JPS62253169A - Silver halide photographic sensitive material improved in stability of dye image - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material superior in color reproducibility, improved in lightfastness of a magenta dye image, and prevented from yellow stains on color nondeveloped areas by incorporating a specified magenta coupler and at least 2 kinds of compounds in the photo graphic sensitive material. CONSTITUTION:The silver halide color photographic sensitive material contains at least one of the magenta couplers represented by formula I, and at least one of each of the compounds represented by formulae II and III, respectively. In these formulae, Z is a nonmetallic atomic group necessary to form an N- containing heterocyclic group; X is H or a substituent to be released by the coupling reaction with the oxidation product of a color developing agent; R is H or a substituent; R<1> is an aliphatic, cycloalkyl, aryl, or heterocyclic group; Y is a nonmetallic atomic group necessary to form a morpholine or thiomorpholine ring together with N; each of R<2>, R, and R<5> is H, alkyl, cycloalkyl, or the like; R<6> is alkyl, cycloalkyl, or the like; R<4> is a substituent; m is 0-4; and J is formula IV or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material. This invention relates to silver chemical color photographic materials.

[US technology]

Conventionally, by imagewise exposing a silver halide color photographic light-sensitive material and performing color development, an oxidized product of an aromatic primary amine color developing agent and a color forming agent undergo a coupling reaction, resulting in, for example, India 7 E 7 It is well known that dyes such as ole, indoaniline, indamine, azomethine, phenoxazine, 7-enazine, and similar dyes are produced and dye images are formed. In such photographic systems, a subtractive color reproduction method is usually adopted, and color forming agents having additional color relationships are added to blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver halide emulsion layers, that is,
A silver halide color photographic material containing couplers that develop yellow, magenta and cyan colors is used.

Examples of couplers used to form the above-mentioned yellow dye image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, virazolobenzimigsol,
Pyrazolotriazole or indacylon couplers are known, and as couplers for use with cyan dyes of the se type, for example, phenol or 7-tole couplers are generally used.

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

However, in the case of magenta couplers, fading due to light in uncolored areas, Y-stain due to moist heat, and light in dye image areas is extremely severe compared to yellow couplers and cyan couplers, which poses a problem.

Couplers commonly used to form magenta dyes are 5-pyrazolones. The dye formed from this magenta coupler of 5-pyrazolones has a wavelength of 550 nm.
In addition to the main absorption near 430 nm, a major problem is that it has a sub-absorption near 430 nm, and various studies have been conducted to solve this problem.

Magenta couplers having an anilino group at the 3-position of 5-pyrazolones have small side absorption and are particularly useful for obtaining color images for printing. Regarding these technologies, for example, U.S. Patent No. 2,343°703, British Patent No. 1,
No. 059,994, etc.

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

As another means for reducing the side absorption near 430 nm of the magenta coupler, British Patent No. 1.047,6
virazolobenzimidazoles described in US Pat. No. 3,770,447, as well as ingzolones described in US Pat. No. 3,725,067, British Patent No. 1, . 25
IH- described in No. 2,418 and No. 1,334,515
Pyrazolo [5,1-cl 1,2,4-) lyazole type coupler, JP-A-59-171956, Research.
IH described in Diskrono A--No. 24531
-Pyrazolo[1°5-bl-1,2,4-triazole coupler, Research Disclosure No. 24
IH-virazo o[1,5cl-1,2,
3) Riazole coupler, JP-A-59-162548
I H-imidazo[1,2-bl pyrazole coupler described in JP-A-60-43659, Research Disclosure No. 24531, Research Disclosure No. 24531.

I H-pyrazolo[1,5-bl pyrazole type coupler described in JP-A-60-33552, Research Disclosure y-No. Magenta couplers such as the following have been proposed. Among these,
IH-pyrazoo[5,1-cl 1,2-4-triazole type coupler, IH-pyrazolo[1,5-bl-1
.

2.4-) Riazole coupler, IH-pyrazolo[1
,5-cl 1.2.3-triazole type coupler,
IH-imidazo N, 2-bl pyrazole type coupler, I
The dye formed from the H-pyrazolo[1,5-bl pyrazole coupler and the IH-pyrazolo[1,5-dl tetrazole coupler] has a subabsorption near 430 nm that is 5 having an anilino group at the 3-position. - It is significantly smaller than pigments formed from pyrazolones and is favorable for color reproduction;
Furthermore, the occurrence of Y-stain in uncolored areas due to light, heat, and humidity is extremely small, which is a desirable advantage.

However, the light fastness of the azomethine dyes formed from these couplers is extremely low, and furthermore, the dye 1i is easily discolored by light, seriously impairing the performance of color photographic materials, especially printed color photographic materials. However, it has not been put to practical use in printed color photographic materials.

Furthermore, in JP-A-59-125732, by using a 1H-pyrazolo[5,1-cl-1,2,4-triazole type magenta coupler together with a phenol compound or a phenyl ether compound, Techniques have been proposed to improve the light fastness of magenta dye images obtained from IH-virazo o[5,1cl 1,2,4 ) lyazole type magenta couplers. 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.

[Purpose 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 silver halide photographic sensitizer which is suitable for color reproducibility and has significantly improved light fastness of magenta dye images. The purpose is to provide 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 the V
Another object of the present invention is 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 coupler represented by the following general formula [I] and a magenta coupler represented by the following general formula [XI].
This is achieved by a silver halide photographic material containing at least one compound represented by formula I] and at least one of compounds represented by the following general formulas CXIIIa) and [XIb).

For general formulas] In the formula, 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.

General formula [■] In the formula, R1 represents an aliphatic group, a cycloalkyl group, an aryl group, or a heterocyclic group, and Y represents a group of nonmetallic atoms necessary to form a morpholine ring or a thiomorpholine ring together with the nitrogen atom. represent.

General formula (XI[[) ■ In the formula, l(2, R3 and R5 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, and R6 represents an alkyl group, a cycloalkyl group, group, alkenyl group, or aryl group. R4 represents a substituent, and 鴩 represents 0, ■, 2.3, or 4.

R7 and R8 each represent a hydrogen atom, an alkyl group or an aryl group), and n represents O or 1.

Further, R2 and P may be bonded to each other to form a 5-shell or 6-shell ring. When m is 2 or more, R4 may be the same or different. When l is 1 to 4, one R4 may be bonded to R2 or R3 to form a ring together with the nitrogen atom bonded to R2 and R3. When (2) is 2 or more, the two 84s may be bonded to R2 and R3, respectively, to form a ring together with the nitrogen atoms bonded to R2 and R3.

Next, the present invention will be specifically explained.

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

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

Moreover, R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom, 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, endowed hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclicoxy group, siloxy group, acyloxy group , carbamoyloxy group, amide 7 group,
Acylamide 7 groups, sulfonamide groups, imide groups, ureido groups, sulfonamide groups, 7 alkoxycarbonylamino groups, aryloxycarbonylamino groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkylthio groups, arylthio groups, heterocyclic thio groups can be mentioned.

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, sia 7, 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 Substituents via the nitrogen atom such as alkylthio, 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, trifluoromethyl group, 1
-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4'-iα-(4”(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino)
Phenylpropyl group, 3-[4'-(Q-(2", 4"
-di-t-amylphenoxy)butanamido]phenyl)-propyl group, 4-(α-(0-chlorophenoxy)
Examples include tetradecaneamidophenoxy]propyl group, allyl group, cyclopentyl group, and cyclohexyl group.

The aryl group represented by R is preferably a phenyl group, which may have a substituent (for example, an alkyl group, an alkoxy group, an acylamide group, etc.).Specifically, a phenyl group, a 4-t -butylphenyl group, 2,4-di-1-
Amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'-[α-(4”-
Examples include L-butyl7eth7xy)tetradecanamidophenyl group.

The hetero-concentrated group represented by R is preferably one having 5 to 7 shells, and may be substituted or condensed.

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

Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, a-2,4-di-
Examples include furkylcarbonyl groups such as t-amyl72/xybutanoyl group, arylcarbonyl groups such as benzoyl group, 3-pentadecyloxybenzoyl group, and p-chlorobenzoyl group.

The sulfonyl group represented by R includes a methylsulfonyl group, an alkylsulfonyl group such as V-decylsulfonyl 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, 3-7e/xybutylsulfinyl group, arylsulfinyl group such as phenylsulfinyl group, and m-pentadecylphenylsulfinyl group. Examples include groups.

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an arylphosphonyl 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 LP,
For example, N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoylt N-(3-(2,4-di-t -amyl7eth7xy)propyl)carbamoyl group, and the like.

The sulfamoyl group represented by R is substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.,
For example, N-propylsulfamoyl group, N,N-diethylsulfamoyl M, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-1-"decylsulfamoyl group, N-phenyl Examples include sulfamoyl group.

Examples of spiro compound residues represented by R include spiro[
Examples include 3,31-hebutan-1-yl and the like.

Examples of the bridged carbonized compound residue represented by R1l' include bicyclo[2,2,1]heptan-1-yl, tricyclo[3,3,1,1'']decane-1-yl, and 7,7-nomethyl. Examples include tylubicyclo[2,2,1]hebutan-1-yl.

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

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,
Examples include phenoxy group, pt-butylphenoxy group, and transpentadecyl 7-enoxy group.

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

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

The 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 a-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 N-ethylcarbamoyloxy group, N,N-diethylcarbamoyloxy group, N7! Examples include nylcarbamoyloxy group.

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 7 group, an anilino group, an I-chloroani 7 group,
Examples include 7 groups of 3-pentadecyloxyluponylanily, and 7 groups of 2-chloro-5-hexadecaneamide anily.

Examples of the acylamide 7 groups represented by R include alkylcarbonylamide 7 groups, arylcarbonylamide 7 groups (preferably phenylcarbonylamide 7 groups), etc., which may further have a substituent, and specifically, acetamide. group, α-ethylpropanamide group, N-phenylacetamide group,
Dodecanamide group, 2,4-di-t-7 milphenoxyacetamide M, a-3-t-butyl 4-hydroxy 7
Examples include eth/xybutanamide group.

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

Specifically, methylsulfonylamide 7 groups, pentadecylsulfonylamide group, ρ-toluenesulfonamide group, 2-methoxy-
Examples include 5-t-7 milbenzenesulfonamide group.

The imide group represented by R may be open-chain or cyclic, and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a 7-talimide group, Examples include glutarimide group.

The ureido group represented by R is an alkyl group, an aryl group (
Preferred examples include N-ethylureido group, N-methyl-N-decylureido group, N-phenylureido group, and N-p-)lylureido group.

The sul 7 amoylami 7 group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), for example, N. Examples include 7 N-dibutylsulfo-7 amoylamides, 7 N-methylsulfo-7-amoylamides, and 7 N-phenylsulfo-T-moylamide groups.

The alkoxycarbonylamide 7 group represented by R is,
It may further have a substituent, for example, 7 methoxycarbonylamide groups, 7 methoxyethoxycarbonylamide groups,
Examples include 7 octadecyloxycarbonylamide groups.

The aryl-o-λdicarbonylamide 7 groups represented by R may have a substituent, such as the phenoxycarbonylamide 7 groups and the 4-methylphenoxycarbonylamide 7 groups.

The alfkidicarbonyl 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 pennoloxy group. Examples include carbonyl group.

The aryloxycarbonyl group represented by RT may further have a substituent, for example, a 71-dicarbonyl group,
Examples include p-chlorophenoxycarbonyl group, m-pentadecyloxy77ycarbonyl group, and the like.

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-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-7cetamyphenylthio 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 a 2-bilinorthio group, a 2-benzothiazolylthio group, and a 2,4-schifnitxy-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 Examples include groups substituted via.

Examples of groups substituted via a carbon atom include carbo (R1'
is the same as the above R, Z' is the same as the above Z, and R
2' and R5' represent a hydrogen 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, alphkydicarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkoxyoxalyloxy groups. Examples include groups.

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

The aryloxy group is preferably a 7ethoxy group, and the aryl group may further have a substituent.

Specifically, 7ヱ/oxy group, 3-methylphenoxy group, 3
-dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4-[α-(3'-pentadecylphenoxy)butanamide]7e7oxy group, hexydecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methane Sulfonyl 717oxy group, 1-su7tyloxy group, 1
)-methoxyphenoxy group and the like.

The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples include 1-7enyltet2zolyloxy group, 2-benzothiazolyloxy group, and the like.

The acyloxy group includes, for example, an acetoxy group, a fulkylcarbonyloxy 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 alphkyloxy carbonyloxy 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.

As the alkylthio group, butylthio group, 2-thia/
Examples include ethylthio group, 7enethylthio group, and benzylthio group.

The arylthio group includes a phenylthio group, a 4-methanesulfonamidophenylthio group, a 4-dodecyl7enethylthio group, a 4-7fluoropentanamide7enethylthio group, a 4-carboxyphenylthio group, and a 2-ethoxy-5-ethylthio group. Examples include butylphenylthio 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 dodecyloxythio-carbonylthio group.

Examples include those represented by the general formula -N. R4' and R5' are hydrogen atoms, alkyl groups,
Represents an aryl group, heterocyclic group, sulfamoyl group, carbamoyl group, acyl group, sulfonyl group, aryloxycarbonyl group, alkoxycarbonyl group,
5' may be bonded to form a heterocycle. However, R1'
and R5' are never both hydrogen atoms.

-27= The alkyl group may be linear or branched, and preferably has 1 to Z2 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,
Carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamide 7 group, aryloxycarbonylamide 7 group
group, hydroxyl group, carboxyl group, sia/group, and halogen atom.

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

The aryl group represented by R4' or R5' preferably has 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group,
The aryl group may have a substituent, and examples of the substituent include those listed above as a substituent for the alkyl group represented by R1' or Rs', 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 R1' or R5' is 5 to 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-12-pyridyl group, and the like.

The sulfamoyl group represented by R4' or R5' includes N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-arylsulfamoyl group,
, N-noarylsulfamoyl 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 Np-)lylsulfamoyl group.

The carbamoyl group represented by R1' or R5' is
Examples include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-7arylcarbamoyl group, N,N-diarylcarbamoyl group, and these alkyl groups and aryl groups are the same as those mentioned above for the alkyl group and aryl group. It may have a substituent. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-cyanophenylcarbamoyl group, N-
-p-)lylcarbamoyl group.

Examples of the acyl group represented by R4' or R5' 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 hexafluorobutamyl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-7lylcarbonyl group, etc. It will be done.

Examples of the sulfonyl group represented by R4' or Rs' 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 R1' or R5' 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 R5' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a pennoloxycarbonyl group, etc. can be mentioned.

The heterocycle formed by combining R1' and RS' is preferably one with 5 to 6 shells, 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 an N-7 talimide group, an N-conolyl imide group, a 4-N-urazolyl group, a 1-N-hydantoinyl group, and a 3-N-2,4-dioxoxazolidinyl group. , 2-N-1,1-dioxo-3-(2H)-oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, 1-piperidinyl group ,1
-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group, 1-isoindolinyl group,
2-isoindolyl group, 2-isoindolinyl group, 1-
Benzotriazolyl group, 1-pencyimigzolyl group, 1
-(1,2,4-)riazolyl) group, 1-(1,2,3
-) riazolyl) group, 1. -(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1.2,3.4-tetrahydroxy7lyl group, 2-oxo-1-pyrrolidinyl group, 2-IH-pyridone group, 7 Examples include talanone group, 2-oxo-1-piperidinyl group, etc., and these heterocyclic groups include alkyl groups, aryl groups, alkyloxy groups, aryloxy groups, acyl groups, sulfonyl groups, 7 alkylami groups, 7 arylami groups, Acylamide 7 groups, sulfonamide 7 groups, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alfkidicarbonyl group, aryloxycarbonyl group, imido group, nitro group, sia group 7, carboxyl group, halogen atom, etc. May be replaced.

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.

Furthermore, in the general formula [I] and the general formulas [■] to [■] described later, substituents on the heterocycle (for example, R9R1 to R8) are partial, and R'', X and z'' are the general formula It has the same meaning as R, X, and Z in (1). ), it forms a so-called screw-type coupler, which is, of course, included in the present invention. or,
The ring formed by z, z', z'' and 71 (described below) may further include other rings (for example, a 5- to 7-shell cycloalkene).
may be condensed. For example, R5 and R6 in general formula [V] and R7 and R8 in general formula [VI] may be bonded to each other to form a ring (for example, a 5- to 7-shell cycloalkene, benzene).

More specifically, what is represented by the general formula [I] is represented by, for example, the following general formulas [11] to [■].

General formula [■] General formula [1 [[) % formula % General formula [■] N-NH General formula [■] General formula [■] N-N11 General formula [■] NN General formula [11] ~ [ ■] in R, -R, and X
has the same meaning as R and X above.

Also, among the general formula [I], the following general formula [
■].

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

Among the magenta couplers represented by the general formulas (II) to [XII], magenta couplers represented by the general formula (In) are particularly preferred.

Regarding the substituents on the heterocycle in general formulas [1] to [■], R in general formula [1] and R5 in general formulas [11) to [■] satisfy the following condition 1. It is preferable that the following conditions 1 and 2 are satisfied, 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 R1 on the heterocycle are those represented by the following general formula CIX.

General formula [■] R,, -C- Rr+ In the formula, R9,R,. and RII are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group,
heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group,
Shea 7 group, spiro compound residue, a-a hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, ami 7 group, acylami 7 group, sulfonamide group , imide group, ureido group, 7-amoylamino group, alkoxycarbonylamino group, 7-alkoxycarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group, R91R10 and at least two of R11 are not hydrogen atoms11.

Moreover, two of the above R91RIO and R1+, for example, R5
and R10 may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R1 may be further bonded to the ring to constitute a bridged hydrocarbon compound residue. Good too.

The group represented by R9-R11 may have a substituent, and specific examples of the group represented by R8 to R1+ and the substituents that the group may have include the above-mentioned general formula [l] Specific examples of the group represented by R and substituents are listed.

Also, for example, a ring formed by combining R9 and Rlo and R8
Specific examples of the bridged hydrocarbon compound residue formed by ~RI+ and its optional substituents include cyfuroalkyl, cycloalkenyl, and heterocyclic group represented by R in the general formula [1) above] Specific examples of hydrogen compound residues and their substituents are listed.

Among the general formula (IX), (i) R, ~
When two of R11 are alkyl groups, (ii) R, ~
When one of R1, for example R11, is a hydrogen atom, and the other two R9 and RIO combine to form a cycloalkyl together with the root carbon atom, the following is true.

Furthermore, it is preferable among (i) that two of R8 to R11 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, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substitution represented by R in the general formula [I]. Specific examples of the group are listed below.

In addition, substituents that the ring formed by Z in general formula [I] and Z in general formula [■] may have, and R2 in general formulas (IT) to [VI] R is preferably represented by the following general formula [X].

General formula [X] -R'-8Q2-R2 In the formula, R1 represents alkylene and R2 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 the straight chain portion has 1 or more 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 substituents include phenyl.

Preferred specific examples of alkylene represented by R' -CH2
CII2CH2-, -C) ICI(2C112-, -C
IICU2CH2-, -C112C112CH-CH3
C2H5C7H15 -C)12CH2CH-, -CH2CH2C112CH
2-, -CH2CH2CH2CI+-.

CzHs C6H13
The alkyl group represented by R2 has a straight chain with 9 branches ().

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

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

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

Specific examples of the aryl represented by R2 include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as those exemplified as the substituent for R' 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 [I], particularly preferred are those represented by the following general formula CXI.

In the formula, R and X have the same meaning as R and X in general formula [I], and R1 and R2 are R1 and R2 in general formula [X].
is synonymous with

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

-43= 12H25 C2H5 C? 81S C3H? 2H5 7H15 xHs shin3
L;all, f(t)C6H,.

QC) 12CONHCH2CH20Cth0CH2CH
2SO2CH3 2H5 H3 SaH3 C2H5 CH3 CH3 ShiJI7(L) CI.

CH3 ■ CH.

■ し■3 N -N -N N -N -N N -N -NH 2H5 ■ -N-NH rH+ Also, the above coupler is
Rootscyati (Journal of the
Chemical 5ociety) * Perkin 1 (1977), 2047
~2052, U.S. Patent No. 3,725,067, JP-A-5
No. 9-99437, No. 58-42045, No. 59-1
No. 62548, No. 59-171956, No. 60-33
No. 552, No. 60-43659, No. 60-17298
It can be synthesized by referring to No. 2 and No. 60-190779.

The couplers of the invention are typically 1x per mole of silver dendide.
lO-comole 1 mol, preferably lXl0-2 mol-
It can be used in a range of 8×10 −1 mol.

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

One of the magenta dye image stabilizers that is always used is a compound having a morpholine ring or a thiomorpholine ring represented by the above general formula [XII]. Furthermore, another magenta dye image stabilizer used in conjunction with the morpholine or thiomorpholine compound represented by the general formula [XII] is a 1% compound of phenylenediamine represented by the general formula (XI [[)]. at least one selected from
It is one.

Japanese Patent Application No. 60-31297 and No. 60-85194 disclose 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 morpholine or thiomorpholine compounds represented by are effective.

However, in the above specification, regarding stabilization of magenta dye images obtained from the magenta coupler of the present invention, the compound represented by the general formula [XII] of the present invention and the general formula [XI [[] There is no description of the effect when used in combination with at least one selected from the compounds.

As a result of intensive studies, the present inventors have determined that the general formula [1] of the present invention
Together with the magenta coupler represented by the general formula (X
ll) and the general formula [XI[[
They have found that when used in combination with at least one compound selected from the compounds represented by the following formulas, 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 according to the present invention [
(2)] and the compound represented by the general formula [XI[[] is referred to as a magenta dye image stabilizer according to the present invention or simply a dye image stabilizer.

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

General formula [■] In the formula, R1 represents an aliphatic group, a cycloalkyl group, an aryl group, or a heterocyclic group, and Y is a nonmetallic atomic group necessary to form a morpholine ring or a thiomorpholine ring together with the nitrogen atom. represents.

-ff In the formula (Xll), R' represents an aliphatic group, a cycloalkyl group, an aryl group, or a heterocyclic group, but l(
Examples of the aliphatic group represented by + include alkyl groups, alkenyl groups, and alkynyl groups, including those having substituents. Examples of the alkyl group include methyl group, ethyl group, butyl group, octyl group, dotesyl group,
Examples include a tetradecyl group and a hexadecyl group. Examples of the alkenyl group include an ethynyl group and a furohenyl group, and examples of the alkenyl group include an ethynyl group and a propynyl group.

The cycloalkyl group represented by R' is, for example, 5-
7 Specific examples of the true cycloalkyl group include a cyclopentyl group and a cyclohexyl group, including those having substituents.

Examples of the aryl group represented by R1 include a phenyl group and a naphthyl group, including those having a substituent.

Examples of the heterocyclic group represented by R1 include 2-bilinol group, 4-piperidyl group, 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and these also include those having substituents. .

Substituents for the aliphatic group, cyclofurkyl group, 7-aryl group, and heterocyclic group represented by R' include, for example, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbamoyl group, an acylamine group, and a sulfamoyl group. , sulfonamide group, carbonyloxy group, alkylsulfonyl group, arylsulfonyl group, hydroxy group, heterocyclic group,
Examples include an alkylthio group and an arylthio group, and these substituents may further have a substituent.

-1l'la- In the general formula (XI[), Y together with the nitrogen atom,
It represents a group of nonmetallic atoms necessary to form a morpholine ring or a thiomorpholine ring, and the morpholine ring or thiomorpholine ring may have a substituent, such as an alkyl group, Examples include cycloalkyl groups, aryl groups, and heterocyclic groups.

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

2H5 2H5 Some of the above magenta dye image stabilizers according to the present invention are commercially available and can be easily obtained. It also includes the compounds described in Japanese Patent Application Nos. 60-31297 and 60-85194, and can be synthesized according to the synthetic methods described therein.

Moreover, it can be synthesized according to the synthesis method shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound ^-7) 14 g of 4-(3-7minoprovir)morpholine and 2,4
30 g of -not-t-amylphenoxyacetic acid chloride was dissolved in 150 ml of ethyl acetate, and 10 ml of pyridine was added thereto, followed by boiling and refluxing for 5 hours. Precipitated crystals were removed by filtration, and the filtrate was distilled off under reduced pressure. The residue was recrystallized from methanol to obtain 21 g of white crystals. The target 4-(2-
It was confirmed to be (2,4-diE-7milphenoxyacetamido)ethyl)morpholine.

Synthesis Example 2 (Synthesis of Exemplified Compound ^-20) 11 g of thiomorpholine and 30 g of hexadecyl bromide were mixed with 15 g of ethanol.
After dissolving at 0 mZ, 7 g of potassium hydroxide was added. After the solution was boiled and refluxed for 5 hours, precipitated crystals were removed by filtration, and the filtrate was distilled off under reduced pressure. The residue was recrystallized from ethanol to obtain 18 g of white flaky crystals.

Both the am gas spectrum and the mass spectrum supported the structure of 4-hexadecylthiomorpholine.

In the present invention, in addition to the morpholine or thiomorpholine compound represented by the general formula [XII], the magenta coupler of the present invention further includes at least the following general formula [XI].
At least one compound represented by [II] is used in combination. The compound represented by the following general formula [XII[) is a phenyleneamine derivative.

General formula CXIII) Examples of the alkyl groups represented by R2, R3 and R5 in the general formula (XI [[) include methyl group, 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 heteroelements include bilinol group, furyl group, and pyrimidinyl group. R
These groups represented by 2, R3 and R5''C each include those having substituents. For example, substituents for alkyl groups include halogen atoms, aryl groups, acyl groups, alkylcarbamoyl groups, arylcarbamoyl groups, and furkyls. rufamoyl group, arylsulfamoyl group, sia/
groups, alkoxy groups, aryloxy groups, acyloxy groups, alkylsulfonamide groups, arylsulfonamide groups, ami7 groups, alkoxycarbonyl groups, aryloxycarbonyl groups, hydroxyl groups, etc., cycloalkyl groups, alkenyl groups, aryl groups. Examples of substituents for the heterocyclic group include alkyl groups in addition to the examples of substituents for the alkyl group described in 2.

R2 and R3 are preferably alkyl groups, and R5 is preferably a hydrogen atom or an alkyl group.

There are no particular restrictions on the substituent represented by R4, but specific examples include halogen atoms (for example, chlorine atoms, etc.), alkyl groups (
For example, methyl group, ethyl group, etc.), cycloalkyl group (for example, cyclohexyl group, etc.), aryl group (for example, phenyl group, etc.), alkenyl group (for example, allyl group, etc.), heterocyclic group (for example, pyridyl group, etc.), acyl group ( For example, acetyl group, benzoyl group, etc.), sulfonyl group (for example, alkylsulfonyl group such as methylsulfonyl group, 7-arylsulfonyl group such as phenylsulfonyl group, etc.), carbamoyl group (for example, furkylcarbamoyl group such as N-butylcarbamoyl group, N 7-arylcarbamoyl group such as -7xnylcarbamoyl group), sulfamoyl group (e.g. furkylsulfamoyl group such as N-propylsulfamoyl group,
N-phenylsulfamoyl group, etc.), sia/group, alkoxy group (e.g., butoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.),
Acyloxy group (e.g. acetyloxy group, benzoyloxy group, etc.), amide 7 group (e.g. ethylamide 7 group, anilino group, etc.), acylami 7 group (e.g. acetamido group,
phenylcarbonylamide 7 groups, etc.), sulfonamide groups (
For example, an alkylsulfonamide group such as a methylsulfonamide group, an arylsulfonamide group such as a benzenesulfonamide group, etc.), an alkoxycarbonylamide 7 group (for example, an ethoxycarbonyl 7mino group h4), an aryloxycarbonylamide 7 group (such as a phenoxycarbonyl amino group, etc.), alkoxycarbonyl group (e.g., butoxycarbonyl group, etc.), aryloxycarbonyl group (e.g., 7E/xycarbonyl group, etc.), alkylthio group (e.g., dodecylthio group, etc.), arylthio group (e.g., phenylthio group, etc.), etc. Can be mentioned. These groups may further have similar substituents.

Examples of the alkyl group represented by R6 include ethyl group, propyl group, butyl group, undecyl group, dodecyl group, etc., examples of the cycloalkyl group include cyclohexyl group, and examples of the alkenyl group include allyl group, etc. Examples of the aryl group include a phenyl group. These groups represented by R6 include those each having a substituent. For example, substituents for the alkyl group include a halogen atom, an aryl group, an acyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulf77 moyl group, Examples include arylsulfamoyl group, cyano group, alkoxy group, aryloxy group, acyloxy group, alkylsulfonamide group, arylsulfonamide group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, hydroxyl group, etc. Examples of substituents for the kyl group, alkenyl group, and 71-nol group include alkyl groups in addition to the above-mentioned examples of substituents for the alkyl group. R6 is preferably an alkyl group or an aryl group.

OHS R7 R’　　　　H 6HR8H OOR’ Q.C., H.

〇Also, R2 and R3 may be combined with each other to form a 5- or 6-shell ring (for example, when the number of rings is 1 to 4, one R'' is R2 or R3.
and a ring together with the nitrogen atom bonded to R2 and R3, preferably a 5-shell or 6-shell ring (for example, when two R4 are bonded to R2 and R3, respectively,
The nitrogen atom bonded to R2 and R3 together with the ring (for example,
Typical specific examples of the compound represented by the general formula (Xllll) of the present invention are shown below, but the present invention is limited to these: PD-18 PD-28 PD-29 PD-31 PD-33 PD-35 PD-36 PD -38 PD-39 PD-41 PD-42 PD-43 (:H3 PD-44 PD-46 PD-47 PD-48 PD-49 PD-50 PD-51 PD-53 In the general formula (Xll) of the present invention Typical synthesis examples of the represented compounds are shown, but the present invention is not limited thereto.

Synthesis Example 1 (Synthesis of Exemplary Compound PD-1) 21 g of N,N-dimethyl-〇-phenylenecyamine dihydrochloride was added to 10 1 g of water.
After dissolving 1, pyridine 1001 was added, and while stirring at room temperature, p-)luenesulfonyl chloride 2 was dissolved.
01? was added little by little over 30 minutes.

After continuing the reaction for an additional 30 minutes, the mixture was poured into 50O1e ice water and left to stand for a day and night, and then the precipitated crystals were collected by filtration. The obtained crystals were recrystallized twice with methanol to obtain 12 g of white powdery crystals. Melting point 91-95°C.

The results of mass spectra and nuclear magnetic resonance spectra are PD
-1 structure was supported.

Synthesis Example 2 (Synthesis of Exemplary Compound PD-19) N,N-dimethyl-m-phenylenediamine 2fi fi 421g
was dissolved in 10111 of water, 100 zN of pyridine was added, and 20 g of p-toluenesulfonyl chloride was added little by little over 30 minutes while stirring was continued in a 1M room.

After continuing the reaction for an additional 30 minutes, the mixture was poured into 500 MN 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 obtain 18 g of white powdery crystals. Melting point 155-157°C.

The results of mass spectra and nuclear magnetic resonance spectra are PD
-19 structure was supported.

Synthesis Example 3 (Synthesis of Exemplified Compound PD-25) Exemplified Compound P
D-1915g and D-) luenesulfonyl cloide 7
．． After heating and dissolving 5 g in methanol 80a+N, 2.4 g of sodium hydroxide was added, and the solution was boiled and refluxed for 4 hours, then poured into 400xl 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 122-126°C.

The results of mass spectra and nuclear magnetic resonance spectra are PD
-25 structure was supported.

The amount of the magenta dye image stabilizer represented by the general formula [■] and the general formula [X■] of the present invention is 5% to the magenta coupler represented by the general formula [I] of the present invention. ~4
00 mol% is preferable, and more preferably 10 to 250 mol%.

When the compound represented by the general formula [XII] of the present invention and the compound represented by the general formula [XI[I] are used together, the total amount of the magenta dye image stabilizer used is the magenta dye image stabilizer of the present invention. Preferably from 10 to 500 moles relative to the coupler;
More preferably, it is 20 to 400 mol%.

Further, the usage ratio of the compound represented by the general formula [penalty] of the present invention and the compound represented by the general formula (XIII) is:
The molar ratio is preferably 0.1 to 10, more preferably 0.1 to 10.
It is in the range of 25 to 4.0.

In the silver halide photographic material of the present invention, in addition to the magenta dye image stabilizer of the present invention, other magenta dye image stabilizers, such as those disclosed in U.S. Pat. , No. 4,254,216, JP-A-55-21004, JP-A No. 54-145530, British Patent Publication No. 2゜077.455, JP-A No. 2,062,
No. 888, U.S. Pat. No. 3,764.337, U.S. Patent No. 3,43
No. 2,300, No. 3, No. 574, No. 627, No. 3, 5
No. 73.050, JP-A No. 52-152225, No. 53
-20327, 53-17729, 55-6
No. 321, No. 54-48538, No. 56-159
No. 644, British Patent No. 1,347,556, Publication No. 2,
No. 066゜975, Special Publication No. 12337/1986, 4B
Phenol compounds or phenyl ether compounds described in US Pat. No. 3,700,455 and the like 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 color photographic material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but the method of the present invention is particularly effective when using color photographic paper intended for direct viewing. is effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be for monochrome use or 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 light-sensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in silver emulsions can be used.

The silver halide grains used in the silver halide emulsion may be obtained by any one of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are 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, halide ions and silver ions were
HII) A Growth may be performed by controlling and sequentially adding Fl. Conversion methods may be used to change the silver halide composition of the grains after growth.

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

The silver halide grains used in silver halide emulsions are formed with cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. during the grain formation and/or growth process. Metal ions can be added to the inside of the particles and/or on the surface of the particles using complex salts, and reduction-sensitized nuclei can be created inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can be granted.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or the salts may be left in the silver halide emulsion. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643. The silver halide -+37- grains used in the silver halide emulsion of the present invention may consist of uniform layers inside and on the surface, or may consist of different layers.

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

The silver halide grains used in the silver halide emulsion may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of poo1 side to 1llll1 side can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

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

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

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. 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. Good too.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, a silver halide emulsion is applied during chemical ripening, and/or at the end of chemical ripening, and/or after chemical ripening, for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable. Up to this point, compounds known in the photographic industry as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as the pineapple (or protective colloid) for silver halide emulsions; however, gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

Photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using silver halide emulsions are hardened by the use alone or in combination with a hardening agent that crosslinks bainggu (or protective colloid) molecules and increases film strength. Ru. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to such an 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 a light-sensitive material using a silver halide emulsion.

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

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, p-phenylenediamine derivatives, amino7
A dye-forming coupler is used, which forms a dye by performing a coupling reaction with an oxidized form of a compound (such as a chloride derivative). The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the light-sensitive spectrum of the emulsion layer, with yellow dye-forming for the blue light-sensitive emulsion layer. A magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., pencyylacetonilides and pivaloylacetanilides); examples of magenta dye-forming couplers include 5-pyrazolone couplers and vilazolobenlimigsol in addition to the couplers of the present invention; There are couplers such as pyrazolotriazole and open-chain acylacetamide couplers, and examples of cyan dye-forming couplers include lotus 7 toll couplers and phenol couplers.

These dye-synthesizing 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. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either equivalence is acceptable.

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. They can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. 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. Or, by dissolving it in combination with a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, 70-jet mixer, or ultrasonic device, After being emulsified and 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 point oils include phenol derivatives that do not react with the oxidized form of the developing agent, heptatarates, phosphates, citricates, benzoates, alkylamides,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150
An organic solvent having a temperature of ℃ or higher is used.

Anionic surfactants, 7-ionic surfactants, and cations can be used as dispersion aids when hydrophobic compounds are dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using a machine or ultrasound. A surfactant can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same 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 or sharpness. Color antifoggants are used to prevent deterioration and graininess from becoming noticeable.

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

In the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention, an ultraviolet absorber is added to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to U light. May contain.

A color light-sensitive material using a silver halide emulsion can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an ylang-agethane antilayer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the color light-sensitive material during development.

The goal is to reduce the gloss of the light-sensitive material, improve the ability to write on the silver halide emulsion layer of a silver halide light-sensitive material using a silver halide emulsion, and/or other hydrophilic colloid layers, and prevent light-sensitive materials from sticking to each other. A matting agent can be added as a matting agent.

A lubricant can be added to reduce the sliding friction of a photosensitive material using a silver halide emulsion.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion 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 can also be used for colloidal layers ().

Photographic emulsion layer and/or photosensitive material using silver halide emulsion
Other hydrophilic colloid layers may contain various additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitizing). Surfactants are used.

Photographic emulsion layer of light-sensitive material using silver halide emulsion, other layers are baryta layer or α-olefin polymer, flexible reflective support such as paper laminated with synthetic paper, cellulose acetate, cellulose nitrate, polystyrene 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 photosensitive material of the present invention is prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
one or more substrates to improve adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, frictional properties, and/or other properties directly or on the surface of the support. It may be applied via a coating layer.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, 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,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

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, or longer exposures of 1 second or more are possible. The exposure may be performed continuously or intermittently.

An image can be formed using the silver halide photographic material of the present invention 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 amino 7-ether derivatives 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. These compounds are also generally used in concentrations of about 0.1 g to about 30 g for color developer IQ, preferably about 1 g to about 1.5 g for color developer 1Q.

Examples of the amino 7-ethyl-based developer include -aminophenol, p-amino 7-ethyl, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, and 2-amino 7-ethyl.
Includes oxy-3-ami7-1°4-dimethylbenzene.

Particularly useful primary aromatic amino color developers are N, N'
It is a -noalkyl+1-phenylenenoamine 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-phenylenecyamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,
N'-tumethyl-p-phenylenecyamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylami7)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-ami7aniline sulfate, N-ethyl-N-β- Hydroxyethylaminoaniline, 4-
7-3-methyl-N,N'-diethylaniline, 4
-amino-N-(2-methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-9-)luenesulfonate.

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 a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. Its composition is that metal ions such as iron, cobalt, copper, etc. are coordinated with ami-7 polycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such organic acid metal complexes include polycarboxylic acids or amino acids.
Examples include polycarboxylic 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] Imi7noacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid sodium salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid 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 fixing solution and the bleaching constant fixing solution contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and metabisulfite. pH buffering agents consisting of various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It can be used alone or in combination of two or more.

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 solution and the bleach-fix replenisher storage tank, if desired, or a suitable oxidizing agent, e.g. Hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

〔Effect of the invention〕

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

〔Example〕

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 The following layers were sequentially coated on a paper support laminated on both sides with polyethylene from the support side.

1st layer: Emulsion layer Magenta coupler 44 of the present invention was added at 6.0 y/100 y.
2. Silver chlorobromide emulsion (containing 85 mol% silver bromide) is converted to silver at 3.5mg/100cx2, dibutyl 7-thalet is 6.0 g/100c12, and gelatin is 15.0 g/100c12!
? /1. The coating was applied in an amount equal to that of oOcI2.

2nd layer: Middle M (ultraviolet absorber-containing layer) 2-(2-hydroxy-3-sec-butyl-5-
3. tert-butylphenyl)benzotriazole.
0 shoulder g/100c shoulder 2, Nobuchir 7 tallate 3. Oz
y/100cz' and gelatin at 12. Ozy/100
The coating was applied to the amount of C shoulder 2.

3rd layer: protective layer gelatin 8. The coating was applied so that the coating amount was OIIg/100x2.

The sample obtained as described above was designated as Sample 1.

In sample 1 above, magenta dye--as an image stabilizer, 14
71 Exemplary compound of the present invention A-2, ^-7, PD-4, PDi
8. Sample 2 in which l'D-34゜PD-35 and comparative compounds a and b shown below were added in equimolar amounts as the magenta coupler.
, 3.4, 5.6°7.8 and 9 were obtained.

In addition, Samples 10 to 29 were obtained by using two types of the above eight types of magenta dye image stabilizers in combination as shown in Table 1.

In samples 10 to 29, the two types of magenta dye image stabilizers used in combination were each used in a molar ratio of 1:1,
The total amount is used in equimolar amounts with magenta coupler.

Comparative compound α (compound described in JP-A-54-43538) QC6I
+,.

Comparative Compound B (Compound described in JP-A-56-159644) The sample obtained above was exposed to light through an optical wedge according to a conventional method, and then processed 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 30 seconds 33℃
Dry for 3 minutes 50-80
'0 2 minutes The components of each treatment are as follows.

[Color developer] Bennol alcohol 12jp diethylene glycol 1o shoulder! potassium carbonate
25g sodium bromide
0.6g anhydrous sodium sulfite
2. Og hydroxylamine sulfate 2.5g
N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-ami/aniline sulfate 4.5g Water was added to bring the solution to 11, and the pH was adjusted to 10.2 with sodium hydroxide.

[Bleach-fix solution 1 Ammonium thiosulfate 120g Sodium metabisulfite 15g Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to bring the pH to 11 and adjust the pH to 6.7~
Adjusted to 6.8.

The concentrations of Samples 1 to 29 treated above were measured using a densitometer (model KD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions.

Each of the above-mentioned treated samples was exposed to a xenon fade meter for 12 days to examine the light fastness of the dye image. However, the evaluation of the light fastness of the dye image is as follows.

[Residual rate] Percentage of dye remaining after light fastness and moisture fastness tests at an initial density of 1.0.

[Degree of discoloration 1 (yellow density) after light fastness test at initial density 1.0/
(magenta density) to (yellow density) before light fastness test /
(magenta density), and the larger this value is, the easier it is to change the color tone from magenta to yellowish.

Table 1! ! From the results in Table 1'$1, samples (Samples 10, 11, 16.17) and samples prepared by using the magenta coupler of the present invention in combination with the phenylenediamine derivative-based magenta dye image stabilizer of the present invention and a conventional magenta dye image stabilizer (Samples 12, 13,
14, 15, 18, 1.9, 20, 21), it is true that samples prepared by adding a magenta dye image stabilizer to the magenta coupler of the present invention (Samples 2 to 9)
), the dye image survival rate in the light fastness test is improved, but the degree of discoloration is slightly unreasonable.

On the other hand, the magenta coupler of the present invention was prepared by combining two types of magenta dye image stabilizers, the morpholine-based magenta dye image stabilizer of the present invention and the phenylenediamine derivative-based magenta dye image stabilizer of the present invention. In the case of the samples of the present invention (Samples 22 to 29), these results cannot be predicted from the samples prepared by adding the magenta dye image stabilizer of the present invention to the magenta coupler of the present invention (Samples 2 to 7). It can be seen that the survival rate of the dye image in the 1-light test is significantly improved, and the degree of discoloration of the dye image in the 1-light test is also extremely small.

As described above, in the case of a sample prepared by using the coupler of the present invention together with two types of magenta dye image stabilizers of the present invention, the coupler of the present invention was combined with one of the magenta dye image stabilizers of the present invention and a conventional It can be seen that the retention rate of the dye image and the degree of discoloration in the one-light test were significantly improved from the sample prepared using the magenta dye image stabilizer.

Example 2 Coupling coupler and magenta dye image stabilizer in the combinations shown in Table 2 in exactly the same manner as in Example 1, sample 3
0 to 58 were created.

Samples 30-58 were processed as described in Example 1. Further, these samples were subjected to a one-light test in the same manner as in Example 1, and the results shown in Table 2 were obtained.

The total amount of dye image stabilizers added to each sample is equimolar to the coupler whether used alone or in combination, and if used in combination, the ratio of the amounts used of each dye image stabilizer is were made equal to each other.

Table 2 From the results shown in Table 2, the samples prepared by using the magenta coupler of the present invention and the magenta dye image stabilizer of the present invention in combination with two or three types of magenta dye image stabilizers of the present invention are shown in Table 2. It can be seen that the light resistance is significantly improved compared to the sample prepared using the stabilizer 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 46 was obtained.

First scrap: blue-sensitive silver halide emulsion layer yellow coupler α-pivaloyl-α-(2,4
-dioxo-1-pennolimigzolinon-3-yl)
6. -2-chloro-5-[γ-(2,4-cy-1-amylphenoxy)butyramide]acetanilide. EhH
/ 100cm2, blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver is 3.2mg/100cm2
, butyl phthalate was coated at a coating amount of 3.5 ng/100 cm2 and gelatin was coated at a coating amount of 13.5+B/100 cm2.

2nd layer: Intermediate layer 2.5-sheet t-octylhydroquinone at 0.5Io
g/100c1112, 0.5m of dibutyl 7 tallate
g/100cm2 and gelatin at 9. OmH/100
It was coated so that it was cm2.

Third layer: Green-sensitive silver halide emulsion layer The magenta coupler 31 is 4.5B/]000cm
2 Green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver is 2.0 Iog/100 cII + 2, dibutyl 7
3.0B/100cm2 of tallate and 1 gelatin
2. It was coated to give OmH/100cm2.

4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-5ee-butyl-5-t-butylphenyl)benzotriazole 5.0mg/100ca+2, dibutyl 7-thalet 4.0mg/100cm2.2 , 5-cy, 1 octylhydroquine 0.5 II 1 g/100 cm 2 and gelatin 12. O+nH/ ], 000 cm.

5th layer: Red-sensitive silver halide emulsion layer 4.2 mg of 2-[α-(2,4-di-t-pentyl-7ethyl-7xy)butanamide]-4,6-nochloro-5-ethylphenol as a cyan coupler. /1000m2,
3. Red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver. Omg/100cm2, tricresyl phosphate 3,5 ll1g/100 cm2
And gelatin was coated at 11.5mB/100ca+2.

Layer 6: Middle layer A layer composed of exactly the same composition as the fourth layer.

7th layer: protective layer gelatin 8. It was coated so that it was 0mg/100cm2.

In sample 59 described in Section 2, the dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3, and multilayer sample 6
0 to 77 were prepared, exposed and processed in the same manner as in Example 1, and then subjected to a mold light test (irradiated with a xenon fade meter for 14 days). The results are also shown in Table 3.

Table 3 From the results in Table 3, it is clear that when the total amount of the magenta dye image stabilizer of the present invention is kept constant, the magenta dye image of the present invention It can be seen that the light fastness of the magenta dye image can be improved to a large IJ by using a stabilizer in an appropriate ratio.

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

Applicant: Konishiroku Photo Industry Co., Ltd. Procedural amendment (formality) July 4, 1986

Claims (1)

[Scope of Claims] At least one magenta 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 [XIII] A silver halide photographic material comprising at least one compound. 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. Moreover, R represents a hydrogen atom or a substituent. ] General formula [XII] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a group of nonmetallic atoms necessary to form a morpholine ring. ] General formula [XIII] ▲ Numerical formulas, chemical formulas, tables etc. It represents a heterocyclic group, and R^6 represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R^4 represents a substituent, m is 0, 1, 2, 3 or 4
represents. 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^7 and R^8 each represent a hydrogen atom, an alkyl group, or an aryl group), and n is 0 Or represents 1. Further, R^2 and R^3 may be combined with each other to form a 5- or 6-membered ring. When m is 2 or more, R^4 may be the same or different. When m is 1 to 4, 1 R^4
may be bonded to R^2 or R^3 to form a ring together with the nitrogen atom bonded to R^2 and R^3. When m is 2 or more, two R^4 may be bonded to R^2 and R^3, respectively, and form a ring together with the nitrogen atom bonded to R^2 and R^3. ]