JP2524496B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention relates to a silver halide photographic light-sensitive material containing a novel photographic color coupler.

(Prior Art) After exposing a silver halide photographic light-sensitive material to color development, the oxidized aromatic primary amine developing agent reacts with a dye-forming coupler to form a color image. Generally, in this method, a color reproduction method based on a subtractive color method is used, and in order to reproduce blue, green, and red, color images of yellow, magenta, and cyan which are complementary colors to each other are formed.

As the yellow dye image-forming agent, for example, acylacetanilide or a benzoylmethane-based coupler is used, and as the magenta dye image-forming agent, for example, pyrarizolone, pyrazolotriazole, pyrazolobenzimidazole, cyanatoacetophenone or indazolone-based coupler is used. As the cyan dye forming agent, for example, a phenol or naphthol type coupler is used.

By the way, in a multilayer coupler photographic light-sensitive material, in order to reduce color mixture and improve color reproducibility, it is necessary to fix each coupler in a separate layer, and for diffusion resistance of the coupler, Many methods are known.

One method is to introduce a long-chain aliphatic group into the coupler molecule in order to prevent diffusion. Since the coupler by this method is immiscible with the aqueous gelatin solution, it can be dissolved in a high-boiling organic solvent and emulsified and dispersed in the aqueous gelatin solution as disclosed in U.S. Pat.No. 2,322,027 for application. is necessary.

However, in such a method, when the amount of the organic solvent having a high boiling point is reduced in order to reduce the thickness of the coupler-containing layer and improve the sharpness of the dye image, the crystals of the coupler are likely to precipitate in the emulsion layer. Therefore, it is inevitable to use an organic solvent having a high boiling point above a certain amount, and it is difficult to sufficiently reduce the thickness of the coupler-containing layer to improve the sharpness of the dye image. Furthermore, when an organic solvent having a high boiling point is used, a large amount of gelatin is required to soften the coupler-containing layer, resulting in a problem that the sharpness of a dye image is deteriorated.

Another method of making a coupler diffusion resistant is to polymerize the coupler. As the polymerized coupler, a lipophilic polymer coupler and a hydrophilic polymer coupler are known.

The lipophilic polymer coupler may be prepared by dissolving a lipophilic polymer coupler obtained by polymerization of a monomer coupler in an organic solvent and emulsifying and dispersing it in a gelatin aqueous solution in the form of a latex, or by a direct emulsion polymerization method. May be.

U.S. Pat. No. 3,45, for a method of emulsifying a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution.
No. 1,820, US Patent No. 4,080,211 for emulsion polymerization
No. 3,370,952.

However, when these lipophilic polymer couplers are emulsified and dispersed in the form of a latex in an aqueous gelatin solution, the coupler-containing layer is softened in the same manner as in the case of emulsified dispersion of the above long-chain aliphatic group introduced into the coupler molecule. As a result, since a large amount of gelatin is required, the thickness of the coupler-containing layer must be increased. Therefore, it is difficult to sufficiently improve the sharpness of the dye image by using the lipophilic polymer coupler.

On the other hand, in the hydrophilic polymer coupler, since the coupler-containing layer is less softened because it can be uniformly dispersed in the gelatin layer, it is possible to reduce the thickness of the coupler layer by using a small amount of gelatin.

For example, polymer couplers obtained by binding a reactive coupler to a pre-synthesized polymer (acrylic acid homopolymer, p-aminostyrene homopolymer, etc.) or natural polymer compound (gelatin, etc.) are disclosed in US Pat. Nos. 2,698,797 and 2,2, 85
No. 2,381, No. 2,852,383, No. 2,870,712, each specification, Japanese Patent Publication No. 35-16932, No. 44-3661, etc., and a coupler synthesized in the form of an ethylenically unsaturated monomer is used. Polymer couplers obtained by copolymerization with a polymerizable monomer of are British Patent Nos. 880,206 and 955,197.
No., No. 967,503, No. 967,504, No. 955,363,
No. 1,104,658 is disclosed. However, the above-mentioned hydrophilic polymer couplers have a problem that they have insufficient diffusion resistance and are apt to cause color mixing, and in severe cases, they flow out during development processing. To solve this, U.S. Pat.Nos. 4,207,109, 4,215,195, and 4,
Hydrophilic polymer couplers having a phenolic hydroxyl group or an active methylene group as described in JP-A No. 421,915, JP-A No. 58-27139 and JP-A No. 58-28744 have been proposed. Is insufficient and the density of the dye image obtained is low.

Yet another method of making the couplers resistant to diffusion is to use a coupler having a long fatty chain and hydrophilicity in the same molecule. These compounds are described, for example, in British Patent No. 455,55.
No. 6 and No. 465,823, and is called a Fisher-type coupler because it was proposed by Fisher. Since this Fisher type coupler can be uniformly dispersed in the gelatin layer, there is little softening of the coupler layer, and it is possible to reduce the thickness of the coupler layer by using a small amount of gelatin, and it is possible to make it sufficiently diffusion resistant. Is. However, in the Fisher type coupler, since the hydrophilic group in the molecule is likely to interact with gelatin,
A remarkable thickening action occurs, which hinders high-speed uniform coating.
Further, since the water absorbency is strong even during image storage, it has a drawback that it is easily discolored due to the influence of moisture.

Incidentally, the Fisher type coupler has a long-chain fatty chain and a hydrophilic group in the same molecule, and belongs to a so-called "surfactant". Generally, when the surfactant reaches a certain concentration or more in an aqueous solution, several tens to several hundreds of molecules are gathered, and the long-chain fatty chains are directed inward and the hydrophilic groups are directed outward. Micelles) are formed. It is considered that this micelle form is involved in the fact that the Fisher type coupler is capable of achieving sufficient diffusion resistance despite being soluble in water. However, the Fisher type coupler has a structure having only one long fatty chain (hydrophobic group), and a surfactant having such a structure forms about tens to several hundred micelles. As a result, the interaction becomes large, which is considered to bring about a remarkable thickening effect.

On the other hand, a compound having a substituent containing a plurality of hydrophobic groups and a hydrophilic group in the same molecule is similar to phosphatidylcholine (lecithin), which is a structural molecule of a biological membrane having a similar structure, and has a molecular weight of several thousand to tens of thousands. It has been found that endoplasmic reticulum (vesicles) having a huge bilayer structure is formed. For example,
Kunitake et al .: Journal of American Chemical Society No. 99
Volume 3860 (1979) and edited by Norio Ise and Iwao Tafushi, "An Introduction to Specialty Polymer" 6
Chapter 174-196 (Cambridge University Press 1983
Year).

(Problems to be Solved by the Invention) As described above, in improving the color reproducibility of a silver halide color photographic light-sensitive material by diffusion-proofing a conventional coupler,
There are various problems such as thickening due to interaction with gelatin.

Therefore, the first object of the present invention is to provide a novel coupler for a silver halide color photographic light-sensitive material.

A second object of the present invention is to provide a novel coupler having sufficient diffusion resistance to fix it in a dispersed gelatin layer.

The third object of the present invention is to provide a novel coupler which is less likely to soften the dispersed gelatin layer.

A fourth object of the present invention is to provide a novel coupler which is less likely to thicken due to the interaction with gelatin.

A fifth object of the present invention is to provide a silver halide color photographic light-sensitive material having little color mixture and good color reproducibility.

A sixth object of the present invention is to provide a silver halide color photographic light-sensitive material having a dye image with good sharpness.

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

(Means for Solving Problems) The inventors of the present invention have conducted extensive studies to overcome the above-mentioned drawbacks of the silver halide color photographic light-sensitive material. As a result, the coupler residue has a substituent containing a plurality of hydrophobic groups. Based on this finding, the present invention was accomplished based on the finding that a compound added with and hydrophilicity does not interact with gelatin, has excellent diffusion resistance, and exhibits extremely excellent performance as a photographic coupler.

That is, the present invention relates to a photographic coupler containing a compound represented by the following general formula (I) having in one molecule a substituent having a plurality of hydrophobic groups and a hydrophilic group. A photosensitive material is provided.

(In the formula, Q represents a coupler residue capable of coupling with an oxidation product of an aromatic primary amine developing agent, A represents a substituent having a plurality of hydrophobic groups, and E and F represent —COOM— and —SO ₃ M. -,-
O-SO ₃ M or Indicates. Here, M is a hydrogen atom, an inorganic or organic cation. m is a positive integer, and n ₁ and n ₂ are 0 or a positive integer. However, n ₁ and n ₂ cannot be 0 at the same time. ) In the general formula (I), the hydrophobic group represented by A is
It means a hydrocarbon group having 10 or more carbon atoms, and preferably has 10 to 20 carbon atoms. For example, an alkyl group, a cycloalkyl group,
Examples thereof include an aralkyl group, an alkenyl group, an alkynyl group and an aryl group. These groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or the like. It is preferable that the substituent A contains two or three hydrophobic groups.

m is preferably 1 or 2, and n ₁ + n ₂ is preferably 1 or 2.

Among the dye-forming coupler residues represented by Q, the cyan dye-forming coupler residue is phenol type (II),
(III) or those of naphthol type (IV) and (V) (each has an OH group at the 1-position and a hydrogen atom other than the coupling site is eliminated, and is linked to A, E and F of the general formula (I). ) Is preferred.

In the formula, R ¹¹ represents a group capable of substituting on a phenol ring or a naphthol ring, and examples thereof include a halogen atom, a hydroxy group, an amino group, a cyano group, an aliphatic group, an aromatic group, a heterocyclic group, a carbonamido group, and a sulfonamide. Group, carbamoyl group, sulfamoyl group, acyloxy group, acyl group,
Aliphatic oxy group, aliphatic thio group, aliphatic sulfonyl group,
Aromatic oxy group, aromatic thio group, aromatic sulfonyl group,
Examples thereof include a sulfamoylamino group, a nitro group and an imide group. The carbon number of R ¹¹ is 0 to 30.

R ¹² is ^{-CONR 13 R 14, -NHCOR 13,} -NHCOOR 15, -NHSO 2
R ^15, represents -NHCONR ¹³ R ¹⁴ or _{^{-NHSO 2 R 13 R 14, R}} 13
And R ¹⁴ is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (eg, methyl group, ethyl group, butyl group, methoxyethyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, trifluoromethyl Group, heptafluoropropyl group, dodecyloxypropyl group, 2,4-di-tert-aminophenoxypropyl group, 2,4-di-tert-amylphenoxybutyl group, etc.), aromatic group having 6 to 30 carbon atoms ( For example, phenyl group, tolyl group, 2-tetradecyloxyphenyl group, pentafluorophenyl group, 2-chloro-5
-Dodecyloxycarbonylphenyl group, etc.), carbon number 2
To 30 heterocyclic groups (eg, 2-pyridyl group, 4-pyridyl group, 2-furyl group, 2-thienyl group, etc.), R ¹⁵ is an aliphatic group having 1 to 30 carbon atoms (eg, methyl group, ethyl group). Group, butyl group, dodecyl group, hexadecyl group), 6 to 30 aromatic groups (eg, phenyl group, tosyl group, 4-chlorophenyl group, naphthyl group, etc.), heterocyclic groups (eg, 4-pyridyl group, quinolyl group) , 2-helyl group). R ¹³ and R
¹⁴ may combine with each other to form a heterocycle (eg, morpholine ring, piperidine ring, pyrrolidine ring, etc.). p '
Is 0 to 3, q'is 0 to 2, r'and s'are 0 to 4 respectively.
Represents an integer.

X represents an oxygen atom, a sulfur atom or R ¹⁶ N, and R
¹⁶ represents a hydrogen atom or a monovalent group. When R ¹⁶ represents a monovalent group, examples of R ¹⁶ include an aliphatic group having 1 to 30 carbon atoms (eg, methyl group, ethyl group, butyl group, methoxyethyl group, benzyl group, etc.), and 6 to 6 carbon atoms. 30 aromatic groups (eg, phenyl group, tolyl group, etc.), heterocyclic groups having 2 to 30 carbon atoms (eg, 2-pyridine group, 2-pyridine group, etc.),
Carbonamide group having 1 to 30 carbon atoms (eg, formamide group, acetamide group, N-methylacetamide group, benzamide group, etc.), sulfonamide group having 1 to 30 carbon atoms (eg, methanesulfonamide group, toluenesulfonamide group) , 4-chlorobenzenesulfonamide group, etc.),
Imido group having 4 to 30 carbon atoms (for example, succinimide group), —OR ¹⁷ , —SR ¹⁷ , —COR ¹⁷ , —CONR ¹⁷ R ¹⁸ , —COCO
R ¹⁷ , -COCONR ¹⁷ R ¹⁸ , -COOR ¹⁹ , -COCOOR ¹⁹ , -SO ₂ R ¹⁹ , -SO ₂ OR ¹⁹ , -SO ₂ NR ¹⁷ R ¹⁸ and -NR ¹⁷ R ¹⁸ may be mentioned. R ¹⁷ and R ¹⁸ may be the same or different, and each is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (for example, a methyl group, an ethyl group, a butyl group, a dodecyl group, a methoxyethyl group, Trifluoromethyl group, heptafluoropropyl group, etc., aromatic group having 6 to 30 carbon atoms (eg phenyl group, tolyl group, 4
-Chlorophenyl group, pentafluorophenyl group, 4-
Cyanophenyl group, 4-hydroxyphenyl group, etc.) or heterocyclic group having 2 to 30 carbon atoms (eg 4-pyridyl group, 3
-Pyridyl group, 2-furyl group, etc.). R ¹⁷ and R ¹⁸ may be bonded to each other to form a heterocycle (eg, morpholino group, pyrrolidino group, etc.).

Examples of R ¹⁹ include the substituents shown for R ¹⁷ and R ¹⁸ excluding a hydrogen atom.

Z ¹ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Examples of the group capable of splitting off include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), and a carbon number of 1 to 1.
30 aliphatic oxy groups (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, 2-methoxyethoxycarbamoylmethyloxy group, 2-methanesulfonylethoxy group, triazolylmethyloxy group, etc.), carbon number 6
To 30 aromatic oxy groups (for example, phenoxy group, 4-hydroxyphenoxy group, 2-acetamidophenoxy group, 2,4-dibenzenesulfonamidephenoxy group, 4
-Phenylazophenoxy group, etc.), a heterocyclic oxy group having 2 to 30 carbon atoms (eg, 4-pyridyloxy group, 1-phenyl-5-tetrazolyloxy group, etc.), aliphatic thio having 1 to 30 carbon atoms Group (eg, dodecylthio group, etc.), carbon number 6
To 30 aromatic thio groups (eg, 4-dodecylphenylthio group, etc.), heterocyclic thio groups having 2 to 30 carbon atoms (eg, 4-pyridylthio group, 1-phenyltetrazol-5-ylthio group, etc.), carbon number 2 to 30 acyloxy group (for example, acetoxy group, benzoyloxy group, lauroyloxy group, etc.), carbonamido group having 1 to 30 carbon atoms (for example, dichloroacetylamide group, trifluoroacetamide group,
Heptafluorobutanamide group, pentafluorobenzamide group, etc.), sulfonamide group having 1 to 30 carbon atoms (eg, methanesulfonamide group, triene sulfonamide group, etc.), aromatic azo group having 6 to 30 carbon atoms (eg, Phenylazo group, 4-chlorophenylazo group, 4-methoxyphenylazo, 4-pivaloylaminophenylazo group, etc.), aliphatic oxycarbonyloxy group having 1 to 30 carbon atoms (for example, ethoxycarbonyloxy group, dodecyloxycarbonyl) Oxy group, etc.), an aromatic oxycarbonyloxy group having 6 to 30 carbon atoms (eg, phenoxycarbonyloxy group, etc.), a carbamoyloxy group having 1 to 30 carbon atoms (eg, methylcarbamoyloxy group, dodecylcarbamoyloxy group, phenyl) Carbamoyloxy group, etc.), having 1 to 30 carbon atoms and nitrogen atom In the Hajime Tamaki contiguous to the active position of the coupler (e.g., succinimide group, phthalimide group, hydantoinyl group, pyrazolyl group, 2-benzotriazolyl group) and the like.

The couplers represented by the general formulas (II), (III), (IV) and (V) have substituents R ¹¹ , R ¹² , X or Z ¹ of 2 or more.
It may be a dimer or a multimer having more than one bond with each other via a polyvalent or multivalent linking group.

Among the dye-forming coupler residues represented by Q, the magenta dye-forming coupler residue has the following general formula (V
I), (VII), (VIII), (IX), (X), (XI) and (XIII) (Ar, Z ² , R ²⁰ to any one of R ³² in the above general formula (Linked to A, E and F of (I)) are preferred.

Wherein Ar is a substituent of the well-known type at the 1-position of the 2-pyrazolin-5-one coupler, such as an alkyl group, a substituted alkyl group (for example, a haloalkyl such as fluoroalkyl,
Cyanoalkyl, benzylalkyl, etc.), aryl group or substituted aryl group [alkyl group (eg, methyl group, ethyl group, etc.) as substituent, alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenyloxy group) Etc.), alkoxycarbonyl group (eg methoxycarbonyl group etc.), acylamino group (eg acetylamino group), carbamoyl group, alkylcarbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group etc.), dialkylcarbamoyl group (eg dimethylcarbamoyl group) , Arylcarbamoyl group (eg phenylcarbamoyl group), alkylsulfonyl group (eg methanesulfonyl group), arylsulfonyl group (eg phenylsulfonyl group), alkylsulfonamide group (eg If methanesulfonamide group),
Arylsulfonamide group (eg phenylsulfonamide group), sulfamoyl group, alkylsulfamoyl group (eg ethylsulfamoyl group), dialkylsulfamoyl group (eg dimethylsulfamoyl group),
Examples include an alkylthio group (eg, methylthio group, arylthio group (eg, phenylthio group), cyano group, nitro group, halogen atom (eg, fluorine, chlorine, bromine, etc.), and when there are two or more substituents, they may be the same or different. Good.

Particularly preferable substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group and a cyano group. ], A heterocyclic group (eg, triazole, thiazole, benzthiazole, furan, pyridine, quinaldine, benzoxazole, pyrimidine, oxazole, imidazole, etc.).

R ²⁰ represents an unsubstituted or substituted anilino group, an acylamino group (for example, an alkylcarbonamide group, a phenylcarbonamide group, an alkoxycarbonamide group, a phenyloxycarbonamide group) or a ureido group (for example, an alkylureido group, a phenylureido group). As these substituents, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), a linear or branched alkyl group (eg, methyl group, t-butyl group, octyl group, tetradecyl group, etc.), alkoxy Group (for example, methoxy group, ethoxy group, 2-ethylhexyloxy group, tetradecyloxy group, etc.), acylamino group (for example, acetamide group, benzamide group, butanamide group, octanamide group, tetradecanamide group, α- (2,- Di-tert-amylphenoxy) acetami Group, α-2,4- di -tert-
Aminophenoxy) butylamino group, α- (3-pentadecylphenoxy) hexanamide group, α- (4-hydroxy-3-tert-butylphenoxy) tetradecanamide group, 2-oxo-pyrrolidin-1-yl group, 2 -Oxo-5-tetradecylpyrrolidin-1-yl group, N-
Methyl-tetradecane amide group, etc., sulfonamide group (eg, methane sulfonamide group, benzene sulfonamide group, ethyl sulfonamide group, p-toluene sulfonamide group, octane sulfonamide group, p-dodecylbenzene sulfonamide group, N -Methyl-tetradecanesulfonamide group, etc.), sulfamoyl group (for example, sulfamoyl group, N-methylsulfamoyl group,
N-ethylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dihexylsulfamoyl group, N-hexadecylsulfamoyl group, N- [3- (dodecyloxy) -propyl] sulfamoyl Group, N- [4- (2,
4-di-tert-aminophenoxy) butyl] sulfamoyl group, N-methyl-N-tetradecylsulfamoyl group, etc., carbamoyl group (for example, N-methylcarbamoyl group, N-butylcarbamoyl group, N-octadecylcarbamoyl group) , N- [4- (2,4-di-tert-aminophenoxy) butyl] carbamoyl group, N-methyl-N
-Tetradecylcarbamoyl group, etc., diacylamino group (N-succinimide group, N-phthalimido group, 2,5
-Dioxo-1-oxazolidinyl group, 3-dodecyl-
2,5-dioxo-1-hydantoinyl group, 3- (N-acetyl-N-dodecylamino) succinimide group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, tetradecyloxycarbonyl group, benzyloxycarbonyl group, etc.) , An alkoxysulfonyl group (eg, methoxysulfonyl group, butoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group, etc.), aryloxysulfonyl group (eg, phenoxysulfonyl group, p-methylphenoxysulfonyl group, 2,4- Di-tert-amylphenoxysulfonyl group, etc.), alkanesulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, octanesulfonyl group, 2-ethylhexylsulfonyl group, hexadecanesulfonyl group, etc.), aryl Group (for example, benzenesulfonyl group, 4-nonylbenzenesulfonyl group, etc.), alkylthio group (for example, methylthio group, ethylthio group, hexylthio group, benzylthio group,
Tetradecylthio group, 2- (2,4-di-tert-amylphenoxy) ethylthio group, etc.), arylthio group (eg, phenylthio group, p-tolylthio group, etc.), alkyloxycarbonylamino group (eg, methoxycarbonylamino) Group, ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group, etc., alkylureido group (eg, N-methylureido group, N, N-dimethylureido group, N-methyl-N-dodecyl) Ureido group, N-hexadecylureido group, N, N-dioctadecylureido group, etc., acyl group (for example, acetyl group, benzoyl group,
Octadecanoyl group, p-dodecanamidobenzoyl group and the like), nitro group, hydroxy group, trichloromethyl group and the like.

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

R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ ,
R ³⁰ , R ³¹ and R ³² are each a hydrogen atom, a hydroxyl group, or an unsubstituted or substituted alkyl group (preferably having a carbon number of 1 to 20. For example, a methyl group, a propyl group, a t-butyl group. , Trifluoromethyl group, tridecyl group, etc.), aryl group (preferably having 6 to 20 carbon atoms).
For example, phenyl group, 4-t-butylphenyl group, 2,4
-Di-t-aminophenyl group, 4-methoxyphenyl group, etc.), heterocyclic group (for example, 2-furyl group, 2-thienyl group, 2-pyrimidyl group, 2-benzothiazolyl group, etc.),
Alkylamino group (preferably having 1 to 20 carbon atoms, for example, methylamino group, diethylamino group, t-butylamino group, etc.), acylamino group (preferably having 2 to 2 carbon atoms)
20 things. For example, acetylamino group, propylamino group, benzamide group, etc., anilino group (for example, phenylamino group, 2-chloroanilino group, etc.), alkoxycarbonyl group (preferably having 2 to 20 carbon atoms. For example, methoxycarbonyl group, Butoxycarbonyl group, 2-ethylhexyloxycarbonyl group, etc., alkylcarbonyl group (preferably having 2 to 20 carbon atoms, for example, acetyl group, butylcarbonyl group, cyclohexylcarbonyl group, etc.), arylcarbonyl group (eg, preferably Having 7 to 20 carbon atoms, such as benzoyl group, 4-t-butylbenzoyl group, etc., alkylthio group (preferably 1 to 20 carbon atoms)
Stuff. For example, methylthio group, octylthio group, 2-phenoxyethylthio group, etc., arylthio group (preferably having 6 to 20 carbon atoms. For example, phenylthio group, 2-
Butoxy-5-t-octylphenylthio group, etc., carbamoyl group (preferably having 1 to 20 carbon atoms.
N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N-methyl-N-butylcarbamoyl group, etc., sulfamoyl group (preferably having up to 20 carbon atoms. For example, N-ethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-dipropylsulfamoyl group, etc.)
Alternatively, it represents a sulfonamide group (preferably having a carbon number of 1 to 20, for example, methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.).

Z ² represents a hydrogen atom or a group capable of splitting off with an oxidized product of an aromatic primary amine developing agent by a coupling reaction. Examples of the group capable of splitting off include a halogen atom (for example, chlorine atom, bromine atom, etc.) and a coupling splitting off group linked by an oxygen atom (for example, acetoxy group, propanoyloxy group, benzoyloxy group, ethoxyoxaloyloxy group, pill). Vinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxyl group, 4-titanium sulfonamide phenoxy group, α-naphthoxy group, 4-cyanoxyl group, 4-methanesulfonamide-phenoxy group, α-
Naphthoxy group, 3-pentadecylpheninoxy group, benzyloxycarphonyloxy group, ethoxy group, 2-cyanoethoxy group, benzoyloxy group, 2-phenertyoxy group, 2-phenoxy-ethoxy group, 5-phenyl A tetrazolyloxy group, a 2-benzothiazolyloxy group, etc.), a coupling-off group linked by a nitrogen atom (for example, those described in Japanese Patent Application No. 57-189538, specifically a benzenesulfonamide group) , N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3,4,5,
6-pentafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5
-Dimethyl-2,4-dioxy-3-oxazolidinyl group, 1-benzyl-5-ethoxy-3-hydantoinyl group, 2-oxo-1,2-dihydro-1-pyrazonyl group,
Imidazolyl group, pyrazolyl group, 3,5-diethine-1,2,4
-Triazol-1-yl group, 5- or 6-bromobenzotriazol-2-yl group, 5-methyl-1,2,3,4
-Triazol-1-yl group, benzimidazole group, etc.), coupling leaving group linked by a sulfur atom (for example, phenylthio group, 2-methoxy-5-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-
Octanesulfonamide phenylthio group, benzylthio group, 2-cyanoethylthio group, 5-phenyl-2,3,4,5
-Tetrazolylthio group, 2-benzothiazozolyl group, etc.)
Is mentioned. The group capable of splitting off is preferably a halogen atom, a phenoxy group or a coupling splitting group linked by a nitrogen atom, and particularly preferably a halogen atom, a phenoxy group, a pyrazolyl group, an imidazolyl group or a triazolyl group.

Among the dye-forming coupler residues represented by Q, the yellow dye and the forming coupler residue are represented by the following general formula (XIII)
And those represented by (XIV) (Z ³ , R ³³ , R ³⁴ , R ³⁵ ,
In any part of R ³⁶ , A, E in the general formula (I),
Linked to F) is preferred.

In the formula, R ³³ , R ³⁴ , R ³⁵ and R ³⁶ 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, aylsulfamoyl group, aryl It represents a sulfonamide group, an ylureido 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 (XV), (XVI), (XVI
It is represented by I) or (XVIII).

Here, R ³⁷ represents an aryl group or a heterocyclic group which may be substituted, and R ³⁸ and R ³⁹ 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 alkyl group. It represents a sulfonyl group, an alkylsulfinyl group, an unsubstituted or substituted phenyl group or a heterocyclic group, and these groups may be the same or different.

W ¹ in the formula Represents a non-metal atom required to form a 4-membered ring and a 5-membered ring.

Among the general formula (XVIII), preferred are (XI
X) to (XXI).

In the formula, R ⁴⁰ and R ⁴¹ are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group, and R ⁴² , R ⁴³ and R ⁴⁴ are each a hydrogen atom, an alkyl group, an aryl group and an aralkyl group. Or, an acyl group and W ₂ represents an oxygen atom or a sulfur atom.

Next, typical compound examples of the photographic coupler having a substituent having a plurality of hydrophobic groups represented by the general formula (I) and a hydrophilic group in one molecule are shown, but the invention is not limited thereto.

Representative synthetic examples of the present invention are shown below.

Synthesis Example 1 (1) Synthesis of 2-didodecylcarbamoyl-1-naphthol O-naphthoic acid phenyl ester 19.8 g (0.0075 mol)
And didodecylamine 26.5g (0.075mol) are mixed and 140-
The mixture was stirred at 150 ° C for 8 hours. The by-produced phenol was distilled out of the system under reduced pressure.

After completion of the reaction, ethyl acetate (500 ml) was added to the reaction solution to dissolve it, and the mixture was washed with 0.1N NaOH (500 ml), and the ethyl acetate layer was washed twice with water (500 ml). The ethyl acetate layer was dehydrated with anhydrous magnesium sulfate (20 g), and the filtrate was concentrated under reduced pressure to give a viscous liquid. (Yield 37.3
g) The chemical structure was confirmed by nmr, ir and elemental analysis.

(2) Synthesis of Compound Example 1 2-didodecylcarbamoyl-1-naphthol 10.5 g
After dissolving (0.02 ml) in chloroform (40 ml), 1.6 g (0.02 mol) of anhydrous sulfuric acid was slowly added dropwise under ice-water cooling.
After completion of dropping, the mixture was stirred at room temperature for 2 hours and then at 40 ° C. for 1 hour. After concentrating the reaction mixture under reduced pressure, methanol (200 ml)
And was neutralized with a 28% sodium methylate methanol solution. After neutralization, filtration was performed and the filtrate was concentrated under reduced pressure to obtain a wax-like substance.

(Yield: 11.2 g) The chemical structure was confirmed by nm, ir, and elemental analysis.

The photographic coupler according to the present invention may be a 4-equivalent color coupler whose coupling active position is a hydrogen atom as shown in the compound examples or a 2-equivalent color coupler substituted with a leaving group, but the 2-equivalent color coupler is more preferable. The amount of coated silver can be reduced and high sensitivity can be obtained. In addition, there is also a structural design such that the color-developing dye has an appropriate diffusion property, and a structural design that releases a compound useful for improving the image quality such as a development inhibitor, a development accelerator and a photographic dye along with the coupling reaction. It is possible.

The photographic coupler of the present invention is added to the silver halide emulsion layer or its adjacent layer. When the photographic coupler of the present invention is in the same layer as silver halide, the content of the photographic coupler is 0.005 per mol of silver.
It is good to add mol to 0.5 mol, preferably 0.01 to 0.10 mol.

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

In the present invention, in order to add to the photosensitive layer of a photographic coupler having in one molecule a substituent having a plurality of hydrophobic groups represented by the above general formula [I] and a hydrophilic group, water is added under ultrasonic irradiation. Is a method of making the most of the characteristics of the photographic coupler of the present invention.

However, it is also possible to partly use the oil-in-water dispersion method which is generally known as an oil protect method. The photographic couplers according to the present invention can be used to produce natural color photographic materials and black and white photographic materials based on dye images, selected such that these couplers give a neutral grey. For the production of such a light-sensitive material, cyan couplers, magenta couplers, yellow couplers, and other couplers required for image formation and couplers that release compounds useful for image quality improvement by a coupling reaction are all photographed according to the present invention. Although it is desirable to use a coupler for use as a coupler, a coupler having a long-chain aliphatic group and partially emulsified and dispersed using an organic solvent having a high boiling point,
It can be replaced with a polymerized coupler and used in combination with the photographic coupler according to the present invention.

The couplers necessary for image formation that can be used in combination with the photographic couplers of the present invention include Research Disclosure (Re
Search Disclosure) 17643 (December 1978) Item VII-D and Patents cited in 18717 (November 1979) are typical.

In addition to the DIR coupler, the product of the coupling reaction is colorless and a colorless DI that releases the development inhibitor.
An R coupling compound may be added.

Various color couplers can be used in combination in the present invention. Typical examples of useful color couplers include naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention include Research Disclosure 17643.
(December 1978) Item VII-D and 18717 (November 1979)
Are described in the patents cited in.

As for the color coupler incorporated in the light-sensitive material, a two-equivalent color coupler in which the coupling active position is substituted with a leaving group, rather than a four-equivalent color coupler having a hydrogen atom, can reduce the amount of coated silver and obtain high sensitivity. It is also possible to use a coupler in which the color-forming dye has an appropriate diffusivity, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor upon a coupling reaction or a coupler which releases a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. Specific examples thereof, as a yellow coupler that can be used in the present invention, a typical example is an acylacetamide-based oil protect type coupler, for example, U.S. Pat.Nos. 2,407,210, 2,875,057 and 3,
No. 265,506. The use of two equivalent yellow couplers is preferred in the present invention and is described in US Pat.
No. 194, No. 3,447,928, No. 3,933,501 and No. 3
Oxygen atom-releasing yellow couplers described in 4,022,620 or JP-B-58-10739, U.S. Pat.
01,752, 4,326,024, RD18053 (April 1979),
British Patent No. 1,425,020, West German Application Publication No. 2,219,917,
Nos. 2,261,361, 2,329,587 and 2,433,81
A typical example thereof is a nitrogen atom-releasing yellow coupler described in No. 2 and the like. The α-pivaloylacetanilide type coupler is excellent in the fastness of the color forming dye, particularly the light fastness, while the α-benzoylacetanilide type coupler can obtain a high color density.

As the magenta coupler that can be used in combination with the present invention, a pyrazolone-based, pyrazoloazole-based, indazolone-based or cyanoacetyl-based oil-protective coupler is typical, for example, as a 5-pyrazolone-based coupler, U.S. Patent No. 2,311,082, No. 2,343,703, No. 2,
No. 600,788, No. 2,908,573, No. 3,062,653, No.
Nos. 3,152,896 and 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. Further, as the pyrazoloazole-based coupler, pyrazolobenzimidazoles described in US Pat. No. 3,369,879, preferably US Pat. No. 3,725,067.
Pyrazolo [5,1-c] [1,2,4] triazoles, Research Disclosure 24220 (June 1984) and Pyrazolotetrazole and Research Disclosure 24230 (June 1984) ) And the pyrazolopyrazoles described in (1). European Patent No. 119,74 in terms of low yellow sub-absorption of the coloring dye and light fastness
The imidazole [1,2-b] pyrazoles described in No. 1 are preferable, and the pyrazolo [1,5-
b] [1,2,4] triazole is particularly preferred.

Examples of cyan couplers that can be used in the present invention include oil-protection type naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212, 4,146,396, and No. 4,228,233 and No. 4,296,200
As a representative example, the oxygen atom-releasing two-equivalent naphthol-based couplers described in JP-A No. 1994-242242 can be mentioned. Further, specific examples of the phenol-based coupler are described in U.S. Patents 2,369,929 and 2,80.
1,171, 2,772,162 and 2,895,826. Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include phenol cyan couplers described in U.S. Pat.No. 3,772,002, U.S. Pat.
3,758,308, 4,126,396, 4,334,011, and
4,327,173, West German Patent Publication No. 3,329,729 and Japanese Patent Application No. 58.
-42671 described in 2,5-diacylamino-substituted phenol couplers and U.S. Pat.Nos. 3,446,622, 4,333,999, 4,451,559 and 4,427,767.
And the like, which have a phenylureido group at the 2-position and an acylamino group at the 5-position.

In addition to these, the photographic coupler of the present invention releases a development inhibitor with a colored coupler having a color correcting effect, a coupler improving the graininess by utilizing an appropriate diffusibility of a color forming dye, or with development. Coupler (so-called DI
R coupler) can be used together.

By correcting unnecessary absorption in the short wavelength region which the dyes produced from the magenta and cyan couplers have, as a colored coupler useful as a color photosensitive material for photographing, for example, U.S. Pat.No. 4,163,670 and JP-B 57-39413 are disclosed. Yellow colored magenta coupler described or U.S. Pat.
4,929, 4,138,258 and British Patent 1,146,368
Typical examples thereof include magenta colored cyan couplers described in JP-A No. 1994-1999.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such blurred couplers are disclosed in U.S. Pat.No. 4,366,237 and British Patent 2,125,5.
No. 70 shows a specific example of magenta coupler, and European Patent No. 9
No. 6,570 and German Offenlegungsschrift 3,234,533 describe specific examples of yellow, magenta or cyan couplers.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. .

The silver halide grains in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having an irregular crystal shape such as spheres and plates, twin planes, etc. It may have a crystal defect or a composite form thereof.

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

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

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineerin.
g), 14: 248-257 (1970); U.S. Pat. No. 4,434,
No. 226, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157, and can be easily prepared.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide, such as silver rhodanide or 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 also be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-C to G above.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
No. 1,476,760, etc. are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazolone-azole-based compounds are preferable, and U.S. Pat.
0,619, 4,351,897, European Patent 73,636, U.S. Patent 3,061,432, 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355.
No. 2, Research Disclosure No. 24230 (1984
Those disclosed in JP-A-60-43659, U.S. Pat. Nos. 4,500,630, and 4,540,654.

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. 2,895,826, No. 3,772,002, No. 3,758,308,
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,
No. 329,729, European Patent No. 121,365A, U.S. Patent No. 3,446,6
No. 22, No. 4,333,999, No. 4,451,559, No. 4,427,
No. 767, EP 161,626A and the like are preferred.

Colored couplers to correct unwanted absorption of colored dyes are VII of Research Disclosure No. 17643.
-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57-39413,
U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No.
Those described in No. 1,146,369 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. The DIR coupler that releases the development inhibitor is the above-mentioned TD17643, VII-F.
JP-A-57-151944, JP-A-57-154234,
Those described in U.S. Pat. No. 60-184248 and U.S. Pat. No. 4,248,962 are preferable.

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

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

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

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

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

Suitable supports that can be used in the present invention are, for example, those mentioned above.
RD.No. 17643, page 28, and 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.
Developing can be carried out by the usual methods described in 17643, pages 28 to 29, and No. 18716, page 651, left column to right column.

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

The amount of rinsing water in the rinsing process varies widely depending on the characteristics of the light-sensitive material (for example, the material used such as couplers), the application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. Can be set to. this house,
The relationship between the number of flush tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society of Motion
Picture and Television Engineers (Journal of the Socity of Motion Picture and Tele
vision Engineers) Vol. 64, pp. 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above literature, the amount of washing water can be significantly reduced, but bacteria are propagated due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. The problem arises. In processing the color light-sensitive material of the present invention, as a solution to such a problem,
The method for reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents", It is also possible to use the fungicides described in “Microbial Sterilization, Sterilization, and Antifungal Technologies” edited by the Sanitary Technology Association, and “Encyclopedia of Antibacterial and Antifungal Agents” edited by the Society for Antibacterial and Antifungal Society of Japan.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4-9.
And preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the photosensitive material, application, etc., but generally 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C for 30 seconds to
A range of 5 minutes is selected.

Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such stabilization treatment, JP-A-57-8543, JP-A-58-14834,
No. 59-184343, No. 60-220345, No. 60-238832, No.
Nos. 60-239784, 60-239749, 61-4054, 61-
All known methods described in 118749 can be used. In particular, 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazoline-
A stabilizing bath containing a 3-one, a bismuth compound, an ammonium compound or the like is preferably used.

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

(Effect of the Invention) According to the silver halide color photographic light-sensitive material of the present invention,
Since the coupler has excellent resistance to diffusion, color mixture can be prevented and color reproducibility of a photographic image can be improved. Further, in the silver halide color photographic light-sensitive material of the present invention, it is not always necessary to use a high-boiling point organic solvent, and since it is difficult to soften, the coupler-containing layer should be thinned to improve the sharpness of the dye image. You can Furthermore, since the coupler used in the silver halide color photographic light-sensitive material of the present invention does not cause interaction with gelatin and does not cause thickening, it is advantageous for high-speed uniform coating of the coupler-containing layer,
Moreover, since it is hardly affected by moisture, it is possible to form an image with good storage stability.

(Example) The present invention will be described in more detail based on an example.

Example 1 The interaction of a photographic coupler with gelatin was evaluated by the relative viscosity of an aqueous gelatin solution containing the photographic coupler.

Gelatin Alkali-treated gelatin (isoelectric point 5) Preparation of sample for relative viscosity measurement A 3.0% gelatin aqueous solution containing 1.5 × 10 ^-2 M coupler was added to p6.
It was adjusted to 0 and set at 35.0 ± 0.2 ° C.

Viscosity measurement The relative viscosity was measured at 35.0 ± 0.2 ° C using an Ostwald type viscometer. The relative viscosity η _r was calculated by the following formula.

η _r = η / η _O = ρ t / ρ _O t _O η; viscosity of gelatin solution containing coupler η _O : viscosity of water ρ; density of gelatin solution containing coupler ρ _O ; density of water t; gelatin containing coupler Time for the solution to flow down the capillary t _O ; Time for water to flow down the capillary As is clear from this result, in the coupler of the present invention, the thickening of the aqueous gelatin solution is higher than that of the Fisher type coupler having one long-chain fatty chain and a hydrophilic group in the same market. It is clear that there are few.

Example 2 Photosensitive materials, Samples 101 to 105, each having the following composition on a cellulose triacetate support were prepared.

(Sample 101) (1) Emulsion layer Coating amount Negative type silver iodobromide (silver iodide 4 mol%, average grain size 0.6 μm) 0.79 g / m ² gelatin 1.5 g / m ² coupler Cp-1 0.1 per 1 mol of silver mol Dispersion oil Oil-1 1g per 1g coupler (2) Protective layer Gelatin containing polymethylmethacrylate particles (diameter about 1.5 μm) 1.1g / m ^{2 In} addition to the above composition, each layer contains gelatin hardener H-1 and interface. Activator was added.

(Samples 102 to 105) Sample 102 was applied excluding the dispersion oil of Sample 101.
In Samples 103 to 106, the comparative coupler Cp-3 and the couplers of the present invention M-1, M-3, and M-4 were applied in equimolar amounts instead of Cp-1 of Sample 102.

The coupler and the oil for dispersing the coupler contained in the emulsion layer are as follows.

The photographic element was exposed to 25 CMS with a tungsten light source and a filter adjusted to a color temperature of 4800 ° K and then developed at 38 ° C according to the processing steps described below.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 2 minutes 10 seconds Settling 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each process is as follows. It was

Color developer Diethyltriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxyamine sulfate 2.4 g 4- (N -Ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5 g Water added 1.0 l pH10.0 Bleaching agent Ethylenediaminetetraacetic acid secondary ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium 10.0 g Ammonium bromide 150.0 g Ammonium sulfate 10.0 g Water added 1.0 l pH6.0 Stabilizer Ethylenediaminotetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Water is added 1.0 l ph6.6 Stabilizer formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization = 10) 0.3 g Water was added and 1.0 l The photographic results obtained were shown in Table 1.

As is clear from Table 1, the relative sensitivity and the maximum color density of the photographic coupler of the present invention are the same as those of the lipophilic polymer coupler when the dispersed oil having sufficient diffusion resistance is used, and thus the relative sensitivity of the present invention is improved. The photographic coupler has sufficient diffusion resistance to be fixed in the gelatin layer.

Further, from the results of Samples 102, 104, 105 and 106, the lipophilic polymer coupler Cp-1 markedly decreases the maximum color density when the dispersed oil is not used, but the photographic coupler of the present invention has no dispersed oil. Nevertheless, it shows a large maximum color density, which shows that it is an effective material for thinning the light-sensitive material.

Example 3 Sample 201, which is a multi-layer color light-sensitive material consisting of each layer having the composition shown below, was prepared on an undercoated cellulose triacetate film support.

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

1st layer (antihalation layer) Black colloidal silver… 0.2 Gelatin… 1.3 Colored coupler CC-1… 0.06 UV absorber UV-1… 0.1 Same UV-2… 0.2 Dispersion oil Oil-1… 0.01 Same Oil-2 ... 0.01 Second layer (intermediate layer) Fine grain silver bromide (average grain size 0.7μ) ... 0.15 Gelatin ... 0.1 Colored coupler CC-2 ... 0.02 Dispersion oil Oil-1 ... 0.1 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 mol%, average grain size 0.3 µ) ... silver 0.4 gelatin ... 0.6 sensitizing dye I ... 1.0 x 10 ^-4 sensitizing dye II ... 3.0 x 10 ^-4 sensitizing dye III ... 1 × 10 ^-5 Coupler CC-3… 0.06 Coupler CC-4… 0.06 Coupler CC-8… 0.04 Coupler CC-2… 0.03 Dispersed oil Oil-1… 0.03 Same as above Oil-3… 0.012 4th layer (second red) sensitive emulsion layer) bromide emulsion (silver iodide 5 mol%, average particle size 0.5 [mu]) ... 0.7 sensitizing dye I ... 1.0 × 10 sensitized ^-4 dye II ... 3.0 × 10 sensitized ^-4 dye III ... 1 ^10-5 Coupler CC-3 ... 0.24 Coupler CC-4 ... 0.24 Coupler CC-8 ... 0.04 Coupler CC-2 ... 0.04 dispersion oil Oil-1 ... 0.05 Same as above Oil-3 ... 0.10 Fifth Layer (Third Red-sensitive emulsion Layer) Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.7 μ) ... Silver 0.1 Gelatin ... 1.0 Sensitizing dye I ... 1 × 10 ⁴ Sensitizing dye II ... 3 × 10 ^-4 Sensitizing dye III … 1 × 10 ^-5 Coupler CC-6… 0.05 Coupler CC-7… 0.1 Coupler CC-2… 0.03 Dispersed Oil Oil-1… 0.01 Same as Oil-2… 0.05 6th layer (intermediate layer) Gelatin… 1.0 Compound Cpd -A ... 0.03 Dispersed oil Oil-1 ... 0.05 Same as above Oil-2 ... 0.05 Seventh layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (4 mol% silver iodide, average grain size 0.3 .mu.) ... 0.30 Sensitizing dye IV: 5 × 10 ^-4 Sensitizing dye V 2 × 10 ^-4 Gelatin: 1.0 Coupler Cp-1: 0.2 Coupler CC-5: 0.03 Coupler CC-1: 0.03 Dispersion oil Oil-1: 0.5 Eighth layer (Second green feeling Adhesive Layer) silver iodobromide emulsion (silver iodide 5 mol%, average particle size 0.5 [mu]) ... 0.4 Sensitizing dye VI ... 5 × 10 sensitized ^-4 dye V ... 2 × 10 ^-4 coupler Cp-1 ... 0.25 Coupler CC-1 ... 0.03 Coupler CC-10 ... 0.015 Coupler CC-5 ... 0.03 Dispersion oil Oil-1 ... 0.2 Ninth layer (third green sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol% , Average particle size 0.7
μ) Silver 0.85 Gelatin ... 1.0 Sensitizing dye IV ... 3.5 × 10 ^-4 Sensitizing dye V ... 1.4 × 10 ^-4 Coupler CC-11 ... 0.05 Coupler CC-12 ... 0.01 Coupler CC-13 ... 0.08 Coupler CC-1 … 0.02 Coupler CC-15… 0.02 Dispersion oil Oil-1… 0.10 Same as above Oil-2… 0.05 10th layer (yellow filter layer) Gelatin… 1.2 Yellow colloidal silver… 0.08 Compound Cpd-B… 0.1 Dispersion oil Oil-1…. 0.3 11th layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (4 mol% silver iodide, average grain size 0.3
μ) Silver 0.4 Gelatin 1.0 1.0 Sensitizing dye V 2 × 10 ^-4 Coupler CC-14 0.9 0.9 Coupler CC-5 0.07 Dispersion oil Oil-1 0.2 0.2 12th layer (2nd blue sensitive emulsion layer) Iodobromide Silver emulsion (silver iodide 10 mol%, average grain size 1.5 μ) ... Silver 0.5 gelatin ... 0.6 Sensitizing dye V ... 1 × 10 ^-4 coupler C-14 ... 0.25 Dispersion oil Oil-1 ... 0.07 13th layer (third layer) 1 protective layer) Gelatin ... 0.8 UV absorber UV-1 ... 0.1 Same as above UV-2 ... 0.2 Dispersion oil Oil-1 ... 0.01 Dispersion oil Oil-2 ... 0.01 14th layer (2nd protection layer) Fine grain silver bromide emulsion (Average particle size 0.07μ) 0.5 Gelatin ・ ・ ・ 0.45 Polymethylmethacrylate particles (diameter 1.5μ) ・ ・ ・ 0.2 Hardener H-1 ・ ・ ・ 0.4 Formaldehyde scavenger S-1 ・ ・ ・ 0.5 Formaldehyde scavenger S-2 ・ ・ ・ 0.5 The above components in each layer Besides, a surfactant was added as a coating aid. Sample 10 was prepared as described above.
I set it to 1.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

(Samples 202 to 205) Samples 202 to 205 were prepared by changing the coating amounts of the coupler CC-14 and the dispersing oil Oil-1 of the 11th and 12th layers of the sample 201 as shown in Table 2.

Samples 201 to 205 were exposed for sensitometry and exposure for MTF measurement in the same manner as in Example 1 and subjected to the same color development processing. The results of the obtained photographic properties are shown in Table 3.

The MSF value is TH James, “The Theory of the Photograp
hic Process, 4th Ed., p. 605, Macmillan (1977).

The above results indicate that the photographic coupler of the present invention has a higher relative sensitivity in the multilayer system as in the case of the single layer system as compared with the conventionally known water-soluble coupler, and the hydrophobic low molecular weight compound dispersed in the dispersion oil. It shows that it is equal to or higher than the coupler.

Furthermore, Table 3 shows that the photographic couplers of the present invention have MTFs which are comparable to those of hydrophobic low molecular weight couplers dispersed with a dispersing oil.
The value is improved, indicating that the sharpness is improved. Therefore, the polymer coupler of the present invention has sufficient diffusion resistance to be fixed in a dispersed gelatin layer, and is useful for providing a silver halide color photographic light-sensitive material having an improved Sharpel. It is clear.

Preferred Embodiments of the Present Invention 1. A photographic light-sensitive material containing a photographic coupler represented by formula (I) in at least one of the constituent layers of the light-sensitive material.

2. A photographic light-sensitive material containing the photographic coupler substituted with the substituent containing two hydrophobic groups in the above-mentioned preferred embodiment 1.

3. A photographic light-sensitive material containing a photographic coupler substituted with a substituent containing two hydrophobic groups consisting of a linear alkyl group having 10 or more carbon atoms in the above Preferred Embodiment 2.

4. A photographic light-sensitive material containing a photographic coupler in which the hydrophilic group is a carboxylic acid or a salt thereof, or a sulfonic acid or a salt thereof, in the above Preferred Embodiment 1.

5. A photographic light-sensitive material containing the photographic coupler having one hydrophilic group in one molecule in the above Preferred Embodiment 4.

Claims (1)

(57) [Claims] 1. A silver halide containing a compound represented by the following general formula (I), which has a substituent having a plurality of hydrophobic groups and a hydrophilic group in one molecule, as a color coupler for photographic use. Photographic material. (In the formula, Q represents a coupler residue capable of coupling with an oxidation product of an aromatic primary amine developing agent, A represents a substituent having a plurality of hydrophobic groups consisting of a hydrocarbon group having 10 or more carbon atoms, E, F is _{-COOM -, - SO 3 M -} , - O-SO 3 M or Indicates. Here, M is a hydrogen atom, an inorganic or organic cation. m is a positive integer, and n ₁ and n ₂ are 0 or a positive integer. However, n ₁ and n ₂ cannot be 0 at the same time. )