JPH0827510B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material containing a novel color image-forming polymer coupler capable of coupling with an oxidized product of an aromatic primary amine developing agent. Is.

(Prior Art) Indium phenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and a coupler are produced by reacting a coupler with an aromatic primary amine developing agent which is oxidized by color development after exposure of a silver halide color photographic material. It is known that similar dyes are formed and color images are formed. In this method, a subtractive color method is usually used for color reproduction, and a yellow, magenta, and cyan color image forming agents that have a complementary color relationship with a silver halide emulsion that is selectively exposed to blue, green, and red, respectively. Is used.

By the way, in a multilayer color light-sensitive material, it is necessary to fix each coupler in a separate layer in order to reduce color mixture and improve color reproduction. There are many known methods for making the coupler resistant to diffusion.

One method of making the couplers resistant to diffusion is the use of polymer coupler latices obtained by polymerizing monomeric couplers.

The method of adding the polymer coupler in the form of a latex to the hydrophilic colloid composition has many advantages over other methods.

First, since the hydrophobic material is made into a latex, the strength of the formed film is not deteriorated, and since the latex can contain a high concentration of the monomer coupler, it is easy to add a high concentration of the coupler to the emulsion. Can be included,
Moreover, the increase in viscosity is small.

Further, it has the advantages of no color migration due to no migration, and less precipitation of coupler in the emulsion film.

Examples of such polymer couplers added in the form of latex to a gelatin silver halide emulsion include, for example, U.S. Pat.No. 4,080,211, British Patent 1,247,688, U.S. Pat.
451,802, 3,926,436 and West German Patent No. 2,725,591.

Further, a polymer coupler having a function as a surfactant added to a gelatin silver halide emulsion in the form of a polymer latex without the use of a surfactant is described in U.S. Pat.No. 3,926,436. .

Further, a polymer coupler in which an active group capable of reacting with gelatin is introduced into the polymer coupler to prevent the diffusion of the polymer coupler is described in Japanese Patent Application No. 59-165082.

On the other hand, examples of those aiming to improve the color developability by the copolymerization monomer include those described in US Pat. No. 4,612,278.

(Problems to be Solved by the Invention) However, all the silver halide color photographic light-sensitive materials containing the above-mentioned conventional polymer couplers have insufficient color developability or are sufficiently fast against heat and wet heat. Is hard to say and is not satisfactory.

Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel polymer coupler having a remarkably excellent color forming property.

Secondly, the object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel polymer coupler which gives a color photograph having a color image which is fast against heat and moist heat after development.

(Means for Solving the Problems) The present inventor has conducted various studies in view of the above circumstances, and as a result, a polymer containing at least two repeating units represented by the following general formula [I] in the molecular structure. It has been found that the above object can be achieved by using a coupler.

In the polymer coupler used in the present invention, a repeating unit having no ability to oxidatively couple with an aromatic primary amine developing agent as shown by the general formula [I] Is characterized by having.

That is, the present invention is represented by the following general formula (I),
A silver halide color photographic material comprising a polymer coupler composed of at least two kinds of repeating units Is provided.

(In the formula, R ¹ and R ² may be the same or different from each other, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or chlorine, and L ₁ and L ₃ may be the same or different from each other; (R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —COO—, —NHCO— or —OCO—, and L ₂
And L ₄ may be the same or different from each other, and L ₁ and Q
Or a linking group connecting L ₃ and T, m and m ′ represent 0 or 1, n and n ′ represent 0 or 1, and Q is coupled with an oxidized aromatic primary amine developing agent. Represents a coupler residue capable of forming a dye, T represents a sulfonamide group or a sulfamoyl group, x and y represent the content ratio of each unit in the polymer coupler, and x represents 10 to 10
90% by weight, y is 10 to 90% by weight. n'is preferably 1. In the formula, the alkyl group of R ¹ , R ² and R ³ is meant to include not only an unsubstituted alkyl group but also an alkyl group having a substituent. However, the general formula [I] does not particularly define the arrangement state of each repeating unit in the polymer.

In the polymer coupler represented by the above general formula [I], the linking group represented by L ₂ or L ₄ is specifically X ₁
J ₁ -X _{2 p} J ₂ -X _{3 q} J _{3 r s} , J ₁ , J ₂ , J ₃
May be the same or different, --CO--, --SO _2- , (R ³ is as defined above), (R ³ is as defined above), (R ³ is as defined above), (R ³ is as defined above), (R ³ is as defined above, R ⁴ is an alkylene group having 1 to about 4 carbon atoms), (R ³ and R ⁴ are as defined above, R ⁵ is a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms), a substituted alkyl group (having 1 to 6 carbon atoms)), —O—, —S—, (R ³ and R ⁵ are as defined above), (R ³ and R ⁵ are as defined above) -COO-, -OCO-, (R ³ is as defined above), (R ³ is as defined above) and the like.

X ₁ , X ₂ and X ₃ may be the same or different and each represents an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, an aralkylene group or a substituted aralkylene group. p, q, r and s represent 0 or 1.

Examples of the substituent which may be further substituted on the linking group L ₂ or L ₄ are a halogen atom, a nitro group, a cyano group,
Alkyl group, substituted alkyl group, alkoxy group, substituted alkoxy group, a group represented by -NHCOR ⁶ (R ⁶ is an alkyl group,
A substituted alkyl group, a phenyl group, a substituted phenyl group, an aralkyl group, and a substituted aralkyl group), -NHSO ₂ R ⁶ (R ⁶ and the same meanings as described above), -SOR ⁶ (R ⁶ has the same meanings as above), and -SO ₂ R ⁶ (R ⁶ is as defined above), —COR ⁶ (R ⁶ is as defined above), A group represented by (R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, an aralkyl group or a substituted aralkyl group), (R ⁷ and R ⁸ have the same meanings as described above), an amino group (which may be substituted with an alkyl group), a hydroxyl group or a group which is hydrolyzed to form a hydroxyl group.

Furthermore, examples of the substituents of the substituted alkyl group, the substituted alkoxy group, the substituted phenyl group, and the substituted aralkyl group in the above-exemplified substituents include a hydroxyl group, a nitro group, an alkoxy group having 1 to about 4 carbon atoms, and -NHSO ₂ group represented by R ⁶ (R ⁶ is as defined above), - NHCOR
Groups represented by ⁶ (R ⁶ is as defined above), (R ⁷ and R ⁸ are as defined above), A group represented by (R ⁷ and R ⁸ are as defined above), —SO ₂ R ⁶ (R ⁶
Is the same as the above), —COR ⁶ (R ⁶ is the same as the above), a halogen atom, a cyano group, an amino group (which may be substituted with an alkyl group) and the like.

The sulfonamide group represented by T is represented by —NHSO ₂ R ⁶ (R ⁶ is as defined above), and the sulfamoyl group is (R ⁷ and R ⁸ are as defined above).

Next, among the color coupler residues represented by Q in the general formula (I), the cyan color forming coupler residue is
Phenol-type [II] or naphthol-type [III] and [IV] compounds represented by the following general formula (each hydrogen atom is released and linked to L ₁ or L ₂ ) are preferable.

In the formula, R ¹¹ represents a group capable of substituting for 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 cyano group, an aliphatic group, an aromatic group, and a heterocyclic group, Carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyloxy group, acyl group, aliphatic oxy group, aliphatic thio group, aliphatic sulfonyl group, aromatic oxy group, aromatic thio group, aromatic Examples thereof include a sulfonyl group, a sulfamoylamino group, a nitro group and an imide group. The carbon number of R ¹¹ is 0 to 30.

R ¹² is ^{-CONR 14 R 15, -NHCOR 14,} -NHCOOR 16, -NHSO 2
It represents R ^16, -NHCONR ¹⁴ R ¹⁵ or _{^{-NHSO 2 R 14 R 15, R}} 14
And R ¹⁵ is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (eg, 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 group having 6 to 30 carbon atoms ( For example, phenyl group, tolyl group, 2-tetradecyloxyphenyl group, pentafluorophenyl group, 2-chloro-5
-Dodecyloxycarbonylphenyl group, etc.), carbon number 2
To 30 heterocyclic groups (eg, 2-pyridyl group, 4-pyridyl group, 2-furyl group, 2-thienyl group, etc.), R ¹⁶ is an aliphatic group having 1 to 30 carbon atoms (eg, methyl group, ethyl group). Group, butyl group, dodecyl group, hexadecyl group, etc.), 6 to 30 aromatic groups (eg, phenyl group, tolyl group, 4-chlorophenyl group, naphthyl group, etc.), heterocyclic group (eg, 4-pyridyl group, quinolyl group) Group, 2-furyl group, etc.). R ¹⁴
And R ¹⁵ may combine with each other to form a heterocycle (eg, morpholine ring, piperidine ring, pyrrolidine ring, etc.). p'represents an integer of 0 to 3, q'and r'represent an integer of 0 to 4, respectively.

X ⁴ represents an oxygen atom, a sulfur atom or R ¹⁷ N, and R 4
¹⁷ represents a hydrogen atom or a monovalent group. When R ¹⁷ represents a monovalent group, examples of R ¹⁷ include an aliphatic group having 1 to 30 carbon atoms (eg, methyl group, ethyl group, butyl group, methoxyethyl group, benzyl group, etc.), 6 to 6 carbon atoms. 30 aromatic groups (for example, phenyl group, tolyl group, etc.), C2-C30 heterocyclic groups (for example, 2-pyridyl group, 2-pyrimidyl group, etc.), C1-C30 carbonamido group ( For example, formamide group, acetamide group, N-methylacetamide group, benzamide group, etc.), sulfonamide group having 1 to 30 carbon atoms (eg, methanesulfonamide group, toluenesulfonamide group, 4-chlorobenzenesulfonamide group, etc.), Imido group having 4 to 30 carbon atoms (for example, succinimide group), -OR ¹⁸ , -SR ¹⁸ , -COR ¹⁸ , -CONR ¹⁸ R ¹⁹ , -CO.
COR ¹⁸ , -COCONR ¹⁸ R ¹⁹ , -COOR ²⁰ , -COCOOR ²⁰ , -SO ₂ R
^20, can be mentioned _{^{-SO 2 OR 20, -SO 2 NR}} 18 R 19 and -NR ¹⁸ R ^19. R ¹⁸ and R ¹⁹ may be the same or different, and each is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (for example, a methyl group, an ethyl group, a butyl group, a dodecyl group, a methoxyethyl group, Trifluoromethyl group, heptafluoropropyl group, etc.), aromatic group having 6 to 30 carbon atoms (eg, phenyl group, tolyl group, 4-chlorophenyl group, pentafluorophenyl group, 4-cyanophenyl group, 4-
And a heterocyclic group having 2 to 30 carbon atoms (eg, 4-pyridyl group, 3-pyridyl group, 2-furyl group, etc.). R ¹⁸ and R ¹⁹ may combine with each other to form a heterocycle (eg, morpholino group, pyrrolidino group, etc.).

Examples of R ²⁰ include the substituents shown for R ¹⁸ and R ¹⁹ excluding a hydrogen atom.

Z ¹ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Examples of the group capable of splitting off include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), and a carbon number of 1 to 1.
30 aliphatic oxy groups (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, carboxymethyloxy group, 3-carboxypropyloxy group, 2-methoxyethoxycarbamoylmethyloxy group, 2-methanesulfonylethoxy group, 2 -Carboxymethylthioethoxy group, triazolylmethyloxy group, etc.), aromatic oxy group having 6 to 30 carbon atoms (for example, phenoxy group, 4-hydroxyphenoxy group, 2-acetamidophenoxy group, 2,4
-Dibenzenesulfonamidephenoxy group, 4-phenylazophenoxy group, etc.), a heterocyclic oxy group having 2 to 30 carbon atoms (for example, 4-pyridyloxy group, 1-phenyl-5
-Tetrazolyloxy group, etc.), an aliphatic thio group having 1 to 30 carbon atoms (eg, dodecylthio group, etc.), an aromatic thio group having 6 to 30 carbon atoms (eg, 4-dodecylphenylthio group, etc.), carbon Heterocyclic thio groups having 2 to 30 carbon atoms (for example, 4-pyridylthio group, 1-phenyltetrazol-5-ylthio group, etc.), Acyloxy groups having 2 to 30 carbon atoms (for example, acetoxy group, benzoyloxy group, lauroyloxy group, etc.) ,
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.), an aromatic azo group having 6 to 30 carbon atoms (eg, phenylazo group, 4-chlorophenylazo group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, etc.), An aliphatic oxycarbonyloxy group having 1 to 30 carbon atoms (eg, ethoxycarbonyloxy group, dodecyloxycarbonyloxy group, etc.), an aromatic oxycarbonyloxy group having 6 to 30 carbon atoms (eg, phenoxycarbonyloxy group, etc.), A carbamoyloxy group having 1 to 30 carbon atoms (for example, methylcarbamoyloxy group Si group, dodecylcarbamoyloxy group, phenylcarbamoyloxy group, etc.), a heterocyclic group having 1 to 30 carbon atoms and a nitrogen atom continuous to the active position of the coupler (eg, succinimide group, phthalimido group, hydantoinyl group, pyrazolyl) Group, 2-benzotriazolyl group, etc.) and the like.

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

Preferred as R ¹¹ are a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), aliphatic group (eg, methyl group, ethyl group, isopropyl group, etc.), carbonamide group (eg, acetamide group, benzamide group, etc.), A sulfonamide group (eg, methanesulfonamide group, toluenesulfonamide group, etc.) and the like.

Preferred as R ¹² is -CONR ¹⁴ R ¹⁵ , for example, carbamoyl group, ethylcarbamoyl group, morpholinocarbonyl group, dodecylcarbamoyl group, hexadecylcarbamoyl group, decyloxypropyl group, dodecyloxypropyl group, 2,4- Examples include a di-tert-amylphenoxypropyl group and a 2,4-di-tert-amylphenoxybutyl group.

Preferred as X ¹ is R ¹⁷ N, and further R ¹⁷ N
Preferred as -COR ¹⁸ (for example, formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, pentafluorobenzoyl group,
p-chlorobenzoyl group, etc.), —COOR ²⁰ (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, dodecyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group, etc.),
SO ₂ R ²⁰ (eg, methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, hexadecanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, p
-Chlorobenzenesulfonyl group, etc., -CONR ¹⁸ R ¹⁹ (N, N
-Dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, 4-cyanophenylcarbamoyl group, 3,4-dichlorophenylcarbamoyl group, 4-methanesulfonyl Phenylcarbamoyl group, etc.), —SO ₂ NR ¹⁸ R ¹⁹ (for example, N, N-dimethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-dipropylsulfamoyl group, etc.) It is a base. R ¹⁷
More particularly preferred are -COR ¹⁸ , -COOR ^20.
And a group represented by —SO ₂ R ²⁰ .

Preferred groups as Z ¹ are a hydrogen atom, a halogen atom, an aliphatic oxy group, an aromatic oxy group, a heterocyclic thio group and an aromatic azo group.

The coupler represented by the general formula has substituents R ¹¹ , R ¹² and X ¹
Alternatively, it may be a dimer or a multimer in which Z ¹ is bound to each other through a divalent or higher polyvalent linking group. In this case, the number of carbon atoms shown in each substituent is not limited to this.

The magenta color-forming coupler residue is represented by the general formulas [V], [VI], [VII], [VIII], [IX], and [X].
And a coupler residue represented by [XI] (Ar, Z ² , R ²¹
Connect to L _{1 m} L _{2 n} at any part of ~ R ³³ )
Represents

Wherein Ar is a substituent of the well-known type at the 1-position of the 2-pyrazolin-5-one coupler, such as an alkyl group, a substituted alkyl group (for example, a haloalkyl such as fluoroalkyl,
Cyanoalkyl, benzylalkyl, etc.), aryl group or substituted aryl group [as a substituent, an alkyl group (eg, methyl group, ethyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenyloxy) Groups), alkoxysylbonyl groups (eg methoxycarbonyl groups), acylamino groups (eg acetylamino groups), carbamoyl groups, alkylcarbamoyl groups (eg methylcarbamoyl groups, ethylcarbamoyl groups etc.), dialkylcarbamoyl groups (eg dimethylcarbamoyl groups). Group), arylcarbamoyl group (eg phenylcarbamoyl group), alkylsulfonyl group (eg methylsulfonyl group), arylsulfonyl group (eg phenylsulfonyl group), alkylsulfonamide group ( In example methanesulfonamido group),
Aryl sulfonamide group (eg phenyl sulfonamide group), sulfamoyl group, alkylsulfamoyl group (eg ethylsulfamoyl group), dialkylsulfamoyl group (eg dimethylsulfamoyl group), alkylthio group (eg methylthio group, Examples thereof include an arylthio group (eg, phenylthio group), a cyano group, a nitro group, and a halogen atom (eg, fluorine, chlorine, bromine, etc.), and when two or more substituents are present, 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 cyano group. ], A heterocyclic group (eg, triazole, thiazole, benzthiazole, furan, pyridine, quinaldine, benzoxazole, pyrimidine, oxazole, imidazole, etc.).

R ²¹ 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). As these substituents, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), a linear or branched alkyl group (eg, methyl group, t-butyl group, octyl group, tetradecyl group, etc.), alkoxy Group (for example, methoxy group, ethoxy group, 2-ethylhexyloxy group, tetradecyloxy group, etc.), acylamino group (for example, acetamide group, benzamide group, butanamide group, octanamide group, tetradecanamide group, α- (2,4 -Di-tert-amylphenoxy) acetami Group, α- (2,4-di-ter
t-amylphenoxy) butyramide group, α- (3-pentadecylphenoxy) hexanamide group, α- (4-
Hydroxy-3-tert-butylphenoxy) tetradecanamide group, 2-oxo-pyrrolidin-1-yl group, 2
An -oxo-5-tetradecylpyrrolidin-1-yl group,
N-methyl-tetradecanamide group etc.), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, ethylsulfonamide group, p-toluenesulfonamide group, octanesulfonamide group, p-
Dodecylbenzenesulfonamide group, N-methyl-tetradecanesulfonamide group, etc., sulfamoyl group (for example, sulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N, N-dimethylsulfamoyl group) , N, N-dihexylsulfamoyl group,
N-hexadecylsulfamoyl group, N- [3- (dodecyloxy) -propyl] sulfamoyl group, N- [4
-(2,4-di-tert-amylphenoxy) butyl] sulfamoyl group, N-methyl-N-tetradecylsulfamoyl group, etc., carbamoyl group (for example, N-methylcarbamoyl group, N-butylcarbamoyl group, N -Octadecylcarbamoyl group, N- [4- (2,4-di-tert-
Amylphenoxy) butyl] carbamoyl group, N-methyl-N-tetradecylcarbamoyl group, etc., diacylamino group (N-succinimide group, N-phthalimido group, 2,5-dioxo-1-oxazolidinyl group, 3-dodecyl- 2,5-dioxo-1-hydantoinyl group, 3-
(N-acetyl-N-dodecylamino) succinimide group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, tetradecyloxycarbonyl group, benzyloxycarbonyl group etc.), alkoxysulfonyl group (eg methoxysulfonyl group, butoxysulfonyl group). Group, octyloxysulfonyl group, tetradecyloxysulfonyl group, etc.), aryloxysulfonyl group (eg, phenoxysulfonyl group, p-methylphenoxysulfonyl group, 2,4-di-tert-amylphenoxysulfonyl group, etc.), alkanesulfonyl Groups (eg,
Methanesulfonyl group, ethanesulfonyl group, octanesulfonyl group, 2-ethylhexylsulfonyl group, hexadecanesulfonyl group, etc.), arylsulfonyl group (eg, benzenesulfonyl group, 4-nonylbenzenesulfonyl group, etc.), alkylthio group (eg, methylthio group) , Ethylthio group, hexylthio group, benzylthio group,
Tetradecylthio group, 2- (2,4-di-tert-amylphenoxy) ethylthio group, etc.), arylthio group (eg, phenylthio group, p-tolylthio group, etc.), alkyloxycarbonylamino group (eg, methoxycarbonylamino) Group, ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group, etc., alkylureido group (eg, N-methylureido group, N, N-dimethylureido group, N-methyl-N-dodecyl) Ureido group, N-hexadecylureido group, N, N-dioctadecylureido group, etc., acyl group (for example, acetyl group, benzoyl group,
Octadecanoyl group, p-dodecanamidobenzoyl group and the like), nitro group, carboxyl group, sulfo group, hydroxy group, trichloromethyl group and the like.

However, among the above substituents, the number of carbon atoms defined as an alkyl group represents 1 to 36, and the number of carbon atoms defined as an aryl group represents 6 to 38.

R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ ,
R ³¹ , R ^32, and R ³³ are each a hydrogen atom, a hydroxyl group, or an unsubstituted or substituted alkyl group (preferably having a carbon number of 1 to 20. For example, a methyl group, a propyl group, or a t-butyl group. , Trifluoromethyl group, tridecyl group, etc.), aryl group (preferably 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 (for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), alkylamino group (preferably Having 1 to 20 carbon atoms, such as methylamino group, diethylamino group, t-
Butylamino group, etc.), acylamino group (preferably having 2 to 20 carbon atoms, for example, acetylamino group, propylamide group, benzamide group, etc.), anilino group (eg, phenylamino group, 2-chloroanilino group, etc.), alkoxycarbonyl A group (preferably having 2 to 20 carbon atoms. For example, methoxycarbonyl group, butoxycarbonyl group, 2
-Ethylhexyloxycarbonyl group, etc.), alkylcarbonyl group (preferably having 2 to 20 carbon atoms.
Acetyl group, butylcarbonyl group, cyclohexylcarbonyl group, etc., arylcarbonyl group (for example, preferably having 7 to 20 carbon atoms, benzoyl group, 4-t-butylbenzoyl group, etc.), alkylthio group (preferably having 1 carbon atom) To 20. For example, methylthio group, octylthio group, 2-phenoxyethylthio group, etc., arylthio group (preferably having 6 to 20 carbon atoms), for example, phenylthio group, 2-butoxy-5-t-octylphenylthio group. Group), a carbamoyl group (preferably having a carbon number of 1 to 20. For example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N-methyl-N-butylcarbamoyl group, etc.), sulfamoyl group (preferably Having up to 20 carbon atoms, for example, N-ethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N- Dipropylsulfamoyl group) or a sulfonamide group (preferably having a carbon number of 1 to 20, for example, methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.).

Z ² represents a hydrogen atom or a group capable of splitting off with an oxidized product of an aromatic primary amine developing agent by a coupling reaction. Examples of the group capable of splitting off include a halogen atom (for example, chlorine atom, bromine atom, etc.) and a coupling splitting off group linked by an oxygen atom (for example, acetoxy group, propanoyloxy group, benzoyloxy group, ethoxyoxaloyloxy group, pill). Vinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-titaniumsulfonamidophenoxy group, α-naphthoxy group, 4-cyanoxyl group, 4-methanesulfonamido-phenoxy group, α-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxy-ethoxy group, 5-phenyltetrazolyloxy group, 2- Benzothiazolyloxy group, etc.),
Coupling-off group linked by nitrogen atom
No. 57-189538, specifically benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptalfluorobutanamide group, 2,3,4,5,6-
Pentafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, 1
-Benzyl-5-ethoxy-3-hydantoinyl group, 2
-Oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2,4-triazol-1-yl group, 5- or 6-bromo-benzotriazole-1 -Yl group, 5-methyl-1,2,3,4-triazol-1-yl group, benzimidazolyl group, etc.),
Coupling-off groups linked by sulfur atoms (for example, phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, benzylthio group Group, 2-cyanoethylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group, 2
-Benzothiazolyl group, etc.). The releasable group is preferably a halogen atom, a coupling-off group linked by an oxygen atom, a coupling-off group linked by a nitrogen atom, and particularly preferably an aryloxy group, a chlorine atom, a pyrazolyl group, an imidazolyl group, triazolyl. It is a base.

The yellow color-forming coupler residue is an acylacetanilide type, particularly a pivaloylacetanilide type [XII] -1, [XII] -2, benzoylacetanilide type [XIII] -1, [XIII] represented by the following general formula. -2,
[XIV] is preferable.

In the formula, R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ 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 or an alkoxycarbamoyl group. , Aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamide group, arylsulfamoyl group, aryl Represents a sulfonamide group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, and the like,
These substituents may be the same or different.

Z ³ is a hydrogen atom or the following general formula [XV], [XVI] [XVI
I] or [XVIII].

R ³⁸ represents an optionally substituted aryl group or heterocyclic group.

R ³⁹ and R ⁴⁰ are each a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group,
It represents an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group or a heterocycle, and these groups may be the same or different.

W ₁ in the formula Together with, a 4-membered ring, a 5-membered ring and a 6-membered ring represent a non-metal atom required to form a 6-membered ring.

Of the general formula [XVIII], [XIX] to [XXI] are preferable.

In the formula, R ⁴¹ and R ⁴² are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group, and R ⁴³ , R ⁴⁴ and R ⁴⁵ are each a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. Or, an acyl group and W ₂ represents an oxygen atom or a sulfur atom.

Among the compounds represented by the general formula [I], particularly preferable compounds are as follows.

R ¹ and R ² may be the same or different and each is a hydrogen atom or a methyl group, L ₁ and L ₃ are —CONH— or —COO—, m and m ′ are 1, n and n are n and n. ′ Is 0 or 1, T is —NHCOCH ₃ , —NHCOC ₂ H ₅ , —CONH ₂ , —CONHCH.
_{3, -NHSO 2 CH 3, -SO} 2 NH 2, And J ₁ , J ₂ and J ₃ may be the same or different,
_{CO -, - SO 2 -,} - CONH -, - SO 2 NH -, - NH-CO -, -
_{, - - NH-SO 2 O} -, - NHCONH -, - S -, - CO 2 -, -
OCO−, —NHCO ₂ — and —OCONH—, X ₁ , X ₂ and X ₃ may be the same or different, and an alkylene group (having 1 carbon atom).
To 4), an arylene group or a substituted arylene group, p,
q, r and s are 0 or 1.

The polymer coupler represented by the general formula [I] has the general formula [XX
II] and [XXIII].

Here, the monomer [XXII] can be referred to as a monomer coupler, and the monomer [XXIII] can be referred to as a comonomer.

Next, typical examples of the monomers [XXII] and [XXIII] are shown, but the monomers are not limited thereto. In addition, the monomer [XX
Each of II] and [XXIII] may be used alone or in combination of several kinds.

Example of monomer [XXII] Examples of Monomer [XXIII] However, Monomers (32) and (37) to (40) are reference compounds.

In order to adjust the physical and chemical properties (eg, solubility, stability in gelatin, etc.) of the polymer coupler obtained by the general formula [I], in addition to the monomers represented by the general formulas [XXII] and [XXIII], You may use the monomer shown by. This is a monomer [XXII], [XXIII]
Similarly to the above, one kind may be used, or several kinds may be used in combination depending on the purpose.

Other examples include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (for example, methacrylic acid),
Esters or amides derived from these acrylic acids (eg, acrylamide, methacrylamide,
n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methyl acrylate,
Ethyl acrylate, n-propyl acrylate, n-
Butyl acrylate, t-butyl acrylate, iso-
Butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n
-Butyl methacrylate and β-hydroxymethacrylate), vinyl esters (eg vinyl acetate,
Vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, Examples thereof include, but are not limited to, vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-vinyl pyridine. .

As is well known in the field of polymer couplers, the above general formula [XX
II] and the physical and / or chemical properties of the copolymer formed with [XXIII] or further any monomer, such as solubility, the binder of the photographic colloid composition, eg gelatin. The compatibility, its flexibility, thermal stability etc. can be chosen to be favorably influenced.

The polymer coupler used in the present invention may be prepared by emulsifying and dispersing a polymer coupler obtained by polymerizing a monomer coupler in an organic solvent, as described above, in the form of a latex in a gelatin aqueous solution, or It may be directly produced by emulsion polymerization.

US Pat. No. 3,451,820 for emulsifying and dispersing a polymer coupler in the form of a latex in an aqueous gelatin solution.
No. 4,080,211 regarding emulsion polymerization,
The method described in No. 3,370,952 can be used.

The synthesis of the polymer coupler of the present invention is carried out by using, as a polymerization initiator and a polymerization solvent, JP-A-56-5543, JP-A-57-94752, and JP-A-5-19552.
7-176038, JP-A-57-204038, JP-A-58-28745,
JP-A-58-10738, JP-A-58-42044, Japanese Patent Application No. 57-29683
The compound described in No.

The polymerization temperature must be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc.
Polymerization is possible in the range of 30 ° C to 100 ° C, although the temperature can be up to above ℃.

The proportion of the color-forming portion corresponding to the general formula [XXII] in the coupler is usually desired to be 10 to 90% by weight, but the color reproducibility,
From the viewpoint of color developability and stability, 20 to 80% by weight is preferable.
In this case, the equivalent molecular weight (the number of grams of the polymer containing 1 mol of the monomer coupler) is about 250 to 4000, but is not limited thereto.

The polymer coupler latex of the present invention is added to the silver halide emulsion layer or its adjacent layer.

The polymer coupler latex of the present invention is based on the coupler monomer, and when the same layer as silver halide is used, silver 1 is used.
It is preferable to add 0.005 to 0.5 mol, preferably 0.01 to 0.10 mol, per mol.

The coating amount of the case of using a polymer coupler latex of the present invention in the non-photosensitive ^{layer, 0.01g / m 2 ~1.0g / m} 2, preferably in the range of ^{0.1g / m 2 ~0.5g / m 2} .

Typical synthetic examples of the polymer coupler of the present invention are shown below.

[Production Process (I)] Synthesis Example (1) Polymer Coupler I (Copolymer of Monomer Coupler (3) and Monomer (31)) 80 g of Exemplified Monomer (3), 20 g of Exemplified Monomer (31), and N, A mixture of 500 ml of N-dimethylacetamide was heated to 80 ° C. in a nitrogen stream with stirring, and then 10 ml of an ethanol solution containing 0.5 g of dimethyl azobisisobutyrate was added to initiate polymerization. After reacting for 5 hours, the reaction solution was cooled, poured into 1.5 l of water, the precipitated solid was separated by filtration, and further washed sufficiently with water.

By heating and drying this solid under reduced pressure, 95.3 g of polymer coupler (I) was obtained.

This polymer coupler contained 81.3% of the exemplified monomer coupler (3) component in the polymer formed by chlorine analysis.

Synthesis Example (2) Polymer Coupler II (Copolymer of Exemplified Monomer Coupler (14) and Exemplified Comonomer (31)) Exemplified Monomer (14) 80 g, Exemplified Monomer (32) 20 g and N, N-Ditylacetamide 500 ml The mixture was heated to 65 ° C under a nitrogen stream under stirring, and then dimethyl azobisisobutyrate 0.
20 ml of a methyl cellosolve solution containing 4 g was added to initiate polymerization. After reacting for 8 hours, the reaction solution was cooled, poured into water 1 and the precipitated solid was separated by filtration and further thoroughly washed with water.

By heating and drying this solid under reduced pressure, 96.8 g of polymer coupler (II) was obtained.

This polymer coupler contained 80.7% of the exemplified monomer coupler (15) component formed by fluorine analysis.

Synthesis Examples (3) to (15) According to the method of Synthesis Example (1), a polymer coupler was synthesized using a monomer coupler and a comonomer as shown in Table 1 below. The results are shown in the table.

[Production Method (II)] Synthesis Example (16) Polymer Coupler XVI (Copolymer of Exemplified Monomer Coupler (14) and Exemplified Comonomer (31)) 3 g of oleylmethyl tauride is contained in a 2 l flask.
A 1.2 liter aqueous solution was heated to 85 ° C with stirring under a nitrogen stream, and 30 ml of a 2% aqueous solution of potassium persulfate was added to the aqueous solution, and then 20 g of the exemplified monomer coupler (14) and 40 g of the exemplified comonomer (31) were added to methanol. A solution dissolved by heating in 400 ml was added dropwise over 20 minutes.

 After reacting for 2 hours, methanol was distilled off.

After cooling the formed latex with 1N sodium hydroxide
The pH was adjusted to 6.0 and filtered.

The latex formed has a polymer concentration of 5.2%, and fluorine analysis shows that it is 34.0% in the polymer monomer coupler (14).
It was found that the ingredients were included.

According to the method of Synthesis Example (16), a polymer coupler was synthesized by copolymerizing a monomer coupler and a comonomer as shown in Table 2 below. The results are shown in the table.

The polymer couplers of the present invention can be used alone or in admixture of two or more.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodobromide containing about 30 mol% or less of silver iodide. Particularly preferred is about 2 mol% to about 25 mol%
It is a silver iodobromide containing up to silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may have a regular crystal such as a tetradecahedron, an irregular crystal form such as a sphere or a plate, a crystal defect such as a twin plane, or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD), No. 17643 (1978).
December 23, p. 22-23, "I. Emulsion production (Emulsion prepara
and types) ”, and No. 18716 (November 1979)
Mon), p.648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemic et Phisique P
hotographique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photo
graphic Emulsion Chemistry (Focal Press, 1966)),
"Production and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VLZelikman et al, Making and Cating P
It can be prepared using the method described in hotographic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, they may be joined by means of epitaxial joining from silver halides having different compositions, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide.

 Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure No. 1
7643 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in Research Disclosure (RD) No. 17643, VII-C to G mentioned above.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, JP-B-58-10739, UK Patent No. 1,425,020,
Preferred are those described in JP-A No. 1,476,760 and the like.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
No. 619, No. 4,351,897, European Patent No. 73,636, US Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-335.
52, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, US Pat. No. 4,500,630,
Those described in No. 4,540,654 and the like are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,
No. 308, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent 121,365A, U.S. Patent No. 3,446,622, No. 4,333,999, No. 4,451,559,
Those described in, for example, No. 4,427,767 and European Patent No. 161,626A are preferable.

Colored couplers to correct unwanted absorption of colored dyes are Research Disclosure No. 17643 VII-
Paragraph G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, and British Patent 1,14.
Those described in 6,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusibility,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,612,273, British Patent No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler which releases the development inhibitor is RD17643, the patent described in the section VII-F, JP-A-57-151944, and JP-A-57-154234.
And Nos. 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,393,
Multi-equivalent couplers described in JP-A No. 4,310,618 and the like, JP-A-60-
Examples thereof include DIR redox compound releasing couplers described in 185950 and the like, and couplers which release a dye that restores color after separation described in EP 173,302A.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The steps of the latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention are, for example, those mentioned above.
RD, No. 17643, page 28, and No. 18716, page 647, right column to page 648, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD, N
O.17643, pages 28-29, and No. 18716, 651, left column to right column, the development can be carried out by a usual method.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering processing such as fixing or bleach-fixing.

The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as the coupler), the application, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Among these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and T
elevision Engineers) Volume 64, pp.248-253 (1955 No. 5)
It can be obtained by the method described in (Month issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method for reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" It is also possible to use the bactericides described in "Microbial Sterilization, Sterilization, and Antifungal Techniques" edited by the Sanitary Technology Association, "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Society for Antibacterial and Antifungal Society of Japan.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to
9, and preferably 5-8. The washing water temperature and washing time may be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of seconds to 5 minutes is selected.

Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, JP-A-57-8543, 58-14834,
59-184343, 60-220345, 60-238832, 60-
239784, 60-239749, 61-4054, 61-118749
All the known methods described in the publications and the like can be used. Especially 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazoline-3
A stabilizing bath containing -one, a bismuth compound, an ammonium compound and the like is preferably used.

Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. .

(Effect of the Invention) The silver halide color photographic light-sensitive material of the present invention is remarkably excellent in color developability.

Further, the silver halide color photographic light-sensitive material of the present invention has a remarkable effect of giving a color photograph of a color image which is robust against heat and moist heat after development processing.

(Example) Next, the present invention will be described in more detail based on examples.

Example 1 A sample A was obtained by coating an emulsion layer and an auxiliary layer in the following order on a triacetyl cellulose support provided with the following layers (see Table 3 below).

First layer: red-sensitive emulsion layer 2- (heptafluorobutyramide) -5, which is a low molecular weight cyan coupler as compared with a polymer coupler.
{2 '-(2 ", 4" -di-t-aminophenoxy)
Butylamide} -phenol (100 g) was dissolved in tricresyl phosphate (100 cc) and ethyl acetate (100 cc), and 10 g of an aqueous gelatin solution (1 kg) was stirred at high speed to obtain an emulsion (500 g).
The mixture was mixed with 1 kg of a red-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, and the iodine content was 4 mol%) and coated so that the dry film thickness was 2 μm (silver 1.5 g / m ² ).

Second layer: protective layer A 10% gelatin aqueous solution was applied so as to have a dry film thickness of 2 μm.

Next, as shown in Table 3 below, Comparative Polymer Cyan Coupler A 14.3 g or Comparative Polymer Cyan Coupler B
((18) described in U.S. Pat. No. 4,612,278 (R ⁹ =
H)), the polymer cyan coupler of the present invention (I
Equal amounts of I) or (V) were dissolved in 60 ml of ethyl acetate in equimolar amounts with respect to each other, and added to 300 ml of an aqueous solution containing 15 g of gelatin and 1.2 g of sodium lauryl sulfate, and dispersed using a colloid mill. The ethyl acetate was removed under reduced pressure, and the polymer cyan coupler A,
Latex dispersions (a), (b), (c) and (d) corresponding to polymer cyan coupler B, polymer cyan coupler (II) and polymer cyan coupler (V), respectively.
I got

Sample A except that these latex dispersions were used in place of the emulsion of the cyan coupler of sample A in an amount such that the coupler unit was equimolar to the cyan coupler of sample A.
Samples B, C, D and E were obtained in exactly the same manner as in.

These samples A to E were exposed to light and subjected to the following reverse color processing.

The processing steps and processing solutions used here are as follows.

Treatment process Time Temperature First development 6 minutes 38 ℃ Washing with water 2 minutes 〃 Inversion 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Fixing 4 minutes 〃 Water washing 4 minutes 〃 Stable 1 minute Normal temperature Drying The composition was used.

Black-and-white developer Water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid 5 sodium salt 2 g Sodium sulfite 20 g Hydroquinone monosulfonate potassium salt 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4 -Hydroxymethyl-3 pyrazolidone 2g Potassium bromide 2.5g Potassium iodide (0.1% solution) 2ml Thioether compound (shown in Table 1) Water was added 1000ml Reversal solution water 700ml Nitrilosilimethylenephosphonic acid 6Na salt 3g Chloride chloride 1 tin (dihydrate) 1 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water is added to 1000 ml Color developer water 700 ml Nitrilotrimethylenephosphonic acid 6 sodium salt 2 g Sodium sulfite 7 g Sodium triphosphate (12 water) 36g potassium bromide 1g potassium iodide (0.1% solution) 90ml sodium hydroxide 3g citrazinic acid 1.5g N ・Ethyl-N- (β-methanesulfonamidoethyl) -3 ・ methyl-4-aminoaniline ・ sulfate 11g 3,6-dithiaoctane-1,8-diol 1g Water was added 1000ml Preparation water 700ml Sodium sulfite 12g Ethylenediamine , Sodium tetraacetate (dihydrate) 8g
Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water was added 1000 ml Bleaching solution Water 800 ml Ethylenediaminetetraacetic acid sodium salt (dihydrate) 2.0 g
Ethylenediaminetetraacetate Ammonium iron (III) (dihydrate) 120.0g Kalimuu bromide 100.0g Add water 1000ml Fixer water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water 1000ml Stabilizer water 800 ml Formalin (37% by weight) 5.0 ml Fuji Drywell 5.0 ml Water was added to 1000 ml The color density of the cyan image and the color image fastness of the developed sample obtained are shown in Table 3.

From the results in the above table, it is clear that the cyan polymer coupler of the present invention is remarkably excellent in color forming property and forms a color image which is fast against heat and wet heat in a color photograph after development processing.

Example 2 Next, a color reversal photographic light-sensitive material was prepared by coating first to twelfth layers on a triacetate film base in the following order.

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

Second layer: gelatin intermediate layer.

A 2,5-di-tert-octylhydroquinone was dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate, and 2 kg of an emulsion obtained by stirring at high speed with 1 kg of an aqueous solution of 10% gelatin 2 kg was not chemically sensitized. Size 0.06μ, 1
1% of mol% silver iodobromide emulsion was mixed with 1.5 kg of 10% gelatin and coated so that the dry film thickness was 2 μ (silver amount 0.4 g
/ m ^2).

Third layer: low-sensitivity red-sensitive emulsion layer 2- (heptafluorobutylamide) -5- {2 '-(2 ", 4" -di-t-aminophenoxy) butylamide} -phenol 100 g which is a cyan coupler Was dissolved in 100 cc of tricresyl phosphate and 100 cc of ethyl acetate, and 500 g of an emulsion obtained by stirring at high speed with 1 kg of a 10% aqueous gelatin solution, 1 kg of a red-sensitive silver iodobromide emulsion (including 70 g of silver and 60 g of gelatin). , Iodine content was 4 mol%), and applied so that the dry film thickness was 1 μm. (Silver 0.5 g / m ² ) 4th layer; high-sensitivity red-sensitive emulsion layer 2- (heptafluorobutyramide) -5- {2 '-(2 "', 4" -di-t-, which is a cyan coupler. Aminophenoxy) butyramide} -phenol (100 g) was dissolved in tricresyl phosphate (100 cc) and ethyl acetate (100 cc), and 10 g of an aqueous gelatin solution (1 kg) was stirred at high speed to obtain 1000 g of an emulsion, and 1 kg of a red-sensitive silver iodobromide emulsion. (Containing 70 g of silver and 60 g of gelatin and having an iodine content of 2.5 mol%), and coated so that the dry film thickness would be 2.5 μm. (Silver amount: 0.7 g / m ² ) Fifth layer: Intermediate layer 2,5-di-t-octylhydroquinone was dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate, and obtained by stirring at high speed with 1 kg of an aqueous solution in 10% gelatin. Emulsion 1kg
Was mixed with 1 kg of 10% gelatin and applied so as to give a dry film thickness of 1 μm.

Sixth layer: low-green emulsion layer Magenta coupler instead of cyan coupler 1-
(2,4,6-Trichlorophenyl) -3- {3- (2,4-di-t-amylphenoxyacetamide) benzamide}-
300 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 5-pyrazolone was used, and 1 kg of a green-sensitive silver iodobromide emulsion
(Contains 70g silver and 60g gelatin, iodine content is 3mol%)
Was mixed and coated to give a dry film thickness of 1.3 μm. (Silver amount: 0.7 g / m ² ) 7th layer: Highly sensitive green emulsion layer A magenta coupler instead of a cyan coupler 1-
(2,4,6-Trichlorophenyl) -3- {3- (2,4-di-t-amylphenoxyacetamide) benzamide}-
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 5-pyrazolone was used, and 1 kg of a green-sensitive silver iodobromide emulsion
(Containing 70 g of silver and 60 g of gelatin, the iodine content was 2.5 mol%), and coated so that the dry film thickness was 3.5 μm.
(Amount of silver: 0.8 g / m ² ) Eighth layer: yellow filter layer An emulsion containing yellow colloidal silver was coated so as to have a dry film thickness of 1 μm.

Ninth layer: low-sensitivity blue-sensitive emulsion layer α-which is a yellow coupler instead of the cyan coupler
(Pivaloyl) -α- (1-benzyl-5-ethoxy-
3-Hydantoynyl) -2-chloro-5-dodecyloxycarbonylacetanilide was used, except that 1000 g of an emulsion obtained in the same manner as the emulsion of the third layer was used, and 1 kg of a blue-sensitive silver iodobromide emulsion (70 g of silver). , 60 g of gelatin, and the iodine content was 2.5 mol%), and the mixture was applied to give a dry film thickness of 1.5 μm. (Silver amount: 0.6 g / m ² ) 10th layer: High-sensitivity blue-sensitive emulsion layer α- which is a yellow coupler instead of the cyan coupler
(Pivaloyl) -α- (1-benzyl-5-ethoxy-
3-Hydantoynyl) -2-chloro-5-dodecyltooxycarbonylacetanilide was used, except that 1000 g of an emulsion obtained in the same manner as the emulsion of the third layer was used, and 1 kg of the above-mentioned spherical silver iodobromide emulsion B1 (silver The mixture was mixed with 70 g and 60 g of gelatin, and the iodine content was 2.5 mol%), and the mixture was applied so as to have a dry film thickness of 3 μm. (Amount of silver: 1.1 g / m ² ) 11th layer; 2nd protective layer 1 kg of the emulsion used in the 3rd layer was mixed with 1 kg of 10% gelatin and applied so as to give a dry film thickness of 2 μm.

12th layer: 1st protective layer Fine grain emulsion whose surface is fogged (grain size 0.06μ, 1
A 10% aqueous gelatin solution containing (mol% silver iodobromide emulsion) was coated so that the silver coating amount was 0.1 g / m ² and the dry film thickness was 0.8 μ.

The sample manufactured as described above is shown in Table 4 below as Sample No. 101.

Next, the latex dispersion (b) prepared in Example 1,
Samples 102, 103, and 103 were prepared in exactly the same manner as Sample 101, except that (c) and (d) were used instead of the emulsion of the cyan coupler of Sample 101 in an amount of equimolar to the cyan coupler of Sample 101 in coupler units. Got 104.

Next, as shown in Table 4, 14.3 g of the comparative polymer coupler (C) (compound of (3) described in US Pat. No. 4,612,278) or the polymer coupler (XII) of the present invention was used in equimolar amounts with respect to the color-forming unit. Each of them was dissolved in 60 ml of ethyl acetate by heating, added to 300 ml of an aqueous solution containing 15 g of gelatin and 1.2 g of sodium lauryl sulfate, dispersed using a colloid mill, and then ethyl acetate was removed under reduced pressure to disperse each latex (e). , (F) were obtained.

These latex dispersions were used in place of the emulsion of the magenta coupler of sample 101, except that the amount was equimolar to the magenta coupler of sample 101 in coupler unit.
Samples 105 and 106 were obtained in exactly the same manner as 101.

These samples 101 to 106 were exposed to light and treated in the same manner as in Example 1.

The following table shows the results of comparison of the color densities of the cyan and magenta images and the color image fastness of the obtained developed samples.

From the results shown in Table 4, it is apparent that the polymer coupler of the present invention is remarkably excellent in color forming property and forms a color image which is fast against heat and moist heat in a color photograph after development processing.

Example 3 A multi-layer color light-sensitive material (301) having the following compositions was formed on a transparent triacetyl cellulose film support.

1st layer; antihalation layer Black colloidal silver ... 0.15 g / m ² UV absorber U-1 ・ ・ ・ 0.08 g / m ² U-2 ・ ・ ・ Gelatin containing 0.12 g / m ² Layer Second layer; Intermediate layer 2,5-di-t-pentadecylhydroquinone..0.18g / m
² coupler C-1: Gelatin layer containing 0.11 g / m ² 3rd layer; 1st red-sensitive emulsion layer ・ ・ ・ ・ 1.2g / m ² Sensitizing dye I ・ ・ ・ ・ ・ ・ 1.4 × 10 ^-4 mol per 1 mol of silver Sensitizing dye II ・ ・ ・ ・ ・ ・ 0.4 × 10 ^-4 mol per 1 mol of silver III ・ ・ ・ ・ 5.6 × 10 ^-4 mol per 1 mol silver IV ・ ・ ・ ・ 4.0 × 10 ^-4 mol per 1 mol silver Coupler C-2 ・ ・ ・ ・ ・ ・ 0.45 g / m ² coupler C -3 · · · · 0.035 g / m ² coupler C-4 gelatin layer a fourth layer including a ···· 0.018g / m ^2; the second red-sensitive emulsion layer ・ ・ ・ 1.0g / m ² Sensitizing dye I ・ ・ ・ ・ 5.2 × 10 ^-5 moles to 1 mole of silver II ・ ・ ・ ・ ・ ・ 1.5 × 10 ^-5 moles to 1 mole of silver III ・ ・・ ・ 2.1 × 10 ^-4 moles to 1 mole of silver Same IV ・ ・ ・ ・ 1.5 × 10 ^-5 moles to 1 mole of silver Coupler C-2 ・ ・ ・ ・ ・ ・ 0.050 g / m ² coupler C-5 ・・ ・ ・ 0.070g / m ² coupler C-3 ・ ・ ・ Gelatin layer containing 0.035g / m ² Fifth layer; Intermediate layer 2,5-di-t-pentadecylhydroquinone ... 0.08g
/ m ² containing gelatin layer 6th layer; 1st green emulsion layer ・ ・ ・ ・ 0.80g / m ² Sensitizing dye V ・ ・ ・ ・ ・ ・ 4.0 × 10 ^-4 moles / VI silver ・ ・ ・ VI ・ ・ ・ ・ 3.0 × 10 ^-5 moles / VII silver VII ・・ ・ ・ 1.0 × 10 ^-4 mol to 1 mol of silver Comparative coupler A ・ ・ ・ ・ 0.43 g / m ² coupler C-7 ・ ・ ・ ・ ・ ・ 0.13 g / m ² coupler C-8 ・ ・ ・ ・ ・ ・ 0.02 g / m ² coupler C-4 ... Gelatin layer containing 0.03 g / m ² 7th layer; 2nd green emulsion layer Silver iodobromide Silver iodide 8 mol% Average grain size 0.8 μ ・
・ ・ ・ 0.85g / m ² Sensitizing dye V ・ ・ ・ ・ 2.7 × 10 ^-4 moles same as silver 1 mole VI ・ ・ ・ ・ 1.8 × 10 ^-5 moles same as silver 1 mole VII ・ ・· Ag of gelatin layer eighth layer containing 7.5 × 10 ^-5 mol coupler C-6 ···· 0.095g / m ² coupler C-7 ···· 0.015g / m ² relative to moles; yellow filter Layer Yellow colloidal silver ・ ・ ・ ・ ・ 0.08g / m ² 2,5-di-t-pentadecylhydroquinone ... 0.090g /
Gelatin layer containing m ² 9th layer; 1st blue-sensitive emulsion layer ・ ・ 0.37g / m ² Sensitizing Dye VIII ・ ・ ・ ・ ・ ・ 4.4 × 10 ^-4 mol for 1 mol of silver Coupler C-9 ・ ・ ・ ・ ・ ・ 0.71g / m ² Coupler C-4 ・ ・ ・ ・ 0.05g / m ² 10th layer; 2nd blue-sensitive emulsion layer · · 0.55 g / m gelatin layer 11th layer containing to ^two sensitizing dye VIII · · · · 1 mol of silver of 3.0 × 10 ^-4 mol Coupler C-9 ···· 0.23g / m; first protection Layer UV absorber U-1 ・ ・ ・ 0.14 g / m ² same U-2 ・ ・ ・ Gelatin layer containing 0.22 g / m ² 12th layer; 2nd protective layer Gelatin layer containing 0.25 g / m ² polymethacrylate particles (diameter 1.5 μm) 0.10 g / m ^{2 In} addition to the above composition, a gelatin hardener H-1 or a surfactant was applied to each layer.

(Samples 302 to 304) Comparative coupler A contained in the sixth layer of Sample 301
A sample 302 was prepared in the same manner as the sample 301 except that the comparative couplers B and C and the polymer coupler XII of the present invention were replaced by equal weights in order to adjust the film thickness.

The color temperature of these samples is set to 48 with a filter using the A light source.
It was adjusted to 00 ° K, imagewise exposed so as to give a maximum exposure of 20 CMS, and the following color development processing was performed. Measure the density of the treated strips with a green filter (an interference filter that transmits light with a wavelength of 546 nm, manufactured by Fuji Photo Film Co., Ltd.),
Photographic performance is summarized in Table 5.

 Color development (38 ℃) Color development 2 minutes 45 seconds Bleach 6 minutes 30 seconds Washing 2 minutes 10 seconds Fixing 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the processing solution used in each step is as follows. Met.

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 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5g Water added 1.0l pH10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Water added 1.0l pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Water is added 1.0l pH6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization ≈ 10) 0.3g Water added 1.0l It is clear from Table 5 that the color forming performance of the polymer coupler of the present invention is significantly higher than that of the conventional polymer coupler.

Comparative coupler A (lipophilic polymer coupler B described in US Pat. No. 4,367,282) B (polymer coupler synthesized by the method of Synthesis Example 10 described in US Pat. No. 4,080,211) C Compound (3) described in US Pat. No. 4,612,278 Structure of the compound used in Example 3 _{H-1 CH 2 = CH-} SO 2 -CH 2 -CONH (CH 2) 2 NHCO-CH 2 -SO 2 -CH =
CH ₂

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a polymer coupler represented by the following general formula (I) and comprising at least two kinds of repeating units. (In the formula, R ¹ and R ² may be the same or different from each other, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or chlorine, and L ₁ and L ₃ may be the same or different from each other; (R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —COO—, —NHCO— or —OCO—, and L ₂
And L ₄ may be the same or different from each other, and L ₁ and Q
Or a linking group connecting L ₃ and T, m and m ′ represent 0 or 1, n and n ′ represent 0 or 1, and Q is coupled with an oxidized aromatic primary amine developing agent. Represents a coupler residue capable of forming a dye, T represents a sulfonamide group or a sulfamoyl group, and x and y
Represents the content of each unit in the polymer coupler, and x represents 10
~ 90 wt%, y is 10-90 wt%. )