JPH0769590B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

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

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

By the way, in multi-layer color light-sensitive materials,
It is necessary to fix each coupler in a separate layer for better color reproduction. Many methods are known as methods for making the coupler resistant to diffusion.

One of the methods is to introduce a long-chain aliphatic group into the molecule of the low molecular coupler in order to prevent diffusion. Since the coupler produced by this method is immiscible with the gelatin aqueous solution, it is necessary to solubilize it in an alkali and add it to the gelatin solution, or to dissolve it in a high boiling organic solvent to emulsify and disperse it in the gelatin aqueous solution. is there.

Such a color coupler requires a large amount of gelatin because it causes the precipitation of crystals in the emulsion or softens the emulsion layer when an organic solvent having a high boiling point is used.
As a result, the desire to thin the emulsion layer has the opposite effect.

Another way to introduce a coupler into each separate layer is:
This is a method utilizing a polymer coupler latex obtained by polymerizing a monomer coupler.

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

First, since the hydrophobic material is made into a latex, it does not deteriorate the strength of the formed film, and since the latex can contain a high concentration coupler unit, a high concentration coupler can be easily added to the emulsion. Can be included,
Moreover, since the increase in viscosity is small, the film can be made thin and the sharpness can be improved.

Further, since it is non-migrating, there is no color mixing and the coupler is less likely to precipitate in the emulsion film.

Examples of such a polymer coupler added to a gelatin silver halide emulsion in the form of a latex include, for example, U.S. Pat. No. 4,080,211, British Patent No. 1,247,668, U.S. Pat. Equivalent magenta polymer coupler latex is described in West German Patent No. 2,725,591.
U.S. Pat. No. 3,926,436 discloses copolymerized latex with a competing coupler, U.S. Pat. No. 3,767,412 and Research Disclosure 21728.
(1982) cyan polymer Capellalatex is described.

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.

To solve these problems, we have found that a lipophilic polymer coupler obtained by a polymerization reaction using a chain transfer agent having 8 or more carbon atoms is extremely effective. This polymer coupler has excellent coupling activity, and even if it has a high coupler unit content, not only can it maintain a high color-forming property, but it is also sufficient in terms of non-migration property. It has the characteristic that it does not easily deteriorate.

It is presumed that the characteristics of this polymer coupler arise from having a group having 8 or more carbon atoms derived from the partial structure of the chain transfer agent at the end.

However, in this lipophilic polymer coupler, a polymer not having a group having 8 or more carbon atoms at the end is mixed,
When the amount is large, the color development is insufficient with respect to the original performance, and improvement has been desired.

(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 contain a lipophilic polymer coupler, wherein the lipophilic polymer coupler comprises a coupler monomer, a polymerization initiator, and a chain transfer agent having 8 or more carbon atoms. A silver halide photographic light-sensitive material obtained by the polymerization reaction used, wherein 85% by weight or more of the polymer contains a monovalent group having 8 or more carbon atoms at the terminal excluding the repeating unit. Achieved by material.

The lipophilic polymer coupler synthesized by a polymerization reaction using a chain transfer agent having 8 or more carbon atoms used in the present invention is
It is a mixture of polymers of various structures, most of which are
It can be represented by the following general formula [P].

Formula (P) EA _x B _{y X} E represents the number 8 or more monovalent group having a carbon. A represents a repeating unit derived from an ethylenically unsaturated monomer having a coupler residue capable of coupling with an oxidized product of an aromatic primary amine developing agent to form a dye. B represents a repeating unit derived from a copolymerizable ethylenically unsaturated monomer. X represents a monovalent group. x and y are the contents of each repeating unit in the polymer coupler, and x and y
And the weight ratio (x: y) is 10:90 to 100: 0.

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 ¹ each independently represent hydrogen, hydroxyl, halogen atom or 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 X ¹ J ¹ -X ² _p
Represented by _{^{J 2 -X 3 q J 3 r}} s.

J ¹ , J ² and J ³ may be the same or different, and --CO-- and --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 the alkylene group include methylene, methylmethylene,
Examples of the dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene and aralkylene groups include benzylidene,
Examples of the phenylene group include p-phenylene, m-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 alkylene 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. The carbon number of R ¹¹ is 0 to 30.

R ¹² is ^{-CONR 14 R 15, -NHCOR 14,} -NHCOOR 16, -NHSO 2 R 16, -NHC
ONR ¹⁴ R ¹⁵ or —NHSO ₂ R ¹⁴ R ¹⁵ is represented by R ¹⁴ and R ¹⁵ being 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-tert
-Amylphenoxybutyl), an aromatic group having 6 to 30 carbon atoms (for example, phenyl, tolyl, 2-tetradecyloxyphenyl, pentafluorophenyl, 2-chloro-5-).
Dodecyloxycarbonylphenyl), a heterocyclic group having 2 to 30 carbon atoms (for example, 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 (for example, 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, a sulfur 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 , -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 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, dodecylthio), aromatic thio groups having 6 to 30 carbon atoms (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
To a carbamoyloxy group (for example, methylcarbamoyloxy, dodecylcarbamoyloxy, phenylcarbamoyloxy), a heterocyclic group having 1 to 30 carbon atoms and a nitrogen atom which is continuous to the active position of the coupler (for example, 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 fluorine, 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-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 (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, methoxyethoxycarbonyl, phenoxycarbonyl), —SO ₂ R ²⁰ (eg, methanesulfonyl,
Ethanesulfonyl, butanesulfonyl, hexadecanesulfonyl, benzenesulfonyl, toluenesulfonyl,
p-chlorobenzenesulfonyl), -CONR ¹⁸ R ¹⁹ (N, N-
Dimethylcarbamoyl, N, N-diethylcarbamoyl,
N, N-dibutylcarbamoyl, morpholinocarbonyl,
Piperidinocarbonyl, 4-cyano-phenylcarbamoyl, 3,4-dichloro-phenylcarbamoyl, 4-methanesulfonyl Suho sulfonyl phenylene ^{_{carbamoyl), - SO 2 NR 18 R}} 19 ( e.g., N, N-dimethylsulfamoyl, N, N- And a group represented by diethylsulfamoyl, N, N-dipropylsulfamoyl). More particularly preferable ones of R ¹⁷ are
It 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 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] is a coupler residue (any one of Ar, Z ² , R ^{21 to} R ³³ is linked to L ¹ _m L ² _n . In the case of the general formula [V], more preferred is R ²¹ This is the case of directly connecting to the substitution position.).

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 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 (for example, fluorine, chlorine, bromine, etc.), and when there are two or more substituents, they may be the same or different. Group, an alkoxy group, an alkoxycarbonyl group, a cyano group, etc.), 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 are Is a halogen atom (for example, fluorine, chlorine, bromine, etc.), straight chain,
Branched chain alkyl groups (eg, methyl, t-butyl, octyl, tetradecyl), alkoxy groups (eg, methoxy, ethoxy, 2-ethylhexyloxy, tetradecyloxy, etc.), acylamino groups (eg, acetamide, benzamide, butanamide, octane). Amide, tetradecane amide, 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-methyltetradecanamide), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, ethylsulfonamide, p-toluene) Sulfonamide, octane sulfonamide, p-dodecylbenzene sulfonamide, N-methyl-tetradecane sulfonamide), sulfamoyl group (for example, sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N, N-dimethylsulfamide) Famoyl, N, N-dihexylsfamoyl, N-hexadecylsulfamoyl, N- [3- (dodecyloxy)
-Propyl] sulfamoyl, N- [4- (2,4-di-t
ert-amylphenoxy) butyl] sulfamoyl, N
-Methyl-N-tetradecylsulfamoyl, etc.), 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), an alkoxycarbonyl group (for example, methoxy) Carbonyl, tetradecyloxycarbonyl, benzyloxycarbonyl), an alkoxysulfonyl group (for example, methoxysulfonyl, butoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl), an aryloxysulfonyl group (for example, phenoxysulfonyl, p-methylphenoxysulfonyl, 2,4
-Di-tert-amylphenoxysulfonyl and the like), alkanesulfonyl group (for example, methanesulfonyl, ethanesulfonyl, octanesulfonyl, 2-ethylhexylsulfonyl, hexadecanesulfonyl), arylsulfonyl group (for example, 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), alkyloxy Carbonylamino group (eg, methoxycarbonylamino, ethyloxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino), alkylureido group (eg, , N- methylureido, N, N-
Dimethylureido, N-methyl-N-dodecylureido, N-hexadecylureido, N, N-dioctadecylureido), acyl group (for example, acetyl, benzoyl, octadecanoyl, p-dodencanamidebenzoyl), nitro group , A carboxyl group, a sulfo group, a hydroxy group, a trichloromethyl group, and the like.

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

R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² and R
³³ is 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 A 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).
Things. For example, acetylamino, propylamide, benzamide), anilino group (eg phenylamino, 2
-Chloroanilino), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, for example, methoxycarbonyl, butoxycarbonyl, 2-ethylhexyloxycarbonyl), an alkylcarbonyl group (preferably having 2 to 20 carbon atoms, for example, acetyl. , Butylcarbonyl,
Cyclohexylcarbonyl), an arylcarbonyl group (for example, preferably having 7 to 20 carbon atoms, benzoyl, 4-t-butylbenzoyl), an alkylthio group (preferably having 1 to 20 carbon atoms, such as 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. 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-diethylsulfur) Famoyl, 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-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 (see, for example, JP-A-59-99437). Those described, specifically, benzenesulfonamide, N-ethyltoluenesulfonamide, heptafluorobutanamide, 2,3,4,5,6-ventafluorobenzamide, octanesulfonamide, p-cyanophenylureido, 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-tetrazole-
1-yl, benzimidazolyl), a coupling-off group linked by a sulfur atom (for example, phenylthio, 2-carboxyphenylthio, 2-methoxy, 5-octylphenylthio, 4-methanesulfonylphenylthio, 4-octanesulfonamidophenyl) Thio, 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.

The yellow color-forming coupler residue is an acylacetanilide type, particularly a pivaloylacetanilide type [XIII] represented by the following general formula, [XIII '] benzoylacetanilide type [XIV], [XIV'], [XV], [XV ′] is preferable (in the general formula, the free bond is L ¹
_{Connect to m} L ² _n . ) In the formula, R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are each a hydrogen atom or a well-known substituent of a yellow color forming coupler residue such as an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom or an alkoxycarbamoyl group. , Aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamide group, arylsulfamoyl group, aryl Sulfonamide 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
It is represented by [I] 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, an aralkyl group or an acyl group, and W ₂ represents an oxygen or 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-ethoxyethyl 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 are n-butyl acrylate and styrene, and 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, acrylic acid amides,
It is an ethylenically unsaturated monomer that can be bonded to methacrylic acid amides, maleic acid esters, styrenes and a binder directly or via a hardener.

In the above general formula [P], E preferably represents a monovalent group having 8 or more carbon atoms, and examples thereof include those represented by the following general formula [XXIII].

Examples of the general formula [XXIII] E ¹ Y _p E ¹ include an alkyl group having 8 or more carbon atoms, a substituted alkyl group, a substituted aryl group, a substituted naphthyl group and the like.

Examples of the substituent which may be further substituted on these groups include a halogen atom, a cyano group, an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, and -NHCOR ^46.
(R ⁴⁶ represents an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group or an aralkyl group), —NHSO ₂ R
⁴⁶ (R ⁴⁶ is as defined above), - COOR ⁴⁶ (R ⁴⁶ is as defined above), - OCOR ⁴⁶ (R ⁴⁶ is as defined above), -SOR ⁴⁶ (R ⁴⁶ is as defined above), (R ⁴⁷ , R ⁴⁸ ) may be the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, an aralkyl group or a substituted aralkyl group), (R ⁴⁷ and R ⁴⁸ are as defined above), an amino group (which may be substituted with an alkyl group), a hydroxyl group or a group which is hydrolyzed to form a hydroxyl group.

Further, examples of the substituent of the above alkyl group, substituted alkoxy group, substituted phenyl group, and substituted aralkyl group include a hydroxyl group, an alkoxy group having 1 to about 4 carbon atoms, -NHSO ₂ R ⁴⁶ (R ⁴⁶ has the same meaning as above). , -NHCOR ⁴⁶ (R ⁴⁶ is as defined above), -COOR ⁴⁶ (R ⁴⁶ is as defined above), -OCOR ⁴⁶ (R ⁴⁶ is as defined above), (R ⁴⁷ and R ⁴⁸ are as defined above), (R ⁴⁷ and R ⁴⁸ are as defined above), —SO ₂ R ⁴⁶ (R ⁴⁶ is as defined above), —COR ⁴⁶ (R ⁴⁶ is as defined above), halogen atom, cyano group, amino group (alkyl group (May be substituted) and the like.

Preferred examples of E ¹ are shown below, but the invention is not limited thereto.

_{C 8 H 17 -, C 10} H 21 -, C 12 H 25 -, C 14 H 29 -, C 15 H 31 -, C 16 H 33 -, C 18 H 37 -, C 20 H 41 -, C 31 H ₆₃ −, C ₁₆ H ₃₃ SO ₂ NHCH ₂ CH ₂ −, C ₈ H ₁₇ CONHCH ₂ CH ₂ −, C ₁₃ H ₂₇ CONHCH ₂ CH ₂ −, C ₁₅ H ₃₁ CONHCH ₂ CH ₂ −, C ₁₇ H ₃₅ CONHCH ₂ CH ₂ −, C ₁₂ H ₂₅ NHCH ₂ CH ₂ −, C ₁₆ H ₃₃ NHCH ₂ CH ₂ −, C ₁₂ H ₂₅ NHCOCH ₂ −, C ₁₈ H ₃₇ NHCOCH ₂ −, In Y of the general formula [XXIII], -S -, - SO -, - SO 2
Represents-, and p is 0 or 1.

In the general formula [P], X preferably represents a hydrogen atom or a halogen atom (F, Cl, Br, I).

Representative examples of monomer couplers which give coupler units having a coupler residue capable of forming a dye by coupling with an aromatic primary amine developing agent represented by the general formula [I] which is a color-forming portion are shown below. , But is not limited to this.

The monomer couplers may be used individually or in a combination of several types.

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

C ₈ H ₁₇ SH, C ₁₀ H ₂₁ SH, C ₁₂ H ₂₅ SH, C ₁₄ H ₂₉ SH, C ₁₅ H ₃₁ SH, C ₁₆ H ₃₃ SH, C ₁₈ H ₃₇ SH, C ₂₀ H ₄₁ SH, C ₃₁ H ₆₃ SH, C ₁₆ H ₃₃ SO ₂ NHCH ₂ CH ₂ SH, C ₈ H ₁₇ CONHCH ₂ CH ₂ SH, C ₁₃ H ₂₇ CONHCH ₂ CH ₂ SH, C ₁₅ H ₃₁ CONHCH ₂ CH ₂ SH, C ₁₇ H ₃₅ CONHCH ₂ CH ₂ SH, C ₁₂ H ₂₅ NHCH ₂ CH ₂ SH, C ₁₆ H ₃₃ NHCH ₂ CH ₂ SH, C ₁₂ H ₂₅ NHCOCH ₂ SH, C ₁₈ H ₃₇ NHCOCH ₂ SH, BrCH ₂ COOC ₁₂ H ₂₅ , ClCH ₂ COOC ₁₂ H ₂₅ , ICH ₂ COOC ₁₂ H ₂₅ , BrCH ₂ COOC ₁₆ H ₃₃ , ClCH ₂ COOC ₁₈ H ₃₇ , ICH ₂ COOC ₁₈ H ₃₇ , Br ₂ CHCOOC ₁₂ H ₂₅ , Cl ₂ CCOO ₁₆ H ₃₃ , The polymer represented by the general formula [P] synthesized by using a chain transfer agent as in the present invention is called a telomer.

Regarding this telomer, "Oligomer" edited by Shin Okawara et al.
(Kodansha Scientific, 1976) p.10-30 explains in detail.

A brief description of the polymerization reaction in a system in which a chain transfer agent is present is as follows.

Start I → I ・ I ・ ＋ EX → IX + E ・ E ・ + M → EM ・ Stop _{2E · → E-E EM n} · + EM m · → EM n + m E wherein I, M, EX each initiator, monomer, chain transfer agent, a, EM ^· · and En ^· · are growing radical, I ^・ 、
E (Mn) X, E ^· it is. The primary radical, the biopolymer, the chain transfer agent radical, and k represent the rate constants of the respective system reactions.

That is, the polymerization is initiated and continued via the radicals transferred to the chain transfer agent, and the polymer is generated by the chain transfer to the transfer agent.

Here, as a measure showing the chain transfer ability of the chain transfer agent,
There is a chain transfer constant (Cs), which is defined by Cs = ktr / kp.

The synthesis method of the telomer coupler used in the present invention is different from the usual radical polymerization, and the polymerization is initiated and continued via the radical transferred to the chain transfer agent, and further the polymer is produced by the chain transfer to the transfer agent. To do.

The chain transfer agent used is represented by EX (E and X have the same meanings as described above), and the above-mentioned "oligomer" is used.
Carboxylic acids and esters thereof, alcohols, thiols, ethers, artehides, ketones, halogenated hydrocarbons, fatty acid chlorides, halogenated carboxylic acids and the like. Of these, thiol is particularly preferable.

These chain transfer agents are described, for example, by J. Brandrup et al. In Polymer Handbook, (John Wiley & Sons) II-57.
~ 102, and Takayuki Otsu "Radical Polymerization (I)" (Kagaku Dojin, 1971) As described on page 128, the activity of chain transfer reaction varies widely from large to small. The amount of addition depends on the type of chain transfer agent and the polymerization conditions (polymerization concentration, polymerization temperature, amount of initiator, etc.).

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.

Further, a polymerization initiator having 16 or more carbon atoms is preferably used when synthesizing the telomer coupler of the present invention.
By using this initiator, the following general formula [XXV]
The diffusion resistance of the polymer coupler can be increased.

Examples of preferable polymerization initiators are shown below.

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 color-forming moiety in the telomer coupler represented by the general formula [P] 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.

Further, the number average molecular weight of the telomer coupler of the present invention is preferably about 500 to about 10,000, particularly preferably about 500 to about 5,000, from the viewpoint of color developability and sensitivity.

In the polymer coupler obtained through the polymerization reaction using the chain transfer agent used in the present invention, in addition to the compound represented by the general formula [P], compounds represented by the following general formulas [XXIV] and [XXV] are included. About 0.1 to about 20 wt% is mixed.

Formula [XXIV] _{EA x B y E (E,} A, B, x, y have the same meanings as above) the formula [XXV] _{IA x B y X (A,} B, x, y, X is the Has the same meaning as I. represents a group derived from a radical generated by decomposition of a polymerization initiator.) Also, Takayuki Otsu, "Radical Polymerization (I)," p.123-127.
As described in (Chemical Doujin, 1971), in addition to the above general formulas [XXIV] and [XXV], a compound derived from chain transfer to a monomer or chain transfer to a polymerization solvent is a monomer solvent. Corresponding to chain transfer ability, each exists.

From what has been described above, among the polymer couplers obtained in the present invention, the polymer coupler having a monovalent group having 8 or more carbon atoms at the terminal excluding the repeating unit is represented by the general formula [P] or the general formula [P]. XXIV].

Further, by using an initiator having 16 or more carbon atoms at the time of synthesizing the polymer coupler, it is possible to introduce a group having 8 or more carbon atoms into the terminal of the compound represented by the general formula [XXV].

The higher the introduction rate of the group having 8 or more carbon atoms introduced into the terminal, the more excellent the coloring property and the non-migration property are.
% Or more.

In a polymerization reaction using a chain transfer agent, whether or not the chain transfer agent fragment can be efficiently introduced at the terminal generally depends on the chain transfer ability of the chain transfer agent to the ethylenically unsaturated monomer, that is, the chain transfer constant (C _s ). is doing.

The change in the polymerization reaction behavior with respect to the change in the value of the chain transfer constant (C _s ) is generally described as follows.

When C _s > 1, the chain transfer agent is consumed faster in the initial stage of polymerization than in the monomer, so that the chain transfer agent decreases in the latter stage of the polymerization and the polymer does not have a chain transfer agent at the end. Generated a lot. On the other hand, when C _s <1, on the contrary, the monomer is relatively rapidly consumed in the initial stage of the polymerization, and as in the case of C _s > 1, many polymers do not have a chain transfer agent at the end. Will be generated.

Therefore, it is preferred that C _s = 1 but in general
It is difficult to find C _s = 1 in the combination of coupler monomer and chain transfer agent.

However, in the case of C _s > 1, the chain transfer agent is added dropwise to carry out the polymerization, and in the case of C _s <1, the monomer is added dropwise to allow chain transfer to the polymer end. The present inventors have found that the efficiency of introduction of the agent can be increased.

Therefore, in order to synthesize a polymer containing 85% or more of a monovalent group having 8 or more carbon atoms at the end of the present invention, use of the above-mentioned initiator having 16 or more carbon atoms or a chain transfer agent and / or It is clear that dropping the ethylenically unsaturated compound to carry out the polymerization is an extremely effective means.

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.
It is good to add 5 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.
The range is up to 0.5 g / m ² .

In the present invention, the number average molecular weight can be calculated based on the measurement result by the gel permeation chromatography method (GPC method).

The measurement conditions of the GPC method are as follows.

Column: TSKgel (made by Toyo Soda) Solvent: THF Flow rate: 1 ml / min Column temperature: 40 ° C Detector: UV-8modelII (Toyo Soda) TSK standard polystyrene (Toyo Soda) is used to prepare a calibration curve.

The number average molecular weight is calculated by the Society of Polymer Science, "Polymer Science Experimental Method"
(Tokyo Kagaku Dojin, 1981) Calculated using the general method described in p.204-208, that is, the line segment method. The obtained chromatogram was divided into counts (D) at equal intervals, and the peak height from the baseline of the i-th polymer species was set to Hi, and it was determined using the following relational expression (1).

Yotsute Here, Ni represents the number of the i-th polymeric species, and Mi represents the molecular weight of the i-th polymeric species (Mi can be obtained from the above calibration curve).

The amount of the polymer having a C ₈ or more group at the end contained in the polymer can be quantified by using liquid chromatography. For example, the conditions for liquid chromatography performed on the monomer (14) telomer coupler are as follows.

Column; TSK ODS 80TM (manufactured by Toyo Soda Co., Ltd.) Eluent: CH ₃ OH / H ₂ O / NEt ₃ / H ₃ PO ₄ = 92.5 / 7.5 / 0.2 / 0.2 Flow rate; 1 ml / min Synthesis under these conditions When the measurement of the polymer coupler was carried out, first, within a few minutes, a polymer coupler having no C ₈ or more group at the terminal was detected, and thereafter, a coupler having a C ₈ or more group at the terminal (telomer coupler ) Is detected.

The proportion of C ₈ or higher groups at the end is first determined by using a low molecular weight polymer coupler (C _{8 at the} end) synthesized without using a chain transfer agent.
It can be determined by preparing a calibration curve, and quantifying the component having no C ₈ or more group present in each telomer coupler at the end.

As is well known in the field of polymer color couplers, the physical and / or chemical properties of the copolymer represented by the general formula [P], such as solubility, compatibility with the binder of photographic colloidal composition, such as gelatin. , Its flexibility, thermal stability, etc. can be favorably influenced.

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.

Representative synthetic examples of the telomer coupler of the present invention are shown below.

Synthesis Example 1 Telomer Coupler I (Polymer of Monomer Coupler (14)) 20 g of Monomer Coupler (14) and 100 ml of ethanol were placed in a 200 ml three-necked flask and heated and stirred at 75 ° C. under a nitrogen stream.
At the same time as adding 5 ml of an ethanol solution containing 0.20 g of dimethyl azobisisobutyrate, 35 ml of an ethanol solution containing 2.45 g of dodecyl mercaptan (chain transfer constant 2.9 with respect to the monomer coupler (14)) was started to be added over 5 minutes. I went. After reacting for 5 hours after the completion of dropping, the mixture was cooled to room temperature, and 10 g of acrylic acid was added after the reaction.
Was added and the mixture was heated and stirred at 75 ° C under a nitrogen stream.

5m ethanol solution containing 0.1g dimethyl azobisisobutyrate
l was added, and the mixture was heated and stirred for 3 hours.

After the reaction, the cooled reaction solution was poured into 2 liters of water, the precipitated solid was separated by filtration, and washed sufficiently with water. This solid was heated and dried under reduced pressure to give telomer coupler (I) to 21.5.
g got.

This telomer coupler was found by fluorine analysis to contain 90.3% by weight of the coupler unit of the monomer coupler (1) in the polymer.

The number average molecular weight by GPC was 1,900.

From quantification by liquid chromatography, it was found that in the telomer coupler (I), 86.5% of the polymer had a terminal group of 8 or more carbon atoms.

Synthesis Example 2 Telomer Coupler II (Polymer of Monomer Coupler (14)) Except that the polymerization initiator in Synthesis Example 1 was azobisisoacetate dinonyl and the amount of the initiator added was 2.3 times, the same conditions as in Synthesis Example 1 were used. The telomer coupler (II) was obtained. The physical property values are shown in Table 1.

Synthesis Example 3 Telomer Coupler III (Polymer of Monomer Coupler (14)) Synthetic Example 2 except that the initial ethanol amount in Synthesis Example 2 was 50 ml and the ethanol solution containing 2.45 g of dodecyl mercaptan was 20 ml. Telomer coupler (III) was obtained under the same conditions. The physical property values are shown in Table 1.

Synthesis Example 4 Telomer Coupler IV (Polymer of Monomer Coupler (14)) Under the same conditions as in Synthesis Example 1 except that the polymerization temperature was 60 ° C. and the dropping time of the ethanol solution containing mercaptan was 15 minutes, the telomer coupler (IV ) Got. The physical property values are shown in Table 1.

Comparative Synthesis Example 1 (Copolymer of Monomer Coupler (14) and Butyl Acrylate) A mixture of 20 g of monomer coupler (14), 2 g of butyl acrylate and 800 ml of ethanol was heated to 75 ° C. under stirring in a nitrogen stream. Polymerization was initiated by adding 10 ml of an ethanol solution containing 0.5 g of dimethyl azobisisobutyrate. After reacting for 5 hours, the reaction solution was cooled, poured into 4.0 l of water, the precipitated solid was separated by filtration, and further washed sufficiently with water.

By heating and drying this solid under reduced pressure, 22.0 g of a comparative polymer coupler (A) was obtained.

This polymer coupler contained 88.5% by weight of the coupler unit of the monomer coupler (14) in the polymer formed by fluorine analysis.
It was confirmed that it contained. The number average molecular weight by GPC was 4,000.

Comparative Synthesis Example 2 (Polymer of Monomer Coupler (14)) 20 g of Monomer Coupler (14), 135 ml of ethanol, 2.45 g of dodecyl mercaptan, and a 200 ml three-neck flask were heated and stirred at 75 ° C. under a nitrogen stream. Dimethyl azobisisobutyrate 0.
After adding 5 ml of an ethanol solution containing 20 g and heating with stirring for 5 hours, the mixture was cooled to room temperature, 10 g of acrylic acid was further added after the reaction, and the mixture was heated with stirring at 75 ° C. under a nitrogen stream.

5m ethanol solution containing 0.1g dimethyl azobisisobutyrate
l was added, and the mixture was heated and stirred for 3 hours.

After the reaction, the cooled reaction solution was poured into 2 liters of water, the precipitated solid was separated by filtration, and washed sufficiently with water. This solid was heated and dried under reduced pressure to give a comparative telomer coupler (B).
20.9g was obtained.

This telomer coupler was confirmed by fluorine analysis to contain 89.7% by weight of the coupler unit of the monomer coupler (14) in the polymer.

The number average molecular weight by GPC was 2000.

From the quantification by liquid chromatography, it was found that in the comparative telomer (B), there was 79.3% of the polymer having a terminal group of 8 or more carbon atoms.

Comparative Synthesis Example 3 A comparative telomer (C) was synthesized by the same method as in Comparative Synthesis Example 2 except that the amount of ethanol was changed from 135 ml to 70 ml.

The coupler unit of the monomer coupler (14) in the polymer is 90.2
% By weight, the number average molecular weight was 2400, and the polymer having a group having 8 or more carbon atoms was 82.3%.

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, Inc. (GFDuffin, Photographic
Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., VLZelikman et al. Making and Coating Photogra
Phic Emulsion, Focal Press, 1964) and the like.

Monodispersed emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and US Pat. No. 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, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide.

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

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure No.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, 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 in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis 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
-Ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 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), aliphatic carboxylic acid esters (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 thermal phenomenon light-sensitive materials described in, for example, -238056 and European Patent 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 An emulsion layer and a protective layer were coated on a cellulose triacetate film base in the following order.

100 g of the coupler I obtained in the above synthesis example was dissolved in 10 cc of tricresyl phosphate and 250 cc of ethyl acetate by heating at 60 ° C., and this solution was dissolved in 1000 ml of an aqueous solution containing 100 g of gelatin and 10 g of sodium dodecylbenzenesulfonate at 50 ° C.
And mixed at high speed with a homogenizer to obtain a fine coupler dispersion.

To 1000 g of this coupler dispersion, 1000 g of silver iodobromide emulsion containing 80 g of silver and having an iodine content of 3 mol% was added to give a coupler coating amount of 1.2 × 10 ⁻⁴ mol / m ² on the above base. As applied.

On this layer, a gelatin protective layer having a dry film thickness of 2 μm was applied to give Sample 101.

The couplers II, III, and I obtained in the above-mentioned Synthesis Example by the same method.
Samples 102 to 104 were prepared by using V so that the coating amount of the coupler (mol / m ² ) and the mixing ratio of the coupler and silver were the same as those of the sample 101. For comparison, Samples 105 to 107 were prepared in the same manner as above using the couplers (A), (B) and (C) obtained in the above-mentioned Synthesis Example.

After exposing these samples through an optical wedge, color development processing was performed in the following processing steps.

Processing process Process time Temperature First development 6 minutes 38 ℃ Water wash 2 minutes 〃 Reversal 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Fixed arrival 4 minutes 〃 Water washing 4 minutes 〃 Stability 1 The composition of the normal temperature dry solution is as follows.

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 (monohydrate) 30 g 1-phenyl-4methyl-4- Hydroxymethyl-3 pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water added 1000 ml Inversion solution water 700 ml 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 N-Ethyl-N- (β-methanesulphonamidoethyl) -3-methyl-4-aminoaniline ・ sulfate 11g 3,6-dithiaoctane-1,8-diol 1g Water was added to 1000ml Adjustment liquid water 700ml Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Water is added 1000ml Bleach solution 800g Sodium ethylenediaminetetraacetate (dihydrate) 2g Ethylenediaminetetraacetic acid iron (III) ammonium (dihydrate) Salt) 120 g Potassium bromide 100 g Water added 1000 ml Fixer water 800 g 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 (Fuji Film Co., Ltd. surfactant)
5.0 ml water was added to 1000 ml The density and relative sensitivity of the cyan image of these treated samples were measured.

The results obtained are summarized in Table 2.

As is clear from Table 2, the telomer couplers of the present invention show not only high color development and high sensitivity as compared with conventional polymer couplers which do not use a chain transfer agent, but also high sensitivity.
It is clear that the coloring property is improved due to the high content of the polymer having a C ₈ or more group at the terminal.

Claims (3)

[Claims] 1. A lipophilic polymer coupler, the lipophilic polymer coupler being obtained by a polymerization reaction using a coupler monomer, a polymerization initiator and a chain transfer agent having 8 or more carbon atoms, and a polymer. 85% by weight or more of the above contains a monovalent group having 8 or more carbon atoms at the terminal excluding the repeating unit. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the polymerization initiator has 16 or more carbon atoms. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the polymerization reaction is carried out by dropping a chain transfer agent and / or a coupler monomer.