JPH0833626B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

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 about.

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

By the way, in a multilayer color light-sensitive material, it is necessary to fix each coupler in a separate layer in order to reduce color mixture and improve color reproduction. 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 aqueous gelatin solution, it is necessary to solubilize it in an alkali and add it to the gelatin solution, or to dissolve it in an organic solvent having a high boiling point to emulsify and disperse it in the aqueous gelatin solution.

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, and as a result, it is desired to thin the emulsion layer. Has the opposite effect on.

Another method of introducing a coupler into each separated layer is to utilize a polymer coupler latex obtained by polymerizing a monomer coupler.

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

First, since the hydrophobic material is made into a latex, the strength of the formed film is not deteriorated, and since the latex can contain a high concentration coupler unit, a high concentration coupler can be easily added to the emulsion. Since it can be contained and 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.

The addition of the polymer coupler to the gelatin silver halide emulsion in the form of a latex as described above includes, for example, U.S. Pat. No. 4,080,221, British Patent No. 1,248,668 and U.S. Pat. Polymer coupler latex is West German Patent 2,725,591 and U.S. Pat.No. 3,926,436 copolymer latex with competing couplers is U.S. Pat.No. 3,767,412 and Research Disclosure 21728 (1982).
Year) describes a cyan polymer coupler latex.

However, the polymer coupler has the following outstanding problems as well as 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 a sufficient non-migrating property, but the reactivity of the coupling is poor, so that the sensitivity, gradation and dye concentration of the resulting dye are low.

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 is possible to remarkably improve the degree (sharpness), it is an important subject 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 compatible.

To these problems, we have found that a lipophilic polymer coupler obtained by a polymerization reaction using a chain transfer agent, particularly preferably a chain transfer agent containing an SH group, is extremely effective. This polymer coupler has excellent coupling reactivity and has a high coupler unit content,
It is not only ridiculous that it can maintain high color development, it is also sufficient in terms of non-migration property, and it is characterized in that it is less likely to cause color mixing and sensitivity deterioration due to migration.

However, in this lipophilic polymer coupler, the chain transfer agent containing the --SH group used in the synthesis remains in a slight amount, and therefore the fog in the unexposed area and the sensitivity decrease due to suppression in the silver developing process, etc. , Is a new problem, and the removal of the remaining chain transfer agent is an important issue.

(Problems to be Solved by the Invention) Therefore, a first object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity and low fog.

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.

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

A fifth object of the present invention is to provide a method of forming a color image by developing a silver halide emulsion in the presence of a novel coupler dispersion.

A sixth object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel latex of a coupler, 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 is obtained by a polymerization reaction using a chain transfer agent containing a —SH group. And a chain transfer agent remaining after the completion of the polymerization reaction is converted into a compound containing no —SH group.

The lipophilic coupler synthesized by a polymerization reaction using a chain transfer agent containing a --SH group used in the present invention is a mixture of polymers produced by various methods, most of which are represented by the following general formula [P ] Can be represented.

Formula (P) EA _x B _y H E represents a monovalent group obtained by removing a hydrogen atom from a chain transfer agent containing an -SH group. 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 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.

The compound represented by the general formula [P] of the present invention will be described in more detail.

A is a repeating unit having a coupler residue capable of forming a dye by coupling with an oxidized product of an aromatic primary amine developing agent as described above, and is a monovalent unit represented by the following general formula [I]. Induced by the body.

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-, -N
HCO-, -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 X ¹ J ¹
Represented by _{^{-X 2 p J 2 -X 3 q}} J 3 r 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 4 carbon atoms), (R ⁵ and R ⁶ are as defined above, R ⁷ is a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms), a substituted alkyl group (having 1 to 6 carbon atoms)), —O—, —S—, (R 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, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene group such as benzylden, and phenylene group such as p-phenylene, m-phenylene and methylphenylene. and so on.

The substituent of the alkylene group, aralkylene group or phenylene group represented by X ¹ , X ² and X ³ is a halogen atom, a nitro group, a cyano group, an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, group represented by NHCOR ⁸ (R ⁸ represents alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, substituted ^{_{aralkyl), - NHSO 2 R 8 (}} R 8 is as defined above), - SOR ⁸ (R ⁸ is the Synonymous with), —SO ₂ R ⁸ (R ⁸ has the same meaning as 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, 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 substituents of the above 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 —CHCOR ⁸ (R ⁸ is as defined above), (R ⁹ and R ¹⁰ are as defined above), A group represented by (R ⁹ and R ¹⁰ are as defined above), —SO ₂ R ⁸
(R ⁸ has the same meaning as above), —COR ⁸ (R ⁸ has the same meaning as above), a halogen atom, a cyano group, an amino group (which may be substituted with alkyl) and the like.

Next, among the color coupler residues represented by Q in the general formula [I], the cyan color forming coupler residue is
Phenol type [II] represented by the following general formula,
[V] or a compound of naphthol type [III] or [IV] (each hydrogen atom other than the hydrogen atom of the hydroxyl group is desorbed and linked to L ¹ _m L ² _n ) is preferable.

In the formula, R ¹¹ represents a group capable of substituting for a phenol ring or a naphthol ring, and examples thereof include a halogen atom, a hydroxy group, an amino group, a carboxy group, a sulfo group, a cyano group, an aliphatic group, an aromatic group and a heterocyclic group carvone. Amide 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,
Examples thereof include an aromatic thio group, an aromatic 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, -NHS
O ₂ R ^16, represents -NHCONR ¹⁴ R ¹⁵ or _{^{-NHSO 2 R 14 R 15, R}} 14 and R ¹⁵ are a hydrogen atom, an aliphatic group having from 1 to 30 carbon atoms (e.g., methyl, ethyl, butyl, methoxyethyl ,
n-decyl, n-dodecyl, n-hexadecyl, trifluoromethyl, heptafluoropropyl, dodecyloxypropyl, 2,4-di-tert-amylphenoxypropyl, 2,4-di-tert-aminophenoxybutyl), carbon Aromatic groups of the number 6 to 30 (eg, 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 (for example, methyl, ethyl,
Butyl, dodecyl, hexadecyl), 6-30 aromatic groups (eg phenyl, tolyl, 4-chlorophenyl, naphthyl), heterocyclic groups (eg 4-pyridyl, quinolyl,
2-furyl). R ¹⁴ and R ¹⁵ may be bonded to each other to form a heterocycle (eg, morpholine ring, piperidine ring, pyrrolidine ring). p'is 0 to 3, s'is 0
˜2, q ′ and r ′ each represent an integer of 0 to 4.

X ⁴ represents an oxygen atom, a sulfur atom or R ¹⁷ N, and R ¹⁷ represents a hydrogen atom or a monovalent group. R ¹⁷ is 1
When representing a valent 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 (eg, phenyl, Tolyl), a heterocyclic group having 2 to 30 carbon atoms (for example,
2-pyridyl, 2-pyrimidyl), a carbonamido group having 1 to 30 carbon atoms (for example, formamide, acetamide,
N-methylacetamide, benzamide), carbon number 1 to
30 sulfonamide groups (for example, methanesulfonamide, toluenesulfonamide, 4-chlorobenzenesulfonamide), imide groups having 4 to 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, -SO 2 NR 18 R 19 and -NR ¹⁸ R ¹⁹
Can be mentioned. R ¹⁸ and R ¹⁹ may be the same or different and each represents a hydrogen atom or a carbon number of 1 to
30 aliphatic groups (eg methyl, ethyl, butyl, dodecyl, methoxyethyl, trifluoromethyl, heptafluoropropyl), aromatic groups 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 developer.
Examples of eliminable halogen atoms (eg fluorine, chlorine, bromine, iodine), aliphatic oxy groups having 1 to 30 carbon atoms (eg methoxy, ethoxy, 2-hydroxyethoxy, carboxymethyloxy, 3-carboxypropyloxy). , 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
~ 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, fluorine, chlorine, bromine, etc.), an aliphatic group (eg, methyl, ethyl, isopropyl), a carbonamido 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, hexadexylcarbamoyl, decyloxypropyl, dodecyloxypropyl, 2,4-di-tert-amylphenoxypropyl. , 2,4
-Di-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-dibutylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, 4-cyanophenylcarbamoyl, 3,4-dichlorophenylcarbamoyl,
4-, methanesulfonylphenylcarbamoyl), -SO
₂ NR ¹⁸ R ¹⁹ (eg, N, N-dimethylsulfamoyl, N, N
N-diethylsulfamoyl, N, N-dipropylsulfamoyl). Particularly preferred R ¹⁷ are groups represented by —COR ¹⁸ , —COOR ²⁰ and —SO ₂ R ²⁰ .

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

The coupler represented by the general formula has substituents R ¹¹ , R ¹² ,
It may be a dimer or a multimer of X ^{4 and} Z ¹ which are bonded to each other via a divalent or higher polyvalent linking group. In this case, the number of carbon atoms shown in each substituent is not limited to this.

The magenta color-forming coupler residue is represented by the general formula [V
I], [VII], [VIII], [IX], [X], [X1] and [XII] of the coupler residue (Ar, Z ² , R ^{21 to} R ^21
Connect to L ¹ _m L ² _n at any part of ³³ . In the case of the general formula [V], more preferable is the case of directly linking to the substitution position of R ²¹ . ) Is represented.

Wherein Ar is a substituent of the well-known type at the 1-position of the 2-pyrazolin-5-one coupler, such as an alkyl group, a substituted alkyl group (for example, a haloalkyl such as fluoroalkyl,
Cyanoalkyl, benzylalkyl, etc.), an aryl group or a substituted aryl group [as a substituent, an alkyl group (eg, methyl, ethyl), an alkoxy group (eg, methoxy, ethoxy), an aryloxy group (eg, phenyloxy), an alkoxycarbonyl group ( Eg methoxycarbonyl), an acylamino group (eg acetylamino),
Carbamoyl group, alkylcarbamoyl group (eg methylcarbamoyl, ethylcarbamoyl), dialkylcarbamoyl group (eg dimethylcarbamoyl), arylcarbamoyl group (eg phenylcarbamoyl), alkylsulfonyl group (eg methylsulfonyl), arylsulfonyl group (eg phenylsulfonyl) , An alkylsulfonamide group (eg methanesulfonamide), an arylsulfonamide group (eg phenylsulfonamide), sulfamoyl, an alkylsulfamoyl group (eg ethylsulfamoyl), a dialkylsulfamoyl group (eg dimethylsulfamoyl) , Alkylthio groups (eg methylthio, arylthio groups (eg phenylthio), cyano groups, nitro groups, halogen atoms (eg fluorine, chlorine) Bromine) and the like, may be the same or different when this substituent is two or more. Particularly preferred substituents include 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 is an unsubstituted or substituted anilino group, an acylamino group (eg, alkylcarbonamide, phenylcarbonamide, alkoxycarbonamide, phenyloxycarbonamide), a ureido group (eg, alkylureido,
Phenylureido), and as these substituents, a halogen atom (eg, fluorine, chlorine, bromine, etc.), a linear or branched alkyl group (eg, methyl, t-butyl, octyl, tetradicyl), 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-methyltetradecanamide), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, ethylsulfonamide, p-toluenesulfonamide, octanesulfonamide, p-dodecylbenzenesulfone) Amide, N-methyl-tetradecane sulfonamide), 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, 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 groups (preferably having 6 to 20 carbon atoms, for example, phenyl, 4-t-butylphenyl, 2,4-di-
t-amylphenyl, 4-methoxyphenyl), heterocyclic group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), alkylamino group (preferably having 1 to 20 carbon atoms, for example, methyl). amino,
Diethylamino, t-butylamino), acylamino group (preferably having 2 to 20 carbon atoms, for example, acetylamino, propylamide, benzamide), anilino group (eg phenylamino, 2-chloroanilino), alkoxycarbonyl group (preferably Having 2 to 20 carbon atoms,
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 a carbon number of 1 to 20. For example, methylthio, octylthio, 2-phenoxyethylthio), an arylthio group (preferably having a carbon number of 6 to 6).
20 things. For example, phenylthio, 2-butoxy-5-
t-octylphenylthio), a carbamoyl group (preferably having a carbon number of 1 to 20. For example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl, N-methyl-N
-Butylcarbamoyl), a sulfamoyl group (preferably having up to 20 carbon atoms, for example, N-ethylsulfamoyl, N, N-diethylsulfamoyl, N, N-dipropylsulfamoyl) or a sulfonamide group (preferably Has 1 to 20 carbon atoms, for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide).

Z ² 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.
As a group capable of leaving, a halogen atom (for example, chlorine,
Bromine), a coupling-off group linked by an oxygen atom (for example, acetoxy, propanoyloxy, benzoyloxy, ethoxyoxaloyloxy, pyrivinyloxy,
Cinnamoyloxy, phenoxy, 4-cyanophenoxyl, 4-methanesulfonamide-phenoxy, α-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy,
Benzyloxy, 2-phenethyloxy, 2-phenoxy, ethoxy, 5-phenyltetrazolyloxy, 2-
Benzothiazolyloxy), a coupling-off group linked by a nitrogen atom (for example, those described in JP-A-59-99437, specifically benzenesulfonamide, N-ethyltoluenesulfonamide, heptafluorobutane) Amide, 2,3,4,5,6-pentafluorobenzamide, 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, particularly preferably an arylthio group, a chlorine atom, a pyrazolyl group, an imidazolyl group, a triazolyl group. Is.

The yellow color-forming coupler residue is an acylacetanilide type, particularly a pivaloylacetanilide type [XIII], [XIII '], a benzoylacetanilide type [XIV], [XIV'], [XV] represented by the following general formula. , [X
V ′] is preferable (the free bond portion in the general formula is connected to L ¹ _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 It represents a sulfonamide group, an arylureido group, a carboxy group, a sulfo group, 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],
It is represented by [XVIII] or [XIX].

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

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

W ₁ is in the formula Together with a non-metallic atom required to form a 4-, 5- or 6-membered ring.

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

In the formula, R ⁴¹ and R ⁴² are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group, and R ⁴³ , R ⁴⁴ and R ⁴⁵ are each a hydrogen atom, an alkyl group, an aryl group and an aralkyl group. Or an acyl group, 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 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 (alkoxy group further contains a plurality of substituted alkoxy groups), β-sulfonamidoethylacrylamide, β-
Carbonamido ethyl acrylamide etc.), vinyl ester (eg vinyl acetate, vinyl laurate), acrylonitrile, methacrylonitrile, dienes (eg butanediene, isoprene), aromatic vinyl compounds (eg styrene, divinylbenzene and its derivatives, eg vinyl) Toluene, vinyl acetophenone and sulfone styrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic anhydride, maleic acid ester, N-vinyl-2-pyrrolidone, N-
Vinyl pyridine, and 2- and 4-vinyl pyridine, ethylene, propylene, 1-butene, isobutene, etc. are mentioned.

Two or more ethylenically unsaturated monomers used herein can be used together.

For example, ethyl acrylate and n-butyl acrylate, n-butyl acrylate and styrene, methyl methacrylate and diacetone acrylamide, and the like.

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-,
−COO−, −OCO−, , M represents 1, and n represents 0 or 1.
L ² is represented by X ¹ J ¹ -X ² _p J ² -X ³ _q J ³ _r , and among these, particularly preferable ones are J ¹ ,
J ² and J ³ may be the same or different, and -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; s represents 0 or 1.

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

In the general formula [P], B represents a monovalent group,
For example, those represented by the following general formula [XXII] can be mentioned.

Examples of the general formula [XXIII] E ¹ -Y-E ¹ include an alkyl group, a substituted alkyl group, a substituted aryl group and a substituted naphthyl group.

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 is 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 synonymous with the above), (R ⁴⁷ and 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.

In addition, examples of the substituents 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 is as defined 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 (an alkyl group). (May be substituted) and the like.

As E ¹ , those having 8 or more carbon atoms are particularly preferable.

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 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 16 H 33 NHCH 2 CH 2} -, C 12 H 25 NHCOCH 2 -, C 18 H 37 NHCOCH 2 -, In the general formula [XXIII], Y is -S-, -SO-, -S.
Represents O ₂ −.

Next, typical 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. However, it is not limited to this.

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

The chain transfer agent containing a —SH group used in the present invention is
A polymer coupler having 8 or more carbon atoms is particularly preferable in terms of color developability and non-migration property. Examples of preferable 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 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 ₁₆ H ₃₃ NHCH ₂ CH ₂ SH, C ₁₂ H ₂₅ NHCOCH ₂ SH, The above chain transfer agents may be used alone or in combination of two or more during polymerization.

Used in the present invention. In the polymer coupler obtained by the polymerization reaction using a chain transfer agent, in addition to the compound represented by the general formula [P], the following general formulas [XXIV] and [XXV]
The compound represented by 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 the 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.

As in the present invention, a polymer represented by the general formula [P] synthesized by using a chain transfer agent is a telomer.
Called. About this telomer, Shin Okawara et al. "Oligomer" (Kodansha Scientific, 1976) P.10
~ 30 are described in detail.

One of the features of the method for synthesizing the telomer coupler used in the present invention is that a chain transfer agent having 8 or more carbon atoms is used, unlike ordinary radical polymerization. In this case, 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.

The chain transfer agent used is represented by E ¹ -SH, where E ¹ has the same meaning as above.

The synthesis of the telomer coupler of the present invention is carried out by using a polymerization initiator and a polymerization solvent as disclosed in JP-A-56-5543, JP-A-57-94752 and JP-A-57-4752.
176038, JP-A-57-204038, JP-A-58-28745, JP-A-58-
10738, JP-A-58-42044, JP-A-58-145944, JP-A-59-
Performed using the compound described in 42543.

A polymerization initiator having 20 or more carbon atoms is preferably used when synthesizing the telomer coupler of the present invention. By using this initiator, the diffusion resistance of the polymer coupler represented by the general formula [XXV] 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.

These chain transfer agents are described in, for example, J. Brandrup et al., 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 is wide-ranging. It varies depending on the type of agent and polymerization conditions (polymerization concentration, polymerization temperature, amount of initiator, etc.), and also depends on the required molecular weight of the telomer.

The polymerization concentration must be set in relation to the molecular weight of the telomer produced, the type of initiator, etc.
Polymerization is possible in the range of 30 ° C to 100 ° C, although the temperature can be up to above ℃. Higher temperatures are preferred for telomer synthesis, preferably in the range of about 70-100 ° C.

The proportion of the color-forming moiety A 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.

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

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

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

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

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.

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

The number average particle molecular weight was calculated using the general method described in "Polymer Science Experimental Method" edited by The Polymer Society of Japan (Tokyo Kagaku Dojin, 1981), p. 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).

By Here, Ni represents the number of the i-th macromolecular species, and Mi represents i.
Represents the molecular weight of the second macromolecular species (Mi can be determined from the above calibration curve).

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 [I], such as solubility, compatibility with a binder of a photographic colloid composition, for example, gelatin. , Its flexibility, thermal stability, etc. can be favorably influenced.

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

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

The method for treating the residual chain transfer agent of the present invention will be described in detail below.

The first method of treating the residual chain transfer agent is to add the ethylenically unsaturated compound to the reaction solution containing some of the chain transfer agent after the completion of the polymerization of the telomer coupler, and to carry out the polymerization reaction (hereinafter referred to as “after This is referred to as "polymerization").

By this post-polymerization reaction, the remaining chain transfer agent (-SH
The compound containing a group) is incorporated into the polymer by a chain transfer reaction during the polymerization and converted into a residue in the telomer of the newly added ethylenically unsaturated compound.

As the ethylenically unsaturated compound used in this post-polymerization reaction, the ethylenically unsaturated monomer which gives the repeating units represented by A and B can be used.

The use of an ethylenic unsaturated compound giving the repeating unit represented by B in the post-polymerization reaction lowers the content of the coupler unit in the polymer, which is disadvantageous in terms of thinning the light-sensitive material layer. However, when an ethylenically unsaturated monomer, which makes the polymer water-soluble, is used, after the post-polymerization, it is put into water to carry out re-precipitation or extraction operation with water so that only the polymer produced by the post-polymerization is obtained. Can be efficiently removed, so that the content of the coupler unit is not substantially reduced. Therefore, in terms of thinning the photosensitive material layer,
This is an extremely advantageous method.

Use of the ethylenically unsaturated compound which gives the repeating unit represented by A to the post-polymerization reaction does not decrease (rather increase) the content of the coupler unit in the polymer.
That is preferable.

However, in the post-polymerization reaction, since the concentration of the chain transfer agent is low, the number of polymer compounds that do not become telomers represented by the general formula [XXV] increases, and in terms of color forming property per unit weight of the coupler, It is not always preferable.

Thus, the preferred ethylenically unsaturated compounds used in the post-polymerization of the present invention provide the ethylenically unsaturated monomer that provides the repeating unit represented by A, and the repeating unit represented by B where the polymer is water soluble. An ethylenically unsaturated monomer, particularly preferably,
An ethylenically unsaturated monomer that provides the repeating unit represented by B, where the polymer is water soluble.

Preferred examples of the ethylenically unsaturated monomer that gives the water-soluble polymer are listed below, but the invention is not limited thereto.

Acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-acryloylmorpholine, N-acryloylpiperidine, acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, sodium styrenesulfonate,
Itaconic acid, N-vinylpyrrolidone, N-vinylimidazole, The second method of treating the residual chain transfer agent is a method in which after the completion of the polymerization of the telomer coupler, the residual chain transfer agent (compound containing an --SH group) is oxidized to a disulfide, sulfoxide or sulfone compound. .

Specific examples include blowing air or oxygen gas, or using an oxidizing agent (for example, hydrogen peroxide, peroxy acid, peracetic acid, perbenzoic acid, monoperphthalic acid, halogen (for example, I ₂ )) and the like. .

The amount of the chain transfer agent remaining during the synthesis of the telomer coupler varies considerably depending on the polymerization conditions, but it is about 0.05 (500 ppm) to about 1.0 wt% (10000 ppm) with respect to the telomer coupler. When the processing method of the present invention is used, the amount of the remaining chain transfer agent can be reduced to about 100 ppm or more, so that it can be at a level that does not adversely affect the characteristics of the photographic light-sensitive material.

Synthesis Example 1. Synthesis of telomer coupler (I) (monomer coupler (4
Copolymerization telomer of 9) and butyl acrylate) 24 g of monomer coupler (49), 6.6 g of butyl acrylate, 3.7 g of octadecyl mercaptan and 170 ml of dioxane were placed in a 300 ml three-necked flask and heated and stirred at 80 ° C. under a nitrogen stream. Dioxane solution containing dimethyl azobisinbutyrate 0.3g 10ml
Was added to initiate polymerization. After reacting for 5 hours, it was cooled to room temperature, 10.3 g of acrylic acid was added, and again under a nitrogen stream, 7
The mixture was heated and stirred at 5 ° C. 5 ml of a dioxane solution containing 0.1 g of dimethyl azobisinbutyrate was added to initiate polymerization, and the reaction was carried out for 3 hours, followed by cooling to room temperature.

The obtained reaction liquid was poured into 2 liters of water, and the precipitated solid was further thoroughly washed with water. By heating and drying this solid under reduced pressure, 32.5 g of telomer coupler (1) was obtained.

This telomer coupler was confirmed by nitrogen analysis to contain 68.1% by weight of the coupler unit of the monomer coupler (49) in the polymer. The number average molecular weight by GPC was 1,700.

Synthesis Examples 2 to 11 In the same manner as in Synthesis Example 11, telomer couplers (II) to (X) shown in Table 1 were synthesized. Type of chain transfer agent used,
The amount, the kind of the monomer used for the post-treatment, etc. were changed appropriately.

Comparative Synthesis Example 1 (Copolymer of Monomer Coupler (49) and Butyl Acrylate) 20 g of Monomer Coupler (49), 20 g of butyl acrylate and 200 ml of dioxane were placed in a 500 ml three-necked flask and heated and stirred at 80 ° C. under a nitrogen stream. . Dimethyl azobisinbutyrate 0.
10 ml of a dioxane solution containing 3 g was added to initiate polymerization.
After reacting for 5 hours, the mixture was cooled to room temperature and the reaction solution was mixed with water.2.
The mixture was poured into 0 l, the precipitated solid was filtered off, and further washed thoroughly with water.

By heating and drying this solid under reduced pressure, 36.9 g of a comparative polymer coupler (A) was obtained.

It was found that this polymer coupler contained 48.5% by weight of the unit of the monomer coupler (49) in the polymer formed by nitrogen analysis. The number average molecular weight by GPC was 35,000.

Comparative Synthesis Example 2 (Copolymer of Monomer Coupler (49) and Butyl Acrylate) In the same manner as in Comparative Synthesis Example 1, the monomer coupler (49) was used.
A comparative polymer coupler (B) was synthesized using 28 g and 12 g of butyl acrylate. The content of the coupler unit of the monomer coupler (49) by nitrogen analysis was 69.2% by weight.
The number average molecular weight by C was 27,000.

Comparative Synthetic Examples 3 and 4 (Copolymer of Monomer Coupler (44) and Butyl Acrylate) Comparative Comparative Examples 1 and 2 were compared with Comparative Synthetic Examples 1 and 2 except that (44) was used as the monomer coupler. Polymer couplers (C) and (D) were obtained. The content of the coupler monomer and the number average molecular weight in the obtained polymer are shown in Table 2.

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

Silver halide grains in photographic emulsions are cubic, octahedral,
It may have a regular crystal such as a tetradecahedron, a spherical shape, an irregular crystal shape such as a strip, a crystal defect such as a twin plane, or a composite shape 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 (1973).
Year 12), pp. 22-23, "I. Emulsion prepara
and types) ”, and No. 18716 (November 1979)
Mon), 648 pages, "The Physics and Chemistry of Photography," by Graphide, published by Paul Montel (P.Glafkides, Chemic et Ph.
isique Photographique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuff
in, Photographic Emulsion Choemistry (Focal Press, 1
966)), "Production and coating of photographic emulsions" by Zelikmann et al.,
Published by Focal Press (VLZelikman et al. Making an
d Coating Photographic Emulsion, Focal Press, 1964)
And the like.

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

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); US Patent No.
4,434,226, 4,414,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, 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. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, the relevant parts are summarized in the table below.

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

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

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

As the magenta coupler, 5-prazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,
Nos. 619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552
Issue, Research Disclosure No. 24230 (June 1984
JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No.
Those described in 3,446,622, 4,333,999, 4,451,559, 4,427,767, European Patent 161,626A and the like are preferable.

Colored couplers to correct unwanted absorption of colored dyes are VII of Research Disclosure No. 17643.
-G section, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39414,
U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No.
Those described in No. 1,146,368 are preferable.

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

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

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are RD17643, VII-F described above.
Patents described in paragraphs, JP-A-57-151944 and 57-154234
And Nos. 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

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

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,424, U.S. Pat.Nos. 4,283,472, and 4,338,393.
Multi-equivalent couplers described in JP-A No. 4,310,618 and the like, JP-A-60-
185950, 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, bleach accelerator releasing couplers described in JP-A-61-2201247 and the like, and ligand releasing couplers described in US Pat. No. 4,553,477 and the like.

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

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

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

Specific examples of 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, disirohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid Esters of (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 (isosteryl alcohol, 2,4-di-tert-amylphenol etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate) , Glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert)
-Octylaniline, etc.), hydrocarbons (paraffin,
Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably an organic solvent of 50 ℃ or more and about 160 ℃ or less can be used, as a typical example, ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

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

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

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

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

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

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane)
Like 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, sodium boron hydride. Various fogging agents, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1
-Diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof It can be raised as an example.

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

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

The photographic emulsion tank 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. In order to further speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used, and further processing with two continuous bleach-fixing 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
-Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid, etc .; persulfate; bromate; permanganate; nitrobenzenes, etc. Can be. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleach-fixing agent can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,98.
No. 8, JP-A-53-32,736, JP-A-53-57,831, and JP-A-53-37,418
No. 53-72,623, No. 53-95,630, No. 53-95, 631,
No. 53-10,4232, No. 53-124,424, No. 53-141,623, No.
53-28,426, Research Disclosure No.17,129
Compounds having a mercapto group or a disulfide group as described in JP-A No. 1978 (July 1978); thiazolidine derivatives described in JP-A-50-140,129; JP-B-45-8,506 and JP-A-52-2.
0,832, 53-32,735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, JP-A-5
Iodide salts described in 8-16,235; West German Patent No. 966,410,
Polyoxyethylene compounds described in No. 2,748,430;
Polyamide compounds described in JP-B-45-8836; Other JP-A-49-42,434, 49-644, 53-94,927, 54-35,
Compounds described in Nos. 727 and 55-26,506 and 58-163,940; 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 particularly, US Pat. No. 3,893,858, West Patent
The compounds described in 1,290,812 and JP-A-53-95,630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

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

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the purpose, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above document, the amount of washing water can be greatly reduced. The increase in the residence time of water in the tank causes problems such as bacteria breeding and the produced floating substances adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in Japanese Patent Application No. 61-131632 can be very effectively used. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

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

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and as an example, it is used as a final bath of a color light-sensitive material for photographing. Examples include a stabilizing bath containing formalin and a surfactant. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in various steps such as a desilvering step.

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

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

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save 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.

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

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

Example 1 A telomer coupler was synthesized under exactly the same conditions as in Synthesis Examples 1 to 10, except that post-polymerization with acrylic acid, acrylamide, etc. was not performed after the polymerization of the monomer coupler was completed, and the respective numbers were assigned. To give comparative compounds I ′ to X ′.

The content of coupler units in the solids obtained for the compounds I to X of the synthesis examples and the comparative compounds I ′ to X ′ was determined by elemental analysis, and the amount of the chain transfer agent (mercaptan) contained in the solids was determined by gas chromatography. Was quantified and compared.

 The results are shown in Table 3.

As is clear from Table 3, it is clear that the telomer coupler of the present invention was one in which the remaining chain transfer agent (mercaptan) was efficiently removed.

In addition, after polymerizing a monomer containing a coupler unit, a monomer (acrylic acid, acrylamide, etc.) which gives a water-soluble polymer is added and post-polymerization is carried out. Since the content hardly changes,
It is clear that the addition amount of the telomer coupler for obtaining the same color developability is small and it is particularly excellent in terms of thinning the light-sensitive material layer. (Comparison of Compounds I to X and XI) Example 2 Sample 201, which is a multilayer color light-sensitive material having each layer having the composition shown below, was prepared on an undercoated cellulose triacetate film support.

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

1st layer (antihalation layer) Black colloid layer 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 2nd layer (intermediate layer) Gelatin 1.0 UV-1 0.03 ExC-4 0.02 ExF-1 0.004 Solv-1 0.1 Solv-2 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.5)
μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio
3.0) Coating silver amount 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of sphere equivalent diameter 15%, spherical particles, diameter / thickness ratio
1.0) Coating 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 ExC-8 0.03 4th Layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type with 1: 1 core-shell ratio, sphere equivalent diameter 0.7μ, variation coefficient of sphere equivalent diameter 15%, tabular grains, diameter / Thickness ratio 5.0) Silver coating amount 0.7 Gelatin 1.0 ExS-1 3 × 10 ^-4 ExS-2 2.3 × 10 ^-5 ExC-6 0.11 ExC-7 0.05 ExC-4 0.05 Solv-1 0.05 Solv-3 0.05 Fifth layer (Intermediate layer) Gelatin 0.5 Cpd-1 0.1 Solv-1 0.05 Sixth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio 1: 1 surface high AgI type, equivalent spherical diameter 0.5) μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Coating silver amount 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent 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-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type with core-shell ratio 1: 3, spherical equivalent diameter 0.7 μ, variation coefficient of spherical equivalent diameter) 20%, plate-like particles, diameter / thickness ratio 5.0) Coating silver amount 0.8 Gelatin 0.5 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 0.04 Solv-1 0.2 Solv-4 0.01 Eighth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.05 Solv-1 0.02 Ninth layer (donor of multi-layer effect for red-sensitive layer) Layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type with core-shell ratio 2: 1, equivalent sphere diameter 1.0 μ, variation coefficient of equivalent sphere diameter 15%, tabular grains, diameter / thickness ratio 6.0) coated silver 0.35 silver iodobromide emulsion (AgI 2 mol%, core-shell ratio 1: 1 Part height AgI type, sphere equivalent diameter 0.4μ, coefficient of variation of sphere equivalent diameter 20%, plate-shaped 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 Solv-1 0.13 Cpd-1 0.10 11th layer (low sensitivity blue emulsion layer) Iodobromide Silver emulsion (AgI 4.5 mol%, uniform AgI type, sphere equivalent diameter)
0.7μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 7.0) Coating silver amount 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio
7.0) Coating silver amount 0.15 Gelatin 1.6 ExS-6 2 × 10 ^-4 ExC-16 0.05 ExC-2 0.10 ExC-3 0.02 ExY-13 0.07 Coupler (I) 1.0 Solv-1 1.0 12th layer (high sensitivity) of the present invention Blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent spherical diameter)
1.0μ, 25% variation coefficient of equivalent spherical diameter, multiple twin plate-like particles,
Diameter / thickness ratio 2.0) Coating silver amount 0.5 Gelatin 0.5 ExS-6 1 × 10 ^-4 Coupler (I) of the present invention 0.20 ExY-13 0.01 Solv-1 0.20 13th layer (1st protective layer) Gelatin 0.8 UV-4 0.1 UV-5 0.15 Solv-1 0.01 Solv-2 0.01 14th layer (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 particle diameter 1.5 μ 0.2 H-1 0.4 Cpd-5 0.5 Cpd-6 0.5 Cpd-8 0.2 In addition to the above components, each layer contains an emulsion stabilizer Cpd-3.
(0.04 g / m ² ) surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate Next, the polymer coupler (I) added to the eleventh layer and the twelfth layer of the sample 201 was added to the telomer couplers (II) and (I
V), (V) and the comparative telomer couplers (I '), (II'), (IV '), (V') shown in Example 1 and the comparative polymer couplers shown in the comparative synthesis examples ( A),
(B), (C), and (D), respectively, so that the coating amount (mol / m ² ) of the replaceable coupler is the same,
Created 212.

The obtained samples 201 to 212 were exposed to 20 CMS with a sensitometer whose color temperature was adjusted to 4800 ° K, and the following development processing was performed. For both fog and maximum density, the yellow density of the sample processed from the bleaching step was measured, and the density (Dmin) was set to 0 for evaluation. The results are shown in Table 1.

The color photographic light-sensitive material as described above was exposed and then processed by the method described below.

 Processing method Process processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching 6 minutes 30 seconds 38 ℃ Washing with water 2 minutes 10 seconds 24 ℃ Settling 4 minutes 20 seconds 38 ℃ Washing with water (1) 1 minute 05 seconds 24 ℃ Wash with water (2) 2 minutes 10 seconds 24 ℃ stability 1 minute 05 seconds 38 ℃ dry 4 minutes 20 seconds 55 ℃ Next, write the composition of the treatment liquid.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N- Ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5 Water 4.5 Add water 1.0l pH 10.05 (bleaching solution) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0
Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonium water (27%) 6.5ml Add water 1.0l pH 6.0 (fixer) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Aqueous ammonium thiosulfate solution (70%) 170.0 ml Water was added to 1.0 l pH 6.7 (Stable solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0 l pH 5.0-8.0 From the above, the telomer coupler of the present invention has a structure similar to that of a conventional polymer coupler having almost the same coupler unit.
Not only the color density is extremely high, but also the residual chain transfer agent (mercaptan) is remarkably reduced, so the fog density is low, and it is clear that the compound is extremely excellent in photographic performance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 62-198854 (JP, A) JP 62-276548 (JP, A) JP 62-288832 (JP, A) JP 1- 133047 (JP, A) JP 1-13348 (JP, A) JP 1-134357 (JP, A) JP 1-134453 (JP, A) JP 1-145657 (JP, A) JP-A-2-6946 (JP, A)

Claims (5)

[Claims] 1. A chain transfer agent containing a lipophilic polymer coupler, wherein the lipophilic polymer coupler is obtained by a polymerization reaction using a chain transfer agent containing a —SH group, and remains after the completion of the polymerization reaction. A silver halide photographic light-sensitive material, which has been subjected to a treatment for converting the compound into a compound containing no —SH group. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the above-mentioned processing is to newly add an ethylenically unsaturated compound and carry out a polymerization reaction again. 3. A silver halide color photographic light-sensitive material according to claim 1, wherein the above-mentioned processing is performed by adding an oxidizing agent. 4. The silver halide color photographic light-sensitive material according to claim (2), wherein the newly added ethylenically unsaturated compound is a compound whose homopolymer is water-soluble. 5. The silver halide color photographic light-sensitive material according to claim 1, wherein the chain transfer agent containing the --SH group has 8 or more carbon atoms.