JPH0769591B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION 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, storability and sharpness. It is a thing.

(Prior Art) Recently, color photographic materials are moving toward higher image quality,
Objects with image quality that can withstand viewing even when stretched from a small format such as 110 size have been developed. However, there is a strong demand for further progress in graininess and sharpness.

Among them, the sharpness is described in JP-A-59-36249 and JP-A-54-36249.
There are a method of using the DIR compound represented by -145135 and a method of emphasizing 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, since there is a problem in the diffusion resistance of the coupler, it is difficult to extremely reduce it due to the precipitation of the coupler and the deterioration of the color developability, and it is not possible to expect a significant thinning.

In contrast, polymerizing the coupler and adding it to the hydrophilic colloid composition in the form of a latex has many advantages.

First, since the hydrophobic material is made into latex, the strength of the formed film is not deteriorated, and the latex can contain a high concentration of coupler in the emulsion, and the viscosity does not increase much. The point is that the film can be made thinner and the sharpness can be improved.

Further, since it is non-migrating, there is little color mixing, and couplers are less likely to precipitate in the emulsion film.

The addition of the polymer coupler in the form of a latex to a gelatin silver halide emulsion as described above includes, for example, U.S. Patent No. 4,080,211, British Patent No. 1,247,668, U.S. Patent No.
No. 3,451,820 shows its production method and a 4-equivalent magenta polymer coupler latex, and West German Patent No. 2,725,591 and US Pat. No. 3,926,436 have copolymerized latex with competitive couplers. Ya (Research Disclosure) 21728 (1982
Year) describes a cyan polymer coupler latex.

However, the polymer coupler has the following excellent problems while having the above-mentioned excellent characteristics.

1. A polymer coupler having a relatively high molecular weight (a number average molecular weight of about 10,000 or more) has sufficient non-migrating property but poor coupling reactivity, resulting in low sensitivity, gradation and dye concentration.

2. When the content of the coupler unit (content of the repeating unit having a coupler residue) in the polymer coupler is high, the color developability per unit weight (of the coupler unit) is significantly reduced.

3. On the other hand, a polymer coupler having a lower molecular weight has a higher dye concentration, but is insufficient in terms of non-migrating property, resulting in color mixing and sensitivity deterioration.

If a polymer with a high coupler unit content can maintain high color development, it is possible to reduce the thickness of the light-sensitive material film because the emulsion can contain a higher concentration and a small amount of coupler, resulting in a sharp image. Since it becomes possible to remarkably improve the degree (sheepness), it is one of the important subjects to improve the color developability in a polymer having a high coupler unit content.

Further, in polymer couplers, it is another important task to make both non-migrating property and coupling reactivity be compatible.

(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 having high sensitivity.

The second object of the present invention is to provide a novel coupler having high sensitivity and excellent color forming property.

The third object of the present invention is to provide a novel coupler having a high coupler unit content and exhibiting a high color forming property.

The fourth object of the present invention is to provide a silver halide color photographic light-sensitive material which is free from color mixing due to the non-migrating property of the coupler.

A fifth object of the invention is to develop a silver halide emulsion in the presence of a dispersion of novel couplers by
A method of forming a color image is provided.

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

(Means for Solving Problems) An object of the present invention is to provide a silver halide color photographic light-sensitive material containing at least one oil-soluble polymer coupler represented by the following general formula [P]. Was achieved.

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 exhibiting the same hue during color development. It may be two or more kinds of repeating units derived from an ethylenically unsaturated monomer having a residue. 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. Further, E or B contains a fluorine group or a group which is bonded to the binder directly or through a hardener. X represents a monovalent group. x and y are the contents of each repeating unit in the polymer coupler, and the weight ratio of x to y (x: y) is 10:90 to 100: 0.

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

The 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, and -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, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, and phenylene groups such as p-phenylene and m-.
Examples include phenylene and 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 represents alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, or 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 as defined 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 have the same meanings as described above), an amino group (which may be substituted with alkyl), a hydroxyl group or a group which is hydrolyzed to form a hydroxyl group. 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 a hydroxyl group, a nitro group, an alkoxy group having 1 to about 4 carbon atoms, and -NH.
SO ₂ R ⁸ (R ⁸ is as defined above), a group represented by —NHCOR ⁸ (R
⁸ is synonymous with the 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], as cyan color forming coupler residues, phenol type [II], [V] represented by the following general formula,
Alternatively, a naphthol type [III] or [IV] compound (each hydrogen atom other than the hydrogen atom of the hydroxyl group is released to form L ¹
linked to _m L ² _n ) is preferred.

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. R ¹¹ has 0 to 30 carbon atoms.

R ¹² is ^{-CONR 14 R 15, -NHCOR 14,} -NHCOOR 16, -NHSO 2 R
¹⁶ , --NHCONR ¹⁴ R ¹⁵ or --NHSO ₂ R ¹⁴ R ^15, which represents 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, dodecyloxypropyl, 2,
4-di-tert-amylphenoxypropyl, 2,4-di-te
rt-amylphenoxybutyl), an aromatic group having 6 to 30 carbon atoms (eg, phenyl, tolyl, 2-tetradecyloxyphenyl, pentafluorophenyl, 2-chloro-5)
-Dodecyloxycarbonylphenyl), carbon number 2-30
A heterocyclic group (eg, 2-pyridyl, 4-pyridyl, 2
-Furyl, 2-thienyl), R ¹⁶ is an aliphatic group having 1 to 30 carbon atoms (eg, methyl, ethyl, butyl, dodecyl, hexadecyl), an aromatic group of 6 to 30 (eg, phenyl, tolyl, 4-chlorophenyl) , Naphthyl) and a heterocyclic group (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'represents an integer of 0 to 3, s'represents an integer of 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 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), an aromatic group having 6 to 30 carbon atoms ( For example, phenyl,
Tolyl), heterocyclic group 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), carbon number 1-30 sulfonamide group (for example, methanesulfonamide, toluenesulfonamide, 4-chlorobenzenesulfonamide), an imide group having 4-30 carbon atoms (for example, succinimide), -OR ¹⁸ , SR ¹⁸ , -COR ¹⁸ , -CONR ¹⁸ R ¹⁹ , -COCOR
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 are a halogen atom (eg, fluorine, chlorine, bromine, iodine), an aliphatic oxy group having 1 to 30 carbon atoms (eg, methoxy, ethoxy, 2-hydroxyethoxy, carboxymethyloxy, 3-carboxy). Propyloxy, 2-methoxyethoxycarbamoylmethyloxy, 2-methanesulfonylethoxy, 2-carboxymethylthioethoxy, triazolylmethyloxy), an aromatic oxy group having 6 to 30 carbon atoms (for example, phenoxy, 4-
Hydroxyphenoxy, 2-acetamidophenoxy,
2,4-dibenzenesulfonamidophenoxy, 4-phenylazophenoxy), a heterocyclic oxy group having 2 to 30 carbon atoms (for example, 4-pyridyloxy, 1-phenyl-5-tetrazolyloxy), 1 carbon atom To 30 aliphatic thio groups (eg, todecylthio), 6 to 30 carbon aromatic thio groups (eg, 4-dodecylphenylthio), 2 to 30 carbon atoms
A heterocyclic thio group (eg, 4-pyridylthio, 1-phenyltetrazol-5-ylthio), an acyloxy group having 2 to 30 carbon atoms (eg, acetoxy, benzoyloxy, lauroyloxy), a carbonamido group having 1 to 30 carbon atoms ( For example, dichloroacetylamide, trifluoroacetamide, heptafluorobutanamide, pentafluorobenzamide), a sulfonamide group having 1 to 30 carbon atoms (for example, methanesulfonamide, toluenesulfonamide), an aromatic azo having 6 to 30 carbon atoms. Group (eg, phenylazo, 4-chlorophenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo), an aliphatic oxycarbonyloxy group having 1 to 30 carbon atoms (eg, ethoxycarbonyloxy, dodecyloxycarbonyloxy) ), Carbon number 6-30 Group oxycarbonyl group (e.g., phenoxycarbonyloxy), a carbon number 1
~ 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 a halogen atom (eg phen, chlorine, bromine etc.), an aliphatic group (eg methyl, ethyl, isopropyl), a carbonamide group (eg acetamide, benzamide), a 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-di-
There is tert-amylphenoxybutyl.

Preferred as X ⁴ is R ¹⁷ N, and further preferred as R ¹⁷ is —COR ¹⁸ (eg, 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, toluene) sulfonyl, p- ^{chlorobenzenesulfonyl), - CONR 18 R 19 (} N, N- dimethylcarbamoyl, N, N-diethylcarbamoyl, N, N-dibutyl carbamoyl, morpholinocarbonyl, piperidinocarbonyl, 4 Cyanophenylcarbamoyl, 3,4
- dichloro phenylcarbamoyl, 4-methanesulfonyl-phenylcarbamoyl) -SO ₂ NR ¹⁸ R ¹⁹ (e.g., N, N
-Dimethylsulfamoyl, N, N-diethylsulfamoyl, N, N-dipropylsulfamoyl). More particularly preferred one of R ¹⁷ is -CO
It is a group represented by R 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 is a dimer or a multimer of the substituents R ¹¹ , R ¹² , X ⁴ or Z ¹ which are bonded to each other through a divalent or higher polyvalent linking group. May be. 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 [VI],
[VII], [VIII], [IX], [X], [XI] and [X]
II] in the case of the general formula [V] in which a coupler residue (Ar, Z ² , R ^{21 to} R ³³ is linked to L ¹ _m L ² _n at any part thereof), more preferred is substitution of R ²¹ This is the case when the position is directly connected.).

In the formula, Ar is a substituent of a 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, haloalkyl such as fluoroalkyl, cyanoalkyl, benzylalkyl, etc.), an aryl group or a substituted group. Aryl group [As a substituent, an alkyl group (eg, methyl, ethyl), an alkoxy group (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 groups (eg phenyl sulfonamide), sulfamoyl, alkylsulfamoyl groups (eg ethylsulfamoyl), dialkylsulfamoyl groups (eg dimethylsulfamoyl), alkylthio groups (eg methylthio), arylthio groups (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
-Hydantoinyl, 3- (N-acetyl-N-dodecylamino) succinimide), alkoxycarbonyl group (e.g. methoxycarbonyl, tetradecyloxycarbonyl, benzyloxycarbonyl), alkoxysulfonyl group (e.g. methoxysulfonyl, butoxysulfonyl, octyl). Oxysulfonyl, tetradecyloxysulfonyl), aryloxysulfonyl group (eg, phenoxysulfonyl, p-methylphenoxysulfonyl, 2,4-di-tert-amylphenoxysulfonyl, etc.), alkanesulfonyl group (eg, methanesulfonyl, ethanesulfonyl) , Octanesulfonyl, 2-ethylhexylsulfonyl, hexadecanesulfonyl),
An arylsulfonyl group (eg, benzenesulfonyl,
4-nonylbenzenesulfonyl), an alkylthio group (eg, methylthio, ethylthio, hexylthio, benzylthio, tetradecylthio, 2- (2,4-di-tert-amylphenoxy) ethylthio, etc.), an arylthio group (eg, phenylthio, p -Tolylthio), an alkyloxycarbonylamino group (eg, methoxycarbonylamino, ethyloxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino), an alkylureido group (eg, N-methylureido, N, N-dimethylureido) , N-methyl-N-dodecylureido, N-hexadecylureido, N, N-dioctadecylureido), an acyl group (for example, acetyl, benzoyl, octadecanoyl, p-dodecanoamidobenzoyl), a nitro group, Examples thereof include a ruboxyl 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 and a hydroxyl group,
An unsubstituted or substituted alkyl group (preferably having a carbon number of 1 to 20, for example, methyl, propyl, t-butyl, trifluoromethyl, tridecyl, etc.), an aryl group (preferably having a carbon number of 6 to 20). For example, phenyl,
4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-methoxyphenyl), a heterocyclic group (for example, 2-
Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), alkylamino group (preferably having 1 carbon atom)
~ 20 things. 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 carbon number). 2 to 20. For example, methoxycarbonyl, butoxycarbonyl, 2-ethylhexyloxycarbonyl), alkylcarbonyl group (preferably having 2 to 20 carbon atoms, for example, acetyl, butylcarbonyl, cyclohexylcarbonyl), arylcarbonyl group ( For example, preferably those having 7 to 20 carbon atoms, such as benzoyl, 4-t-butylbenzoyl) and alkylthio groups (preferably those having 1 to 20 carbon atoms. For example, methylthio,
Octylthio, 2-phenoxyethylthio), arylthio group (preferably having 6 to 20 carbon atoms, for example, 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-butylcarbamoyl), 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 1 to 20 carbon atoms, such as 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- 99
No. 437, 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-dioxo-
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-methane) Sulfonylphenylthio, 4-octanesulfonamidophenylthio, 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 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, arylsulfone Amide group, arylureido group, carboxy group, sulfo group,
It represents a nitro group, a cyano group, a thiocyano group, etc., and these substituents may be the same or different.

Z ³ is a hydrogen atom or the following general formula [XVI], [XVII], [XVI
II] 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, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, unsubstituted or substituted. Represents a phenyl group or a heterocycle, which groups may be the same or different.

W ₁ in the formula Represents a non-metal atom required to form a 4-membered ring, 5-membered ring 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 Xyl 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 (some alkoxy groups further include a plurality of substituted alkoxy groups), β-sulfonamidoethylacrylamide, β-
Carbonamidoethyl acrylamide etc.), vinyl esters (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.

Two or more kinds of the ethylenically unsaturated monomers used here can be used together.

For example, ethyl acrylate and n-butyl acrylate,
Examples include n-butyl acrylate, styrene methyl methacrylate, and diacetone acrylamide.

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

R ¹ represents a hydrogen atom or a methyl group, L ¹ represents -CONH-, -CO
O-, -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 , and particularly preferred among them is that 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, and a substituted arylene group, and p, q, r, and s are Represents 0 or 1.

Particularly preferred among B are acrylic acid esters, methacrylic acid esters, maleic acid esters, and styrenes.

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 not limited thereto. .

Preferred examples of the ethylenically unsaturated monomer forming the repeating unit represented by B in the general formula [P] which does not couple 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 , Methacrylamides, vinyl ethers,
Examples thereof include styrenes. 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, te
Examples thereof include rt-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate and 2-ethoxyethyl methacrylate. Examples of crotonic acid esters include butyl crotonic acid and hexyl crotonic acid. Vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl methoxyacetate and vinyl benzoate. 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 itaconic acid, dimethyl itaconic acid and dibutyl itaconic acid. Examples of acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, isopropyl acrylamide, n-butyl acrylamide, hydroxymethyl acrylamide, diacetone acrylamide, acryloylmorpholine, and acrylamido-2-methylpropanesulfonic acid. 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, vinylbenzoic acid methyl ester, 2-methylstyrene, styrenesulfonic acid, vinylbenzoic acid and the like can be mentioned.

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

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.

Next, preferred examples of the ethylenically unsaturated monomer forming a repeating unit containing a fluorine group among the repeating units represented by B in the general formula [I] are shown, but the present invention is not limited thereto.

As a method for introducing a monovalent group having 3 or more carbon atoms represented by E in the general formula [I], a chain transfer agent having 3 or more carbon atoms is used, or a chain transfer agent having a reactive group or initiation. There is a method in which a polymerization reaction is performed using an agent 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-1C ₃ H ₇ SH, T-2C ₄ H ₉ SH T-3C ₆ H ₁₃ SH, T-4C ₈ H ₁₇ SH T-5C ₁₂ H ₂₅ SH, T-6C ₁₅ H ₃₁ SH T-7C ₁₆ H ₃₃ SH, T-8C ₁₈ H ₃₇ SH T-9C ₃₁ H ₆₃ SH, T-13C ₃ H ₇ SO ₂ NHCH ₂ CH ₂ SH T-15C ₄ H ₉ CONHCH ₂ CH ₂ SH T-16C ₁₃ H ₃₇ CONHCH ₂ CH ₂ SH T-19C ₄ H ₉ NHCH ₂ CH ₂ SH T-30BrCH ₂ COOCH ₃ T-31ClCH ₂ COOC ₂ H ₅ The following are specific examples of the chain transfer agent having a group which is bonded to the binder directly or via a hardener, but the present invention is not limited thereto.

T-40ClCH ₂ CH ₂ SO ₂ CH ₂ CONHCH ₂ CH ₂ SH T-41CH ₂ = CH-SO ₂ CH ₂ CH ₂ CONHCH ₂ CH ₂ SH _{T-43SHCH 2 CH 2 COOCH 2} CH 2 CN Specific examples of the chain transfer agent preferable for obtaining the polymer of the present invention which easily forms a micelle structure are shown below.

T-45C ₈ F ₁₇ CH ₂ CH ₂ SH T-48R _f CH ₂ CH ₂ SH T-49C ₈ F ₁₇ CONHCH ₂ CH ₂ SH T-50C ₈ F ₁₇ SO ₂ NHCH ₂ CH ₂ SH T-51C ₆ F ₁₃ CH ₂ CH ₂ SH T-52C ₈ F ₁₇ CH ₂ CH ₂ SCH ₂ CH ₂ SH T-53C ₁₂ F ₂₅ CH ₂ CH ₂ OCH ₂ CH ₂ SH In the present invention, oil solubility means that the obtained polymer coupler (telomer coupler) has a solubility in water of 1.0 wt%.
Less than.

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. 58-2874
5, JP 58-10738, JP 58-42044, JP 5
It is carried out using the compounds described in 8-145944 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.

It is necessary to set the polymerization temperature in relation to the molecular weight of the telomer produced, the type of initiator, etc.
Although the above is possible, polymerization is usually carried out in the range of 30 ° C to 100 ° C. 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 10 to 95% by weight, but 20 to 90% by weight is preferable in terms of color reproducibility, color development and stability. 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 preferably about 1000 to about 10,000, particularly preferably about 1000 to about 5,000, from the viewpoint of color developability and sensitivity.

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, 0.001 per mol of silver.
5 mol to 0.5 mol, preferably 0.01 to 0.10 mol may be added.

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.
The range is up to 0.5 g / m ² .

The telomer coupler of the present invention may be prepared by emulsifying and dispersing a coupler obtained by polymerization of a monomer coupler in an organic solvent in the form of latex in an aqueous gelatin solution,
Alternatively, it may be directly produced by an emulsion polymerization method.

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

Synthesis example (1) 1- (2,4,6-trichlorophenyl) -3
-Methacrylamido-4-pyrazolyl-5-pyrazolone copolymer of butyl acrylate and glycidyl methacrylate Synthesis of polymer coupler (P-1) 25.0 g of coupler monomer (22), butyl acrylate 20.
500 ml of a mixture of 0 g, glycidyl methacrylate 3.0 g, dodecyl mercaptan 2.0 g and dimethylformamide 20 ml
The flask was placed in a three-necked flask and heated to 70 ° C under stirring in a nitrogen stream. Dimethyl azobisisobutyrate 50 as a polymerization initiator
10 ml of a dimethylformamide solution containing 0 mg was added to initiate polymerization.

After polymerization for 4 hours, the polymerization solution was cooled, poured into water 1 and the precipitated solid was separated by filtration, washed with water, and dried by heating under reduced pressure to obtain P-1 45.2 g.

P-1 shows 50.3wt% of monomer (22) by elemental analysis
I knew it was included.

The number average molecular weight was 4,200.

Synthesis example (2) Copolymerization of 5- (acrylamido) -2- (perfluoropropylamido) phenol and methyl methacrylate Synthesis of polymer coupler (P-2) Coupler monomer (16) 25.0 g, methyl methacrylate 2
A mixture of 0.0 g, perfluorobutyl mercapran 5.0 g and ethyl acetate 250 ml was placed in a 500 ml three-necked flask and heated to 70 ° C. under stirring in a nitrogen stream.

10 ml of an ethyl acetate 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 and ethyl acetate was distilled off under reduced pressure to obtain P-2 (48.5 g).

P-2 is 49.2wt% of monomer monomer (16) by elemental analysis
I knew it was included.

The number average molecular weight was 3,900.

The polymers P-3 to P-24 of the present invention were synthesized as shown in Table 1 by the same method as in Synthesis Examples (1) and (2) above.

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 iodochlorobromide 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.

The silver halide grains in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, 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), pp. 22-23, "I. Emulsion preparati
on and types) ”, and No. 18716 (November 1979),
648, Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P.Glafkides, Chemic et Phisique Photogr
aphique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographi
c Emulsion Ghemistry (Focal Press, 1966)), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZelikman et al. Making and Coating Photog
It can be prepared using the method described in raphic Emulsion, Focal Press, 1964).

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, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, a compound other than silver halide such as silver rotan and lead oxide may be bonded.

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.176.
43 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, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,401,7
Those described in No. 52, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020, 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,61
No. 9, No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
Issue, Research Disclosure No. 24230 (June 1984
JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and U.S. Pat.
4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162,
No. 2,895,826, No. 3,772,002, No. 3,758,308
No. 4,334,011, 4,327,173, West German Patent Publication 3,329,729, European Patent 121,365A, U.S. Patent 3,4.
46,622, 4,333,999, 4,451,559, 4,
Those described in 427,767, EP 161,626A and the like are preferable.

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

As the coupler in which the color forming dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) 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 are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned patents RD17643, VII to F, JP-A-57-151944 and 57-154234.
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 2,13.
Those described in 1,188, 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, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP 60-1
85950, DIR redox compounds or DIR coupler-releasing couplers or DIR coupler-releasing couplers or redox described in JP-A-62-24252 and the like, couplers that release dyes that undergo color recovery after separation according to EP 173,302A, RD
No. 11449 and No. 24241, bleaching accelerator releasing couplers described in JP-A-61-2201247 and the like, ligand releasing couplers described in US Pat. No. 4,553,477 and the like.

Specific examples of the color coupler that can be used in the present invention are shown below, 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 the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used for the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bisyl phthalate. (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 Kinds (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, -diethyllauryl) Amides, N-tetradecylpyrrolidone, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-tert.
-Amylphenol, etc.), aliphatic carboxylic acid ester (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivative (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 of the latex dispersion method, effects, and specific examples of the 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.

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 include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same No.18716 From right column 6
See page 48, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.
The development processing can be carried out by a usual method described on pages 28 to 29 of 643 and 651 left column to right column of No. 18716.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N, N-diethylaniline. Methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 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.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or a development inhibitor or a fog. Generally, it contains an inhibitor and the like. 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 agents such as sodium boron hydride. , 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by 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, Representative examples are N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts.

When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developer, a known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol is used alone. Alternatively, they can be used 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 developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. 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. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. 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 diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic 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 bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but a lower pH can be used for speeding 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, 2,059,988.
No. 5, JP-A-53-32,736, JP-A-53-57,831, and JP-A-53-37,4
No. 18, No. 53-72,623, No. 53-95,630, No. 53-95,631
No. 53, No. 1042323, No. 53-124, 424, No. 53-141, 62
No. 3, No. 53-28,426, Research Disclosure N
Compounds having a mercapto group or a disulfide group, such as those described in JP-A No. 17-129 (July 1978);
Thiazolidine derivatives described in No. 9; Japanese Examined Patent Publication No. 45-8,506,
JP-A-52-20832, JP-A-53-32735, U.S. Pat.
Thiourea derivatives described in 6,561; West German Patent No. 1,127,715
And iodide salts described in JP-A-58-16235; West German Patent No.
Polyoxyethylene compounds described in 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836;
Other JP-A-49-42,434, 49-59,644, 53-9
4,927, 54-35,727, 55-26,506, 58-163,9
Compounds described in No. 40; bromide ion and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and in particular, US Pat.
Compounds described in 893,858, West Patent 1,290,812 and JP-A-53-95,630 are preferable. Further, U.S. Pat.
The compounds described in No. 4 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 light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is the most widely used. Can be used for 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 is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in Jour.
nal of the Society of Motion Picture and Televisio
n 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 and magnesium ions described in Japanese Patent Application No. 61-131,632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and 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.
And preferably 5-8. The temperature of washing water and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15-45 ° C, and preferably 30 at 25-40 ° C.
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 stabilization treatment, Japanese Patent Laid-Open 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 antifungal agents 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 accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff's base type compounds described in Research Disclosures 14,850 and 15,159, aldol compounds described in No. 13,924, metals described in U.S. Pat.No. 3,719,492. Salt complex, JP-A-5
The urethane compound described in 3-135,628 can be mentioned.

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 Nos. 56-64,339, 57-144,547, and 58.
-115,438 etc. are 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 silver in 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.

The silver halide light-sensitive material of the present invention is described in US Pat.
0,626, JP-A-60-133449, 59-218443, 61
It can also be applied to the photothermographic materials described in, for example, No. 238056 and European Patent No. 210,660A2.

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

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

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 spherical 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) Coated silver 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 6th layer (low sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core shell ratio 1: 1 surface height A)
gI type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Silver coating amount: 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent to sphere) Diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 25%, spherical particles, diameter / thickness ratio
1.0) Silver coating amount …… 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, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter / thickness ratio 5.0) Silver coating 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, equivalent sphere diameter 1.0μ, variation coefficient of equivalent sphere 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) Coating silver amount …… 0.3 Silver iodobromide emulsion (AgI 13 mol%, uniform AgI type, equivalent spherical diameter 0.3)
μ, coefficient of variation of equivalent spherical diameter 25%, plate-shaped 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 twinned plate-like particles, diameter / thickness ratio 2.0) Coating 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 No. 14 layers (2nd protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter)
0.07μ) ...... 0.5 Gelatin ...... 0.45 Polymethylmethacrylate particles 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 stability Agent Cpd-3 (0.0
4 g / m ² ) Surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid. Other compounds below Cpd-5 (0.5g / m ² ) ~
Cpd-6 (0.5 g / m ² ) was added.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate Preparation of Samples 102 to 106 In Sample 101, the couplers shown in Table 1 were used instead of the couplers ExM-8 in the sixth and seventh layers, and the amount of the coupler residue was
It was produced in the same manner as in the trial sample 101, except that it was added in an equimolar amount to ExM-8. Couplers A-1 and A-2 added to Samples 102 to 103 are the couplers shown below.

The obtained samples 101 to 106 were subjected to wet exposure with green light and then subjected to the following development processing.

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 liquid 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 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 2.0g 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 pH7.3 <Rinse solution> Ethylenediamine tetraacetic acid disodium salt 0.4g Add water 1 pH 7.0 with sodium hydroxide <Stabilizer> Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization about 10) 0.3g Add water Results having conducted the concentration measured for the sample obtained as above 1.0l Te are summarized in Table 1.

From the results in Table 1, it is clear that the telomer coupler of the present invention has high sensitivity and high color density as compared with the conventional polymer coupler having substantially the same coupler unit content.

Example 2 The same sample preparation, measurement, and evaluation as in Example 1 were carried out except that only the treatment steps in Example 1 were subjected to the treatments described below.

As a result, the same effect as in Example 1 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%) 240ml Add water 1 pH with ammonia water (28%) 6.8 <Wash water> Tap water is H type strong acid cation exchange resin (Amberlite IR-120B by Rohm and Haas) and OH. Type strong 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 magnesium to 1 mg / l or less, 0.02 g of sodium isocyanurate dichloride was added per 1 and used.

<Stabilizer> Formalin (37% w / v) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization of about 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water is added 1 pH 6.0 Example 3 On a subbed cellulose triacetate film support,
A multilayer color light-sensitive material having the following composition was prepared and used as Sample 301.

1st layer: Anti-halation layer Black colloidal silver 0.25g / m ² UV absorber U-1 0.04g / m ² UV absorber U-2 0.1g / m ² UV absorber U-3 0.1g / 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 0.05 g / m ² Compound 1-1 0.05 g / 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 3mol%) Silver amount ... 0.8g / m ² Coupler F-1 0.55g / m ² coupler F-2 0.14 g / m ² compound I-2 1 × 10 ⁻³ g / m ² high boiling point organic solvent Solv-1 0.33 cc / m ² dye D-1 0.02 g / m ² containing gelatin layer (Dry film thickness 2.5 μ) 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 (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 Gelatin layer containing high boiling organic solvent Solv-1 0.26 cc / m ² (dry film thickness 1 μm) 7th layer: second green emulsion 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 ² coupler F-4 0.10 g / m ² coupler F -5 0.10 g / m ² gelatin layer containing a high-boiling organic solvent ^Solv-2 0.05cc / m 2 dye D-3 0.05g / m ² (燥膜thickness 2.5 [mu]) Eighth layer: Intermediate layer Compound CpdC 0.05g / m ² gelatin layer containing a high-boiling organic solvent ^Solv-2 0.1cc / m 2 Dye D-4 0.01g / m ² (dry film thickness 1 [mu]) Ninth 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 High boiling organic solvent Oil-2 0.04 cc / m ² is included. Gelatin layer (dry film thickness 1 μm) 10th layer: first 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 High boiling point organic solvent Solv-1 Gelatin layer containing 0.1 cc / m ² (dry film thickness 1.5 μm) Eleventh layer: second blue feeling Emulsion layer Tabular silver iodobromide emulsion containing sensitizing dye S-6 (average grain size 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 0.23cc / m ² dye D- Gelatin layer containing 0.02 g / m ² (dry thickness 3.mu.) 12th layer: 1st protective layer UV absorber U-1 0.02g / m ² UV absorber ^U-2 0.32g / m 2 UV absorber U- 3 0.03 g / m ² High boiling organic solvent Solv-2 Gelatin layer containing 0.28 cc / m ² (dry film thickness 2 μ) 13th layer: 2nd protective layer Fine grain silver iodobromide emulsion with surface fogged Silver amount ... 0.1 g / m ² (iodine content 1 mol%, average particle size 0.06 μ) Gelatin layer containing polymethylmethacrylate particles (average particle size 1.5 μ) (dry film thickness 2.5 μ) In addition to the above composition in each layer, Gelatin hardener H-1 (same as in Example 1), and surfactant were 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 302 to 306 In Sample 301, the couplers shown in Table 5 were used instead of the couplers F-1 of the third and fourth layers, and the number of coupler residues was F.
A sample was prepared in the same manner as Sample 301 except that it was added in an equimolar amount to -1.

Couplers A-3 and A-4 added to Samples 302 to 303 are the couplers shown below.

The obtained samples 301 to 306 were exposed to light and subjected to the following reverse color processing. In this case, two processes were carried out: one in which the first development carried out normal processing for 6 minutes and one in which the first development carried out sensitization processing for 10 minutes. Treatment process Process time 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 Use the following: First developer water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2 g Sodium sulfite 20 g Hydroquinone monosulphonate 30 g Sodium carbonate (-water salt) 30 g 1-phenyl-4methyl-4- Hydroxymethyl-3 pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water 1000ml Inverted water 700ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3g stannous chloride (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 Tribasic sodium phosphate (12-hydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazine acid 1.5g - ethyl-N-(beta-methanesulfonyl Huong amide ethyl) -3-methyl-4-amino aniline acid sulfate 11g 3,6-dithiaoctane-1,8-diol 1g water 1000ml adjusting liquid water 700ml sulfite added Sodium 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Water added 1000ml Bleached water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2g Ethylenediaminetetraacetate iron (III) ammonium (dihydrate) ) 120 g Potassium bromide 100 g Water added 1000 ml Fixer water 800 ml Sodium thiosulfate 80.0 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water added 1000 ml Stabilized water 800 ml Formalin (37% by weight) 5.0 ml Fuji Drywell ( FUJIFILM Corporation surfactant)
The results of concentration measurement of the sample obtained by adding 5.0 ml water to 1000 ml or more are summarized in Table 2.

As is clear from Table 2, the sample containing the telomer coupler of the present invention showed remarkably high color developability regardless of the coupler content.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material containing at least one oil-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 exhibiting the same hue during color development. It may be two or more kinds of repeating units derived from an ethylenically unsaturated monomer having a residue. 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. Further, E or B contains a fluorine group or a group which is bonded to the binder directly or through a hardener. X represents a monovalent group. x and y are the contents of each repeating unit in the polymer coupler, and the weight ratio of x to y (x: y) is 10:90 to 100: 0.