

The magenta dye image stabilizer represented by the general formula [XVII] of the present invention is disclosed in Japanese Patent Publication No. 59-32785, and is obtained from a pyrazolone, indashilon or cyanoacetyl type magenta coupler! ii@
It is said that it is particularly useful as a magenta dye image stabilizer obtained from a 5-pyrazolone type magenta coupler. However, there is no suggestion that the magenta coupler of the present invention, which has a different structure from the magenta coupler described above, is useful as a stabilizer for magenta dye images. When used in combination with a magenta dye image stabilizer represented by the general formula [XII] above, it exhibits an unexpected and specific effect on the preservation of magenta dye images obtained from the magenta coupler of the present invention. This is completely unpredictable from the above publication.

The above general formula [XII] and general formula [XVII] of the present invention
The magenta dye image stabilizer represented by is preferably used in an amount of 5 to 400 E/%, more preferably 10 to 250 mol%, relative to the magenta coupler represented by the general formula [I] of the present invention. The total amount of the magenta dye image stabilizers represented by the general formula [XI[] and general formula [XVII] of the present invention combined is 10 to 500 mol% based on the magenta coupler of the present invention. Preferably, it is more preferably 20 to 400 mol%.

Further, the usage ratio of the magenta dye image stabilizer represented by the general formula [XII] and the magenta dye image stabilizer represented by the general formula [XVII] of the present invention is 0.1 to 10 in terms of molar ratio. is preferable, more preferably 0.25 to
It is in the range of 4.0.

In the silver halide photographic light-sensitive material of the present invention, in addition to the magenta dye image stabilizer of the present invention, other magenta dye image stabilizers, such as U.S. Pat.
No. 6, No. 3,982,944, No. 4,254,216
No., JP-A-55-21004, JP-A No. 54-145530
No. 2,077.455, British Patent Publication No. 2,062
, No. 888, U.S. Pat. No. 3,764.337, No. 3,
No. 432,300, No. 3,574,627, No. 3,
No. 573,050, Japanese Unexamined Patent Publication No. 52-152225, No. 5
No. 3-20327, No. 5317729, No. 55-63
No. 21, No. 54-48538, No. 56-159644
No., British Patent No. 1.347.556, Publication No. 2,066
．． No. 975, Special Publication No. 54-12337, No. 48-31
Phenol compounds or phenyl ether compounds described in No. 625, US Pat. No. 3,700,455, etc. can also be used in combination.

Although it is preferred that the magenta couplers of the invention and the magenta dye image stabilizers of the invention are used in the same layer, the stabilizers may be used in layers adjacent to the layer in which the couplers are present.

The silver halide photographic light-sensitive material of the present invention can be applied to, for example, color negative and positive films, color photographic paper, etc., but the present invention particularly applies when applied to color photographic paper used for direct viewing. The effects of this will be effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are usually used. has a structure in which layers are laminated on a support in an appropriate number and order of layers, but the number and order of layers may be changed as appropriate depending on the important performance and purpose of use.

The silver halide emulsion used in the silver halide photographic material of the present invention (hereinafter referred to as the silver halide emulsion of the present invention).
Any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, can be used as the silver halide.

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

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
Growth may be performed by controlling H and pAo and adding them sequentially or simultaneously. Conversion methods may be used to change the silver halide composition of the grains after growth.

When producing the silver halide emulsion used in the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. , iron salts or complex salts,
Metal ions can be added to the inside of the particles and/or on the surface of the particles by adding metal ions, and reduction-sensitized nuclei can be added to the inside of the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. .

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 they may be left contained. When removing the salts,
This can be carried out based on the method described in Research Disclosure v-17643.

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

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

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

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

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

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

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range 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. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide is used during and/or at the end of chemical ripening and/or after the end of chemical ripening. Compounds known in the photographic industry as antifoggants or stabilizers can be added before coating the emulsion.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, gelatin derivatives, graft polymers of gelatin and other polymers, proteins, $1! Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric materials such as single or copolymers can also be used.

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

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic material of the present invention.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic material of the present invention may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention undergoes a camping reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, amine phenol derivatives, etc.) during color development processing. A dye-forming coupler is used that forms a dye. The dye-forming coupler absorbs light in the emulsion layer's sensitive spectrum for each emulsion layer.

A yellow dye-forming coupler is typically selected to form dyes in the blue light-sensitive emulsion layer, a magenta dye-forming coupler in the green light-sensitive emulsion layer, and a red dye-forming coupler in the red light-sensitive emulsion layer. A cyan dye-forming coupler is used in the layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides); examples of magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, and pyrazolobenzimidazole couplers. Examples include zontriazole, open-chain acylacetonitrile couplers, and cyan dye-forming couplers include naphthol couplers and phenol couplers.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Also, these dye-forming couplers only require reduction of two silver ions, even if they are 4-equivalent, meaning that four silver ions need to be reduced to form one molecule of dye. Either of the two is fine.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. It can be appropriately selected depending on the chemical structure of the hydrophobic compound. The oil-in-water emulsion dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a high boiling point organic solvent having a boiling point of about 150°C or higher, and if necessary, a low boiling point and/or a high boiling point organic solvent. Alternatively, it can be dissolved using a water-soluble organic solvent and emulsified using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After being dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling organic solvents include phenol derivatives, phthalate esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, etc. that do not react with the oxidized form of the developing agent. Specific solvents are used.

Anionic surfactants, nonionic surfactants, cations are used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water using a machine or ultrasound. A surfactant can be used.

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

The antifoggant agent may be used in the emulsion layer itself, or may be used in an intermediate layer provided between adjacent emulsion layers.

To prevent fogging caused by discharge caused by frictional charging of the photosensitive material in hydrophilic colloid layers such as the protective layer and intermediate layer of the silver halide photographic light-sensitive material of the present invention, and to prevent image deterioration due to UV light. It may also contain an ultraviolet absorber.

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

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is matted with the aim of reducing the gloss of the light-sensitive material, increasing the ease of writing, and preventing mutual sticking of the light-sensitive materials. agent can be added.

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

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

The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Other hydrophilic colloid layers may contain various additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (such as development acceleration, high contrast, and sensitization). surfactants are used.

The photographic emulsion layer and other layers of the silver halide photographic light-sensitive material of the present invention are a baryta layer or an α-olefin polymer, a flexible reflective support such as paper laminated with a synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, etc. It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide photographic material of the present invention can be improved in adhesion, antistatic properties, and dimensional stability directly or on the surface of the support after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. , may be coated via one or more subbing layers to improve abrasion resistance, hardness, antihalation properties, frictional properties, and/or other properties.

When coating the silver halide photographic light-sensitive material of the present invention, a thickener may be used to improve coating properties.Coating methods include exdolsion coating, which allows two or more layers to be coated simultaneously; Curtain coatings are particularly useful.

The silver halide photographic material of the present invention can be exposed to electromagnetic waves in a spectral region to which the emulsion layer constituting the silver halide photographic material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps,
Light emitted from phosphors excited by mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, X-rays, gamma rays, alpha rays, etc. , any known light source can be used.

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

The silver halide photographic material of the present invention can be used to form an image by color development as known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds generally have a concentration of about 0.1 g to about 3 (Ig) per color developer 111, preferably about 1 g to about 1 g per color developer 11.
Used at a concentration of 5 (II).

Examples of amine phenol developers include 0-amine phenol, p-7 minophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful aromatic primary amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, an example of a particularly useful compound is N,N'-diethyl-p-phenylenediamine salt M
salt, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-p-phenylene, diamine hydrochloride,
2-amino-5-(N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfone 7midoethyl-3-methyl-4-aminoaniline sulfate, N
-ethyl-N-β-hydroxyethylaminoaniline,
4-Amino-3-methyl-N.

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

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, Alkaline agent such as potassium carbonate, alkaline metal 1fil! ! Optionally, salts, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like can be included. The I)H value of this color developer is usually 7 or more, most commonly about 10 to about 13.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as the bleaching agent used in the bleaching process, and the metal complex oxidizes the gold and silver produced by development to convert it into silver halide, and at the same time colors the uncolored part of the color former. It has a composition in which metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

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

In again! p of salts, oxalates, acetates, carbonates, phosphates, etc.
Those known to be added to ordinary bleaching solutions, such as H1llj agents, alkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid p consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
One or more types of HM buffer may be included.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) contains thiogI.
M salt, thiocyanate, sulfite, etc. may be contained, or the bleach-fixing replenisher may contain these salts and be replenished into the processing bath.

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

[Specific Effects of the Invention] The silver halide photographic light-sensitive material of the present invention not only has excellent color reproducibility and less occurrence of Y-stin in uncolored areas against light and moist heat, but also has improved light fastness of magenta dye images. The properties are significantly improved and discoloration due to light is prevented.

[Specific Examples of the Invention] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side.

1st layer: Emulsion layer Magenta coupler 44 of the present invention was added at 6.0 mg/100C.
1", silver chlorobromide emulsion (containing 85 mol% silver bromide) 3.5 ma/100 cv in terms of silver, dibutyl phthalate 6.0 a+g/?0 Ocv and gelatin 15
．． The coating was applied so that the coating thickness was Qmq/100cf.

2nd layer: Intermediate layer (ultraviolet absorber-containing layer) 2-(2-hydroxy-3-5ec-butyl-5-
5. tert-butylphenyl)benzotriazole.
01111/100Cr, Jeep Thilphthalate 3
．． 0ma/100cr and gelatin 12.0mQ/
The coating was applied so that the coating amount was 100C1''.

Third layer: Protective layer gelatin was coated to give a smooth coating of 8.0 mg/100 Ci'.

The sample obtained in the manner described above was designated as Sample 1.

The exemplary compound of the present invention CH-35,0H-38°Hl-25,l was added to Sample 1 as a magenta dye image stabilizer.
-11-28 and samples 2.3, 4.5.6 in which the comparative compounds a and b shown below were added in equimolar amounts as the magenta coupler.
and 7 were obtained.

In addition, two of the above six types of magenta dye image stabilizers were used in combination as shown in Table 1.

Fees 8, 9, 10. -11.12.13.14.15゜1
6.17.185 and 19 were obtained.

In Samples 8 to 19, the two types of magenta dye image stabilizers used in combination were each used in a molar ratio of 1=1, and the total amount was equivalent to that of the magenta coupler.

Comparative compound a (compound described in JP-A No. 54-48538)
ll(y) Comparative Compound b (Compound described in JP-A-56-159644) The sample obtained above was exposed to light through an optical model according to a conventional method, and then treated in the following steps.

[Processing process] Processing temperature Processing time Color development
33℃ 3 minutes 30 seconds bleach constant @ 33
℃ Wash with water for 1 minute 30 seconds 33℃
Dry for 3 minutes 50-80℃
The components of each 2-minute treatment solution are as follows.

[Color developer] Benzyl alcohol 121g Diethylene glycol 10g Potassium carbonate
25 (sodium monobromide
0.6g anhydrous sodium sulfite
2.0g hydroxylamine sulfate
2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 4.5 g water was added to make 12, and adjusted to I) Hlo, 2 with NaOH.

[Bleach-fix solution] Ammonium thiosulfate 120 g Sodium metabisulfite 15 g Anhydrous sodium sulfite 3 g EDTA ferric ammonium salt 650 Add water to 11 and pH to 6.
．． Adjust to 7-6.8.

The concentration of each of the samples 1 to 1 treated above was measured using a densitometer (model KD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions.

Each of the above-mentioned processed samples was exposed to a xenon fade meter for 14 days to examine the light fastness of the dye image.

However, the evaluation of each item of the light fastness of the dye image is as follows.

[Residual rate] Percentage of dye remaining after side light and moisture resistance test at initial density 1.0.

[Degree of discoloration] (yellow density) after both light test at initial density 1.0/
(magenta density) to (yellow density) before both light tests/
(magenta density), and the larger this value is, the easier it is to change the color tone from magenta to yellowish.

The results are shown in Table 1.

From the results in Table 1 in Table 1 below, we can see that a sample (Sample 8) was prepared by using the magenta coupler of the present invention in combination with the chroman-based magenta dye image stabilizer of the present invention and a conventional magenta dye image stabilizer. .9.12.13) and samples prepared by using the magenta coupler of the present invention in combination with the hydroxyindan-based magenta dye image stabilizer of the present invention and a conventional magenta dye image stabilizer (Samples 10, 11. 14 and 15), it is true that samples prepared by adding a magenta dye image stabilizer to the magenta coupler of the present invention (Samples 2 to 15) are true.
Although the dye image survival rate in both light tests is improved compared to 7), it is recognized that the degree of discoloration is somewhat large.

On the other hand, a sample according to the present invention (Sample 1) was prepared by using the magenta coupler of the present invention in combination with two types of magenta dye image stabilizers, chroman type and hydroxyindan type according to the present invention.
In the case of 6 to 19), the difference in both light tests was unexpected from the samples (Samples 2 to 5) prepared by adding the magenta dye image stabilizer of the present invention to the magenta coupler of the present invention. It can be seen that the residual rate of the dye image is improved, and the degree of discoloration of the dye image in both light tests is also extremely small.

As described above, in the case of a sample prepared by combining the coupler of the present invention with two types of magenta dye image stabilizers of the present invention, one type of magenta dye image stabilizer of the present invention is added to the power/blur of the present invention. and conventional magenta dye i! It can be seen that the retention rate of the dye image and the degree of discoloration in both light tests are greatly improved from the samples prepared using the image stabilizer.

Example 2 Sample 2 was coated in exactly the same manner as in Example 1 with the coupler and magenta dye image stabilizer combinations shown in Table 2.
0 to 48 were created. Samples 20-48 were processed as described in Example 1. Further, these samples were subjected to a double-light test in the same manner as in Example 1, and the results shown in Table 2 were obtained.

From the results shown in Table 2 below, the sample prepared by using the magenta coupler of the present invention together with the two types of magenta dye image stabilizers of the present invention has the magenta coupler of the present invention and the two types of magenta dye image of the present invention. It can be seen that the light resistance is significantly improved compared to the sample prepared by adding either one of the stabilizers alone.

Example 3 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic light-sensitive material, and Sample 49 was obtained.

1st layer: Blue-sensitive silver halide emulsion layer α-pivaloyl-α-(2,4
-dioxo-1-benzylimidazolidin-3-yl)
-2-chloro-5-[γ-(2゜4-di-t-amylphenoxy)butyramide]acetanilide at 6.81
11CI/ 100Ci", blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver is 3,2a+a/
100cf1 dibutyl phthalate 3.51g/100
Ct' and gelatin at 13.5+++g/100cf
It was painted so that

2nd layer: Intermediate layer 0.51f of 2.5-di-t-octylhydroquinone
iQ/100Ct”, dibutyl phthalate 0.51
! IQ/100Cf and gelatin at 9.0rnQ/
It was painted so that it would be 100 cf.

Third layer: green-sensitive silver halide emulsion layer containing magenta coupler 28 of the present invention at 3.51! ;l/10
0cl, green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver: 2.5mg/100cf, dibutyl phthalate: 3.011 (1/100Cf and gelatin: <12.0mg/l) It was painted so that it became OC,2.

4th M = 2-(2-hydroxy-3-5ec as intermediate layer UV absorber)
-butyl-5-t-butylphenyl)benzotriazole 5. Otg/100cr, di-butyl phthalate 6.011 (1/100Cf, 2,5-di-t
-0.511 octylhydroquinone! II/1(
lOcv' and gelatin 12.011g/100Cf
It was painted so that

5th layer: Red-sensitive silver halide emulsion layer 2-[α-(2,4-di-1-pentylphenoxy)butanamide]-4°6-dichloro-5-ethylphenol was added as a cyan coupler at 4.2 UJ/100C, 2,
Red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) was converted into silver to be 3.0111+7/100 Ct', tricresyl phosphate was 3.5111 g/100 cv, and gelatin was 11.5 mq/100 cf. It was painted on.

Layer 6: Middle layer A layer composed of exactly the same composition as No. 4M.

7th layer: Protective layer Gelatin was coated at a concentration of 8.0 mg/1 (locllz).

In the above sample 49, the magenta dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3 to prepare multilayer samples 50 to 59, which were exposed and processed in the same manner as in Example 1. After that, a light emission test (a xenon fade meter was irradiated for 16 days) was conducted. The results are also shown in Table 3.

From the results shown in Table 3 in the margin below, it can be seen that when the total amount of the magenta dye image stabilizer of the present invention is kept constant, the use of two types of the magenta dye image stabilizer of the present invention is more effective than using only the magenta dye image stabilizer of the present invention. It can be seen that the light fastness of the magenta dye image can be greatly improved by using the magenta dye image stabilizer of the invention in an appropriate ratio.

Furthermore, the samples according to the present invention had excellent color reproducibility and little Y-stain occurrence.

Claims (1)

[Scope of Claims] At least one magenta image-forming coupler represented by the following general formula [I], at least one compound represented by the following general formula [XII], and at least one compound represented by the following general formula [X
A silver halide photographic material comprising at least one compound represented by [VII]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. You may. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ] General formula [X
II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_4 are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups,
represents 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 group, or an alkoxycarbonyl group, and R^2 is a hydrogen atom, an alkyl group, an alkenyl group, Represents an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R^3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, or a sulfonamide group. group, cycloalkyl group or alkoxycarbonyl group. Also R^2 and R
^3 may be closed with each other to form a 5- or 6-membered ring. Furthermore, R^2 and R^3 may form a methylenedioxy ring. Y_1 represents an atomic group necessary to form a chroman or coumaran ring. ] General formula [XVII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1^1 and R^1^3 are hydrogen atoms, respectively.
Represents a halogen atom, alkyl group, alkenyl group, alkoxy group, hydroxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group, R^1^2 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group,
It represents an acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group. Further, R^1^2 and R^1^3 may be ring-closed with each other to form a 5- or 6-membered hydrocarbon ring. Y_2 represents an atomic group necessary to form an indane ring. ]