JPH0833627B2 - 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, and more particularly to a silver halide color photographic light-sensitive material excellent in color developability and sharpness. .

(Prior Art) In recent years, color photographic materials have been moving toward higher image quality, and materials having image quality that can withstand viewing even when stretched from a small format such as 110 size have been developed. However, further progress is strongly desired in terms of graininess and sharpness.

Among them, the sharpness is described in JP-A-59-36249 and 54-54.
There are methods of using the DIR compound represented by -145135 to emphasize the edge effect and a method of minimizing the light scattering by thinning the coating film. It is shown in JP-A-59-36249 that these means give a greater effect when used in combination.

 In order to achieve a thin layer, the ballast group of the coupler should be small.

Reduce the amount of high-boiling organic solvents used as coupler solvents.

The coupler is polymerized in order to densify the color-forming groups.

However, there is a problem in the diffusion resistance of the coupler, and it is difficult to extremely reduce it due to the precipitation of the coupler or the deterioration of the color developability, and it is not possible to expect a significant thinning. In the polymerized coupler, a latex-type coupler or one which is used by emulsifying and dispersing is used, and when the amount of gelatin is reduced to make the layer extremely thin, the film strength becomes weak, and the raw film, during processing and It had a defect that the film after processing was easily scratched.

On the other hand, a polymer coupler having hydrophilicity, for example, a polymer coupler obtained by binding a reactive coupler to a pre-synthesized polymer (acrylic acid homopolymer, p-aminostyrene homopolymer, etc.) or natural polymer compound (gelatin, etc.) is U.S. Pat.Nos. 2,698797, 2,852,381, 2,852,383, 2,870,712, and Japanese Patent Publication No. 35-1
6932, 44-3661, etc., a polymer coupler obtained by copolymerizing a coupler synthesized in the form of an ethylenically unsaturated monomer with another polymerizable monomer is Patent Nos. 880,206, 955,197, 96
7,503, 967,504, 995,363, 1,104,6
No. 58 is disclosed in each specification. However, since the polymer coupler having the hydrophilicity has insufficient diffusion resistance, there is a problem that inter-layer color mixing is likely to occur, and the coupler may flow out into the treatment liquid during treatment, so that it cannot be put to practical use. It was

In order to solve these drawbacks, US Pat.
No. 9, No. 4,215, 195, JP-A No. 57-205735, No. 58-2713.
No. 9 and No. 58-28744, a water-soluble polymer coupler using a group capable of crosslinking with gelatin through a hardener (for example, a hydrophilic polymer coupler having a phenolic hydroxyl group or an active methylene group). There is. However, since these are cross-linked with gelatin via a hardening agent, the cross-linking speed with gelatin is slow. Further, the efficiency of cross-linking the coupler and the gelatin through the reaction of the cross-linking between the coupler and the gelatin through the hardener is low and the diffusion resistance is insufficient.

On the other hand, in order to achieve further thinning in the polymer coupler, it is necessary to increase the density of the coloring mother nucleus unit, but in the water-soluble polymer compound, the coloring mother nucleus is hydrophobic and the hydrophilic mother nucleus is hydrophilic. Therefore, a certain amount of the hydrophilic group-containing monomer unit is required. This is an obstacle to increasing the density of the coloring mother nucleus unit.

As a method for improving it, there is disclosed a water-soluble polymer coupler in which a water-soluble polymer coupler is improved by incorporating a hydrophilic group in the color-developing nucleus, and the density of the color-developing nucleus is increased.
Nos. 58-27139 and 58-28744 are disclosed in the respective specifications.
However, this water-soluble polymer coupler having a high content of a coupler unit having a hydrophilic group-containing color-developing nucleus for attaining high density of the color-developing nucleus was insufficient in terms of color-forming property.

(Problems to be Solved by the Invention) Accordingly, the first object of the present invention is to provide a silver halide color photographic light-sensitive material containing a water-soluble polymer coupler excellent in color forming property.

Secondly, to provide a silver halide color photographic light-sensitive material excellent in sharpness.

Thirdly, to provide a silver halide color photographic light-sensitive material containing a water-soluble polymer coupler excellent in diffusion resistance.

Fourthly, to provide a silver halide color photographic light-sensitive material having a strong film strength.

(Means for Solving the Problems) As a result of various researches conducted by the present inventors, the above-mentioned various objects are as follows. It has been found that this can be achieved by a silver halide color photographic light-sensitive material.

(1) A silver halide color photographic light-sensitive material containing at least one water-soluble polymer coupler represented by the following general formula [P].

In formula (P) EA _x B _y X Formula, E is representative of the two or more monovalent group carbon atoms. A represents a repeating unit derived from an ethylenically unsaturated monomer having a coupler residue capable of coupling with an oxidation product of an aromatic primary amine developing agent to form a dye, and a coupler residue showing the same hue during color development. It may be two or more kinds of repeating units derived from an ethylenically unsaturated monomer having a group. B represents a repeating unit derived from a copolymerizable non-color-forming ethylenically unsaturated monomer, and may be two or more kinds of repeating units. X represents a monovalent group. x and y are the contents of each repeating unit in the polymer coupler, and the weight ratio (x: y) of x and y is 1
It is from 0:90 to 90:10.

(2) In the general formula [P], E has a group which is bonded to the binder directly or through a hardening agent, and the silver halide color according to claim (1). Photographic material.

(3) The above general formula [P] is characterized in that B contains at least one repeating unit derived from an ethylenically unsaturated monomer containing a group which is bonded to the binder directly or via a hardening agent. A silver halide color photographic light-sensitive material according to claim (1).

Preferred examples of the ethylenically unsaturated monomer forming the repeating unit represented by A in the general formula [P] capable of forming a dye by coupling with an oxidized product of an aromatic primary amine developing agent used in the present invention are It is represented by [I].

General formula [I] In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and L ¹ is (R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group having 1 to 6 carbon atoms), —COO—, —NHC
O-, -OCO-, (R ³ and R ⁴ each independently represent hydrogen, hydroxyl, a halogen atom or a substituted or unsubstituted alkyl, alkoxy, acyloxy or aryloxy), (R ² , R ³ and R ⁴ are the same as above), L ² represents a linking group connecting L ¹ and Q, m represents 0 or 1, n represents 0 or 1, and Q is oxidized. Represents a coupler residue capable of forming a dye by coupling with an aromatic primary amine developing agent.

Linking group represented by L ² is specifically represented by _{^{X 1 J 1 -X 2 p J}} 2 -X 3 q J 2 s.

J ¹ , J ² and J ³ may be the same or different, -CO-,
−SO ₂ −, (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), (R ⁵ is as defined above), (R ⁵ is as defined above, R ⁶ is an alkylene group having 1 to about 4 carbon atoms), (R ⁵ and R ⁶ have the same meanings as described above, R ⁷ represents a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms) and a substituted alkyl group (having 1 to 6 carbon atoms)), —O—, —S—, (R ⁵ and R ⁷ are as defined above), (R ⁵ and R ⁷ are as defined above), —COO—, —OCO—, (R ⁵ is as defined above), (R ⁵ 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.

In the above general formula [I], X ¹ , X ² and X ³ may be the same or different and each represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or a phenylene group, and an alkylene group. The group may be linear or branched. Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, and phenylene groups such as p-phenylene, m-phenylene, For example, methylphenylene.

Further, X ¹ , X ² , an alkylene group represented by X ³ , a substituent of an aralkylene group or a phenylene group, a halogen atom, a nitro group, a cyano group, an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, A group represented by —NHCOR ⁸ (R ⁸ is alkyl, substituted alkyl, phenyl,
Substituted phenyl, aralkyl, substituted ^{_{aralkyl), - NHSO 2 R 8 (}} R 8 is as defined above), - SOR ⁸ (R ⁸ is as defined ^{_{above), - SO 2 R 8 (}} R 8 is as defined above) , -COR ⁸ (R ⁸
Is synonymous with the above), A group represented by (R ⁹ and R ¹⁰ may be the same or different from each other and represent a hydrogen atom, alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, or substituted aralkyl), (R ⁹ and R ¹⁰ are as defined above), an amino group (which may be substituted with alkyl), a hydroxyl group and a group which forms a hydroxyl group by hydrolysis. When there are two or more substituents, they may be the same or different.

Further, examples of the substituent of the above-mentioned substituted alkyl group, substituted alkoxy group, substituted phenyl group and substituted aralkyl group include:
Hydroxyl group, nitro group, alkoxy group having 1 to about 4 carbon atoms,-
NHSO ₂ R ⁸ (R ⁸ is as defined above), - group represented by NHCOR ⁸ (R ⁸ is as defined above), (R ⁹ and R ¹⁰ are as defined above), A group represented by (R ⁹ and R ¹⁰ are as defined above), —SO ₂ R ⁸ (R ⁸
Is the same as the above), —COR ⁸ (R ⁸ is the same as the above), a halogen atom, a cyano group, an amino group (which may be substituted with alkyl) and the like.

Next, among the color coupler residues represented by Q in the general formula [I], the cyan color forming coupler residue is
Phenol type [II] represented by the following general formula,
Compounds of [V] or naphthol type [III] and [IV] (each hydrogen atom other than the hydrogen atom of the hydroxyl group is released and linked to L ¹ _m L ² _n ) 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 (for example, methyl, ethyl, butyl, methoxyethyl, n-decyl, n-dodecyl, n-hexadecyl, trifluoromethyl, heptafluoropropyl, dodecyloxy). Propyl, 2,4-di-tert-amylphenoxypropyl, 2,4
-Di-tert-amylphenoxybutyl), carbon number 6 to 30
An aromatic group (eg, phenyl, tolyl, 2-tetradecyloxyphenyl, pentafluorophenyl, 2-chloro-5-dodecyloxycarbonylphenyl), a heterocyclic group having 2 to 30 carbon atoms (eg, 2-pyridyl, 4-pyridyl, 2-furyl, 2-thienyl), R ¹⁶ has 1 to 3 carbon atoms.
0 aliphatic groups (eg, methyl, ethyl, butyl, dodecyl, hexadecyl), 6 to 30 aromatic groups (eg, phenyl, tolyl, 4-chlorophenyl, naphthyl), heterocyclic groups (eg, 4-pyridyl, Quinolyl, 2-furyl). R ¹⁴ and R ¹⁵ may combine with each other to form a heterocycle (eg, morpholine ring, piperidine ring, pyrrolidine ring). p'is 0 to 3, s'is 0 to 2,
q'and r'represent an integer of 0 to 4, respectively.

X ⁴ represents an oxygen atom, an ion 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, ethyl, butyl, methoxyethyl,
Benzyl), aromatic groups having 6 to 30 carbon atoms (eg, phenyl, tolyl), heterocyclic groups having 2 to 30 carbon atoms (eg, 2-
Pyridyl, 2-pyrimidyl), carbonamido group having 1 to 30 carbon atoms (eg, formamide, acetamide, N-
Methylacetamide, benzamide), a sulfonamide group having 1 to 30 carbon atoms (for example, methanesulfonamide, toluenesulfonamide, 4-chlorobenzenesulfonamide), an imide group having 4 to 30 carbon atoms (for example, succinimide), -OR ¹⁸ , SR ¹⁸ , -COR ¹⁸ , CONR ¹⁸ R ¹⁹ , -COCO
R ¹⁸ , -COCONR ¹⁸ R ¹⁹ , -COOR ²⁰ , -COCOOR ²⁰ , -SO
_{^{2 R 20, -SO 2 OR 20}} , can be mentioned -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, methyl, ethyl, butyl, dodecyl, methoxyethyl, trifluoromethyl, hepta). Fluoropropyl), an aromatic group having 6 to 30 carbon atoms (eg, phenyl,
Tolyl, 4-chlorophenyl, pentafluorophenyl, 4-cyanophenyl, 4-hydroxyphenyl) or a heterocyclic group having 2 to 30 carbon atoms (for example, 4-pyridyl, 3
-Pyridyl, 2-furyl). R ¹⁸ and R ¹⁹ may combine with each other to form a heterocycle (eg, morpholino, pyrrolidino).

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 leaving group include a halogen atom (eg, fluorine,
Chlorine, bromine, iodine), an aliphatic oxy group having 1 to 30 carbon atoms (for example, methoxy, ethoxy, 2-hydroxyethoxy, carboxymethyloxy, 3-carboxypropyloxy, 2-methoxyethoxycarbamoylmethyloxy, 2-methane Sulfonylethoxy, 2-carboxymethylthioethoxy, triazolylmethyloxy), an aromatic oxy group having 6 to 30 carbon atoms (for example, phenoxy, 4-
Hydroxyphenoxy, 2-acetamidophenoxy,
2,4-dibenzenesulfonamidephenoxy, 4-phenylazophenoxy), a heterocyclic oxy group having 2 to 30 carbon atoms (for example, 4-pyridyloxy, 2-phenyl-5-tetrazolyloxy), 1 carbon atom To 30 aliphatic thio groups (eg, dodecylthio), C6 to C30 aromatic thio groups (eg, 4 dodecylphenylthio), C2 to C30 heterocyclic thio groups (eg, 4-pyridylthio, 1- Phenyltetrazol-5-ylthio), an acyloxy group having 2 to 30 carbon atoms (for example, acetoxy, benzoyloxy, lauroyloxy), a carbonamido group having 1 to 30 carbon atoms (for example, dichloroacetylamide, trifluoroacetamide, heptafluorobutane) Amide, pentafluorobenzamide), sulfonamide group having 1 to 30 carbon atoms (eg, methanesulfonamide) Toluenesulfonamide), an aromatic azo group having 6 to 30 carbon atoms (e.g., phenylazo, 4-chlorophenyl azo, 4-methoxyphenyl azo, 4-pivaloyl amino phenyl azo), 1 carbon atoms
To 30 aliphatic oxycarbonyloxy groups (eg, ethoxycarbonyloxy, dodecyloxycarbonyloxy), C6 to C30 aromatic oxycarbonyloxy groups (eg, phenoxycarbonyloxy), 1 to 1 carbon atoms
30 carbamoyloxy groups (eg, methylcarbamoyloxy, dodecylcarbamoyloxy, phenylcarbamoyloxy), heterocyclic groups having 1 to 30 carbon atoms and continuous at the active position of the coupler with a nitrogen atom (eg, succinimide, phthalimide) , Hydantoinyl, pyrazolyl,
2-benzotriazolyl) and the like.

Y'represents a group of atoms necessary for forming a 5- to 7-membered ring together with the carbon atom to which it is bonded. More specifically,
-O-, -S-, -N =, = N-, Represents either alone or in combination. R ″ and R each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, an arylcarbonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, or a cyano group.

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

Preferred as R ¹¹ are halogen atom (eg phen, chlorine, bromine etc.), aliphatic group (eg methyl, ethyl, isopropyl), carbonamido group (eg acetamide, benzamide), sulfonamide group (eg,
Methanesulfonamide, toluenesulfonamide) and the like.

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

Preferred as X ⁴ is R ¹⁷ N, and further R ¹⁷ N
Preferred as -COR ¹⁸ (for example, formyl,
Acetyl, trifluoroacetyl, chloroacetyl, benzoyl, pentafluorobenzoyl, p-chlorobenzoyl), -COOR ²⁰ (for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, methoxyethoxycarbonyl, phenoxycarbonyl), -SO. ₂ R ²⁰ (for example, methanesulfonyl, ethanesulfonyl, butanesulfonyl, hexadecanesulfonyl, benzenesulfonyl, toluenesulfonyl, p-chlorobenzenesulfonyl), -CONR ¹⁸ R
¹⁹ (N, N-dimethylcarbamoyl, N, N-diethylcarbamoyl, N, N-dibutylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, 4-cyanophenylcarbamoyl, 3,4-dichlorophenylcarbamoyl, 4
- methanesulfonyl-phenylcarbamoyl), - SO ₂ NR
¹⁸ R ¹⁹ (for example, N, N-diethylsulfamoyl, N, N-
And a group represented by diethylsulfamoyl, N, N-dipropylsulfamoyl). More particularly preferable one of R ¹⁷ is a group represented by —COR ¹⁸ , —COOR ²⁰ and —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 ⁴
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 formula [V
I], [VII], [VIII], [IX], [X], [XI] and [XII] represented by a coupler residue (Ar, Z ² , R ^{21 to} R
^In the case of the general formula [V] in which any one of ³³ is linked to L ¹ _m L ² _n , more preferable is the case of directly linking to the substitution position of R ²¹ . ) Is represented.

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.), an aryl group or a substituted aryl group [as a substituent, an alkyl group (eg, methyl, ethyl), alkoxy (eg, methoxy,
Ethoxy), aryloxy groups (eg phenyloxy), alkoxycarbonyl groups (eg methoxycarbonyl), acylamino groups (eg acetylamino), carbamoyl groups, alkylcarbamoyl groups (eg methylcarbamoyl, ethylcarbamoyl), dialkylcarbamoyl groups (eg dimethyl). Carbamoyl), arylcarbamoyl group (eg phenylcarbamoyl), alkylsulfonyl group (eg methylsulfonyl), arylsulfonyl group (eg phenylsulfonyl), alkylsulfonamide group (eg methanesulfonamide),
Aryl sulfonamide group (eg phenyl sulfonamide), sulfamoyl, alkylsulfamoyl group (eg ethylsulfamoyl), dialkylsulfamoyl group (eg dimethylsulfamoyl), alkylthio group (eg methylthio), arylthio group (eg Phenylthio), a cyano group, a nitro group, and a halogen atom (eg, fluorine, chlorine, bromine, etc.), and when there are two or more substituents, they may be the same or different. Particularly preferred substituents are a halogen atom, an alkyl group,
Examples thereof include an alkoxy group, an alkoxycarbonyl group and a cyano group. ], A heterocyclic group (for example, triazole, thiazole, benzthiazole, furan, pyridine, quinaldine, benzoxazole, pyrimidine, oxazole,
Represents imidazole).

R ²¹ represents an unsubstituted or substituted anilino group, an acylamino group (eg, alkylcarbonamide, phenylcarbonamide, alkoxycarbonamide, phenyloxycarbonamide), a ureido group (eg, alkylureido,
Phenylureido), and these substituents include a halogen atom (eg, fluorine, chlorine, bromine, etc.), a linear or branched alkyl group (eg, methyl, t-butyl, octyl, tetradecyl), an alkoxy group (eg, Methoxy, ethoxy, 2-ethylhexyloxy, tetradecyloxy and the like), acylamino group (for example, acetamide, benzamide, butanamide, octanamide, tetradecanamide, α- (2,4-di-tert-amylphenoxy) acetamide, α- (2,4-di-tert-
Amylphenoxy) butyramide, α- (3-pentadecylphenoxy) hexanamide, α- (4-hydroxy-3-tert-butylphenoxy) tetradecanamide, 2-oxo-pyrrolidin-1-yl, 2-oxo-
5-tetradecylpyrrolidin-1-yl, N-methyl,
Tetradecane amide), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, ethylsulfonamide, p-toluenesulfonamide, octanesulfonamide, p-dodecylbenzenesulfonamide, N-methyl-tetradecanesulfonamide), sulfamoyl group (For example, sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N, N'-dimethylsulfamoyl, N, N-dihexylsulfamoyl, N-hexadecylsulfamoyl, N- [3 -(Dodecyloxy) -propyl] sulfamoyl, N- [4
-(2,4-di-tert-amylphenoxy) butyl] sulfamoyl, N-methyl-N-tetradecylsulfamoyl, etc., a carbamoyl group (for example, N-methylcarbamoyl, N-butylcarbamoyl, N-octadecylcarbamoyl, N- [4- (2,4-di-tert-amylphenoxy) butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl), diacylamino group (N-succinimide, N-phthalimide, 2,5-dioxo- 1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-
Hindertoinyl, 3- (N-acetyl-N-dodecylamino) succinimide), alkoxycarbonyl group (eg, methoxycarbonyl, tetradecyloxycarbonyl, benzyloxycarbonyl), alkoxysulfonyl group (eg, methoxysulfonyl, butoxysulfonyl, octyloxy). Sulfonyl, tetradecyloxysulfonyl), aryloxysulfonyl group (for example,
Phenoxysulfonyl, p-methylphenoxysulfonyl, 2,4-di-tert-amylphenoxysulfonyl, etc.), alkanesulfonyl group (eg, methanesulfonyl, ethanesulfonyl, octanesulfonyl, 2-ethylhexylsulfonyl, hexadecanesulfonyl), arylsulfonyl group (For example, benzenesulfonyl, 4
-Nonylbenzenesulfonyl), an alkylthio group (for example, methylthio, ethylthio, hexylthio, benzylthio, tetradecylthio, 2- (2,4-di-tert-amylphenoxy) ethylthio, etc.), an arylthio group (for example, phenylthio, p- Tolylthio), an alkyloxycarbonylamino group (for example, methoxycarbonylamino, ethyloxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino), an alkylureido group (for example, N-methylureido, N, N-dimethylureido, N-methyl-N-dodecyl ureido, N-hexadecyl ureido, N, N-dioctadecyl ureido), acyl group (for example, acetyl, benzoyl, octadecanoyl, p-dodecanamidobenzoyl), nitro group, cal Examples thereof include a voxyl group, a sulfo group, a hydroxy group and a trichloromethyl group.

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, methyl, propyl, t
-Butyl, trifluoromethyl, tridecyl, etc.), aryl group (preferably having 6 to 20 carbon atoms, for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-methoxyphenyl) ), A heterocyclic group (eg, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-
Benzothiazolyl), alkylamino group (preferably having 1 to 20 carbon atoms, for example, methylamino, diethylamino, t-butylamino), acylamino group (preferably having 2 to 20 carbon atoms, for example, acetylamino, propylamide) , Benzamide), anilino group (eg phenylamino, 2-chloroanilino), alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, eg methoxycarbonyl, butoxycarbonyl, 2-ethylhexyloxycarbonyl), alkylcarbonyl group (preferably Has 2 to 20 carbon atoms, such as acetyl, butylcarbonyl, cyclohexylcarbonyl, and arylcarbonyl groups (eg, preferably 7 to 20 carbon atoms).
Benzoyl, 4-t-butylbenzoyl), alkylthio group (preferably having 1 to 20 carbon atoms, for example, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (preferably having 6 to 20 carbon atoms.
Phenylthio, 2-butoxy-5-t-octylphenylthio), carbamoyl group (preferably having 1 to 20 carbon atoms. For example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl, N-methyl-N-butyl. Lucarbamoyl), a sulfamoyl group (preferably having up to 20 carbon atoms, for example, N-ethylsulfamoyl, N, N-diethylsulfamoyl, N, N-dipropylsulfamoyl).
Alternatively, it represents a sulfonamide group (preferably having a carbon number of 1 to 20, for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide).

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 and bromine), a coupling splitting off group linked by an oxygen atom (for example, acetoxy, propanoyloxy, benzoyloxy,
Ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxyl, 4-titanium sulfonamide phenoxy, α-naphthoxy, 4-cyanoxyl, 4-methanesulfonamide-
Phenoxy, α-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2
-Cyanoethoxy, benzoloxy, 2-phenethyloxy, 2-phenoxy-ethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy), a coupling-off group linked by a nitrogen atom (for example, JP-A-59- 994
No. 37, specifically benzenesulfonamide, N-ethyltoluenesulfonamide, heptafluorobutanamide, 2,3,4,5,6-pentafluorobenzamide, octanesulfonamide, p-cyano Phenylureido, N, N-diethylsulfamoylamino,
1-piperidyl, 5,5-dimethyl-2,4-di-oxo-3
-Oxazolidinyl, 1-benzyl-5-ethoxy-3
-Hydantoinyl, 2-oxo-1,2-dihydro-1-
Pyridinyl, imidazolyl, pyrazolyl, 3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6-
Bromobenzotriazol-1-yl, 5-methyl-1,
2,3,4-triazol-1-yl, benzimidazolyl), a coupling-off group linked by a sulfur atom (for example, phenylthio, 2-carboxyphenylthio, 2-methoxy-5-octylphenylthio, 4-methanesulfonylphenyl) Thio, 4-octanesulfonamide phenylthio, benzylthio, 2-cyanoethylthio, 5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolyl). 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.

As the yellow color-forming coupler residue, an acylacetanilide type, particularly a pivaloylacetanilide type [XIII], a benzoylacetanilide type [XIV] or [XV] represented by the following general formula is preferable (free in the general formula Connect to L ¹ _m L ² _n at the bond.) In the formula, R ³⁴ , R ³⁵⁶ , 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. Group, an aliphatic amide group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylureido group, an alkyl-substituted succinimide group, an aryloxy group, an aryloxycarbonyl group, an asylcarbamoyl group, an arylamide group, an arylsulfamoyl group, Represents an arylsulfonamide 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 [XVI], [XVII], [X
VIII] or [XIX].

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 non-metallic atom required to form a 4-, 5- or 6-membered ring.

Of the general formula [XIX], [XX] to [XXII] 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.

Preferable examples of the ethylenically unsaturated monomer providing the repeating unit represented by B include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid), and esters or amides derived from these acrylic acids. (For example, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, 2-methoxyethyl 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, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, β-alkoxyethyl (meth) acrylate (for example, 2-methoxyethyl acrylate, 2
-Methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2
-Ethoxyethyl methacrylate, 2-butoxyethyl acrylate, 2-n-propyloxyethyl methacrylate, 2- (2-methoxy) ethoxyethyl acrylate, etc.), β-sulfonamidoethyl (meth) acrylate, β-carbonamidoethyl ( (Meth) acrylate, β-alkoxyethylacrylamide (the alkoxy group may further include a plurality of substituted alkoxy groups), β-sulfonamidoethylacrylamide, β-
Carbonamidoethylacrylamide etc.), vinyl ester (eg vinyl acetate, vinyl laurate), acrylonitrile, methacrylonitrile, dienes (eg butadiene, isoprene), aromatic vinyl compounds (eg styrene, divinylbenzene and its derivatives, eg vinyl) Toluene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid,
Vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether), maleic anhydride, maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine, and 2- and 4-vinyl pyridine, ethylene, propylene, 1-butene. , Isobutene and the like.

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 and an aralkyl. A group or an acyl group, and W ₂ represents an oxygen or sulfur atom.

Particularly preferred compounds among the compounds represented by the general formula [II] are shown below.

R ¹ represents a hydrogen atom or a methyl group, L ¹ represents -CONH-,-
COO−, −OCO−, , M represents 1, and n represents 0 or 1.
L ² is represented by X ¹ J ¹ −X ² _p J ² −X ³ _q J ³ _{r s.} Among them, particularly preferable one is J ¹ ,
J ² and J ³ may be the same or different, -CO-, -SO ₂
-, - CONH -, - SO 2 NH -, - NHCO -, - NHSO 2 -, - O
-, -NHCONH-, -S-, -COO-, -OCO-, -NHCOO
Represents-, --OCONH--, X ¹ , X ² , and X ³ may be the same or different, and represent an alkylene group (having 1 to 4 carbon atoms), an arylene group, or a substituted arylene group, and p, q, r And s represents 0 or 1.

Examples of the ethylenically unsaturated monomer having a coupler residue capable of forming a dye by coupling with an oxidized product of an aromatic primary amine developing agent used in the present invention are shown below, but are not limited thereto. Absent.

Preferred examples of the ethylenically unsaturated monomer forming the repeating unit represented by B in the general formula [P] which is not coupled with the oxidation product of the aromatic primary amine developing agent used in the present invention are shown. For example, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid esters, crotonic acid, crotonic acid esters, vinyl ester, maleic acid, maleic acid diester, fumaric acid, fumaric acid diester, itaconic acid, itaconic acid diester, acrylamide And methacrylamides, vinyl ethers, styrenes and the like. These acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions.

More specific examples of these monomers include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 3-acryloylpropane sulfonic acid, acetoacetoxyethyl acrylate, acetoxy. Examples thereof include ethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, and 2- (2-methoxyethoxy) ethyl acrylate. As the methacrylic acid ester, methyl methacrylate, ethyl methacrylate, n-
Propyl methacrylate, n-butyl methacrylate,
Examples thereof include tert-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate and the like. Examples of crotonic acid esters include butyl crotonic acid and hexyl crotonic acid. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like. Examples of the maleic acid diester include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumarate diester include diethyl fumarate, dimethyl fumarate, dibutyl fumarate and the like. Examples of the itaconic acid diester include diethyl itaconate, dimethyl itaconate, and dibutyl itaconate. Examples of acrylamides include acrylamide, methylacrylamide, ethylacrylamide, isopropylacrylamide, n-butylacrylamide, hydroxymethylacrylamide, diacetoneacrylamide, acryloylmorpholine, acrylamide-2-methylpropanesulfonic acid, and the like. As methacrylamides, methyl methacrylamide, ethyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, 2-methoxy methacrylamide,
Examples thereof include dimethyl methacrylamide and diethyl methacrylamide. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and dimethylaminoethyl vinyl ether. As styrenes, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene,
Methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrene, vinyl benzoic acid methyl ester, 2-methylstyrene, styrene sulfonic acid, vinyl benzoic acid and the like can be mentioned.

Examples of other monomers include allyl compounds (eg, allyl acetate), vinyl ketones (eg, methyl vinyl ketones), vinyl heterocyclic compounds (eg, vinyl pyridine), unsaturated nitriles (eg, acrylonitrile, etc.).

Among these monomers, those having high hydrophilicity are particularly preferable.

Next, preferred examples of the ethylenically unsaturated monomer forming a repeating unit containing a group bonded to the binder directly or through a hardener among the repeating units represented by B in the general formula [I] are shown below. It is not limited to these.

As a method for introducing a monovalent group having 3 or more carbon atoms represented by E in the general formula [P], a chain transfer agent having 2 or more carbon atoms is used, or a chain transfer agent having a reactive group or There is a method in which a polymerization reaction is carried out using an initiator and a group having 3 or more carbon atoms is introduced by a polymer reaction.

Preferred chain transfer agents used in the present invention are shown below, but the present invention is not limited thereto.

T-1 C ₃ H ₇ SH T-2 C ₄ H ₉ SH T-3 C ₆ H ₁₃ SH T-4 C ₈ H ₁₇ SH T-5 C ₁₂ H ₂₅ SH T-6 C ₁₅ H ₃₁ SH T- 7 C ₁₆ H ₃₃ SH T-8 C ₁₈ H ₃₇ SH T-9 C ₃₁ H ₆₃ SH T-13 C ₃ H ₇ SO ₂ NHCH ₂ CH ₂ SH T-15 C ₄ H ₉ CONHCH ₂ CH ₂ SH T-16 C ₁₃ H ₃₇ CONHCH ₂ CH ₂ SH T-19 C ₄ H ₉ NHCH ₂ CH ₂ SH T-30 BrCH ₂ COOCH ₃ T-31 ClCH ₂ COOC ₂ H ₅ T-32 ICH ₂ COOCH ₃ The following are specific examples of the chain transfer agent having a group which is bonded to the binder directly or via a hardening agent, but the present invention is not limited thereto.

T-40 ClCH ₂ CH ₂ SO ₂ CH ₂ CONHCH ₂ CH ₂ SH T-41 CH ₂ = CH-SO ₂ CH ₂ CH ₂ CONHCH ₂ CH ₂ SH T-43 SHCH ₂ CH ₂ COOCH ₂ CH ₂ CN The synthesis of the telomer coupler of the present invention is performed by using a polymerization initiator and a polymerization solvent as JP-A-56-5543, JP-A-57-94752, JP-A-57-176038, JP-A-57-204038, and JP-A-57-204038. 58-28745
No. 58, JP-A-58-10738, JP-A-58-42044, JP-A-58-1
It is carried out using the compounds described in 45944 and JP-A-59-42543.

The polymerization initiator is used in the range of about 0.01 to about 10 mol% with respect to the monomer, but 0.01 to 2.0 mol% is preferable.

The polymerization temperature must be set in relation to the molecular weight of the telomer 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 ℃. Higher temperatures are preferred for telomer synthesis, preferably in the range of about 70-100 ° C.

The proportion of the colored portion in the telomer coupler represented by the general formula [I] is usually preferably 10 to 95% by weight, but the color reproducibility,
From the viewpoint of color developability and stability, 20 to 90% 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 200 to 4000, but is not limited thereto.

The number average molecular weight of the telomer coupler of the present invention is
From the viewpoint of color developability and sensitivity, it is preferably about 1,000 to about 10,000, and particularly preferably about 1,000 to about 5,000.

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

The telomer coupler of the present invention is based on the coupler monomer, and in the case of the same layer as the silver halide, it is 0 per mol of silver.
It is good to add 005 mol to 0.5 mol, preferably 0.01 to 0.10 mol.

The coating amount when the telomer coupler of the present invention is used in the non-photosensitive layer is 0.01 g / m ^{2 to} 1.0 g / m ² , preferably 0.1 g / m ² .
It is in the range of m ^{2 to} 0.5 g / m ² .

Water-soluble in the present invention means that the obtained polymer coupler is
It means that 1.0 wt% or more is dissolved in water. Preferably 10 wt
When it is dissolved in water in an amount of not less than%, it is preferable for production.

The polymer coupler of the present invention can be added to a coating solution as an aqueous solution, and a lower alcohol, TH
It can also be dissolved in a mixed solvent of water and an organic solvent miscible with water, such as F or acetone, and added.

Further, it may be added after being dissolved in an alkaline aqueous solution or a mixed solution of an alkaline water-containing organic solvent. It is also possible to disperse it in a gelatin solution or add a small amount of a surfactant.

In any case, the water-soluble polymer coupler of the present invention is not in the form of oil droplets or a latex in the coating liquid and the coating film, and is considered to interact with the hydrophilic binder to some extent. Be done.

Therefore, it is considered that the film strength is superior to that of the oil-soluble (including latex type) polymer coupler.

Synthesis Example (1) Copolymerization of α-pivaloyl-α- (4-acrylamidophenoxy) -N- (2,5-dichlorophenyl) acetamide with sodium 2-acrylamido-2-methylpropanesulfonate and glycidyl methacrylate Synthesis of polymer coupler (P-1) Coupler monomer (37) 23.0 g, sodium 2-acrylamido-2-methylpropanesulfonate 25.0 g, glycidyl methacrylate 2.0 g, dodecyl mercaptan 2.
A mixture of 0 g and 200 ml of dimethylformamide was placed in a 500 ml three-necked flask and heated to 70 ° C. under stirring in a nitrogen stream.

10 ml of a dimethylformamide solution containing 500 mg of dimethyl azobisisobutyrate as a polymerization initiator was added to initiate polymerization.

After polymerization for 3 hours, the polymerization solution was cooled, poured into ethyl ether 1 and the precipitated solid was separated by filtration, washed with ethyl ether and dried by heating under reduced pressure to obtain P-1 (48.7 g). P
-1 is 48.6wt% of coupler monomer by elemental analysis (37)
I understand that it includes a unit.

Synthesis Example (2) 1- (2,4,6-trichlorophenyl) -3-methacrylamido-4-pyrazol-5-pyrazolone and sodium 2-acrylamido-2-methylpropanesulfonate copolymerized polymer coupler (P- 2) Synthesis of coupler monomer (22) 22.0 g, sodium 2-acrylamido-2-methylpropanesulfonate 25.0 g, glycidyl mercaptan 3.0 g, dimethylformamide 180 m
The mixture of 1 was put into a 500 ml three-necked flask and heated to 70 ° C. under stirring in a nitrogen stream.

10 ml of a dimethylformamide solution containing 500 mg of dimethyl azobisisobutyrate as a polymerization initiator was added to initiate polymerization.

After polymerization for 3 hours, the polymerization solution was cooled, 300 ml of water was added, dialysis was performed for 3 days, and then freeze-dried to obtain 46.1 g of P-2. It was found from elemental analysis that P-2 contained 45.5 wt% of coupler monomer (22) units.

The polymers P-3 to P-25 of the present invention were synthesized as shown in Table 1 in the same manner as in Synthesis Examples (1) and (2) above.

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 iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide containing from about 2 mol% to about 25 mol% 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, "The Physics and Chemistry of Photography" by Graphide, published by Paul Monten (P.Glafkides, Chemic et Phisique P.
hotographique Paul, Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press, "GF Duffin, Pho
tographic Emulsion Chemistry (Forcal Press, 196
6)), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VLZelikman et al. Making and
Coating Photographic Emulsion, Forcal 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 in Gutoff, 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, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide such as rotan silver 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. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, 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, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

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,
No. 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552
Issue, Research Disclosure No. 24230 (June 1984
JP-A-60-43659, US Pat. Nos. 4,500,630, and 4,540,654 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. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No.
Those described in 3,446,622, 4,333,999, 4,451,559, 4,427,767, European Patent 161,626A and the like are preferable.

Colored couplers to correct unwanted absorption of colored dyes are VII of Research Disclosure No. 17643.
-G section, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413,
U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No.
Those described in No. 1,146,368 are preferable.

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. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the aforementioned RD17643, VII to F patents, 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, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.No. 4,283,472, 4,338,393, multiequivalent couplers described in 4,310,618 and the like, JP 60-18
5950, DIR redox compounds or DIR coupler-releasing couplers or DIR coupler-releasing or redox described in JP-A-62-24252, couplers for releasing dyes that recover color after separation described in European Patent 173,302A, RD No. 11449. ,
No. 24241, the bleaching accelerator releasing coupler described in JP-A-61-2201247 and the like, and the ligand releasing coupler described in US Pat. No. 4,553,477 and the like.

Hereinafter, specific examples of the color coupler that can be used in the invention will be described, but the invention is not limited thereto.

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.

Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid ester (Trifel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexyl phenylphosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-tert
-Octylaniline, etc.), hydrocarbons (paraffin,
Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably an organic solvent of 50 ℃ or more and about 160 ℃ or less can be used, as a typical example, ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

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

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

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

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

The color developer used for the development processing of the light-sensitive material of the present invention,
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent, but p-
A phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N.
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulphonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
Examples include -β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Various chelating agents represented by viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid. , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine -Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is performed, black and white development is usually performed before color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developers is
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 l or less per 1 m 2 of the light-sensitive material and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, the contact area with the air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. Bleach-fixing may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether amine tetraacetic acid or complex salts such as citric acid, tartaric acid and ring acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,98.
No. 8, JP-A-53-32,736, JP-A-53-57,831, and JP-A-53-37,418
No. 53-72,623, No. 53-95,630, No. 53-95, 631,
No. 53-10,4232, No. 53-124,424, No. 53-141,623, No.
53-28,426, Research Disclosure No.17,129
Having a mercapto group or a disulfide group described in JP-A-50-140,129; thiazolidine derivatives described in JP-A-50-140,129; JP-B-45-8,506; JP-A-52-2.
Nos. 0,832 and 53-32,735; U.S. Patent No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715,
Iodide salts described in 8-16,235; West German Patent No. 966,410,
Polyoxyethylene compounds described in No. 2,748,430;
Pyriamine compounds described in JP-B-45-8836; Other JP-A-49-42,434, 49-59,644, 53-94,927, 54-
Compounds described in Nos. 35,727 and 55-26,506 and 58-163,940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West Patent No. 1,290,812 and JP-A-53-95,630 are particularly preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodide salts, and the use of thiosulfates is common.
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. 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 a coupler), the purpose, 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. Of 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
It can be determined by the method described in elevision Engineers Volume 64, P.248-253 (May 1955 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 of reducing calcium ion and magnesium ion described in Japanese Patent Application No. 61-131632 can be very effectively used. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 15-45 ° C. for 20 seconds-10 minutes, preferably 25-40 ° C. for 30 seconds.
A range of seconds-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 a stabilization process, Japanese Unexamined Patent Publication No.
All known methods described in Nos. 8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed 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. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat. Examples thereof include salt complexes and urethane compounds described in JP-A-53-135,628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64,339, JP-A-57-144,547, and JP-A-58-11.
No. 5,438 is described.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

Further, the silver halide light-sensitive material of the present invention is described in US Pat.
500,626, JP-A-60-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in 238056 and European Patent 210,660A2.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Sample 101, which is a multi-layer color light-sensitive material consisting of each layer having the composition shown below, was prepared on an undercoated cellulose triacetate film.

(Composition of photosensitive layer) First layer (emulsion layer) Monodisperse (variation coefficient 14%) Silver iodobromide emulsion (4 mol% silver iodide, average grain size 0.5 μ) 0.8 g / m ² Gelatin 1.0 g / m ² Second layer (clear layer) Hydroxyethyl cellulose 0.2 g / m ² Third layer (coupler containing layer) Same as the first layer Silver iodobromide emulsion 0.8 g / m ² Coupler A-1 1.0 g / m ² Gelatin 1.0 g / m ² 4th layer (protective layer) Gelatin 0.8 g / m ² Polymethyl acrylate particles 0.2 g / m ² Hardener 0.4 g / m ² Preparation of samples 102 to 108 Coupler A- of sample 101 3rd layer Sample No. 1 was prepared in the same manner as Sample 101 except that the amount of coupler residue was added to the coupler shown in Table 1 in an equimolar amount.

The water-soluble polymer coupler used in the examples is 5 wt%
20 minutes before coating, the solution was added to the coating solution and coated.

Compounds used in comparative examples A part of the obtained samples 101 to 108 was left as it was, and another part was peeled from the peeling layer, and then 38 ° C according to the following treatment steps.
Was developed.

Then, the ratio of the yellow density D _{1 in the} case of no peeling and the yellow density D _{2 in} the case of peeling was taken as a measure of the diffusion of the added coupler to other layers.

The results are shown in Table 2. It can be seen that each of the couplers of the present invention has little diffusion into other layers.

<Processing process> Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 2 minutes 10 seconds Fixing 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each step is as follows. It was on the street.

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 Add water 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 Add water 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 Add water 1.0l pH6.6 <Stabilizer> Formalin (37% w / v) 2.0 ml polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g ethylenediaminetetraacetic acid disodium salt 0.05 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.03 g Add water 1 pH 6.0 <Wash water> Tap water is H type strong acid cation exchange resin (Amberlite IR-120B made by Rohm and Haas) and OH type strong salt. 1: 1 basic anion exchange resin (Amberlite IRA-400 manufactured by the same company)
The mixture was passed through a column mixed and packed in a volume ratio of 1 to treat both calcium and magnesium at 1 mg / l or less, and then 0.02 g of sodium isocyanurate dichloride was added per 1 to be used.

Example 2 (Samples 201 to 207) A coupler A-1 for the third layer of Sample 101 was prepared in the same manner as Sample 101 except that the couplers A-1 were replaced as shown in Tables 2 and 3.

The obtained sample was subjected to the same treatment evaluation as in Example 1. The results are shown in Table 3.

As in Example 1, it was found that the water-soluble polymer coupler of the present invention has little diffusion into other layers regardless of the type of the mother nucleus of the coupler.

Example 3 A sample 301, which is a multi-layer color light-sensitive material having each layer having the composition shown below, was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

1st layer (anti-halation layer) Black colloidal silver …… 0.2 Gelatin …… 1.3 ExM-9 …… 0.06 UV-1 …… 0.03 UV-2 …… 0.06 UV-3 …… 0.06 Solv-1 …… 0.15 Solv- 2 …… 0.15 Solv-3 …… 0.05 Second layer (intermediate layer) Gelatin …… 1.0 UV-1 …… 0.03 ExC-4 …… 0.02 ExF-1 …… 0.004 Solv-1 …… 0.1 Solv-2 …… 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.5)
μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio
3.0) Coating silver amount …… 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 15%, spherical particles, diameter / thickness ratio
1.0) Silver coating amount …… 0.6 Gelatin …… 1.0 ExS-1 …… 4 × 10 ^-4 ExS-2 …… 5 × 10 ^-5 ExC-1 …… 0.05 ExC-2 …… 0.50 ExC-3 …… 0.03 ExC-4 ...... 0.12 ExC-5 ...... 0.01 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 1: 1 internal high A)
gI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like particles, diameter / thickness ratio 5.0) Coating silver amount …… 0.7 Gelatin …… 1.0 ExS-1 …… 3 × 10 ^-4 ExS- 2 …… 2.3 × 10 ^-5 ExC-6 …… 0.11 ExC-7 …… 0.05 ExC-4 …… 0.05 Solv-1 …… 0.05 Solv-3 …… 0.05 Fifth layer (intermediate layer) Gelatin …… 0.5 Cpd -1 ...... 0.1 Solv-1 ...... 0.05 Sixth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core shell ratio 1: 1 surface highly uniform AgI type, equivalent spherical diameter 0.5 μ, Coefficient of variation of spherical equivalent diameter 15%,
Plate-like grain, diameter / thickness ratio 4.0) Coating silver amount …… 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent spherical diameter 0.3)
μ, coefficient of variation of equivalent sphere diameter 25%, spherical particles, diameter / thickness ratio
1.0) Amount of coated silver …… 0.20 Gelatin …… 1.0 ExS-3 …… 5 × 10 ^-4 ExS-4 …… 3 × 10 ^-4 ExS-5 …… 1 × 10 ^-4 ExM-8 …… 0.4 ExM− 9 …… 0.07 ExM-10 …… 0.02 ExY-11 …… 0.03 Solv-1 …… 0.3 Solv-4 …… 0.05 7th layer (high-sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core shell) Internal height A of ratio 1: 3
gI type, sphere equivalent diameter 0.7μ, variation coefficient of sphere equivalent diameter 20%, plate-shaped particles, diameter / thickness ratio 5.0) Coating silver amount …… 0.8 ExS-3 …… 5 × 10 ^-4 ExS-4 …… 3 × 10 ^-4 ExS-5 …… 1 × 10 ^-4 ExM-8 …… 0.1 ExM-9 …… 0.02 ExY-11 …… 0.03 ExC-2 …… 0.03 ExM-14 …… 0.01 Solv-1 …… 0.2 Solv-4 ...... 0.01 8th layer (intermediate layer) Gelatin ...... 0.5 Cpd-1 ...... 0.05 Solv-1 ...... 0.02 9th layer (donor layer of the multi-layer effect for the red-sensitive layer) Silver iodobromide emulsion (AgI2 Internal high A with mol% and core shell ratio 2: 1
gI type, sphere equivalent diameter 1.0μ, variation coefficient of sphere equivalent diameter 15%, plate-like grain, diameter / thickness ratio 6.0) coating silver amount …… 0.35 silver iodobromide emulsion (AgI 2 mol%, core shell ratio 1: 1) Internal height A
gI type, sphere equivalent diameter 0.4μ, variation coefficient of sphere equivalent diameter 20%, plate-like particles, diameter / thickness ratio 6.0) Coating silver amount …… 0.20 Gelatin …… 0.5 ExS-3 …… 8 × 10 ^-4 ExY- 13 …… 0.11 ExM-12 …… 0.03 ExM-14 …… 0.10 Solv-1 …… 0.20 10th layer (yellow filter layer) Yellow colloidal silver …… 0.05 Gelatin …… 0.5 Cpd-2 …… 0.13 Cpd-1… … 0.10 11th layer (low-sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, spherical equivalent diameter 0.7)
μ, coefficient of variation of spherical equivalent diameter 15%, plate-like particles, diameter / thickness ratio
7.0) Amount of coated silver: 0.3 Silver iodobromide emulsion (AgI 13 mol%, uniform AgI type, equivalent spherical diameter 0.3)
μ, coefficient of variation of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio
7.0) Coating silver amount …… 0.15 Gelatin …… 1.6 ExS-6 …… 2 × 10 ^-4 ExC-16 …… 0.05 ExY-13 …… 0.07 ExY-15 …… 1.5 Solv-1 …… 0.20 12th layer ( High-sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, spherical equivalent diameter 1.
0μ, coefficient of variation of equivalent spherical diameter 25%, multiple twin plate particles, diameter / thickness ratio 2.0) Coated silver amount …… 0.5 Gelatin …… 0.5 ExS-6 …… 1 × 10 ^-4 ExY-15 …… 0.20 ExY-13 …… 0.01 Solv-1 …… 0.10 13th layer (first protective layer) Gelatin ・ ・ ・ 0.8 UV-4 0.1 UV-5 0.15 Solv-1 …… 0.01 Solv-2 …… 0.01 14th layer 2 Protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter)
0.07μ) ...... 0.5 Gelatin ...... 0.45 Polymethylmethacrylate particle diameter 1.5μ ...... 0.2 H-1 0.4 Cpd-3 0.5 Cpd-4 0.5 In addition to the above components in each layer, emulsion stabilizer Cpd-3
(0.04 g / m ² ) surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid. Other compounds Cpd-5 (0.5g /
^{m 2) ~Cpd-6 (0.5g} / m 2) was added.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate Preparation of Samples 302 to 309 In Sample 301, the high boiling point organic solvents of the 11th and 12th layers were removed, and instead of the coupler ExY-15, the couplers shown in Table 4 were used, and the amount of coupler residues was ExY-15. The sample 301 was prepared in the same manner as the sample 301 except that it was added so as to be equimolar.

Couplers ExY-16, E added to Samples 302-304 and 307
xY-17, ExY-18 and A-3 are couplers shown below.

All water-soluble polymer couplers were added to the emulsion layer as a 5 wt% aqueous solution.

The obtained samples 301 to 309 were subjected to a wet exposure with green light and then subjected to the following development processing.

The density of the obtained sample was measured, and the yellow density of the magenta color-developing layer was evaluated to give a measure of the diffusion of the coupler from the blue-sensitive layer to the green-sensitive layer.

In order to measure the strength of the emulsion film, Samples 301 to 309 were measured for Vickers hardness (Knoop indenter was used in this case) using a Terazawa microhardness meter (MM-2 type). For Bitzkers hardness, D. Tabor, The Physical Meaning of Inde
ntation and Scratch Hardness, British Journal of Ap
plied Physics, Vol. 7, p. 260 (1956).

 The results are shown in Table 4.

It can be seen that when the compound of the present invention is used, the diffusion resistance is greatly improved and the film strength is also greatly improved over the known water-soluble polymer coupler.

Color development 3 minutes 15 seconds 38 ° C Bleach 30 seconds 〃 Bleach-fixing 1 minute 30 seconds 〃 Rinse 1 minute 40 seconds 〃 Stable 40 seconds 〃 The composition of the processing solution used in each step is 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 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Add water 1.0l pH10.0 <Bleaching solution> Ammonium bromide 100g Ethylenediaminetetraacetic acid ferric ammonium salt 120g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium nitrate 10.0g Bleach accelerator 2.0 g Ammonia water 17.0 ml Add water 1 pH 6.5 <Bleaching fixer> Ammonium bromide 50.0 g Ethylenediaminetetraacetic acid ferric ammonium salt 50.0 g Ethylenediaminetetraacetic acid disodium salt 5.0 g Ammonium nitrate 5.0 g Sodium sulfite 12.0 g Ammonium thiosulfate aqueous solution (70%) 240ml Ammonia water 10.0ml Add water 1 pH 7.3 <Rinse solution> Ethylenediaminetetraacetic acid disodium salt 0.4g Add water 1 pH 7.0 with sodium hydroxide <Stable solution> Formalin (40%) 2.0ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization about 10) 0.3g In addition 1.0l Example 4 The same sample preparation, measurement, and evaluation as in Example 3 were carried out except that the following treatment was carried out only in the treatment steps in Example 3.

 As a result, the same effect as in Example 3 was observed.

<Processing process> Color development 3 minutes 15 seconds 38 ° C Bleaching fixing 2 minutes 00 seconds 〃 Washing with water 1 minute 40 seconds 〃 Stable 40 seconds 〃 <Color developer> Diethylenetriamine pentaacetic 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 Add water 1 pH10.00 <Bleaching fixer> Ethylenediaminetetraacetic acid ferric ammonium salt 80.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Bleach accelerator 1.5g Sodium sulfite 12.0g Thio Ammonium sulfate aqueous solution (70%) 240 ml Add water 1 pH with ammonia water (28%) pH 6.8 <Wash water> Tap water is H type strong acid cation exchange resin (Amberlite IR-120B by Rohm and Haas) and OH type Strongly basic anion exchange resin (Amberlite IRA-400 manufactured by the same company) 1: 1
Pass through a column packed mixed in a volume ratio of
After treatment with both magnesium and 1 mg / l or less, 0.02 g of sodium diisocyanurate was added per one and used.

<Stabilizer> Formalin (37% w / v) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water is added to 1 pH 6.0 Example 5 Undercoat On a cellulose triacetate film support having been subjected to the above procedure, a multilayer color light-sensitive material having the following composition was prepared, and a sample 401 was prepared.

1st layer: Anti-halation layer Black colloidal silver 0.25g / m ² UV absorber U-1 0.04g / m ² UV absorber U-2 0.1 g / m ² UV absorber U-3 0.1 g / m ² High boiling point Organic solvent Solv-2 Gelatin layer containing 0.01 cc / m ² (dry film thickness 2μ) Second layer: Intermediate layer Compound CpdC 0.05g / m ² Compound 1-1 0.05g / m ² High boiling point organic solvent Solv-1 0.05 Gelatin layer containing cc / m ² (dry film thickness 1 μm) Third layer: first red emulsion layer Silver bromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.3 μm) , AgI content 4 mol%) Silver amount ... 0.5 g / m ² coupler F-1 0.2 g / m ² coupler F-2 0.05 g / m ² compound I-2 2 × 10 ⁻³ g / m ² high boiling organic solvent Solv-1 Gelatin layer containing 0.12 cc / m ² (dry film thickness 1 μm) Fourth layer: second red-sensitive emulsion layer Silver bromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average) Particle size: 0.6μ, AgI content: 3 mol%) Silver amount: 0.8 g / m ² Coupler F- 1 0.55 g / m ² coupler F-2 0.14 g / m ² compound I-2 1 × 10 ⁻³ g / m ² high boiling organic solvent Solv-1 0.33 cc / m ² dye D-1 0.02 g / m ² Containing gelatin layer (2.5 μm dry film thickness) Fifth layer: Intermediate layer Compound CpdC 0.1 g / m ² High boiling point organic solvent Solv-1 0.1 cc / m ² Dye D-2 0.02 g / m ² Gelatin layer containing (dry) Film thickness 1 μ) Sixth layer: first green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (average grain size 0.3 μm, AgI content 4 mol%) Silver amount ... 0.7 g / m ² coupler F-3 0.20 g / m ² coupler F-5 0.10 g / m ² high-boiling organic solvent Solv-1 gelatin layer containing 0.26 cc / m ² (dry film thickness 1 [mu]) seventh layer: second green Emulsion-sensitive layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (average grain size: 0.6 μm, AgI content: 2.5 mol%) Silver amount: 0.7 g / m
Gelatin layer containing a ² coupler F-4 0.10g / m ² Coupler F-5 0.10g / m ² High-boiling organic solvent Solv-2 0.05 cc / m ² Dye D-3 0.05g / m ² (dry thickness 2.5μ ) 8th layer: Intermediate layer Compound CpdC 0.05g / m ² High boiling point organic solvent Solv-2 0.1 cc / m ² Dye D-4 0.01g / m ² gelatin layer containing 0.01g / m ² 9th layer: Yellow Filter layer Yellow colloidal silver 0.1 g / m ² compound CpdC 0.02 g / m ² compound CpdB (same as in Example 1) 0.03 g / m ² Gelatin layer containing high boiling point organic solvent Oil-1 0.04 cc / m ² (dry film) Thickness 1 μ) 10th layer: 1st blue-sensitive emulsion layer Tabular silver iodobromide emulsion containing sensitizing dye S-5 (average grain size 1.3 μm, average aspect ratio 8, AgI content 2 mol%) Silver amount ... 0.6 g / m ² coupler F-6 0.5 g / m ² Gelatin layer containing high boiling organic solvent Solv-1 0.1 cc / m ² (dry film thickness 1.5 μm) 11th layer: 2nd blue-sensitive emulsion layer Sensitizing dye Tabular silver iodobromide emulsion containing S-6 (average grain Diameter 7.0 μm, average aspect ratio 12, AgI content 2 mol%) Silver amount ... 1.1 g / m ² coupler F-6 1.2 g / m ² high boiling organic solvent Solv-1 0.23 cc / m ² dye D-5 0.02 g / m ² containing gelatin layer (dry film thickness 3 μm) 12th layer: 1st protective layer UV absorber U-1 0.02 g / m ² UV absorber U-2 0.32 g / m ² UV absorber U-3 0.03 g / m ² High boiling point organic solvent Solv-2 Gelatin layer containing 0.28 cc / m ² (dry film thickness 2μ) 13th layer: 2nd protective layer Fine grained silver iodobromide emulsion with surface fog ... 0.1 g / m
² (iodine content mol%, average particle size 0.06μ) Gelatin layer containing polymethylmethacrylate particles (average particle size 1.5μ) (dry film thickness 2.5μ) In addition to the above composition, gelatin hardener H- 1
(Same as in Example 1), and surfactant added.

 The compounds used to make the samples are shown below.

The high boiling point organic solvents Solv-1 and 2 are the same as those used in Example 1.

Preparation of Samples 402 to 406 In Sample 401, the high boiling point organic solvents of the third and fourth layers were removed, and instead of coupler F-1, the couplers shown in Table 5 had the same number of coupler residues as F-1. A sample was prepared in the same manner as Sample 401 except that it was added so as to have a molar ratio.

All water-soluble polymer couplers were added to the emulsion layer as a 5 wt% aqueous solution.

The obtained samples 401 to 406 were subjected to wet exposure with red light and then subjected to the following development processing.

 The concentration of the obtained sample was measured and shown in Table-5.

It can be seen that the water-soluble polymer coupler of the present invention has higher color developability than other water-soluble polymer couplers.

From the above results, by using the coupler of the present invention, a color photographic light-sensitive material was obtained in which the diffusion to other layers was suppressed, the color development was good, and the film strength was strong.

Processing process Process temperature Temperature 1st 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 Room temperature The composition of the processing solution is Use the following:

First developer Water 700 ml Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4 -Hydroxymethyl-3
-Pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Water was added 1000ml Inversion solution Water 700ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3g Chloride chloride 1 tin (dihydrate) 1g p-aminophenol 0.1g sodium hydroxide 8g glacial acetic acid 15ml Water added 1000ml color developer water 700ml nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3g sodium sulfite 7g Trisodium phosphate (12-hydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazic acid 1.5g N-ethyl-N- (β-methanesulphonamidoethyl) -3 -Methyl-4-aminoaniline / sulfate 11g 3,6-dithiaoctane-1,8-diol 1g Water was added to 1000ml Adjusted water 700ml Sodium sulfite 12g Ethylenediaminetetraacetic acid sodium Thorium (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Water added 1000ml Bleached water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2g Ethylenediaminetetraacetic acid iron (III) ammonium (dihydrate) 120g Potassium bromide 100g Water added 1000ml Fixer Water 800ml Sodium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Water added 1000ml Stabilizer Water 800ml Formalin (37% by weight) 5.0ml Fuji Drywell (Fujifilm Corporation) (Made of surfactant)
5.0 ml

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 62-198854 (JP, A) JP 62-276548 (JP, A) JP 62-288832 (JP, A) JP 1- 131556 (JP, A) JP 1-13147 (JP, A) JP 1-133048 (JP, A) JP 1-134357 (JP, A) JP 1-145657 (JP, A) JP-A-2-6946 (JP, A)

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one water-soluble polymer coupler represented by the following general formula [P]. In formula (P) EA _x B _y X Formula, E is representative of the two or more monovalent group carbon atoms. A represents a repeating unit derived from an ethylenically unsaturated monomer having a coupler residue capable of coupling with an oxidation product of an aromatic primary amine developing agent to form a dye, and a coupler residue showing the same hue during color development. It may be two or more kinds of repeating units derived from an ethylenically unsaturated monomer having a group. B represents a repeating unit derived from a copolymerizable non-color-forming ethylenically unsaturated monomer, and may be two or more kinds of repeating units. X represents a monovalent group. x and y are the contents of each repeating unit in the polymer coupler, and the weight ratio (x: y) of x and y is 1
It is from 0:90 to 90:10. 2. The halogenated compound according to claim 1, characterized in that, in the general formula [P], E has a group which is bonded to the binder directly or through a hardening agent. Silver color photographic light-sensitive material. 3. In the above general formula [P], B contains at least one repeating unit derived from an ethylenically unsaturated monomer containing a group which is bonded to a binder directly or via a hardening agent. The silver halide color photographic light-sensitive material according to claim (1).