JPS6215544A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To form a latex of a polymer coupler having an excellent coloring property by incorporating the polymer coupler having a specific coupler residue as a repeating unit to the titled material. CONSTITUTION:The titled material is comprised the polymer coupler having the coupler residue shown by formula I as the repeating unit. The representative example of the monomeric coupler having the repeating unit (the coupler unit) shown by formula I is comprised the monomeric coupler shown by formula I-1. The ratio of the repeating unit shown by formula I contg. in the copolymer coupler is preferably to be 20-85wt% from the color reproducibility, the coloring property and the stability points of view. The latex of the polymer coupler is added to the silver halide emulsion layer or its adjacent layer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing a latex of a novel polymer coupler capable of coupling with an oxidized aromatic-amine developer. And□
Ru. □ (Prior art) When a silver halide photographic light-sensitive material is exposed to light and then subjected to color development, an oxidized aromatic-grade amine developer reacts with a dye-forming coupler, and a color image is often obtained. Are known.

By the way, in multilayer color photosensitive materials, color mixing is reduced and
It is necessary to fix each coupler in separate layers to improve color reproduction.

Many methods are known for making couplers diffusion resistant.

One method is to utilize a polymer coupler obtained by polymerizing monomeric couplers in the form of a latex.

The method of adding polymeric couplers to lipophilic colloid compositions in latex form has many advantages over other methods. □ First, since the hydrophobic material is made into latex, the strength of the formed film will not deteriorate.Also, since latex can contain a high concentration of monomeric coupler, it is easy to use a high concentration of coupler. can be incorporated into the emulsion, and since the increase in viscosity is small, the film can be made thinner and the sharpness can be improved.

Furthermore, since it is completely non-migratable, there is little color mixing, and there is little chance of coupler precipitation in the emulsion film.

Examples of polymer couplers added to gelatin silver halide emulsions in the form of latex include, for example, US Pat. No. 4,080,211 and US Pat. No. 1,247,66.
No. 8, U.S. Pat. No. 3,451.820 describes its manufacturing method and 4-equivalent magenta polymer coupler latex;
No. 36 has a copolymerized latex with a competitive coupler, which is disclosed in U.S. Patent No. 3,767.412 and Research Disclosure.
2172& (1982) describes a cyan polymer coupler latex.

(Problems to be Solved by the Invention) However, although the polymer coupler latex has the above-mentioned excellent characteristics, it also has the following problems that should be improved.

1. Due to the poor coupling reaction rate, the resulting dye has low sensitivity, gradation, and dye density.

2. When the content of a repeating unit (hereinafter referred to as a coupler unit) having residual coupler in the polymer coupler increases, the color development per unit weight (of one coupler unit) decreases significantly. If a polymer coupler with a high coupler unit content can maintain high color development, a higher concentration of the coupler can be included in a smaller amount in the emulsion, allowing for even thinner layers and even greater sharpness. It has the advantage that it can be improved. Accordingly, the first object of the present invention is to provide a novel polymer coupler latex that exhibits significantly superior coloring properties.

The second objective of the present invention is to provide a novel polymer coupler latex that has a high coupler unit content and can maintain high color development.

A third object of the present invention is to provide a method for forming color images by developing silver halide emulsions in the presence of a latex of the novel polymer coupler.

A fourth object of the present invention is to provide a silver halide color photographic material containing a novel latex of a polymer coupler, a photographic processing method thereof, and an image forming method.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide color photograph characterized by containing a polymer coupler having a repeating unit having a coupler residue, represented by the following general formula [I]. achieved by the material.

(In the formula, R1 represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom.

R2 and R each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted 7-aryloxy group, a substituted or unsubstituted It represents an alkylamino group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted 7syl amino group, a substituted or unsubstituted sulfonamide group, a carboxyl group, a hydroxyl group, or a halogen atom.

J is -co, -1-CON-1 and R5 are each independently a hydrogen atom or a carbon number of 1 to 6
, Q represents a coupler residue capable of a coupling reaction with the oxidized product of an aromatic primary amine developing agent. Among the color coupler residues represented by Q, cyan color-forming coupler residues As a group, a phenol type [11] or a naphthol type [ml, [IV] compound (each hydrogen atom other than OH is removed to form the above general formula [I]
In the formula, R11 represents a group capable of substituting a phenol ring or a naphthol ring, and examples thereof include a halogen atom, a hydroxy group, an amino group, a carboxy group, a sulfo group, a cyan group, an aliphatic group, Aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, acyloxy group, acyl group, aliphatic oxy group, aliphatic thio group, aliphatic sulfonyl group, aromatic oxy group, aromatic group Examples include a thio group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, and an imide group. The number of carbon atoms in R11 is 0 to 30.

Rjf-CONR13R14, -N HCOR”’.

-NHCOO-R15, -N, H5OR15, -NHC
ONRR or -NH302RR, R.13 and R14 are hydrogen atoms, aliphatic groups having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, butyl group, methoxyethyl group, n-decyl group, n-dodecyl group) , n-hexadecyl group, trifluoromethyl group, heptafluoropropyl group,
dodecyloxypropyl group, 2,4-di-tert-
amylphenoxypropyl group, 2,4-di-tert-
amylphenoxybutyl group, etc.), aromatic groups having 6 to 30 carbon atoms (e.g., phenyl group, tolyl group, 2-tetradecyloxyphenyl group, pentafluorophenyl group, 2-
chloro-5-dodecyloxycarbonylphenyl group, etc.)
, a heterocyclic group having 2 to 30 carbon atoms (e.g., 2-pyridyl group, 4-pyridyl group, 2-furyl group, 2-chenyl group, etc.)
, R15 is an aliphatic group having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, butyl group, dodecyl group, hexadecyl group, etc.) or an aromatic group having 6 to 30 carbon atoms (e.g., phenyl group, tolyl group, 4-chlorophenyl group) group, naphthyl group, etc.), and a heterocyclic group (eg, 4-pyridyl group, quinolyl group, 2-furyl group, etc.). R13 and R14 may be bonded to each other to form a heterocycle (eg, a morpholine ring, a piperidine ring, a pyrrolidine ring, etc.). p' is O~3, q/, r'
each represents an integer from O to 4.

X represents an oxygen atom, a sulfur atom or R16N2,
R16 represents a hydrogen atom or a monovalent group.

When R16 represents a monovalent group, when R16 is bent, an aliphatic group having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, butyl group, methoxyethyl group, benzyl group, etc.), 6 carbon atoms
~30 aromatic groups (e.g., phenyl, tolyl, etc.)
, a heterocyclic group having 2 to 30 carbon atoms (e.g., 2-pyridyl group, 2-pyrimidyl group, etc.), a carbonamide group having 1 to 30 carbon atoms (e.g., formamide group, acetamido group, N
-methylacetamide group, benzamide group, etc.), sulfonamide group having 1 to 30 carbon atoms (e.g. methanesulfonamide group, toluenesulfonamide group, 4-chlorobenzenesulfonamide group, etc.), imide group having 4 to 30 carbon atoms ( For example, succinimide group), -OR, SR, -CO
R17, +7 17 - c ON R17R18, -COCOR17, -C
Mention may be made of OCONR,R, C0OR"", +7 18 - -cocoOR+9, -8OR19, zuO0R19, zu02NR17R18 and -NRR. Here, R17 and R18 may be the same or different, and each represents a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, butyl group, dodecyl group, methoxyethyl group, trifluoro methyl group, heptafluoropropyl group, etc.), carbon number 6-3
0 aromatic group (e.g., phenyl group, tolyl group, 4-chlorophenyl group, pentafluorophenyl group, 4-cyanophenyl group, 4-hydroxyphenyl group, etc.) or a heterocyclic group having 2 to 30 carbon atoms (e.g., 4- pyridyl group, 3-pyridyl group, 2-furyl group, etc.). R17 and R18
may be bonded to each other to form a heterocycle (eg, morpholino group, pyrrolidino group, etc.).

Examples of R include the substituents shown in R17 and R18 excluding the hydrogen atom.

Zl represents a hydrogen atom or a group that can be separated by a carp-pulling reaction with an oxidized aromatic primary amine developer.

Examples of groups that can be separated include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), aliphatic oxy groups having 1 to 30 carbon atoms (e.g., methoxy group, ethoxy group, 2- hydroxyethoxy group, carboxymethyloxy group, 3-carboxypropyloxy group, 2-methoxyethoxycarbamoylmethyloxy group, 2-methanesulfocholethoxy group, 2-carboxymethylthioethoxy group, triazolylmethyloxy group), number of carbon atoms 6
~30 aromatic oxy groups (e.g., phenoxy, 4-
human b-xyphenoxy group, 2-acetamidophenoxy group, 2,4-dibenzenesulfonamidophenoxy group,
4-phenylazophenoxy group, etc.), C2-C30 heterocyclic oxy group (e.g., 4-pyridyloxy group, ■-
phenyl-5-tetrazolyloxy group, etc.), carbon number 1-
30 aliphatic thio groups (e.g. dodecylthio group etc.), aromatic thio groups having 6 to 30 carbon atoms (e.g. 4-dodecyl phenylthio group etc.), heterocyclic thio groups having 2 to 30 carbon atoms (e.g. 4- Pyridylthio group, 1-phenyltetrazole-
5-ylthio group, etc.), an acyloxy group having 2 to 30 carbon atoms (e.g. acetoxy group, benzoyloxy group, lauroyloxy group, etc.), a carbonamide group having 1 to 30 carbon atoms (
For example, dichloroacetylamide group, trifluoroacetamide group, heptafluorobutanamide group, pentafluorobenzamide group, etc.), sulfonamide group having 1 to 30 carbon atoms (for example, methanesulfonamide group, toluenesulfonamide group, etc.), Aromatic azo group having 6 to 30 carbon atoms (e.g., phenylazo group □, 4-chlorophenylazo group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, etc.), aliphatic group having 1 to 30 carbon atoms Oxycarbonyloxy group (e.g. ethoxycarbonyloxy group, dodecyloxycarbonyloxy group, etc.), aromatic oxycarbonyloxy group having 6 to 30 carbon atoms (e.g. phenoxycarbonyloxy group, etc.), carbon number 1 to 30
carbamoyloxy group (e.g., methylcarbamoyloxy group, dodecylcarbamoyloxy group, phenylcarbamoyloxy group, etc.), a heterocyclic group having 1 to 30 carbon atoms and having a nitrogen atom connected to the active position of the coupler (e.g., succinimide group, phthalimide group, hydantoinyl group,
pyrazolyl group, 2-benzotriazolyl group, etc.).

Next, examples of substituents preferably used in the present invention are listed below.

Preferred examples of R11 include halogen atoms (e.g., fluorine, chlorine, bromine, etc.), aliphatic groups (e.g., methyl, ethyl, isopropyl, etc.), carbonamide groups (e.g., ayatoamide, benzamide, etc.), and sulfone. These include amide groups (eg, methanesulfonamide group, toluenesulfonamide group, etc.).

Preferred R12 is 100NR13R'', examples include carbamoyl group, ethylcarbamoyl group, morpholinocarbonyl group, dodecylcarbamoyl group, hexadecylcarbamoyl group, decyloxypropyl group, dodecyloxypropyl group, 2,4 -Di-tert-amylphenoxypropyl group, 2,4-di-tert-amylphenoxybutyl group, and the like.

Also preferred is R1θN-, roughly R
16 is preferably 100R17 (e.g., formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, pentafluorobenzoyl group, p-chlorobenzoyl group, etc.'), -COOR19
(For example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, dodecyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group, etc.)', -3o R19 (For example, methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group,
hexadecanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, p-kugolobenzenesulfonyl group, etc.), '-CONR17R''8 (N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N
', 'N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, 4-cyanophenylcarbamoyl group, 3.4-dichlorophenylcarbamoyl group, 4-methanesulfonylphenylcarbamoyl group, etc.), -3o NR17R18 (e.g. , N,N-dimethylsulfamoyl group, N,N=nidiethylsulfamoyl, N,N-dipropylsulfamoyl group, etc.). More particularly preferred among R16 are -0OR17゜-COOR18 and -8O2R1
This is a group represented by 9.

Preferred groups as Zl are a hydrogen atom, a halogen atom, an aliphatic oxy group, an aromatic oxy group, a heterocyclic thio group, and an aromatic azo group. Couplers represented by general formulas [■■], [■], [IV] have 2 in their substituent R11, R12, X or Z.
They may be kudzu dimers or higher multimers that are bonded to each other via a multivalent or higher-valent linking group.
In this case, the number of carbon atoms shown in each of the above-mentioned substituents is not limited to this.

As the magenta color forming coupler residue, the general formula [V],
[VI], [■], [■], []X], [X] and [
Coupler residues represented by X[] (Ar, Z,
RR is connected to J in the general formula [I] above.

Preferred is when these residues are linked at a point other than Z. In the case of general formula [V], it is more preferable that J is directly bonded to the substitution position of R (3-position of 5-pyrazolone).

General formula [■] 8 General formula [■] General formula [ν; Substituents of known types such as alkyl groups, substituted alkyl groups (e.g. haloalkyl such as fluoroalkyl,
cyanoalkyl, benzylalkyl, etc.), aryl group or substituted aryl group.

[Substituents include alkyl groups (e.g., methyl group, ethyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), ary, ruoxy groups (e.g., phenyloxy group, etc.), alkoxycarbonyl7! : (for example, methoxycarbonyl group, etc.), acylamino group (for example, acetylamino group), carbamoyl group, alkylcarbamoyl group (for example, methylcarbamoyl group, ethylcarbamoyl group, etc.), dialkylcarbamoyl group (for example, dimethylcarbamoyl group), arylcarbamoyl group groups (e.g. phenylcarbamoyl group), alkylsulfonyl groups (
For example, methylsulfonyl group), arylsulfonyl group (
(e.g. phenylsulfonyl group), alkylsulfonamide F group (e.g. methanesulfonamide group), arylsulfonamide F group (e.g. phenylsulfonamide group), sulfamoyl group, alkylsulfamoyl group (e.g. ethylsulfamoyl group), dialkyl Examples include sulfamoyl groups (e.g. dimethylsulfamoyl group), alkylthio groups (e.g. methylthio group, arylthio group (e.g. phenylthio group), cyanogen group, nitro group, halogen atoms (e.g. fluorine, chlorine, bromine, etc.). When there are two or more substituents, they may be the same or different.

Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyan group. ], represents a heterocyclic group (eg, triazole, thiazole, benzthiazole, furan, pyridine, quinaldine, benzoxazole, pyrimidine, oxanol, imidazole, etc.).

R2° represents an unsubstituted or substituted anilino group, an acylamino group (for example, an alkylcarbonamide group, a phenylcarbonamide group, an alkoxycarbonamide group, a phenyloxycarbonamide group), or a ureido group (for example, an alkylureido group, a phenylureido group); , these substituents include /\ rogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), straight chain, branched alkyl group (e.g. methyl group, t-butyl group, octyl group, tetradecyl group, etc.) , alkoxy groups (e.g. methoxy group, ethoxy group, 2-ethylhexyloxy group, tetradecyloxy group, etc.), acylamino group (e.g. acetamido group, benzamide group, butyramide group, octaneamide group, tetradecaneamide group, α -(2,-jeeter
t-amylphenoxy)acetamide group, α-2,4-
di-tert-amylphenoxy)butyramide group, α
-(3-pentadecylphenoxy)hexanamide group,
α-(4-hydroxy-3=t'ert-butylphenoxy)tetradecanamide group, 2-oxo-pyrrolidin-1-yl group, 2-oxo-5-tetradecylpyrrolidin-1-yl group, N-methyl- (tetradecanamide group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, ethylsulfonamide group, l1l-)luenesulfonamide group, octane sulfonamide group, p-dodecylbenzenesulfonamide group, N -methyl-tetradecanesulfontamide group, etc.)
, sulfamoyl group (e.g. sulfamoyl group, N-
Methylsulfamoyl group, N-ethylsulfamoyl group, N,N-dimethylsulfamoyl group, N,N-dihexylsulfamoyl group, N-hexadecylsulfamoyl group, N-[3-(dodecyl oxy)-propyl]sulfamoyl group, N-[4-(2,4-di-tert-amylphenoxy)butylcarbamoyl group, N-methyl-
N-tetradecylsulfamoyl group, etc.), carbamoyl group (e.g. N-methylcarbamoyl group, N-butylcarbamoyl group, N-octadecylcarbamoyl group, N-
[4-(t,4-di-tert-amylphenoxy)butylcarbamoyl group, N-mer≠-N-tetradecyl group, etc.), diacylamino group (N-succinimide group, N-phthalimide group, 2.5- Dioxo-1
-oxazolidinyl group, 3-dodecyl-2,5-dioxo-1-hydantoynyl group, 3-(N-acetyl-N
-dodecylamino)succinimide group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, tetradecyloxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxysulfonyl group (e.g., methoxysulfonyl group, butoxysulfonyl group, trimethyloxy sulfonyl group, tetradecyloxysulfonyl group), aryloxysulfonyl group (e.g. phenoxysulfonyl group, p-methylphenoxysulfonyl group, 2
, 4-di-tert-amylphenoxysulfonyl group, etc.), alkanesulfonyl group (e.g., methanesulfonyl group, ethanesulfonyl group, +methanesulfonyl group, 2
-ethylhexylsulfonyl group, hexadecanesulfonyl group, etc.), arylsulfonyl group (e.g., benzenesulfonyl group, 4-nonylbenzenesulfonyl group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, hexylthio group, benzylthio group, tetradecylthio group, 2-(2,4-jert-amylphenoxy)ethylthio group, etc.), arylthio group (e.g.
phenylthio group, p-tolylthio group, etc.), alkyloxycarbonylamino group (e.g., methoxycarbonylamino group, ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group, etc.)'', alkylureido group (e.g. ,
N-methylureido group, N,N-dimethylureido group, N-methyl-N-dodecylureido group, N-hexadecylureido group, N,N-di-tadecylureido group, etc.), acyl group (for example, acetyl-ureido group), group, benzoyl group,
Examples include octadecanoyl group, p-dodecanamidobenzoyl group, etc.), nitro group, carboxyl group, sulfo group, hydroxy group, and trichloromethyl group.

However, among the above substituents, those defined as alkyl groups have 1 to 36 carbon atoms, and those defined as aryl groups have 6 to 38 carbon atoms.

R21, R22, R23, R24, R25, R26, R
27, R28, R28, R30, R31 and R32 are each a hydrogen atom, a hydroxyl group, or an unsubstituted or substituted alkyl group (preferably one with 1 to 20 carbon atoms. For example, a methyl group, a propyl group, a t -butyl group, trifluoromethyl group, tridecyl group, etc.), aryl group (
Preferably one having 6 to 20 carbon atoms. For example, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amylphenyl group, 4-methoxyphenyl group, etc.), heterocyclic group (such as 2-furyl group, 2-chenyl group, 2- pyrimidinyl group, 2-benzothiazolyl group, etc.), alkylamino group (preferably one with 1 to 20 carbon atoms; for example, methylamino group, diethylamino group, t-butylamino group, etc.)
, acylamino group (preferably one with 2 to 20 carbon atoms, such as an acetylamino group, a propylamide group, a benzamide group, etc.), anilino group (such as a phenylamino group, 2
-chloroanilino group, etc.), alkoxycarbonyl group (preferably one with 2 to 20 carbon atoms, such as methoxycarbonyl group, butoxycarbonyl group, 2-ethylhexyloxycarbonyl group, etc.), alkylcarbonyl group (preferably one with 2 to 2 carbon atoms), ~20 things.

For example, acetyl group, butylcarbonyl group, cyclohexylcarbonyl group, etc.), arylcarbonyl group (e.g., preferably one with 7 to 20 carbon atoms, benzoyl group, 4
-t-butylbenzoyl group, etc.), alkylthio group (preferably one with 1 to 20 carbon atoms, such as methylthio group, octylthio group, 2-phenoxyethylthio group, etc.), arylthio group (preferably one with 6 to 20 carbon atoms) For example, phenylthio group, 2-butoxy-5-t-octylphenylthio group, etc.), carbamoyl group (preferably one having 1 to 20 carbon atoms. For example, N-ethylcarbamoyl group,
N,N-dibutylcarbamoyl group, N-methyl-N-butylcarbamoyl group, etc.), sulfamoyl group (preferably one having up to 20 carbon atoms. For example, N-ethylsulfamoyl 1,N,N-diethylsulfamoyl group) moyl group, N,N-dipropylsulfamoyl group, etc.) or a sulfonamide group (preferably one having 1 to 20 carbon atoms).

For example, it represents a methanesulfonamide group, a benzenesulfonamide group, a p-)luenesulfonamide group, etc.).

Z2 represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Examples of detachable groups include halogen atoms (e.g., chlorine atom, bromine atom, etc.), coupling-off groups linked with oxygen atoms (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, ethoxyoxaloyloxy group, pyloxy group, etc.). Vinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenokyl group, 4-titanesulfonamidophenoxy group, α-naphthoxy group, 4-cyanoxyl group, 4-methanesulfonamido-phenoxy group, α-naphthoxy group , 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzoyloxy group, 2-phenethyloxy group, 2-phenoxy-ethoxy group, 5-phenyltetrazolyloxy group, 2 -benzothiazolyloxy group, etc.),
Coupling-off groups linked via a nitrogen atom (other examples include those described in Japanese Patent Application No. 189538/1983, specifically benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide F group, 2,3
,4,5.6=pentafluorobenzamide group, octane sulfonamide group, p-cyanophenylureido group,
N,N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4-dioki/-3-
Oxazolidinyl group, 1-benzyl-5-ethoxy-3
-hydantoinyl group, 2-oxo-1,2-dihydro-
1-Viridinyl group, imidazolyl group, pyrazolyl group, 3
,5-diethy)re 1.2.4-triazol-1-yl group, 5- or 6-promobenztriazol-1-
yl group, 5-methyl-1,2,3,4-)lyazole-
1-yl group, benzimidazolyl group, etc.), coupling-off groups linked via a sulfur atom (e.g., phenylthio group,
2-carboxyphenylthio group, 2-methoxy-5-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group,
benzylthio group, 2-cyanoethylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group, 2-benzothiazozolyl group, etc.). The group capable of leaving l111 is preferably a halogen atom, a phenoxy group, or a coupling-off group connected via a nitrogen atom, and particularly preferably a halogen atom, a phenoxy group, a pyrazolyl group, an imidazolyl group, or a doriazolyl group.

Yellow color-forming coupler residues include those of the acylacetanilide type, especially pivaloylacetanilide ffi.
[XI[], benzoylacetanilide type [Xll1
], [ ] are preferred.

In the formula, R, R, R and R3B are each a hydrogen atom or a well-known substituent of a yellow color-forming coupler residue, such as an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl group,
Aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group 1. Alkylureido group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamide group, arylsulfamoyl group, arylsulfonamide group, arylureido group, carboxy group, sulfo group, nitro group , represents a cyano group, a thiocyano group, etc.
These substituents may be the same or different.

Z3 is a hydrogen atom or the following general formula [XV], [XVT],
[XV11] or ['R].

R37 represents an optionally substituted aryl group or heterocyclic group.

R38 and R39 are each hydrogen atom, halogen atom, carboxylic acid ester group, amino group, alkyl group, alkylthio group, alkoxy group, alkylsulfonyl group, alkylsulfinyl group, carboxylic acid group, sulfonic acid group, unsubstituted or substituted phenyl group or represents a heterocyclic group, and these groups may be the same or different.

゛・wl、-" Represents a nonmetallic atom required to form a membered ring.

Among the general formula arguments, the preferred one is [XIX] ~
[XX] is mentioned.

(2) In the formula, R40 and R41 are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group, and R42, R43 and R are each a hydrogen atom,
In the alkyl group, aryl group, aralkyl group or acyl group, W2 represents an oxygen or sulfur atom.

Representative examples of monomeric couplers that provide a repeating unit (one coupler unit) represented by the general formula [I] are shown below, but the invention is not limited thereto.

The polymer coupler of the present invention is a homopolymer consisting only of repeating units represented by the general formula
It may also be a non-color-forming ethylenically unsaturated monomer door copolymer (copolymer) having the ability to couple with an aromatic amine developer.

Examples of non-chromogenic ethylenically unsaturated monomers used to synthesize copolymer polymer couplers include: However, the comonomers used in the present invention are not limited to these.

Acrylic acid, α-chloroacrylic acid, α-alacrylic acid (such as methacrylic acid), esters or amides derived from these acrylic acids (such as acrylamide, methacrylamide, n-butylacrylamide, L-butylacrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n
-propyl acrylate, n-butyl acrylate-h,
t-butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate.

methyl methacrylate, methyl methacrylate, n-butyl methacrylate, β-hydroxy methacrylate and ethylene glycol dimethacrylate), vinyl ethyl (e.g. vinyl acetate, vinyl propionate and vinyl laurel), acrylonitrile, methacrylaterile, Aromatic vinyl compounds (e.g. styrene and its derivatives 1 such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, -crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), Examples include maleic acid, maleic ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine.

Among these, especially acrylic acid, acrylic ester, methacrylic acid, varnish methacrylate, maleic acid,
Maleic acid esters are preferred.

Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. Examples include ethyl acrylate, n-butyl acrylate, n-butyl acrylate, n-styrene methyl methacrylate, and diacetone acrylamide.

As is well known in the field of polymer color couplers, the ethylenically unsaturated monomer to be copolymerized with the monomeric coupler providing the repeating unit represented by the general formula [I] depends on the physical properties of the copolymer formed. and/or chemical properties such as solubility, compatibility with binders such as gelatin of the photographic colloidal composition, its flexibility, thermal stability, etc. can be selected to be highly influenced.

The polymer coupler latex used in the present invention may be prepared by dissolving a polymer coupler obtained by polymerizing a monomer coupler in an organic solvent as described above and dispersing it in the form of a latex in an aqueous gelatin solution. Alternatively, it may be produced by a direct emulsion polymerization method.

A method of emulsifying and dispersing a polymer coupler in an aqueous gelatin solution in the form of a wax is described in U.S. Patent No.
For emulsion polymerization, the methods described in US Pat. No. 4,080,211 and US Pat. No. 3,3370.952 can be used.

The synthesis of the polymer coupler of the present invention is carried out using a polymerization initiator and a polymerization solvent as described in JP-A-56-5543 and JP-A-57-94.
No. 752, #Opening/closing No. 57-176038, JP-A-57-
No. 204038, JP-A-58-28745, JP-A-Sho 5
This is carried out using compounds described in JP-A No. 8-10738, JP-A-58-42044, and JP-A-58-145944.

The polymerization temperature must be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc.
Although it can be used up to temperatures below 2'°C, it usually polymerizes in the range of 30°C to 100°C.

The proportion of the repeating unit represented by general formula [I] in the copolymer coupler is usually preferably 10 to 90% by weight, but preferably 20 to 85% by weight in terms of color reproducibility, color development and stability. The equivalent molecular weight (grams of polymer containing 1 mole of monomeric coupler) in this case is approximately 250-40
00, but it is not constant.

The polymeric coupler latex of this invention is added to the silver halide emulsion layer or to a layer adjacent thereto.

The polymeric coupler latex of the present invention is based on coupler monomer and contains 9.9% per mole of silver when in the same layer as silver halide. ．． 005 mol to 0.5 mol, preferably 0.0
It is preferable to add 1 to 0.10 moj, l<.

In addition, when the polymer coupler latex of Seven Mei Kinai is used for the non-photosensitive layer, the coating amount is 0.01 g, /m'-,
1,0,g/rn', preferably 0,1 g/r
It ranges from rf to 0.5 g,/go.

A typical synthesis example of the polymer coupler of the present invention is shown below.

[Synthesis of monomeric coupler] Synthesis of monomeric coupler example (1)
A solution dissolved in 300 m4 of dimethylacetamide was stirred under water cooling until the internal temperature reached 3 to 5°C, and 55.8 g of vinylbenzoic acid chloride (compound (i)) was added dropwise over 10 minutes.

After stirring as it was for 30 minutes, the mixture was further stirred at room temperature for 1 hour. The contents were poured into 11 water, the precipitated crystals were collected by filtration, and recrystallized with a mixed solvent of ethyl acetate/ethanol (4/1) to obtain 59.8 g of white monomeric coupler (1) crystals.
I got it. (Yield: 68.6%) 1) (ii) Other monomeric couplers were also synthesized in the same manner.

[Production method (I) of polymer coupler] Production method example Polymer coupler (1) (copolymer of monomer coupler (1) and butyl acrylate) Monomer coupler (1,1
A mixture of 10 g of dimethylacetamide, 10 g of dimethyl azobisisoacetate, and 100 m of dimethylacetamide was heated to 80° C. under stirring in a nitrogen atmosphere, and then 10 mJl of a dimethylacetamide solution containing 0.5 g of dimethyl azobisisoacetate was added to initiate polymerization. After reacting for 5 hours, the reaction solution was cooled and 1.5 liters of water was added.
The solids poured into JL were filtered and washed thoroughly with water.

This solid was preheated under reduced pressure to obtain 18.6 g of a polymer coupler (1) represented by the following formula.

This polymer coupler was shown to contain 50.6% monomeric coupler (1) in the polymer formed by nitrogen analysis.

X: 50.6 Weight coefficient y: 49.4 Weight Manufacturing method example (2) Polymer coupler (2) (Exemplary monomer coupler, (1
) and monoethyl ester of maleic anhydride) 20 g of monomer coupler (1), 4.8 g of maleic anhydride
g was dissolved in 100 mJl of dioxane and heated to 80° C. under stirring in a nitrogen bath, and then 10 ml of a dioxane solution containing 0.5 g of dimethyl azobisisobutyrate was added to initiate polymerization. After reacting for 6 hours, the temperature of the reaction solution was brought to 70°C, 5 g of ethanol was added, and the mixture was heated and stirred at 70°C for 2 hours. Thereafter, the reaction solution was cooled, poured into 1.5 g of water, and the precipitated solid was filtered out and washed thoroughly with water.

This solid was preheated under reduced pressure to obtain 21.0 g of polymer coupler (2).

This polymer coupler was shown to contain 75.2% by weight of monomeric coupler (1) in the polymer formed by nitrogen analysis.

Table 1 shows examples of polymer couplers similarly synthesized using production method (I).

[Polymer production method (II)] Production method example (17) Polymer coupler (17) Copolymer latex of l-mer coupler (1) and butyl acrylate) 1.5 g of oleyl methyl tauride in a 1M flask
An aqueous solution containing 0.6 g of
Heat to 5°C and add 15+n9. of 2% potassium persulfate aqueous solution to the aqueous solution. 20g of monomeric coupler (1)
A solution obtained by heating and dissolving 20 g of butyl acrylate in 100 mL of ethanol was added dropwise over 20 minutes, and the mixture was allowed to react for 4 hours. The formed latex was cooled, adjusted to pH 6.0 with IN sodium hydroxide, and filtered.

The polymer concentration of the latex formed was 5.3%, and nitrogen analysis showed that the polymer contained 49.0% by weight of monomeric coupler (1).

Table 2 shows examples of polymer couplers synthesized in the same manner using production method (II).

In preparing the silver halide color photographic light-sensitive material of the present invention, the polymer couplers of the present invention can be used alone or in combination of two or more.

The polymer coupler of the present invention is disclosed in JP-A-58-28745, JP-A-58-43955, JP-A-58-12025, JP-A-57-947.52, JP-A-58-145944,
No. 58-145944, No. 58-1.79838,
No. 587211756, No. 58-224352, No. 59-36249, No. 59-65844, No. 59-
No. 86048, British Patent No. 967.503, 1,13
0, 58.1, 1,247,688, U.S. Pat. No. 3,37.0.952, 3,767.412, West German Patent 2,304,319, They can also be used together.

The silver halide photographic material of the present invention may be a monochromatic color photographic material having one light-sensitive silver halide emulsion layer on a support, and at least two electrolytic layers having different spectral sensitivities on the support. It may also be a color photographic material.

Multilayer color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.・The silver halide multilayer color photographic light-sensitive material of the present invention usually uses yellow, magenta, and cyan color-forming couplers, but the couplers of the present invention can be used for all three colors, and if necessary, , some of the couplers can be replaced with conventionally known color couplers. Pa ′,
- Useful color couplers are cyan, magenta and yellow colored couplers, typical examples of which are naphthol or phenolic compounds, pyrazolones or pyrazoloazoles and closed or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that may be used in the present invention are provided in Research Disclosure.
h[]Lsclosure) 17643 (1978
6) Color couplers other than the present invention incorporated into light-sensitive materials also have a ballast group or are polymerized. A two-equivalent color coupler substituted with a leaving group is preferable to a four-equivalent color coupler in which the coupling active position is a hydrogen atom, which is preferable to have diffusion resistance by reducing the amount of coated silver and provides higher sensitivity. It is also possible to use couplers in which the color-forming dye to be used has appropriate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction.

A representative example of the yellow coupler that can be used in combination with the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
No. 7,210, No. 2゜875.057 and No. 3
, No. 265, 506, etc. As a two-equivalent yellow coupler, U.S. Pat. No. 3,408,194
No. 3.447.928, No. 3.933.50
1 and No. 4,022,620, etc., or the yellow coupler of the oxygen atom detachment type, or the Japanese Patent Publication No. 1983
-10739, U.S. Patent No. 4,401,752, U.S. Patent No. 4,326,024, RD18053 (1979
), British Patent No. 1,425,020, West German Application No. 2.219,917, West German Patent Application No. 2.261,361
No. 2,329,587 and No. 2,433.
A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in combination with the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. 2.3 of the same
No. 43.703, No. 2, No. 606, No. 788, No. 2.908.573, No. 3. o62.653, 3.152;896 and 3,936,015
It is written in the number etc. As #degrouping of two equivalent 5-pyrazolone couplers, U.S. Pat. No. 4,310,619
or U.S. Pat. No. 4,3
The arylthio group described in European Patent No. 51.897 is particularly preferred, and the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably pyrazolo[5,1-cl[1,2,4]) as described in U.S. Pat. No. 3,725.067.
Riazoles, Research Disclosure 2422
0 (June 1984) and Research Table Disclosure 24230 (1
In view of the low yellow side absorption and light fastness of color-forming dyes, the imidazo [described in European Patent No. 119,741]
1,2”-b] pyrazoles are preferred, such as pyrazolo[1,5-b] as described in EP 119,860.
[1,2,4]) Riazole is particularly preferred.

Cyan couplers that can be used in combination with the present invention include oil-protected naphthol couplers and phenol couplers, such as naphthol couplers described in U.S. Pat. No. 2,474,293, and preferably U.S. Pat. No. 4,05
No. 2,212, No. 4.146,396, No. 4.2
Typical examples include the oxygen atom dissociation type dicarbohydrate naphthol couplers described in No. 28,233 and No. 4.296.200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369,929, U.S. Pat.
No. 801,171, No. 2,772.1132, No. 2,895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
72,002, a phenolic cyan coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus; US Pat. No. 2,772,162;
No. 758.308, No. 4,126.396, No. 4
, No. 334,011, No. 4.327,173, West German Patent Publication No. 3,329.729 and Japanese Patent Application No. 1983-4
2,5-diacylamino-substituted phenolic couplers described in U.S. Pat. No. 2671, etc. and U.S. Pat.
．． These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 559 and No. 4,427,767.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in color sensitive materials for photography, as disclosed in U.S. Pat. Kosho 57-
Yellow-colored magenta couplers described in US Pat. No. 39413, etc. or U.S. Pat.
Typical examples include the magenta-colored cyan couplers described in No. 38.258 and British Patent No. 1,146,368.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 4,366.237 and British Patent No. 2,
No. 125,570 contains specific examples of magenta couplers, and European Patent No. 96,570 and West German Application No. 3,2
No. 34.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and special couplers described above may form dimers or more polymers; a typical example of a polymerized dye-forming coupler is described in U.S. Pat. No. 3,451,820.
No. 4,080°211.

A specific example of a polymerized magenta coupler is described in British Patent No.
, 102, 173 and U.S. Pat. No. 4,367.
It is described in No. 282. These couplers may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR couplers, colorless D
IR coupling compounds may also be included. I) In addition to the IR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development.

The above coupler is used in U.S. Pat.
, No. 272,191, No. 2,304,940, No. 2,
311,020, 2,322.027, 2,3
No. 60,289, No. 2゜772.163, No. 2,80
No. 1,170, No. 2.801.171, No. 3,619
, No. 195, British Patent No. 1,151,59.0, German Patent No. 1.143,707, etc. A dispersion dispersed in a hydrophilic colloid is prepared by the method described in JP-A-51-39853, etc. Alternatively, the coupler described above can be used as the polymer coupler of the present invention as described in JP-A-51-59942, JP-A-54-32552, U.S. Pat. No. 4,199.363, etc. It can also be used by impregnating (loading) it using the method described in the following. Impregnated (loaded) here means a state in which the coupler is contained within the polymer coupler latex or a state in which the coupler is deposited on the surface of the coupler latex. However, the exact mechanism by which impregnation (loading) occurs is not known.

In order to satisfy the characteristics required for a photosensitive material, two or more of the above-mentioned couplers can be used together in the same photographic layer, or the same compound can be introduced into two or more different layers. You can also do that.

The couplers of the present invention and couplers that can be used in combination can be introduced into the silver halide emulsion layer by known methods, such as those described in US Pat. No. 2,322. A method such as that described in '027 is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric esters (
diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl lauryl amide) , fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesate esters (e.g. tributyl trimesate), etc., or organic solvents with a melting point of about 30°C to 150°C, such as ethyl acetate, butyl acetate. Lower alkyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
After dissolving in methyl cellosolve acetate etc., it is dispersed in a wood-loving colloid.

The above-mentioned high-boiling point organic solvent and low-boiling point organic solvent may be used in combination.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5.9
The polymer dispersion method described in No. 943 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other woody colloids can also be used alone or together with gelatin. .

In the present invention, the gelatin may be either lime-treated or acid-treated. For details on how to make gelatin, see Arthur Ice.
Veis), The Macromolecule Conflict of Gelatin (The Macromolecule)
lar Chemistry of Gelatin)
, (Academic Pre
ss), published in 1964).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 12 mol % silver iodide.

The average size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, and the edge length in the case of cubic grains, and is expressed as an average based on the projected area) is not particularly limited. It is preferable that the distance is 3 hiro or less.
- Particle size may be narrow or wide.

Silver halide grains in photographic emulsions may have regular crystal bodies such as cubic or octahedral, or may have spherical,
It may have an irregular crystal shape such as a plate shape, or it may have a composite shape of these crystal shapes. It may also consist of a mixture of particles of various crystal systems.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particles.

The photographic emulsion used in the present invention is B-graphkide (P
, 'Glafkides), 'hi'mie ext Physique Photography (C: hi'mie etP)
hysique' Photographique)”
(Paul Monte'l, 1966), V.
, L., Zelikman, et al., “Making and Coating Photography 4-/Re-emulsion (Making and Coating Photography)”
photographic Emulsion” (The Focal Pres.
s) published by Shasha, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt includes the one-sided mixing method,
Either a simultaneous mixing method or a combination thereof may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondroald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
Cadmium salts, zinc salts, lead salts, tanum salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. may be present together.
・゛Silver halide emulsions are usually chemically sensitized. For chemical sensitization, see, for example, Fieser, Fieser, ed.
[lieGrundlagender Pkotogr
apheschen Prozesge'mltSil
ber) Ialogeniden)” (Akademitsushi z”Verlaksgesellschaft
, scheVerlagggesel'1schaft
), pp. 675-734 can be used.
・In other words, 1/1 sulfur sensitization method using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines): Reducing substances (e.g., stannous salts, amines,
Reduction sensitization method using hydrazine derivatives, form, amidine sulfinic acid, silane compounds): Noble metal compounds (for example, total complex salts and pt.

A noble metal sensitization method using complex salts of metals of group (I) of the periodic table such as Ir and Pd can be used alone or in combination. - The photographic emulsion used in the present invention can contain various compounds for the purpose of - preventing fog during the manufacturing process of the light-sensitive material, - storage or photographic processing, or stabilizing photographic properties. . That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles,
Bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercabutotetrazole) ); mercaptopyrimidines; mercaptotriazones: thioketo compounds such as oxadolinthion; 7
) tetraazaindene), pentaazaindene, etc.: benzenethiosulfonic acid, benzenesulfinic acid,
A number of compounds known as antifoggants or stabilizers can be added, such as benzenesulfonic acid amides and the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention is coated with a β-adhesive agent, antistatic, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast). It may contain various surfactants for various purposes such as oxidation, sensitization, etc.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, for the purpose of increasing sensitivity or accelerating development.
It may also contain thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, and 3-pyrazolidones.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other wood-loving colloid layer for the purpose of improving dimensional stability. Alkyl acrylate, alkyl methacrylate, alkoxyalkyl acrylate, alkoxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid , methacrylic ugly, α
, β-unsaturated dicarboxylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate,
Polymers containing combinations of styrene sulfonic acid and the like as monomer components can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.: nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbons are fused to these nuclei, i.e., indolenine nuclei, benzindolenine nuclei,
Indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothia, sol nucleus,
A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes have a ketomethylene structure, including a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2
, 4-dione strain 1, thiazolidine-2,4-dione core,
A 5- to 6-membered heterocyclic nucleus such as a rhodanine nucleus or a thiobarbic acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. .

Along with sensitizing dyes, dyes that themselves do not have spectral sensitizing action or substances that do not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. Nos. 2,933,390, 3, 63,
5. ．． 741), aromatic organic acid formaldehyde condensates (e.g. U.S. Pat. No. 3,743,5'
10), cadmium salts, azaindene compounds, etc.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer and other wood-philic colloid layers.
For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1, 3).

5-triacroyl-hexahydro-5-1 riazine,
1,3-vinylsulfonyl-2-propatol, etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-5-)riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination.

In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the wood-philic colloid layer, they may be mordanted with a cationic polymer or the like.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminephenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g. those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g. U.S. Pat. No. 3,314, '794)
No. 3,352゜681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat.
, 70'5, No. 805, No. 3,707,375), butadiene compounds (for example, those described in U.S. Pat.
045.299) or benzoxazole compounds (e.g., those described in U.S. Pat. No. 3,700,455);
) can be used. Ultraviolet absorbing couplers (eg, α-naphthol cyan dye-forming couplers), ultraviolet absorbing polymers, etc. may be used, and these ultraviolet absorbers may be mordanted in a particular layer.

The photosensitive material produced using the present invention may contain a water-soluble dye in the wood-philic colloid layer as a filter dye or for various purposes such as preventing irradiation. , oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

Photographic processing of layers comprising photographic emulsions made using the present invention includes, for example, Research Disclosure No. 176 No. 2
Any of the known methods and known treatment liquids as described on pages 8 to 30 can be applied. The treatment temperature is usually chosen between 18°C and 50°C, but N3'C
It may be a lower G1 temperature or a temperature exceeding 50°C.

The color developer is generally an alkaline aqueous solution containing a color-forming/developing agent.
-amino-N,N-diethylaniline, 3-methyl-4
-amino-N,N-diethylaniline, -4-amino-N-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4
-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, F. K. Mason (F, A, Maso
n), “Photographic Processing Chemistry”
cessing Chemistry)” (Focal Press’), 196
6), pp. 226-229, U.S. Patent No. 2.193,
No. 015, No. 2,592.364, Japanese Unexamined Patent Publication No. 1986-64
Those described in No. 933 may also be used.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can include. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, It may also contain a fogging agent such as sodium boron hydride, an auxiliary developer such as l-phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, and the like.

After color development, the photographic emulsion layer is usually subjected to a bleaching process. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (■), cobalt (m), chromium (■), and copper (II), peracids, quinones, and nitroso compounds.

For example, ferricyanide, dichromate, iron (III)
) or Kobal) (IIT), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propatoltetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid. Complex salt: persulfate, permanganate: 2) 'tf
f-sophenol and the like can be used. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (I
II) Sodium mulla and iron ethylenediaminetetraacetate (II)
I) Ammonium is particularly useful. Ethylenediaminetetraacetic acid iron (m) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Here, after the fixing step or bleach-fixing step, washing with water,
Although it is common practice to perform treatment steps such as stabilization, only a water washing step is performed, or conversely, only a stabilization treatment step is performed without a substantial water washing step (Japanese Patent Laid-Open No. 57-854).
It is also possible to use a simple processing method such as Japanese Patent Publication No. 3).

The washing water used in the washing step may contain known additives as required. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid;
Bactericidal agents and antifungal agents to prevent the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, and surfactants to prevent drying load and unevenness can be used. Or L.E. West (L, E.

West), °゛Water Quality Criteria
Photographic Science and Engineering (Photo, Sci, and Eng),
Vol, 9 No. 6, pp. 344-359 (19
65) etc. can also be used.

Further, the washing step may be carried out using two or more tanks if necessary, and the washing water may be saved by carrying out multi-stage countercurrent washing (for example, 2 to 9 stages).

As the stabilizing solution used in the stabilization step, a processing solution that stabilizes the dye image is used. For example, 1, pH 3-6
A liquid having a buffer such as 1,000 ml, a liquid containing an aldehyde (for example, formalin), etc. can be used. Optical brighteners, chelating agents, bactericidal agents, fungicides, hardeners, surfactants, and the like can be used in the stabilizing liquid as necessary.

In addition, the stabilization process may be performed using two or more tanks if necessary, and the stabilizing liquid can be saved by performing multi-stage countercurrent stabilization (for example, 2 to 9 stages), and the water washing process can also be omitted. can.

(Effects of the Invention) The silver halide color photographic light-sensitive material of the present invention has extremely excellent color development. In particular, this color photographic material is significantly different from conventional polymer couplers in that it can maintain high color development despite having a high content of coupler units. Therefore, in the color photographic material of the present invention, the coupler-containing emulsion layer can be made thinner and the sharpness can be improved.

(Examples) Next, the present invention will be described in more detail based on Examples. Details of couplers other than the polymer coupler of the present invention and other additives used in sample preparation in each example are given in Example 3.
They are summarized at the end of the page.

Example 1 Sample 101 was obtained by coating an emulsion layer and an auxiliary layer in the following order on a triacetylcellulose support provided with the following layers.

1st layer: red-sensitive emulsion layer 2-(heptafluorobutyramide)-5-(2'-(2''), a low molecular weight cyan coupler.

100 g of 4″-di-t-7minophenoxy)butyramide)-phenol was added to 100 g of tricresyl phosphate.
cc and 500 g of emulsion obtained by dissolving in 100 cc of ethyl acetate and stirring at high speed with 1 kg of 10% gelatin aqueous solution.
1 kg of red-sensitive silver iodobromide (70 g of silver, 60 g of gelatin)
(silver content: 4 mol %) and coated to a dry film thickness of 2 JL (1.5 g silver/G).

2nd layer: Protective layer A 10% gelatin aqueous solution was applied to give a dry film thickness of 2p.

Next, 20 g of the comparative cyan polymer coupler A described below and the cyan polymer couplers (1), (3), and (7) of the present invention were added to the comparative polymer coupler A for one coupler unit (the repeating unit represented by the general formula CI). Equimolar amounts of 3, each containing 15 g of gelatin and 1.2 g of sodium lauryl sulfate, were dissolved by heating in 60 mfL of ethyl acetate.
After adding to 00 mJ1 aqueous solution and dispersing using a colloid mill, ethyl acetate was removed under reduced pressure to obtain latex dispersions (a), (b), and (c).

Sample 102 was prepared in exactly the same manner as Sample 101, except that these latex dispersions were used in place of the cyan coupler emulsion of Sample 101 in an amount such that one unit of coupler was equimolar to the cyan coupler of Sample 101. 103 and 1
I got 04.

These samples 101 to 104 were exposed to light and subjected to the following reversal color processing.

Treatment process Step Time Temperature first phenomenon
6 minutes ゛ Wash with water at 38℃ ° 2
Min' 11 inversion 2
Minutes ゛/1 color development phenomenon 6 minutes 〃
Adjustment: 2 minutes Bleaching: 6 minutes / Fixing: 4 minutes // Washing with water: 4 minutes Stabilization: 1 minute Normally wet and dry A processing solution having the following composition was used.

Supervisor 1 Water 700m
Sentence "Nitrilo-N,N',N-trimethylenephosphonic acid pentasodium salt 2g Sodium sulfite 2.0g Hydroquinone monosulfonate potassium salt 30gψ□ Sodium carbonate (monohydrate) 30g 1-phenyl-4 methyl 4 - Hydroxymethyl-3-pyrazolidone 2g Potassium bromide 2.5g Potassium iodide (0,
1% solution)', 2mJlj・Thioether compound (shown in Table 1) Add water and 100
0m kawarutanmi water -700m nitrotrimethylenephosphonic acid 6Na salt 3g stannous chloride (dihydrate) 1g p-aminophenol 0.1g sodium hydroxide 8g glacial acetic acid
Add 15m Bunsui 1
700m
Nitrilotrimethylenephosphonic acid hexasodium salt 2g Sodium sulfite 7g Sodium triphosphate (decahydrate) 36g Bromic power 1
1g potassium iodide (0.1% solution) 90ml sodium hydroxide 3g citrazic acid 1.5g N.ethyl-N-(β
-methanesulfonamidoethyl) -3-fold methyl-4-amine aniline Q sulfate 11g3.6-cythiaoctane-1.8 diol 1g add water
loooom Bunho! Kanesui 700
Sodium sulfite 12g Ethylenediamine, Sodium tetraacetate (dihydrate) 8g Thioglycerin 0.4m Glacial acetic acid
Add 3mm ice water 1
000m Bunka Page” Wednesday 80
0g Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Iron (m) ethylenediaminetetraacetate Ammonium (dihydrate) 120.0g Potassium bromide 100.0g Add water
1000m Bunsokukansui 800
Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5. Add Ob water
1000m Friendship Naginaki 800m
Bun formalin (37% by weight) 5. , Om Bun Fuji Drywell 5. Add Om Fumiki
When the color density of the cyan image of each development sample obtained in 1000 m was measured, the results shown in the table below were obtained.

Table 3 From these results, it is clear that the cyan polymer coupler of the present invention has extremely excellent coloring properties and can maintain high coloring properties despite having a high coupler unit content.

Example 2 Next, the first to twelfth layers were coated on a triacetate film base 2 in the following order to prepare a color reversal photographic material (201).

First layer: antihalation layer (gelatin layer containing black colloidal silver).

Second layer: gelatin middle layer.

2.5-di-t-octylhydroquinone was dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate, and 2 kg of the emulsion obtained by stirring at high speed with 1 kg of a 10% gelatin aqueous solution was made into fine particles that were not chemically sensitized. 1 kg of emulsion (grain size 0.06..1 mol% silver iodobromide emulsion) was mixed with 1.5 J of 10% gelatin and coated to a dry film thickness of 2 l (silver content 0, 4 g/rrf). ).

Third layer: low-speed red-sensitive emulsion layer 2-(heptafluorobutyramide)-5-(2'-(2''), which is a low molecular weight cyan coupler.

100 g of 4″-di-aminophenoxy)butyramide)-phenol, 100 g of tricresyl phosphate
cc and 100 cc of ethyl acetate, and 500 g of emulsion obtained by stirring at high speed with L kg of 10% gelatin aqueous solution
was mixed with 1 kg of red-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, iodine content was 4 mol %) and coated to a dry film thickness of 1 l. (Amount of silver 0,5 g/
nf) Fourth layer: Highly sensitive red-sensitive emulsion layer 2-(heptafluorobutyramide)-5-(2'-(2''), which is a low molecular weight cyan coupler.

100 g of 4″-di-t-7minophenoxy)butyramide)-phenol was added to 100 g of tricresyl phosphate.
cc and 1'0 Occ of ethyl acetate, and stirred at high speed with 1 kg of 10% gelatin aqueous solution to obtain an emulsion 100
0 g to 1 kg of red-sensitive silver iodobromide emulsion (silver 70
g, contains 60 g of gelatin, iodine content is 2.5 mol%
) and applied to a dry film thickness of 2.5 cm.

(Amount of silver 0.7 g/m') 5th layer: Intermediate layer 2.5-di-t-octylhydroquinone was dissolved in 10'Occ of dibutyl phthalate and 100 cc of ethyl acetate, and 1 kg of an aqueous solution was added to 10% gelatin. 1 kg of the emulsion obtained by high-speed stirring was mixed with 1 kg of 10% gelatin and coated to a dry film thickness of 1 l.

6th layer; Low green-sensitive emulsion layer 1-(2,4,6-)chlorophenyl)-3-' which is a magenta coupler instead of a cyan coupler.
(32(2,4-di-t-7milphenoxyacetamide)benzamide)-5-pyrazolone was used, but 300 g of the emulsion obtained in the same manner as the emulsion of the third layer was added to a green-sensitive emulsion. It was mixed with 1 kg of silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, and the iodine content was 3 mol%) to give a dry film thickness of 1.
I applied it so that there were 3 coats. (Amount of silver: 0.7 g/d) 7th layer: Highly sensitive green-sensitive emulsion layer 1-(
2,4,6-dolichlorophenyl)-3-(3-(2,
1000 g of the emulsion obtained in the same manner as the emulsion of the third layer except that 4-di-t-amylphenoxyacetamido)benzamide)-5-pyrazolone was used was mixed into a green-sensitive silver iodobromide emulsion. 1 kg (containing 70 g of silver and 60 g of gelatin, iodine content is 2.5 mol%) and coated to give a final dry film thickness of 3.5 g/d. (Amount of silver: 0, 8 g/d) No. 8
R: Yellow filter A yellow emulsion containing colloidal silver was coated to a dry film thickness of tg.

9th layer: low-sensitivity blue-sensitivity emulsion layer α-(
pivaloyl)-α-(1-benzyl-5-ethoxy-3
-Hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used, but 1000 g of the emulsion obtained in the same manner as the emulsion of the third layer was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (70 g of silver, Contains 60g of gelatin,
The iodine content is 2.5 mol%), and the dry film thickness is 1.5%.
I applied it for use. (Amount of silver o, e g/rn
') 10th layer; highly sensitive blue-sensitive emulsion layer α-(
pivaloyl)-α-(1-benzyl-5-ethoxy-3
-Hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used, but 1000 g of the emulsion obtained in the same manner as the emulsion of the third layer was mixed with 1 kg of the above-mentioned spherical silver iodobromide emulsion B (70 g of silver, (containing 60 g of gelatin, iodine content is 2.5 mol%), and the dry film thickness is 3.
It was applied so that it became IL. (Amount of silver 1.1g/rn') Layer ii: 2nd protective layer 1kg of the emulsion used in the 3rd layer was mixed with 1kg of 10% gelatin.
The mixture was mixed and applied to a dry film thickness of 2 JL.

12th layer: Fine grain emulsion covered with the surface of the first protective layer (grain size 0.06JL)
A 10% gelatin aqueous solution containing 1 mol % silver iodobromide emulsion) was coated to give a coating weight of 0.1 g of silver and a direct dry film thickness of 0.8.

Sample 201 was created as described above.

Next, the latex dispersion prepared in Example 1 (a), (
Sample 20 except that b) and (-c) were used in place of the cyan coupler emulsion of Sample 201 in an amount such that one unit of coupler was equimolar to the cyan coupler of Sample 201.
Samples 202, 203. '204 was obtained.

Next, 20 g of the comparative polymer coupler B described later and the polymer coupler (11) of the present invention in equimolar amounts as the comparative polymer coupler B in terms of the coupler unit portion were each heated and dissolved in 60 ml of ethyl acetate, followed by 15 g of gelatin and 1.2 g of sodium lauryl sulfate. After dispersing using a colloid mill, ethyl acetate was removed under reduced pressure to obtain latex dispersions (a) and (b).

Sample 205 was prepared in exactly the same manner as Sample 201, except that these latex dispersions were used in place of the magenta coupler emulsion of Sample 201 in an amount such that one unit of coupler was equimolar to the magenta coupler of Sample 201. I got .206.

These samples 2.01 to 206 were exposed to light and processed in the same manner as in Example 1.

Table 4 below shows the results of measuring the color saturation and color image fastness of the cyan and magenta images of each of the development samples obtained.

Example 3 A multilayer color photosensitive material consisting of each layer having the composition shown below on a transparent triacetylcellulose film support (
301) was created.

1st layer; antihalation layer black colloid chain tube...@0.15g/rn' UV absorber U, -1---, 0.08g/rrl' same
Gelatin layer containing U, -2--0,12 g/rn' Second layer: Intermediate layer 2,5-di-t-pentadecylhydroquinone Φ-0,18 g/rn' Force, puller C-1-- -0.11g/-m' 3rd layer of rich gelatin layer; 1st red-sensitive emulsion layer...1.3g, /, m' Sensitizing dyestuff 11%/per mole of medium chain Te1,,4X
10-' mol sensitizing dye ■...0.4 x 10-' mol per mol of silver ■... 5.6 x 10' mol per mol of silver IV-... 1 mol of silver 4.0X10-' molar coupler C-2----0,45'g/rn' coupler C-39Φ conflict・O, O'35 glITf coupler C-4,--,0,025g/rn' Gelatin layer 4th layer containing; second red-sensitive emulsion layer...1.1 g/gold sensitizing dye I-'...5.2 x 10-' per mole of silver
5 moles II-Medium/e 1.5 x 10-5,000 l per mole of silver ■...ll11 2. lX10
Molar IV-...=5 for 1 mole of silver 1.5X1. O mole coupler C-2...φo, 050g/go coupler
C-5...φ0.070g/Go coupler C-3...
・5th layer of gelatin layer containing φ0.035g/d; intermediate layer 2.5-di-t-pentadecylhydroquinone 6th layer of gelatin layer containing O, OBg/d: 1st green-sensitive emulsion layer e- -*0.80g/m' Sensitizing dye V...4.0XIO-' mole per 1 mole of silver ■...3.0XIO equal to eφ1 mole of silver ■---... '1.0X10' for 1 mole of silver
Mol coupler c-6---a, 45g7rf caprani
C-7... 0.13g/ is a coupler C-8... 0.02g/rn' coupler C-4... Participation 0.0
7th layer of gelatin layer containing 4*/ba; 2nd green-sensitive emulsion layer... Φ 0.85 g/G sensitizing dye Vφ-... 2.7x1 o-' mole equivalent to 1 mole of silver ■-. ... 1,8 X i'o-5 mole per mole of silver ■φ・◆・7.5X1 stroke per mole of silver Molar coupler 〇-6---0.095g/rn' coupler C -7--Ichiban o, 8th layer of gelatin layer containing OL5g/G; yellow filter one layer yellow colloidal silver...φ・0.08g/nt'2.5-
Gelatin layer containing di-t-pentadecylhydroquinone - 0,090 g/m' 9th layer: 1st blue-sensitive emulsion layer 1, 0.37 g/rrl' Sensitizing dye ■φ... per mole of silver 4, :4XlO-' molar coupler 〇-9----0.71 g/rrI' coupler C-4-...0,07 g/P 10th layer: 2nd
Blue-sensitive emulsion layer - Gelatin layer containing 0', 55 g/rn' sensitizing dye ■... 3.0 x 10 molar coupler C-9 for 1 mole of silver *0.23 g/m' 11 layers; 1st protective layer ultraviolet absorber U-1-, -0,14g/rn'
U-2... 12th layer of gelatin layer containing 0.22g/gold; 2nd protective layer...0.25g/rn' Polymethacrylate particles (diameter 1, 51L) - gelatin containing 0.10g/gold In addition to the above composition, gelatin hardener H-1 and a surfactant were applied to each layer.

Next, oil-soluble coupler C- added to the third layer of sample 301.
Sample 3 except that 2 was replaced with equimolar amounts of comparative polymer coupler A and inventive coupler (17), respectively.
Samples 302 and 303 were prepared in the same manner as 01.

For these samples, use the A light source and set the color temperature to 4 with a filter.
After adjusting the temperature to 800°K and giving imagewise exposure such that the maximum exposure amount was 20CM, S, the following color development process was performed at 38°C. Red filter processed strips
(Interference filter with maximum transmittance at 646 nm)
The density was measured in Table 5, and the results of the photographic properties are summarized in Table 5.

Color Gen Q 3 minutes 15 seconds bleach 6 minutes 30 seconds water wash 2 minutes 10 seconds fix 4 minutes 20 seconds water wash
3 minutes 15 seconds stable 1 minute 0
The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide 1.4g
Potassium iodide 1.3 mg hydroxylamine sulfate tx 2,4 g 4-(N-ethyl-N-β-hydroxyethylamino)-2 monomethylaniline sulfate 4.5 g Add water
1.0 sentences pH 10.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate
Add 10.0g water
j, og pH6,0 Fixer Ethylenediaminetetraacetic acid disodium salt 1. Og subfE thorium resistant 4.0g ammonium thiosulfate aqueous solution (70%) 175. Om Sodium bisulfite 4.6g Add water
1.0 or P) (60.6 Stable liquid formalin (40%) 2.0m polyoxyethylene-p-monononi J-lephenyl ether (average degree of polymerization 〒10) Add 0.3g water
1.0 The results of Table 5 show that the color development of the polymer coupler of the present invention is better than that of conventional polymer couplers and oil-protected couplers.

Comparative polymer coupler A (compound according to Synthesis Example 9 described in U.S. Pat. No. 3,767,412) x : y-36: 64 (weight ratio) Structure α of the compound used in Example 3 C-2 (described in U.S. Pat. No. 2,895,826 Compound V)
H -J H C-jOH C-t α Month 1 α -r α 11:2 l-7 CI-12-('H-802-CI-12-CON+-
1(CH2)2NHCO-CH2-5o2-CII=C
I-+2 sensitizing dye 11: ( 2H5 ■ 2H5 C2H5 ■

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material containing a polymer coupler having a repeating unit having a coupler residue, represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, R^1 represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom. R^2 and R ^3 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted acylamino group,
Represents a substituted or unsubstituted sulfonamide group, carboxyl group, hydroxyl group, or halogen atom. J is -CO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ -SO_3-, ▲ Mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲
Represents a mathematical formula, chemical formula, table, etc.▼ or ▲A numerical formula, chemical formula, table, etc. exists▼ (R^4 and R^5 each independently represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. Q represents a coupler residue capable of a coupling reaction with an oxidized form of an aromatic primary amine developing agent.)