JPS62208048A - Silver halide photographic sensitive material having improved fastness of dye image - Google Patents

Abstract

PURPOSE:To improve color reproducibility and the fastness of a magenta dye image to light and to prevent the generation of Y-stains by incorporating the magenta coupler and compds. expressed by prescribed formulas into a photosensitive material. CONSTITUTION:At least one of the compd. expressed by formula I and at least one of the compd. expressed by formula II are incorporated into the silver halide photographic sensitive material which forms colors when subjected to exposing and developing. Z in formula I is the nonmetallic atomic group necessary for forming a nitrogenous heterocycle, X is a hydrogen atom or substituent which can be eliminated by the reaction with the oxidant of a color developing agent, R denotes a hydrogen group. R<1>, R<2>, R<4> in formula II are respectively a hydrogen group, alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, R<6> is an alkenyl group, cycloalkenyl group, alkenyl group or aryl group, R<3> is a substituent, J is the compd. expressed by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic R light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved dye image fastness. This invention relates to a silver halide color photographic light-sensitive material in which a magenta dye image is stable against heat and light, and the occurrence of staining is prevented.

[Background of the Invention] Conventionally, a silver halide color photographic light-sensitive material is imagewise exposed to undergo a color development phenomenon, whereby an oxidized product of an aromatic primary amine color developing agent and a color former undergo a coupling reaction. For example, it is well known that indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine, and similar pigments are produced to form color images. In this type of photography, a subtractive color method is usually used to reproduce colors.
A silver halide color photographic light-sensitive material is provided, in which blue-sensitive, green-sensitive and red-sensitive light-sensitive halide emulsion layers contain color formers that are related to the respective residual colors, that is, couplers that develop colors of yellow, magenta and cyan. used.

Examples of couplers used to form the yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, and indacylon 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 rv, the dye formed from magenta couplers of 2-pyrazolo-5-ones has an absorption of 430 rv.
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, etc.

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 D1 absorption near 430 nm of the magenta coupler, British Patent No. 1.047,
Pyrazolobenzimidazoles described in US Pat. No. 612, indasilones described in US Pat. No. 3,770,447, and US Pat.
2.418, 1 day described in 1.334.515-
Pyrazolo[5,1-C]-]1,2,4-triazole type coupler 1H-bilazolo[1/5-b]-] described in JP-A-59-111956, Research Disclosure No. 24.531 1.2.4-Triazole type coupler research disclosure NO.

1H-pyrazolo[1,5-c]- as described in 24.626
1,2,3-triazole type coupler, JP-A-59-1
No. 62548, Research Disclosure t-No.

1-imidazo[1,2-b] described in 24.531
- Pyrazole type coupler, JP-A No. 60-43659,
18-pyrazolo[1,5-b]pyrazole type coupler described in Research Disclosure No. 24,230, 1H-pyrazolo[1] described in JP-A-60-33552, Research Disclosure No. 24,220
, 5-d ] Magenta couplers such as tetrazole couplers have been proposed. Among these, 1H-pyrazolo [
5,1-C]-]1.2.4-triazole coupler 1 day-pyrazolo[1,5-b]-1,2゜4-triazole coupler, 1 day-pyrazolo[1,5-c coupler 1
．． 2.3-triazole type coupler, 1-imidazo [
1,2-b cobyrazole type coupler, 1-pyrazolo [
The dye formed from the 1,5-d] pyrazole coupler and the 1-pyrazolo[1°5-d]tetrazole coupler has a subabsorption near 430 nm of the 1,2-pyrazole coupler having an anilino group at the 3-position. Compared to dyes formed from pyrazol-5-ones, it is significantly smaller and preferred in terms of color reproduction;
Furthermore, the occurrence of Y-stin in uncolored areas due to light, heat, and humidity is 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-59-125732 discloses that a 1H-pyrazolo[5,1-C]-]1.2.4-triazole type magenta coupler 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 1-pyrazolo[5,1-c]-1,2°4-triazole type magenta coupler. However, it has been recognized that even the above techniques are still not sufficient to prevent 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 in which a magenta dye image exhibits less 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 photographic material in which staining is prevented from occurring.

[Structure of the Invention] The above object of the present invention is to provide at least one magenta coupler represented by the following general formula [I] and the following general formula [A]
This is achieved by a silver halide photographic material containing at least one of the compounds represented by:

[In the formula, 2 represents a nonmetallic atomic group 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.

Further, R represents a hydrogen atom or a substituent. ] General formula [A
[In the formula, R1, R2 and R4 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl length, an aryl group or a heterocyclic group, and R5 represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. represent. R
3 represents a substituent, and 3 represents Oll, 2.3 or 4. J represents and R6 and R7 each represent a hydrogen atom, an alkyl group or an aryl group. ), m is in the ortho or meta position. Furthermore, R1 and R2 may be combined with each other to form a 5- or 6-membered ring. When 2 is 2 or more, R3 may be the same or different. When 2 is 1 to 4, one R3 may be bonded to R1 or R2 to form a ring together with the nitrogen atom bonded to R1 and R2. When R is 2 or more, the two R3 are each R1
and R2, and may form a ring together with R+ and the nitrogen atom bonded to R2. 1 [Detailed Description of the Invention] Below is a blank space. In the magenta coupler represented by the general formula (1) according to the present invention, Z is a nonmetal necessary to form a nitrogen-containing heterocycle. Represents an atomic group, 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, sia/group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heta-a ring oxy group, siloxy group , acylk t jr group, carbamoyloxy group, amine 7 group, 7 syl amino group, sulfonamide group, imide group, ureido group, sulf 7 amoylami 7 group, alkoxycarbonyl 7 mi 7 group, 7 lyloxycarponyl amine 7 group , an alkoxycarbonyl group, an aryloquinecarbonyl group, an alkylthio group, a 7-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'7:' has 1 to 3 carbon atoms.
2, alkenyl groups and alkynyl groups preferably have 2 to 32 carbon atoms; cycloalkyl groups and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms; The group may be straight chain or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., 7-aryl, cyano, halogen atom, heterocycle, cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon In addition to compound 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 aryl Oxy, heterocyclic oxy,
Those substituted through an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, amino (including noalkylamino 7, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido those substituted through the nitrogen atom such as, furkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl,
(such as those substituted via a sulfur atom such as sulfamoyl, and 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, 1
-hexylnonyl group, 1.1'-dipentylnonyl group,
2-chloro-butyl group, 1J fluoromethyl group,
1-Ethoxytridecyl group, 1-nodoxyisopropyl group, methanesulfonylethyl i, 2,4-di-t-7milphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-II+-butanesulfone Aminophenoxypropyl group, 3-4'-(α-(4''(p-hydroxybenzenesulfonyl)phenoxy)dodecanoyl 7
mino+722probyl group, 3-14'-(α-(2”
, 4''-sheet t-7milphenoxy)butane7mido]phenyl l-propyl group, 4-[α-(〇-chlorophenoxy)tetradecanamidophenoxy]propyl group, allyl group, cyclopentyl group, cyclohexyl group, etc. .

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

Specifically, phenyl group, 4-t-butyl 7-enyl group,
2,4-di-t-7mylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-t-butyl 7eth/xy)tetradecanamidophenyl group, etc. can be mentioned.

The heterocyclic group represented by R is preferably one with 5 to 7 shells, and may be substituted or fused.
Specific examples include 2-7lyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R include an acetyl group, a phenylacetyl group, a dodeca/yl group, a fulkylcarbonyl group such as an α-2-4-di[-7-methylphenoxybutanoyl group, benzoyl i, 3 Examples include 7-aryl carbonyl groups such as -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 thereof include a benzenesulfonyl group, a p-)luenesulfonyl group, and the like.

Examples of the sulfinyl group represented by R include furkylsulfinyl IIs such as ethylsulfinyl group, octylsulfinyl group, and 3-phenoquinebutylsulfinyl group;
Examples include arylsulfinyl groups such as 7xnylsulfinyl group and m-pentadenulfenylsulfinyl group.

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphonyl group such as an octyloquinephosphonyl group, a chiaryloquinephosphonyl group such as a 7znoxyphosphonyl group,
Examples include arylphosphonyl groups such as phenylphosphonyl groups.

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-91thylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-Fdecylcarbamoyl group, N-(3-(2,4- ]-t-7 milphenoxy)propyl carbamoyl group, and the like.

The sulfamoyl group represented by the margin R below may be substituted with a furkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-noethylsul7γmoyl i, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-72nylsul7 Examples include an amoyl 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[2,2,1]heptan-1-yl, tricyclo[3
, 3,1,1'°']decane-1-yl, 7,7-tumethyl-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, 7enethyloxyethoxy group, and the like.

The aryloxy group represented by R is preferably 7-ethyloxy, 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 heterocyclic oxy group represented by Rt' preferably has 5 to 7 heterocycles, and the heterocycle may further have a substituent, for example, 3゜4.5.6-tetrahydro Examples include biranyl-2-oxy group and 1-phenyltetrazole-5-oxy group.

The siloxy group represented by R7' may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, and a trimethylbutylsiloxy group.

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 carbamoyl oxine 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. Can be mentioned.

The amine 7 group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethyl amine group, an anilino group, an m-chloroanilino group, a 3-pentadecyloxycarbonyl aniline group, etc. / group, 2
-chloro-5-hexadecaneamide 7ni7 groups and the like.

Examples of the acylamino group represented by R include alkylcarbonylamino groups, arylcarbonylamino 7 groups (preferably phenylcarbonylamino 7 groups), etc., which may further have a substituent, specifically acetamino group, α−
Examples include ethylpropanamide group, N-phenylacetamide group, dodecanamide group, 2,4-not-t-amylphenoxyacetamide group, α-3-butyl 4-hydroxy 7e/xybutanamide group, and the like.

Examples of the sulfonamide group represented by R''ch include 7 alkylsulfonylamide groups and 7 arylsulfonylamide groups, which may further have a substituent.

Specifically, 7 groups of methylsulfonylamide, 7 groups of Venter r' silsulfonylamide, benzenesulfonamide lip
, p-) luenesulfonamide group, 2-methoxy-5-
Examples include t-7 milbenzenesulfonamide group.

The imide group represented by R'C' may be open-chain or cyclic, and may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group,
Examples include a 7-talimide group, a glutarimide group, and the like.

The ureido group represented by R is a furkyl group, an aryl group (
Preferably, it may be substituted with a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-decylureido group, an N-7222lureido group, an N-p)dylureido group, and the like.

The sul7amoyl7mi7 group represented by R''C may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N, N-dibutylsul77moylami7 group, N-methylsul7 Examples thereof include an amoylamino group, an N-phenylsul7 amoylamino group, and the like.

The alkoxycarbonylamide 7 group represented by R is,
It may further have a substituent (e.g., 1-toxyluponylamine group, methoxyethoxycarbonylamino group,
Examples include 7 octadecyloxycarbonylamide groups.

The aryloxycarbonylamide 7 groups represented by R may have a substituent, and examples thereof include phenoxycarbonylamide 7 groups and 4-methyl 7e/xycarbonylamide 7 groups.

The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloquinecarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. Examples include groups.

The 7-aryloxycarbonyl group represented by R may further have a substituent, for example, a 7-ethyloxycarbonyl group,
Examples include p-chloro7e/oxycarbonyl 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 7enethylthio 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, 2-1-octylphenylthio group, 3-octatecylphenylthio group, 2-carboxyphenylthio group, and p-7cetaminophenylthio group.

The heterocyclic thio group represented by R't' 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 separated by reaction with the oxidized product of the color developing agent represented by
Examples include groups substituted via an RM atom or a nitrogen atom.

In addition to carboxyl groups, examples of the group substituted via a carbon atom include the general formula (R3' is the same as R, Z' is the same as Z, R2' and R7' are hydrogen atoms, aryl groups, , which represents an alkyl group or a heterocyclic group, a hydroxymethyl group, and a triphenylmethyl group.

Examples of groups substituted via an oxygen atom include flucoquine group, aryloxy group, heterocyclicoxy group, 7syloxy group, sulfonyloxy group, flukoxyluponyloxy group, aryloxycarbonyloxy group, alkyloxalyloxy group, and alkoxyoxalyloxy group. Examples include groups.

The phenoxy group may further have a substituent (for example,
Examples include nidoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, 7enethyloxy group, p-chlorobenzyloxy group and the like.

The 7-aryloxy group is preferably a 7-ethyloxy group, and the aryl group may further have a substituent, specifically, a phenoxy group, a 3-methylphenoxy group, a 3-
Dodecylphenoxy group, 4-notanesulfonamidophenoxy group, 4-(a-(3'-pentadecylphenoxy)butanamido]phenoxy group, hexydecylcarbamoylmethquine group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group group, 1-7tyloxy group, p-
Examples include nodoxy72/oxy 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, specifically, 1-phenyltetrazoli and 2-benzothiazolyloxy group.

The acyloxy group includes, for example, an acetoxy group, an alkylcarbonyloxy group such as a butafluoxy group, an alkenyloxy 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 alphkyloxy carbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group.

Examples of the aryloxycarbonyl group include a 7-ethyloxycarbonyloxy 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.

As the alkylthio group, butylthio group, 2-Schiff 7
Examples include ethylthio group, 7enethylthio group, and bennorthio group.

The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecyl7enethylthio group, 4-nonafluoropentanamido7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-L-butyl Examples include phenylthio group.

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

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group.

For example, those represented by the general formula -N represent an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, and an alkoxycarbonyl group, and R4J and Rs' are bonded together. A heterocycle may also be formed. However, R4' and R5
' cannot both be hydrogen atoms.

The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, 7 alkylamides, 7 arylamides, 7 acylamides, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group,
Examples thereof include a carbamoyl group, a sulfur group, an alkoxycarbonyl group, a 7-aryloxycarbonyl group, an alkyloxycarbonyl amine 7 group, an aryloxycarbonyl amine 7 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 R or R57 has 6 to 32 carbon atoms, preferably a phenyl group or a naphthyl group,
The aryl 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 R5' and an alkyl group. Specific examples of the aryl group include a phenyl group, a 1-su7tyl group, and a 4-methylsulfonylphenyl group.

The heterocyclic group represented by R4/ or R, / is 5-6
Shellfish are preferred, and 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-bilinol group.

The sulfamoyl group represented by R4' or R5' includes N-furkylsulfamoyl group, N,N-noalkylsul7amoyl group, N-7lylsul7amoyl group, N-furkylsulfamoyl group, N-7lylsul7amoyl group,
, N-diarylsulfamoyl group, etc., and these alkyl groups and 7-aryl groups may have the substituents listed above for the alkyl groups and aryl groups.Specific examples of the sul-77 moyl group include For example, N, N-diethylsulfamoyl group, N-methylsulfamoyl group, N
-Fy” Silsul 77 moyl Ils, Np)
! J Rusul 7 Amoyl group is mentioned.

As the carbamoyl group represented by R4' or R, /,
N-furkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-7arylcarpamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and 7-aryl groups are Specific examples of the carbamoyl group which may have the substituents listed above include N,N-noethyl carbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl-X, N-p-cyanophenylcarbamoyl basis,
N-p-)lylcarbamoyl group is mentioned.

Examples of the 7-sil group represented by R1' or R, / include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, the aryl group, and the heterocyclic group are substituted. Specific examples of the acyl group which may have a group include a hexafluorobuta/yl group, a 2°3.4.5.6-pentafluorobenzoyl group, an acetyl group, a benzoyl group, and a naphthonyl group. , 2-7lyl carbonyl group, and the like.

Examples of the sulfonyl group represented by R1' or R57 include an alkylsulfonyl group, a 7-arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group, Examples include a benzenesulfonyl group, an oftance/lzhonyl group, a naphthalenesulfonyl group, and a p-chlorobenzenesulfonyl group.

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

The alkoxycarbonyl group represented by R4' or R5' may have a substituent listed for the alkyl group, and specific examples include a medoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, etc. can be mentioned.

The heterocycle formed by bonding R1' and R5' preferably has 5 to 6 rings, and may be saturated or unsaturated, and may or may not have aromaticity, or,
Examples of the heterocycle, which may be a condensed ring, include an N-7 talimide group, an N-co/monolimide group, a 4-N-urazolyl group, a 1-N-hydantoynyl group, and a 3-N-2,4-dihydroimide group. Oxooxazolinonino C group, 2-N-1,1-dioxo-3-(2H)-oxo-1,2-benzthiazolyl group, 1-virolyl group, 1-pyrrolidinyl group, 1-pyrazoli group, 1-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-yneindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl group, 1-( 1,2,4-)+77zolyl) group, 1-(
1,2,3-)riazolyl) group, 1-(i, 2.3.
4-tetrazolyl) group, N-morpholinyl group,! ,2,
3. Examples include 4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2-IH-pyridone group, 7-thalassion group, 2-oxo-1-piperidinyl group, and these heterocyclic groups are alkyl groups. , aryl group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkylamino group, aryl7mino group, acylamino group,
Sulfonamide 7 group, carbamoyl group, sulfamoyl group, furkylthio group, arylthio group, ureido group, alkoxycarbonyl group, 7lyloxycarbonyl group, imido group, nitro group, cyano group, carboxyl group, halogen atom, etc. Also by Z or Z' Examples of the nitrogen-containing polychord ring formed 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.

In addition, in general formula (1) and general formulas (II) to [■] described later, the substituent on the heterocycle (for example, R2H, -R,) is a moiety (herein, R'', X and Z II are (synonymous with R, X, and Z in general formula (1)) forms a so-called screw-type coupler, which is of course included in the present invention.

Further, the g ring formed by z, z', z" and 21 described below may be further fused with another ring (for example, a cycloalkene with 5 to 7 shells). For example, in the general formula (V), R
6 and R6, R in general formula (Vl), and R8 may be bonded to each other to form a ring (for example, 5 to 7 cycloalkenes, benzene).

What is represented by the following margin-a formula [1] is more specifically represented by, for example, the following general formulas [■] to [■].

General formula [11] General formula (III) N -N -N General formula (■) N -N -NH General formula (V) General formula [■], General formula [■] Said general formula (n) - [■ ], R, -R, and X have the same meanings as R and X above.

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

General formula [■] In the formula, R, , X and Zl have the same meanings as RlX and Z in the general formula (I).

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

Regarding the substituents on the heterocycle in general formulas (1) to [■], in general formula [1] - is R, and in general formula [n)-(■], R8 is the following It is preferable that Condition 1 is satisfied, and more preferable that Conditions 1 and 2 below are satisfied.
The following condition 1. is particularly preferable.
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 R2 on the heterocycle are those represented by the following general formula (IX).

General formula (ff) R9 R5゜-C- R in the formula R,,R,. and V R+ + are respectively hydrogen atoms,
(g) Rodene atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, 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, alkini group, carbamoyloxy group, ami7 group, 7syl7mi7 group, sulfonamide group, RljRl represents an imide group, a ureido group, a sul77 moylamy7 group, an alfukydicarbonylami7 group, a fulfkidicarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group. and VR +
At least two of the + atoms are hydrogen atoms.1i.

Moreover, the above-mentioned R − = R +. and two of R11, for example R, and R1. may be bonded to form a saturated or unsaturated ring (eg, cycloflucane, cycloalkene, heterocycle), and mathematically R1+ may be bonded to form a bridged hydrocarbon compound residue.

The groups represented by R9 to R11 may have a substituent, and specific examples of the groups represented by R, to R11 and the substituents that some groups may have include the above-mentioned general formula ( 1)
Examples of the conjugate of the group represented by R5f and the V substituent are mentioned.

Also, for example, R, and R,. A ring formed by combining and R,
~R. Specific examples of the bridged hydrocarbon compound residue formed by and the substituents thereof that may have include cycloalkyl, cycloalkenyl, and heterocyclic group represented by R in the above general formula [1]; Specific examples of elementary compound residues and their substituents are listed.

Among the general formulas (IN), (i) R=~R
When two of I+ are alkyl groups, (ii) R=~
One of R I+, for example R11, is a hydrogen atom,
The other two are R, and R,. If is combined with the root carbon atom to form a cycloalkyl, then .

Furthermore, preferred among (i) is a case in which two of R, to R 11 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, dichlorofurkyl, and the substituent thereof include the alkyl, dichlorofurkyl, and the substituent represented by R in the general formula [1] above. Specific examples are given.

In addition, the substituent that the ring formed by Z in general formula (11 and the ring formed by Z in general formula [■]) may have, and the substituent that the ring formed by Z in general formula R is preferably represented by the following general formula (X).

General formula (X) -R1-SQ2-R2 In the formula, R' represents alkylene, and R2 represents alkyl, cycloalkyl or aryl.

The alkylene represented by R' preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 1 to 6 carbon atoms, and it does not matter whether the straight chain has 9 branches or not. Further, this alkylene may have a substituent (1. Examples of the substituent include R in the general formula [I] described above.
When is an alkyl group, the substituents that the alkyl group may have include those shown below.

Preferred substituents include phenyl.

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

The alkyl group represented by R2 does not matter if it is a linear chain with one branch.

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

The cycloalkyl group represented by R2 is preferably 5 to 6, and includes, for example, cyclohexyl.

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

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

In addition, when there are 2g1 or more substituents, those direct substituents are:
They may be the same or different.

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

The general formula is] In the formula, R and X have the same meanings as R and X in the general formula (1), and R1 and R2 are R l in the general formula (X).

It has the same meaning as R2.

Specific examples of compounds applicable to the present invention are shown below.

Margin below 12H25 CH3 ll3 C) I3 CH3 C.I.

■ CH11 Margin below CH3 CH.

HI CH.

C full(+s Jt C2H.

CH.

CH.

♂ CH.

I3 Shire 3 I CJ+s Shire H
U self tl + fu (tJ, I CH.

aH1y (11m C1(.

]4 0CH2CONHCIIzCH20CHi0CH2CH
2SO□CHi 2H5 Z C2H.

C.II.

CH3 CH.

10f 6H13 H3 H3 QC2H.

Cll.

Hx (:1HI7(su) C12 B5 12 feet Ctl.

Robbery CH.

■ 7Hts hCCH3 4G 0 (CH2) 20C12H25 16F 17F St N Js °199 N N Nil Also, the above coupler was published in Journal Op the Chemical
Sosai 7 Tei (Journal of theCh
chemical 5ociety) t Parkin (P
Erkin) I (1977), 2047-20
52, U.S. Patent No. 3,725,067, JP-A-59-9
No. 9437, No. 58-42045, No. 59-1625
No. 48, No. 59-171956, No. 60-33552
No. 60-43659, No. 60-172982, No. 60-190779, and the like.

The coupler of the present invention is usually 1 mole of halogenated JIX
lo-comole can be used in an amount of 1 mol, preferably in the range of I x to' mol to 8X10-' mol.

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

In the following margin general formula [A], the alkyl groups represented by R+, R2 and R4 include, for example, a methyl group, an ethyl group,
Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, etc., examples of the alkenyl group include an allyl group, and examples of the aryl group include a phenyl group. Examples of the heterocyclic group include a pyridyl group, a furyl group, and a pyrimidinyl group. R
These bases represented by 1, R2 and R4 each include those having substituents. For example, substituents for alkyl groups include halogen atoms, aryl groups, acyl groups, alkylcarbamoyl groups, arylcarbamoyl groups, and alkylsulfamoyl groups. group, arylsulfamoyl group, cyano group, alkoxy group, aryloxy group, acyloxy group, alkylsulfonamide group, arylsulfonamide group, amiLL alkoxycarbonyl cyclocarbonyl group, hydroxyl group, etc., and cycloalkyl group, Examples of substituents for alkenyl groups, aryl groups, and heterocyclic groups include alkyl groups in addition to the above-mentioned examples of substituents for alkyl groups.

R1 and R2 are preferably alkyl groups, and R4 is preferably a hydrogen atom or an alkyl group.

There are no particular restrictions on the substituent represented by R3, but specific examples include halogen atoms (for example, chlorine atoms, etc.), alkyl groups (for example, methyl groups, ethyl groups, etc.), cycloalkyl groups (for example, cyclohexyl groups, etc.), and aryl groups. groups (e.g., phenyl group, etc.), alkenyl groups (e.g., allyl group, etc.), heterocyclic groups (e.g., pyridyl group, etc.), acyl groups (e.g., acepyl group, benzoyl group, etc.), sulfonyl groups (e.g., alkylsulfonyl groups such as methylsulfonyl group) arylsulfonyl groups such as wheat gluten, phenylsulfonyl groups, etc.), carbamoyl groups (e.g. arylcarbamoyl groups such as alkylcarbamoylnylcarbamoyl groups such as N-butylcarbamoyl group),
Sulfamoyl groups (for example, alkylsulfamoyl groups such as N-propylsulfamoyl groups, arylsulfamoyl groups such as N-phenylsulfamoyl groups, etc.), cycloalkyl groups (for example, butoxy groups, etc.), aryloxy groups ( For example, phenoxy group, etc.), acyloxy group (for example, acetyloxy group, benzoyloxy group, etc.), amino group (
(e.g., ethylamino group, anilino group, etc.), acylamino group (e.g., acetamido group, phenylcarbonylamino group, etc.), sulfonamide group (e.g., alkylsulfonamide group such as methylsulfonamide group, arylsulfonamide group such as benzenesulfonamide group) ), alkoxycarbonylamino groups (e.g., ethoxycarbonylamino groups, etc.), aryloxycarbonylamino groups (e.g., phenoxycarbonylamino groups, etc.), alkoxycarbonyl groups (e.g., butoxycarbonyl groups, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl groups, etc.) base, etc.)
, an alkylthio group (eg, dodecylthio group, etc.), an arylthio group (eg, phenylthio group, etc.), and the like.

These groups may further have similar substituents.

Examples of the alkyl group represented by R5 include ethyl group,
Examples of the cycloalkyl group include a cyclohexyl group, examples of the alkenyl group include an allyl group, and examples of the aryl group include a phenyl group. Can be mentioned. These groups represented by R5 include those each having a substituent. For example, as a substituent for an alkyl group, a halogen atom, an aryl group, an acyl group,
Alkylcarbamoyl group, arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group,
Examples include cycloalkyl group, aryloxy group, acyloxy group, alkylsulfonamide group, arylsulfonamide group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, hydroxyl group, etc. Examples of the substituent include an alkyl group in addition to the above-mentioned substituent examples of the alkyl group. R5 is preferably an alkyl group or an aryl group.

-S- is particularly preferred.

In the present invention, any positional relationship is preferably used. In addition, R1 and R2 may be bonded to each other to form a 5-membered to 6m ring (for example, when 2 is 1 to 4, one R3 is bonded to R1 or R2, and R1, R2 is bonded to R1 or R2.
With the nitrogen atom bonded to 2, a ring, preferably a 5- to 6-membered ring (for example, two R3 are bonded to R1 and R2, respectively, and together with the nitrogen atom bonded to R+, R2, the following:
Representative examples of the compound represented by the general formula [A] of the present invention are shown below, but the present invention is not limited thereto.

CH2CHIMH:FsozCH3 The following margins do not show typical synthesis examples of the compound represented by the general formula [A] of the present invention (hereinafter referred to as the magenta dye image stabilizer of the present invention), but the present invention is not limited thereto. It's not something you can do.

Synthesis Example 1 Synthesis of Exemplified Compound A-1 N,N-dimethyl-〇-phenylenediamine dihydrochloride 2
After dissolving 1+It in 10 g of water, 100 g of lysine was added, and while stirring was continued at room temperature, 20 g of p-toluenesulfonyl chloride was added little by little over 30 minutes.

After continuing the reaction for an additional 30 minutes, the mixture was poured into 5001Q ice water and left to stand for a day and night, and the precipitated crystals were collected by filtration. The obtained crystals were recrystallized twice with methanol to give 12(+
A white powdery crystal of was obtained. Melting point 91-95°C.

The results of mass spectrum and nuclear magnetic resonance spectrum are A-
It supported the structure of 1.

Synthesis Example 2 Synthesis of Exemplified Compound A-19 N,N-dimethyl-m-phenylenediamine dihydrochloride 2
After dissolving 1 (l) in 101 g of water, 100 uN of pyridine
was added, and while stirring was continued at room temperature, p-toluenesulfonyl chloride 20a was added little by little over 30 minutes.

After continuing the reaction for another 30 minutes, pour into 500 g of ice water.
After standing for one day and night, the precipitated crystals were collected by filtration. The obtained crystals were recrystallized twice with methanol to obtain 18 g of white powdery crystals. Melting point: 155-151°C.

The results of mass spectrum and nuclear magnetic resonance spectrum are A-
It supported 19 structures.

Synthesis Example 3 Synthesis of Exemplified Compound A-25 After heating and dissolving 7.5 g of Exemplified Compound A-1915 (J and p-toluenesulfonyl chloride in 80 g of methanol, 2.4 g of sodium hydroxide was added, and the mixture was boiled and refluxed for 4 hours. After that, it was poured into 400 g of ice water and the precipitated crystals were collected by filtration.The obtained crystals were recrystallized twice with methanol to obtain 9.5 g of white powdery crystals.Melting point: 122-12
6℃.

The results of mass spectrum and nuclear magnetic resonance spectrum are A-
It supported 25 structures.

The use of the magenta dye image stabilizer of the present invention is from 5 to
300 mol% is preferable, more preferably 10-200
It is mole%.

When using the magenta dye image stabilizer of the present invention, the magenta coupler represented by the general formula [I] of the present invention (
Hereinafter, this will be referred to as the magenta coupler of the present invention. ) for 5
-300 mol% is preferable, more preferably 10-20
It is 0 mol%.

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.

Hydrophobic compounds such as the magenta coupler of the present invention and the magenta dye image stabilizer of the present invention can be prepared by silver halide color photographic sensitization using various methods such as a solid dispersion method, a latex dispersion method, and an oil-in-water emulsion dispersion method. Can be added to materials,
This can be appropriately selected depending on the chemical structure of the hydrophobic compound such as magenta coupler. Various methods for dispersing hydrophobic additives such as magenta couplers can be applied to the TFT one-drop emulsion dispersion method in water, and the boiling point is usually about 1
A high boiling point organic solvent of 50°C or higher, boiling point,
and/or dissolved in combination with a hydrophilic solvent, and using a surfactant in a hydrophilic binder such as gelatin to form an aqueous solution, using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After emulsifying and dispersing it, 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 point organic solvents include phenol y6 which does not react with the oxidized form of the developing agent, phthalate esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, trimesic esters, etc. with a boiling point of 150°C. The above-mentioned solvents are used.

When dissolving a hydrophobic compound such as a magenta coupler in a high boiling point solvent alone or in combination with a low boiling point solvent and dispersing it in water using the above-mentioned dispersion means, anionic surfactants, nonionic surfactants, etc. Using a cationic surfactant and a cationic surfactant, Zz Z ′! ″´Iru・
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 represented by the following general formula [8], ie, phenolic compounds and phenyl Ether compounds can also be used in combination.

General formula [81 In the formula, R8 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, R9, R10, R
j2 and R13 are each a hydrogen atom, a halogen atom,
It represents a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an acylamino group, and RH represents an alkyl group, a hydroxy group, an aryl group or an alkoxy group.

R6 and R9 may be ring-closed with each other to form a 5- or 6-membered ring, in which case R11 represents a droxy group or an alkoxy group. Furthermore, R8 and R9 may be ring-closed to form a methylenedooxy ring. Furthermore, R iO and R1
1 may form a closed ring to form a 5-membered hydrocarbon ring,
R8 at this time represents an alkyl group, an aryl group, or a heterocyclic group. However, the case where R8 is a hydrogen atom and R11 is a hydroxy group is excluded.

In the general formula [81], R8 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, an n-octyl group, Straight chain or branched alkyl groups such as tert-octyl, benzyl group, and hexadecyl group can be mentioned. Moreover, this alkyl group includes those having a substituent. Examples of the alkenyl group represented by R8 include allyl, hexenyl, and octenyl groups. Furthermore, examples of the aryl group for R8 include phenyl and naphthyl groups. This aryl group can have an exchange group, and specific examples include a methoxyphenyl group and a chlorphenyl group. Specific examples of the heterocyclic group represented by R8 include a tetrahydropyranyl group and a rimidyl group.

In general formula [8], R9, Rro, R12 and R
+3 is a hydrogen atom, a halogen atom, and a hydro atom, respectively.

It represents an xy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an acylamino group, among which,
Examples of the alkyl group, alkenyl group, and aryl group include the same alkyl groups, alkenyl groups, and aryl groups as described for R8 above. Furthermore, examples of the halogen atom include atoms such as fluorine, chlorine, and bromine.

Further, specific examples of the alkoxy group include a methoxy group, an ethoxy group, a benzyloxy group, and the like. Further, said acylamino group is represented by R' C0NH-, where R' is an alkyl group (e.g. methyl, ethyl, n-propyl, lobutyl, n-octyl,
tert-octyl, benzyl, etc.), alkenyl groups (e.g. allyl, octenyl, oleyl, etc.),
It represents an aryl group (eg, phenyl, methoxyphenyl, naphthyl, etc.) or a heterocyclic group (eg, pyridyl, pyrimidyl, etc.).

Further, in the general formula [B], R11 is an alkyl group,
It represents a hydroxy group, an aryl group, or an alkoxy group, and among these, for an alkyl group or an aryl group, the above R
The same alkyl groups and aryl groups as shown in 8 can be specifically mentioned. As for the alkoxy group of R 11 , the same alkoxy groups as mentioned above for R 9 , Rjo , R 12 and R+3 can be mentioned.

Among the phenol compounds or phenyl ether compounds represented by the general formula [8], particularly preferred are tetraalkoxybiindane compounds, which can be represented by the following general formula [B].

The following is a blank general formula [B'] In the formula, R17 is an alkyl group (e.g. methyl, ethyl, propyl, n-octyl, tert-octyl, benzyl,
hexadecyl, etc.), alkenyl groups (e.g., allyl, octenyl, oleyl, etc.), aryl groups (
For example, each group such as phenyl, naphthyl, or a heterocyclic group (
For example, tetrahydropyranyl, pyrimidyl, etc.)
represents.

R14 and R15 are hydrogen atoms, halogen atoms, (
For example, fluorine, chlorine, bromine, etc.), alkyl groups (
R16 is a hydrogen atom, an alkyl group (e.g. methyl, ethyl, n-butyl, benzyl, etc.), an alkenyl group (e.g. 2-
(propenyl, hexenyl, octenyl, etc.) or an aryl group (eg, phenyl, methoxyphenyl, chlorphenyl, naphthyl, etc.).

The compound represented by the general formula [B] is disclosed in U.S. Patent No. 3,
No. 935,016, No. 3.982.944, No. 4,2
No. 54,216, JP-A No. 55-21004, No. 54-
No. 145530, British Patent Publication No. 2,077.455,
No. 2,062,888, U.S. Patent No. 3,764,337
No. 3,432,300, No. 3,574,627, No. 3.573.050, JP-A-52-152225
No. 53-20327, No. 53-17729, No. 55-6321, British Patent No. 1,347. ．． No. 556,
Publication No. 2,066.975, Special Publication No. 54-12337
No. 48-31625, U.S. Patent No. 3.700.45
It also includes compounds described in No. 5 and the like.

Typical specific examples of the compound represented by the general formula [B] according to the present invention are shown below, but the present invention is not limited thereto.

The following margin is H-4 H-7 H-8 H-9 H H-12 PH-13CH3'CH3 H3 Hs And the following margin is H-4 H-7 H-8 H-9 H H-12 PH-13CH3'CH3 H3 Hs When a phenyl ether compound is used in combination, it is preferably used in an amount of 200 mol % or less, more preferably 140 mol % or less, based on the magenta dye image stabilizer of the present invention.

The phenol compound and phenyl ether compound have the effect of preventing fading of the magenta dye image obtained from the magenta coupler of the present invention, but have almost no effect of preventing discoloration. Therefore, it is not preferable to use an excessive amount of the phenol compound and phenyl ether compound in the magenta dye image stabilizer of the present invention.

Generally speaking, the magenta dye image obtained from the magenta coupler not only shows significant fading when exposed to light, but also undergoes discoloration due to light, and the color tone of the dye image changes from magenta to yellowish. The magenta dye image stabilizer of the present invention can prevent the magenta dye image obtained from the magenta coupler of the present invention from fading and discoloration due to light, an effect that cannot be achieved with the phenolic compounds and phenyl ether compounds. have.

Therefore, the above-mentioned phenolic compound and phenyl ether compound are used as the magenta dye ii! (ii) When used in combination with an image stabilizer, the base of the phenol compound and phenyl ether compound must be selected to such an extent that discoloration due to light is not noticeable.

When appropriate amounts of the phenol compound and phenyl ether compound are used in combination with the magenta dye image stabilizer of the present invention, a mutually beneficial effect may be observed due to the combined use.

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 especially when applied to color photographic paper to be directly submitted to W Awards. The effects of the invention are effectively exhibited.

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 silver halide emulsion layer are usually used. Although it has a structure in which layers are laminated on a support in an appropriate number and order of layers, the number and order of layers may be changed as appropriate depending on the important performance and the 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 of the present invention, halide ions and silver ions may be mixed at the same time, or one may be mixed in the presence of the other. Further, the growth may be carried out by adding halide ions and silver ions sequentially or simultaneously while controlling I)H and DAQ in the mixing pot, taking into consideration the critical growth rate of silver halide crystals. Conversion methods may be used to change the silver halide composition of the grains after growth.

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

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 using metal ions, and by placing them in an appropriate reducing atmosphere, reduction sensitizing nuclei can be added to the inside of the particles and/or on the surface of the particles. .

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. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion 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 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 silver 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 photographic material of the present invention may be used during chemical ripening and/or for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the material, and/or maintaining stable photographic performance. Alternatively, compounds known in the photographic industry as antifoggants or stabilizers can be added at the end of the chemical ripening and/or after the end of the chemical ripening and before coating the silver halide emulsion.

As the binder (or protective colloid) for the silver halide photographic material of the present invention, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, saccharide conductors, etc. Hydrophilic colloids such as cellulose derivatives, synthetic hydrophilic polymeric substances such as monopolymers 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 can be hardened by crosslinking binder (or protective colloid) molecules and using a hardening or film agent alone or in combination to increase the film strength. be done. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the 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 coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing. A dye-forming coupler is used that forms a dye. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the emulsion layer's sensitive spectrum, with a yellow coupler for the blue-light sensitive emulsion layer; The magenta coupler of the present invention is used in the green light-sensitive emulsion layer, and the cyan coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide photographic materials may be produced using different combinations from the above.

Examples of yellow couplers include acylacetamide couplers (eg, benzoylacetanilides and pivaloylacetanilides), and examples of cyan 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. Furthermore, even though these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions are reduced. Either one with good 2-equivalence is fine.

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

The color antifoggant may be used in the emulsion layer itself, or 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 may be provided with auxiliary layers such as a filter layer, an antihalation aperture, and/or an antiirradiation layer, if necessary. 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 of the silver halide photographic light-sensitive material of the present invention is matted with the aim of increasing the loadability to reduce the gloss of the light-sensitive material, and preventing the light-sensitive materials from sticking to each other. 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 where the emulsion of the support is not h It may also be used as a protective colloid.

The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Or other hydrophilic colloid layers have properties such as improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and (promoting image formation,
Various surfactants are used for the purpose of improving photographic properties (such as increasing contrast and sensitization).

The photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention, the second layer thereof is a baryta layer or a flexible reflective support such as paper laminated with an α-olefin polymer, 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 light-sensitive material of the present invention can be produced by subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or to the support surface to achieve adhesion properties, antistatic properties, and dimensional stability. The coating may be applied through one or more subbing layers to improve properties such as hardness, abrasion resistance, hardness, antihalation properties, frictional properties, and/or other properties.

When coating the silver halide photographic material of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The silver halide photographic material of the present invention can be exposed to electromagnetic waves in a spectral region to which the emulsion layer forming the grooves of 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 are generally used in a concentration of about 0.1 g to about 30 g per color developer, preferably about 1 g to about 15 g per 12 color developer.
Use at + concentration.

Examples of aminophenol-based developers include O-aminephenol, p-aminophenol, 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, 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-methanesulfocyamidoethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-hydroxyethylaminoaniline, 4
-amino-3-methyl-N.

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

In addition to the above-mentioned aromatic primary amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites,
It may optionally contain an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener, a thickening agent, and the like. The IlH value of this color developer is usually 7 or more, most commonly about 10.
〜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. The bleaching agent used in the bleaching process is a metal complex salt of an organic acid, and the metal complex oxidizes the metallic silver produced by the bleaching process and converts it into silver halide, and at the same time decolorizes the uncolored part of the color former. It is composed of aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid coordinating metal ions such as iron, cobalt and copper. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[11 Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching agent used as a sodium salt contains a metal complex salt of a tionic 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.

Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions 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, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate , potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, and the like.

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) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath.

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

[Specific Effects of the Invention] According to the silver halide photographic material containing the magenta coupler of the present invention and the magenta dye image stabilizer of the present invention, magenta, which has conventionally had low fastness particularly to light, heat, and humidity, The fastness of the dye image is improved, and specifically, discoloration and fading due to light, and generation of Y-stain in uncolored areas due to light, heat, and humidity are effectively prevented.

[Examples] 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 double-sided laminated with polyethylene, gelatin (15,0 mo/100 cf), the following comparative magenta coupler a (6,0 ma/100 cf) were mixed with 2,5-di-tert-octylhydroquinone (0,0 mo/100 cf).
8mg/100cr) in tricresyl phosphate and emulsified and dispersed, silver chlorobromide emulsion (silver bromide 8mg/100cr) was dissolved in tricresyl phosphate.
0 mol%, coated silver Q 3 , 8 m iJ/100
CT12) was mixed, applied, and dried to obtain Sample 1.

The above sample 1 was treated with the above P as a magenta dye image stabilizer.
Sample 2 was obtained in which H-13 and magenta coupler were added in an equimolar amount.

Samples 3.7.11 were obtained in the same manner except that the magenta coupler in Sample 1 was replaced with magenta couplers 1.44 and 130 of the present invention, respectively.

Samples 4 and 8.12 were obtained by adding the magenta dye image stabilizer PH-13 in the same molar amount as the coupler to Samples 3.7.11 and further replacing PH=13 with the magenta dye image stabilizer PH-13 of the present invention. -6 was added to the image stabilizer in equimolar amounts as the coupler to obtain 5 and 9.13 degrees of smoke, respectively. Also, the sample 3.7
．． In Step 11, PH-13 and A-6 were combined in a ratio of 1:2 and added in equimolar amounts to the coupler to prepare samples 6.10°14.

The following margin comparison magenta coupler a After exposing the sample obtained above through an optical model according to the usual method,
The treatment was carried out in the following steps.

[Processing process] Processing temperature Processing time Color development
Bleach and fix at 33°C for 3 minutes and 30 seconds 33
℃ Wash with water for 1 minute and 30 seconds 33
℃ 3 minutes drying 50-80℃
The components of each 2-minute treatment solution are as follows.

[Color developer] Benzyl alcohol 12-diethylene glycol 10d potassium carbonate
25g sodium bromide
o, eg anhydrous sodium sulfite
2.0g Hydroxylamine sulfur salt 2
, 5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfur vi salt 4.5g water was added to make one volume, and the pH was adjusted to 10.2 with NaOH.

[Bleach-fix solution] Ammonium thiosulfate 120 g Sodium metabisulfite 15 g Anhydrous sodium sulfite 3
Adjusted to 6.7-6.8.

The concentrations of Samples 1 to 14 treated above were measured using a densitometer (model IKD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions.

Each of the above-mentioned treated samples was irradiated with a xenon fade meter for 10 days to examine the light resistance of the dye image and the Y-stin of the uncolored area, while each sample was exposed to a high temperature and high humidity atmosphere of 60°C and 80% RH. The dye image was left to stand for 14 days, and the moisture resistance of the dye image and the Y-stain of the uncolored area were examined. The results obtained are shown in Table 1.

However, the evaluation of each item of light fastness and moisture 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.

[Y-Stin (Y-8)] Value obtained by subtracting the Y-Stin concentration before the sub-light and humidity resistance test from the Y-stin concentration after the sub-light and humidity resistance test.

[Degree of discoloration] After both light tests at initial concentrations of 1 and 0 (yellow degree)/
(, 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.

Table 1 Below Margin As is clear from Table 1, Sample 3.7.11 made using the magenta coupler of the present invention has a conventional 4 equivalent
It can be seen that Y-stin is extremely less likely to occur in the side light and moisture resistance tests compared to sample 1, which was prepared using a 3-anilino-1,2-pyrazolo-5-one type magenta coupler. From the residual rate and degree of discoloration in the light test, it can be seen that the color easily changes and fades when exposed to light. Sample 4, 8.1
Sample 2 is a sample prepared by using the magenta coupler of the present invention in combination with the conventional (known magenta dye image stabilizer PH-13), which certainly significantly reduces the fading of the dye image due to light. Improved, but cannot improve discoloration.

On the other hand, in sample 5.9.13 prepared using the magenta coupler of the present invention and the magenta dye image stabilizer of the present invention, both discoloration and fading of the dye image were significantly observed in the resistance test against light, heat, and humidity. It can be seen that the coloring has been improved, and Y-staining in uncolored areas hardly occurs.

In addition, in addition to the coupler and magenta dye image stabilizer according to the present invention, Samples 6, 10 and 14, in which a conventional magenta dye image stabilizer was added, showed further improvement in dye persistence in the side light test. I know that there is.

Example 2 Samples 15 to 3o were prepared by applying magenta couplers and magenta dye image stabilizers in combinations shown in Table 2 in exactly the same manner as in Example 1. Samples 15-3o were processed as described in Example 1. Furthermore, these samples were subjected to a light resistance test and a moisture resistance test in the same manner as in Example 1.
The results shown in the table were obtained.

Note that the comparative magenta coupler b in the table has the following structure.

The following margin comparison magenta coupler b Table 2 As is clear from Table 2, the conventionally used
When the magenta dye image stabilizer of the present invention is used in combination with a 3-anilino-1,2-pyrazolo-5-one coupler of the same type as 4 (Sample 15.16), and when the magenta dye image stabilizer of the present invention is used in combination with the magenta coupler of the present invention, When using a magenta dye image stabilizer (Samples-19, 20, 21, 22), there was no discoloration or fading in the side light test, Y-stin in the uncolored area, and Y-stin in the moisture resistance test. It can be seen that it is not possible to improve all of the above, and that all of the above-mentioned improvements can only be achieved by using the magenta coupler of the present invention in combination with the magenta dye image stabilizer of the present invention.

Example 3 On a set of supports laminated on both sides with polyethylene, the following layers were sequentially applied from the support side to prepare a multicolor silver halide photographic light-sensitive material, and sample P131 was obtained.

1st layer: Blue-sensitive silver halide emulsion layer α-pivaloyl-α-(2,4
-dioxo-1-benzylimidazolidin-3-yl)
6.8 m
g/100C12, blue-sensitive silver chlorobromide emulsion (silver bromide 85
3.2mg/100cf of silver (containing mol%)
, dibutyl phthalate 3.5mg/100CI”
, and gelatin at 13.510CI/1100C'
The coating was applied so that it would have a coating opening.

2nd layer: middle layer 0.5 mg of 2.5-di-t-octylhydroquinone
/ 100cf, dibutyl phthalate 0.5m (]
/ 100Ci+' and gelatin at 9. oma/10
It was coated so that it became 0Cf.

Third layer: green-sensitive silver halide emulsion layer containing the magenta coupler 18 at 3.51110/100
Cf, green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver: 2.5 mg/100 Ci', dibutyl phthalate: 3.0111!1/10Qcf, and gelatin: 12.0 mg/100 Ci' It was coated to give 100C112.

4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-3eC-butyl-5-t-butylphenyl)benzotriazole 7.0mg/100c12, dibutyl phthalate 6.0mg/100c112. 2.5-G°C-octylhydroquinone was coated at 0.5 mg/100 CTI2 and gelatin at 12.0 ml/100 Ct'.

5th layer: red-sensitive silver halide emulsion layer 2-[α-(2,4-G t-
4.2 m (1/100C1
2. Red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted into silver. 3. OmQ/100C1'' 1 tricresyl phosphate was coated at 3.5 mg/100Cf and gelatin at 11.5 mg/100Ci'.

6th layer: Protective layer Gelatin was coated at 8.0 mg/100 Ci'.

In Sample 31, the magenta dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3 to prepare Samples 32 to 40, which were exposed in the same manner as in Example 1. ,
After processing, double light test (15 xenon fade meter)
irradiated for 1 day). The results are also shown in Table 3.

From the results of Table 3 below, the magenta dye image stabilizer of the present invention:
This is effective in stabilizing the dye compatibility of the magenta coupler of the present invention, and the effect becomes greater as the number of addition ports increases. In addition, Samples 32 to 40 showed extremely small discoloration of the dye images in both light tests compared to Sample 31. Furthermore, in the sample of the present invention, the discoloration and fading of the magenta dye are extremely small, and after the light fastness test, the overall color balance with the yellow and cyan couplers as a silver halide color photographic light-sensitive material is good, and the color reproducibility is extremely good. It remained in good condition.

Claims (1)

[Scope of Claims] A silver halide photographic material containing at least one magenta coupler represented by the following general formula [I] and at least one compound represented by the following general formula [A] . 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 [A
] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1, R^2, and R^4 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group. , R^5 is an alkyl group,
Represents a cycloalkyl group, alkenyl group or aryl group. R^3 represents a substituent, and l represents 0, 1, 2, 3 or 4. J is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas , tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^6 and R^7 each represent a hydrogen atom, an alkyl group, or an aryl group.), m is 0 Or represents 1. However, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ are in the ortho or meta position relative to each other. Also, R^1 and R
^2 may be combined with each other to form a 5- or 6-membered ring. When l is 2 or more, R^3 may be the same or different; when l is 1 to 4, one R^3 is R^1 or R
It may be bonded to ^2 to form a ring together with the nitrogen atom bonded to R^1 and R^2. When l is 2 or more, two R^3
are combined with R^1 and R^2 respectively, R^1, R^
may form a ring together with the nitrogen atom bonded to 2. ]