JPH053575B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved color development and contrast. (Prior Art) In silver halide color photographic light-sensitive materials, so-called dye-forming couplers (hereinafter simply referred to as couplers) are used to form dyes by reacting with a light-sensitive silver halide emulsion and an oxidized product of an aromatic primary amino developer. (omitted) is often used. Among these, a combination of yellow coupler, cyan coupler and magenta coupler is usually used for natural color photographic materials. Among these, the 5-pyrazolone coupler, which is frequently used as a magenta coupler, has a major problem in terms of color reproduction because it has sub-absorption near 430 nm and has poor tail cutting on the long wavelength side. Therefore, a compound developed to solve these drawbacks is a pyrazolone azole magenta coupler. However, although this family of compounds has solved the above problems, the rate of coupling with the oxidized product of the aromatic primary amine developer is slow, resulting in a decrease in color development (Damx) and a decrease in D (density). ) vs. logE (exposure energy), a new problem has emerged in that the slope γ of the curve decreases (decreases in contrast, that is, softens the tone). One way to solve these problems is to
As shown in US Pat. No. 4,443,536 and Japanese Patent Application Laid-Open No. 58-42045, a method of introducing a certain kind of functional group into the diffusion-resistant group of a coupler has been proposed. This method may be a solution to the above-mentioned problems, although there is a problem with the manufacturing cost of the coupler. (Objective of the Invention) The first object of the present invention is to provide a novel silver halide color photographic light-sensitive material which has improved color development in a system using a pyrazoloazole coupler by a method other than the above. A second object of the present invention is to provide a novel silver halide color photographic material in which the contrast in a system using a pyrazoloazole coupler is improved by a method other than the above. (Means for Solving the Problems) The above object is to provide a silver halide color photographic material having at least one silver halide photographic light-sensitive layer on a support, which has the following general formula [], [] or [ A silver halide color photographic light-sensitive material comprising at least one pyrazoloazole coupler represented by the formula [] and at least one compound represented by the following general formula []. General formula [] (A is

【formula】 【formula】

[Formula] or

[Formula] is represented, and R ₁ represents an alkyl group, an aryl group, an alkoxy group, an alkylamino group, an anilino group, or a heterocyclic group. R ₂ represents an alkyl group, an alkoxy group, a hydroxyl group, or a halogen atom, and m is an integer from 0 to 4. ) General formula []

【formula】 General formula []

【formula】 General formula []

[Formula] (R ² , R ³ and R ⁴ represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amino developer. (Includes cases in which R ² , R ³ , R ⁴ or coupler or magenta dye-forming polymer coupler having repeating units represented by the following general formula (B) and/or general formula (C), the compound represented by the general formula () is the following general formula [' ] It cannot be a compound represented by General formula (A) (In the formula, R _a and R _b represent an alkyl group or an aryl group, and Z _a represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidation product of a color developing agent.) General formula (B) General formula (C) (In the formula, R _c represents a hydrogen atom, a halogen atom, or an alkyl group, R _d represents an alkyl group, an aryl group, or an alkylthio group, J represents a divalent organic group, and Z _b represents a hydrogen atom or a color developing Represents a group that can be separated by a coupling reaction with the oxide of the active ingredient.) General formula (') (In the formula, R _e represents an alkyl group, an alkoxy group, an aryl group, an alkylamino group, or an anilino group, R _f represents an alkyl group, an alkoxy group, or a halogen atom, and s represents an integer from 0 to 2,
R _f may be the same or different when s is 2. ) achieved by. A is

【formula】

【formula】

【formula】

[Formula], preferably

【formula】

[Formula] More preferably

Represents [formula]. R ₁ is an alkyl group (straight chain or branched alkyl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group having 1 to 32 carbon atoms; these include oxygen atom, nitrogen atom, sulfur atom, carbonyl including substituents linked with groups, hydroxy groups, amino groups, nitro groups, carboxy groups, cyano groups, or halogen atoms),
Aryl group (e.g., phenyl group, 4-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4-tetradecanamidophenyl group, etc.),
Alkoxy groups (e.g., methoxy, ethoxy, benzyloxy, hexadecyloxy,
octadecyloxy group, etc.), alkylamino group (e.g., methylamino group, butylamino group, octylamino group, etc.), anilino group (e.g., phenylamino group, 2-chloroanilino group, 3-dodecyloxycarbonylanilino group, etc.) ), heterocyclic groups (pyrazolyl group, imidazolyl group, triazolyl group, pyridyl group, chiryl group, piperidyl group,
etc.), preferably an aryl group, an alkoxy group, or an anilino group, more preferably an aryl group and an anilino group.
R ₂ is an alkyl group (a linear or branched alkyl group having 1 to 18 carbon atoms, specifically a methyl group, t-butyl group, 2-ethylhexyl group, hexadecyl group, etc.), an alkoxy group ( methoxy group, ethoxy group, hexyloxy group, etc.), hydroxy group, halogen atom (fluorine, chlorine, bromine, etc.), preferably a hydroxy group and a halogen atom, more preferably a halogen atom (chlorine)
It is. m is an integer from 0 to 4, preferably 1. In addition, the alkyl group, alkoxy group, aryl group, alkylamino group, and anilino group of R _e in the general formula (') are
R ₁ and R _f in the general formula (′)
The alkyl group, alkoxy group, and halogen atom are each R ₂ in the general formula (). Next, preferred specific examples of the general formula [] are shown,
The present invention is not limited thereby. The pyrazoloazole coupler used in the present invention is represented by the following general formula [], [] or []. General formula []

【formula】 General formula []

【formula】 General formula []

[Formula] In the general formulas [], [] and [], R ² ,
R ³ and R ⁴ represent a hydrogen atom, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. still,
It also includes cases where R ² , R ³ , R ⁴ or X forms a dimer or more multimer. In the general formulas [] to [], a multimer means one having two or more groups represented by the general formulas [] to [] in one molecule, and bis forms and polymer couplers are also included in this. included. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by the general formula [] to [] (preferably one having a vinyl group, hereinafter referred to as vinyl monomer), or a homopolymer consisting only of a monomer having a moiety represented by the general formula Copolymers may be made with nonchromogenic ethylene-like monomers that do not couple with the oxidation products of grade amine developers. Compounds represented by general formulas [] to [] are 5
A membered ring-5-membered ring fused nitrogen heterocyclic coupler,
The color-producing nucleus exhibits isoelectronic aromaticity with naphthalene, and has a chemical structure that is generally referred to as azapentalene. The coupler compounds represented by the general formulas [] to [] are 1H-imidazo[1,2
-b] Pyrazole, 1H-pyrazolo[1,5-
b] [1,2,4]triazoles, 1H-pyrazolo[5,1-c][1,2,4]triazoles. Among these, preferred is the general formula []
It is a compound represented by The substituents R ² , R ³ and R ⁴ in the general formula [] to [] are hydrogen atoms, halogen atoms, alkyl groups,
Aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfur group Moylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group. Sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group,
represents an aryloxycarbonyl group, and X represents a hydrogen atom, a halogen atom, a carboxyl group, or a group that is bonded to the carbon at the coupling position via an oxygen atom, nitrogen atom or sulfur atom and is decoupled. The case where R ² , R ³ , R ⁴ or X becomes a divalent group and forms a bis body is also included. Furthermore, when the moiety represented by the general formula [] to [] is present in the vinyl monomer, R ² , R ³ or R ⁴ represents a simple bond or a linking group, and the general formula [] A vinyl group is bonded to the portion represented by ~[]. More specifically, R ² , R ³ and R ⁴ are hydrogen atoms,
Halogen atoms (e.g. chlorine atoms, bromine atoms,
), alkyl groups (e.g., methyl group, propyl group, t-butyl group, tolyloromethyl group, tridecyl group, 3-(2,4-di-t-amylphenoxy)propyl group, 2-dodecyloxyethyl group,
3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl group (e.g. phenyl group, 4
-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group,
2-ethynyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloiethoxy group,
-methanesulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group,
etc.), heterocyclic oxy groups (e.g., 2-benzimidazolyloxy group, etc.), acyloxy groups (e.g., acetoxy group, hexadecanoyloxy group, etc.), carbomoyloxy groups (e.g., N-
phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamido group, etc.) benzamide group, tetradecaneamide group,
α-(2,4-di-t-amylphenoxy)butyramide group, γ-(3-t-butyl-4-hydroxyphenoxy)butyramide group, α{4-(4-
hydroxyphenylsulfonyl)phenoxy}decaneamide group, etc.), anilino group (e.g. phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamideanilino group, 2-chloro-5-dodecyloxycarbonylanilino group,
N-acetylanilino group, 2-chloro-5-{α
(3-t-butyl-4-hydroxyphenoxy)
dodecaneamide}anilino group, etc.), ureido group (e.g., phenylureido group, methylureido group, N,N dibutylureido group, etc.), imide group (e.g., N-succinimide group, 3-benzylhydantoinyl group) , 4-(2-ethylhexanoylamino)phthalimide group, etc.), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, ), alkylthio groups (e.g., methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group,
3-phenoxyfuropylthio group, 3-(4-t-
butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, 2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecane amidophenylthio group, etc.), heterocyclic thio group (e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group,
), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, 2,4-di-tert-butylphenoxycarbonylamino group,
etc.), sulfonamide groups (e.g. methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-
methyloxy-5-t-butylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-
Ethylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-{3-(2,4-di-tert-amylphenoxy) propyl}carbamoyl group, etc.),
Acyl group (e.g. acetyl group, (2,4-di-
tert-amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N-(2-dodecyloxyethyl)
sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.) ), sulfinyl groups (e.g., octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl group, butyloxycarbonyl group,
dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (e.g.
phenyloxycarbonyl group, 3-pentadecyloxy-carbonyl group, etc.), and X is bonded through a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom, etc.), a carboxyl group, or an oxygen atom. groups (e.g., acetoxy, propanoyloxy, benzoyloxy, 2,
4-dichlorobenzoyloxy group, ethoxyoxaroyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group, 3-pentadecylphenoxy group, enzyloxycarbonyloxy group, ethoxy group, 2
-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group,
5-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), groups linked via nitrogen atoms (e.g., 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-dioxo-3-
Oxazolidinyl group, 1-benzyl-ethoxy-
3-hydantoinyl group, 2N-1,1-dioxo-3(2H)-oxo-1,2-benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group ,
3,5-diethyl-1,2,4-triazole-
1-yl, 5- or 6-bromo-benzotriazol-1-yl, 5-methyl-1,2,3,4
-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoynyl group, 1
-benzyl-5-hexadecyloxy-3-hydantoynyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4-
(propanoylphenylazo group, etc.) Groups linked by a sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group) , 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2-
(2-Hexanesulfonylethyl)-5-tert-octylphenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,5-
Tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio-5-thiophenylthio group, 2-phenyl-3-dodecyl-1,2,4-
(triazolyl-5-thio group, etc.). In addition, the alkyl group and aryl group of R _a and R _b in general formula (A) are R ₂ and R ₃ in general formula (V), respectively, and Za in general formula (A) is the same as in general formula (A). It is X. When R ² , R ³ , R ⁴ or group, 1,10-decylene group, _{-CH2CH2 -} O- _CH2CH2- , etc. ₎ , substituted or unsubstituted phenylene position (e.g., 1,4-phenylene group, 1,3-phenylene group,

【formula】

[Formula] etc.), -NHCO-R ₂ -CONH- group (R ₂ represents a substituted or unsubstituted alkylene group or phenylene group. Those represented by the general formulas [] to [] are found in vinyl monomers. The linking group represented by R ² , R ³ or R ⁴ in the case of
CH ₂ CH ₂ OCH ₂ CH ₂ -, etc.), phenylene group (substituted or unsubstituted phenylene group, e.g. 1,
4-phenylene group, 1,3-phenylene group,

【formula】

[Formula] etc.), -NHCO-, -CONH-, -O-, -OCO- and aral xylene groups (e.g.

【formula】

【formula】

[Formula], etc.)). Note that the vinyl group in the vinyl monomer may have a substituent other than those represented by the general formulas [] to []. Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms. Non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (such as methacrylic acid), and those derived from these acrylic acids. esters or amides such as acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrydamide, methyl acrylate, ethyl acrylate, n-propylacrylate, n-butylacrylate,
t-Butyl acrylate, iso-butyl arylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-
butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide,
vinyl esters (e.g. vinyl acetate, vinylipropionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives,
vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid,
Citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-
Examples include vinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together. In addition, Z _b in general formula (B) and general formula (C) is X in general formula (V), and general formula (B),
The alkyl group, aryl group, and alkylthio group of R _d in general formula (C) are R ₂ or R ₃ in general formula (V), respectively, and J in general formula (B) and general formula (C) is the general formula This is a linking group represented by R ₂ or R ₃ when the one represented by (V) is present in the vinyl monomer. Compound examples and synthesis methods of couplers represented by the general formulas [] to [] are described in the documents listed below. Compounds of general formula [] are described in Japanese Patent Publication No. 59-102548, etc., and compounds of general formula [] are described in Japanese Patent Publication No. 47-27411.
etc., the compound of the general formula [] is disclosed in JP-A-59-171956.
etc., respectively. In addition, Japanese Patent Application Publication No. 58-42045, Japanese Patent Application No. 58-88940,
The highly color-forming ballast groups described in Patent Nos. 58-52923, 58-52924, and 58-52927 can be applied to any of the compounds of the above general formulas [] to []. Specific examples of the pyrazoloazole coupler used in the present invention are shown below, but the invention is not limited thereto. There are two methods for introducing the compound represented by the general formula [] used in the present invention into a light-sensitive material. One method is to emulsify the coupler with an organic solvent that is sparingly soluble in water, and then add the coupler to the silver halide emulsion after emulsifying the coupler together with the coupler. This is a method in which they are emulsified separately, then mixed and then added to the silver halide emulsion. The effect of the present invention is greater when the former method is adopted. As a modification of the latter method, the coupler and the coupler can be emulsified separately and added to separate layers, but the effect of the present invention is greater when both are introduced into the same layer. It is also possible to add the compound represented by the general formula [] to the developer, but this method does not have the same effect as when it is added to the light-sensitive material. The molar ratio of the coupler to the compound represented by the general formula [] is 0.5 to 20 to 1 coupler,
Preferably it is in the range of 0.5 to 2.5. In the present invention, a known method, such as the method described in US Pat. No. 2,322,027, is used to introduce the compound of the general formula [] and the coupler into the silver halide emulsion layer. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc. , or boiling point approximately 30
organic solvents such as methyl acetate,
After being dissolved in a lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-395853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. Binders or protective colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used alone or in conjunction with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. For more information about gelatin production, see Arthur Vuis, The Macromolecular Chemistry of Gelatin, (Academic Press,
Published in 1964). Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferable is 2
Silver iodobromide containing from mol% to 12 mol% silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
Expressed as an average based on projected area. ) is not particularly limited, but is preferably 3μ or less. The particle size may be narrow or wide. The silver halide grains in the photographic emulsion may have regular crystal structures such as cubic or octahedral shapes, or may have irregular crystal structures such as spherical or plate shapes, or may have irregular crystal structures such as spherical or plate shapes. It can also be a composite of shapes. It may also consist of a mixture of particles of various crystalline forms. Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), written by GFDuhin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
One type of simultaneous mixing method is a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method may also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example “Die
Grundlagender Photographischen Prozesse
mit Siber−halogeniden” (Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thiourea salts, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method;
Noble metal compounds (e.g. silver complex salts, Pt, Ir,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially di-4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pennaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast , sensitization)
Various surfactants may be included for various purposes. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholinic acids, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazoidones, and the like. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nucleus, quinoline nucleus, etc. can be applied.
These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. The present invention
It is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually include a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer,
It is usual that each blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. In the same or other photographic emulsion layer or non-light-sensitive layer of the photographic light-sensitive material produced using the present invention, in addition to the coupler represented by the above general formula [], other dye-forming couplers, that is, color development processing In this method, a compound that can develop color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative or an aminophenol derivative) may be used. For example, magenta couplers include 5-pyrazolone couplers, cyanoacetylcoumaron couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides),
Examples of cyan couplers include naphtho couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions.
It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor.
In addition to forming a DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor during development. The coupler of the present invention and the above-mentioned couplers can be used in combination in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added in two or more different layers. Of course it doesn't matter. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat.
3314794 and 3352681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3705805 and 3707375), butadiene Compounds such as those described in US Pat. No. 4,045,229 or benzoxide compounds (such as those described in US Pat. No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include
Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. For the photographic processing of the layer consisting of the photographic emulsion produced using the present invention, any of the known methods and known processing solutions, such as those described in Research Disclosure No. 176, pages 28-30, can be applied. can do. The treatment temperature is usually chosen between 18°C and 50°C, but it may also be lower than 18°C or above 50°C. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N −
β-methoxyaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
P226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can include. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, It may also contain a fogging agent such as sodium boron hydride, an auxiliary developer such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, and the like. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As the bleaching agent, for example, compounds of polyvalent metals such as iron (), cobalt (), chromium (), copper (), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Complex salts of aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates;
Permanganate; nitrosophenol, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. (Examples) Hereinafter, the present invention will be explained using Examples, but the present invention is not limited thereto. Example 1 10 g of the exemplary magenta coupler (M-6) was dissolved in 20 ml of tricresyl phosphate and 25 ml of ethyl acetate, and this solution was added to 80 g of a 10% gelatin solution containing 10 ml of a 10% aqueous solution of sodium dodecylbenzenesulfonate. Emulsified and dispersed. Next, this emulsified dispersion was mixed with 100 g (containing 5.65 g of Ag) of a green-sensitive silver chlorobromide emulsion (Br 50 mol%), sodium dodecylenzenesulfonate was added as a coating aid, and both sides were laminated with polyethylene. It was coated on a coated paper support. This is designated as sample 1. Coupler application amount is 330
mg/ ^m2 . When making the above emulsified dispersion using the same method, Table 1
Samples 2 to 19 were prepared by adding the compound of the present invention and the magenta coupler in the same layer as shown in Figure 2, and applying the coating in the same manner as Sample 1 except for that. These samples were subjected to a 1 second wedge exposure at 1000 lux and processed with the following processing solution. It was treated with the following treatment solution. Developer Benzyl alcohol 15ml Diethylenetriaminepentaacetic acid 5g KBr 0.4g Na ₂ SO ₃ 5g Na ₂ Co ₃ 30g Hydroxyamine sulfate 2g 4-Amino-3-methyl-N-β-(methanesulfonamide)ethylaniline 3/2H ₂ SO ₄・
H ₂ O 4.5g Make up to 1000ml with water PH10.1 Bleach-fix ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 5g Na [Fe (EDTA)] 40g EDTA 4g Make up to 1000ml with water PH6.8 Treatment process Temperature Time Developing solution: 33°C, 3 minutes 30 seconds Bleach-fixing solution: 33°C, 1 minute 30 seconds Washing: 28-35°C, 3 minutes Agricultural clock FCD
(manufactured by Fujifilm) and the results shown in Table 1 were obtained. As a result, it was revealed that the additive of the present invention is a pyrazoloazole coupler and has the effect of increasing the color density and increasing the gradation (contrast, γ).

[Table] Example 2 Color photographic materials 20 to 23 were prepared by coating the first layer (lowest layer) to the seventh layer (top layer) on double-sided polyethylene laminated paper as shown in Table 2. A coating solution for each emulsion layer was prepared according to the method of Example 1. These samples were fitted with a B-R-G3 color separation filter and exposed and processed in the same manner as in Example 1. The color images of each sample thus obtained were all clear and highly saturated. As in Example 1, the maximum concentration (Dm) of each sample,
The gradation (γ) was measured and the results shown in Table 3 were obtained. As a result, it was found that the effect of increasing the color density and increasing the contrast of the additive of the present invention was clearly observed even in the multilayer sample.

【table】

【table】

[Table] Example 3 On a triacetyl cellulose film support,
A multilayer color photosensitive material sample consisting of each layer having the composition shown below was prepared. 1st layer; antihalation layer; gelatin layer containing black colloidal silver; 2nd layer; intermediate layer; gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone; 3rd layer; 1st red-sensitive emulsion layer; odor Silver emulsion (silver iodide; 5 mol%)... Silver coating amount 1.6 g/ ^m2 Sensitizing dye... 4.5 x 10 ^-4 mol per 1 mol of silver Sensitizing dye...... per 1 mol of silver 1.5×10 ^-4 mol Coupler EX-1...0.04 mol to 1 mol of silver Coupler EX-3...0.03 mol to 1 mol of silver Coupler EX-9...0.0006 to 1 mol of silver
Mol 4th layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 10 mol %)... Silver coating amount 1.4 g/m ² Sensitizing dye... 3 x 10 ^- per 1 mol of silver ⁴ mol Sensitizing dye...1 x 10 ^-4 mol per mol of silver Coupler EX-1...0.002 mol per mol of silver Coupler EX-3...0.02 mol per mol of silver Coupler EX- 9...0.0016 per mole of silver
5th molar layer; Intermediate layer 6th layer same as the 2nd layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 4 mol%)... Silver coating amount 1.2 g/m ² Sensitizing dye... ...5 x 10 ^-4 mol per mol of silver Sensitizing dye...2 x 10 ^-4 mol per mol of silver Pyrazoloazole coupler...0.05 mol per mol of silver 7th layer; 2nd layer Green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 8 mol%)... Silver coating amount 1.3 g/m ² Sensitizing dye... 3 x 10 ^-4 mol per 1 mol of silver Sensitizing dye... 1.2 x 10 ^-4 mol per mol of silver Pyrazoloazole coupler...0.017 mol per mol of silver 8th layer; Yellow filter layer Yellow colloidal silver and 2,5 mol per mol of silver
- Gelatin layer 9th layer containing an emulsified dispersion of di-t-octylhydroquinone; first blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol%)...Silver coating amount 0.7 g/m ² Coupler EX-4...0.25 mol per mol of silver Coupler EX-5...0.015 mol per mol of silver 10th layer; 2nd blue-sensitive emulsion layer Silver iodobromide (silver iodide; 6 mol%) )……Amount of silver coating
0.6g/m ² Coupler EX-4...0.06 mol per mol of silver 11th layer; 1st protective layer Silver iodobromide (silver iodide 1 mol%, average grain size 0.07μ)
...Silver coating amount: 0.5 g/m ² 12th layer of gelatin layer containing an emulsified dispersion of ultraviolet absorber UV-1; 2nd protective layer Polymethyl methacrylate particles (diameter approx.
Apply a gelatin layer containing 1.5μ). In addition to the above composition, gelatin hardener H-1 and a surfactant were added to each layer. As described above, samples 24 and 25 used (M-6) as the pyrazoloazole coupler, and sample 25 had additive (1) added to the same layer. Samples 26 and 27 used (M-15) as the pyrazoloazole coupler, and sample 27 had additive (1) added to the same layer. The development process used here was carried out at 38°C as described below. 1 Color development... 3 minutes 15 seconds 2 Bleaching... 6 minutes 30 seconds 3 Washing... 3 minutes 15 seconds 4 Fixing... 6 minutes 30 seconds 5 Washing... 3 minutes 15 seconds 6 Stabilization... 3 minutes 15 seconds each The composition of the treatment liquid used in the process is as follows. Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Ammonia water (28%) 25.0cc Diethylenediamine-tetraacetic acid sodium iron salt
130.0g Glacial acetic acid 14.0cc Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0cc Sodium bisulfite 4.6g Add water 1 Stabilizer formalin 8.0cc Add water 1 The maximum density (Dmax) and gradation (γ) of each sample thus obtained were measured, and the results shown in Table 4 were obtained. As a result, it was found that the effect of increasing the color density and the effect of increasing the gradation of the additive of the present invention were clearly observed even in the negative samples.

【table】

【table】

Structural formula of the compound used in Example 3 H-1 ( _CH2 = _{CHSO2CH2CONHCH2 ) -- 2} Example 4 Sample A was obtained by coating an emulsion layer and an auxiliary layer in the following order on a triacetyl cellulose support provided with an undercoat layer. 1st layer; low red-sensitivity emulsion layer cyan coupler 2-(heptafluorobutyramide)-5-{2'-(2'',4''-di-t-
500 g of an emulsion obtained by dissolving 100 g of aminophenoxy)butyramide}-phenol in 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate and stirring at high speed with 1 kg of a 10% aqueous gelatin solution.
1 kg of red-sensitive, low-iodophilic silver bromide emulsion (within a range of ±40% of the average grain size of silver halide grains)
It is silver iodobromide with a size distribution in which the number of particles exists in
It was applied so that (Amount of silver 0.5g/m ² ). 2nd layer; medium red-sensitive emulsion layer cyan coupler 2-(heptafluorobutyramide)-5-{2′-(2″,4″-di-t-
1000 g of emulsion obtained by dissolving 100 g of aminophenoxy)butyramide}-phenol in 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate and stirring at high speed with 1 kg of 10% aqueous gelatin solution.
was mixed with 1 kg of a red-sensitive medium silver iodobromide emulsion (the size distribution mentioned in the first layer emulsion is 76%, containing 70 g of silver, 60 g of gelatin, and the iodine content is 6 mol%), The coating was applied to a dry film thickness of 1 μm (silver amount: 0.4 g/m ² ). 3rd layer: Highly sensitive red-sensitive emulsion layer Cyan coupler 2-(heptafluorobutyramide)-5-{2'-(2'',4''-di-t-
1000 g of emulsion obtained by dissolving 100 g of aminophenoxy)butyramide}-phenol in 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate and stirring at high speed with 1 kg of 10% aqueous gelatin solution.
was mixed with 1 kg of a highly sensitive, low-sensitivity silver bromide emulsion (the above size distribution is 78%, containing 70 g of silver and 60 g of gelatin, and the iodine content is 6 mol %) to give a dry film thickness of 1 μm. Coated (silver amount 0.4g/
^m2 ). 4th layer; Intermediate layer 2,5-di-t-octylhydroquinone, dibutylflate 100 c.c. and ethyl acetate 100 c.c.
cc and stirred at high speed with 1 kg of 10% gelatin aqueous solution, 1 kg of emulsion was mixed with 1 kg of 10% gelatin.
Kg and applied to a dry film thickness of 1 μm. 3rd layer; low green sensitivity emulsion layer Emulsion 500 obtained in the same manner as the emulsion of the first layer except that a pyrazoloazole coupler, which is a magenta coupler, was used instead of the cyan coupler.
g, 1 kg of green-sensitive low-iod silver bromide emulsion (the above size distribution is 81%, 70 g of silver, 60 g of gelatin)
(with an iodine content of 5.2 mol%),
Coated to a dry film thickness of 2.0μ (silver content 0.7
g/ ^m2 ). 6th layer; medium green emulsion layer Emulsion 100 obtained in the same manner as the emulsion of the first layer except that a pyrazoloazole coupler, which is a magenta coupler, was used instead of the cyan coupler.
g, 1 kg of green-sensitive highly iodine silver bromide emulsion (the above size distribution is 75%, 70 g of silver, 60 g of gelatin)
(with an iodine content of 5.2 mol%),
Coated to a dry film thickness of 1μ (silver content 0.35)
g/ ^m2 ). 7th layer: highly green-sensitive emulsion layer Emulsion 1000 obtained in the same manner as the emulsion of the first layer except that a pyrazoloazole coupler, which is a magenta coupler, was used instead of the cyan coupler.
g, 1 kg of green-sensitive highly iodine silver bromide emulsion (the above size distribution is 75%, 70 g of silver, 60 g of gelatin)
(with an iodine content of 5.2 mol%),
Coated to a dry film thickness of 1 μm (Amount of silver coated)
0.35g/ ^m2 ). 8th layer: Intermediate layer 1 kg of the emulsion used in the 4th layer was mixed with 1 kg of 10% gelatin and coated to a dry film thickness of 1 μm. 9th layer; Yellow filter layer: An emulsion containing yellow colloidal silver is coated with a dry film thickness of 1 μm.
It was applied to make it look like this. 10th layer; low-sensitivity blue-sensitivity emulsion layer α-(pivaloyl)-α-(1-benzyl-5-ethoxy-3-hydantoylnyl)-2, which is a yellow coupler instead of a cyan coupler
-1000 g of an emulsion obtained in the same manner as the emulsion of the first layer except that chloro-5-dodecyloxycarbonylacetanilide was used was mixed with 1 kg of a blue-sensitive low-iodophilic silver bromide emulsion (the above size distribution is 77%). (containing 70 g of silver, 60 g of gelatin, and iodine content of 5.5 mol%) was mixed and coated to a dry film thickness of 1.0 μm (coated silver amount: 0.6 g/m ² ). 11th layer; medium blue-sensitive emulsion layer: yellow coupler instead of cyan coupler, α-(pivaloyl)-α-(1-benzyl-5-ethoxy-3-hydantoylnyl)-2
-1000 g of an emulsion obtained in the same manner as the emulsion of the first layer except that chloro-5-dodecyloxycarbonylacetanilide was used was mixed with 1 kg of a blue-sensitive medium-sensitive silver iodobromide emulsion (the above size distribution is 72%). (containing 70 g of silver, 60 g of gelatin, and iodine content of 5.5 mol%) was mixed and coated to a dry film thickness of 1.0 μm (coated silver amount: 0.5 g/m ² ). 12th layer; medium blue-sensitive emulsion layer: α-(pivaloyl)-α-(1-benzyl-5-ethoxy-3-hydantoylnyl)-2, which is a yellow coupler instead of a cyan coupler.
-1000 g of an emulsion obtained in the same manner as the emulsion of the first layer except that chloro-5-dodecyloxycarbonylacetanilide was used was mixed with 1 kg of a blue-sensitive medium-sensitive silver iodobromide emulsion (the above size distribution is 72%). (containing 70 g of silver, 60 g of gelatin, and iodine content of 5.5 mol%) was mixed and coated to a dry film thickness of 2.0 μm (coating: 0.5 g/m ² ). 13th layer: 2nd protective layer 1 kg of the emulsion used in the 3rd layer was mixed with 1 kg of 10% gelatin and coated to a dry film thickness of 2 μm. 14th layer; 1st protective layer Fine grain emulsion that is not chemically sensitized (grain size
A 10% aqueous gelatin solution containing 0.15 μm, 1 mol % silver iodobromide emulsion) was coated to give a silver coating amount of 0.3 g/m ² and a dry film thickness of 1 μm. Samples 28 and 29 are pyrazoloazo couplers (M
-6) was used, and additive (1) was added to sample 29 in the same layer. Samples 30 and 31 used (M-15) as pyrazoloazocarpler, and sample 31 had additive (1) added to the same layer. The films were exposed through a neutral gray sensitometric wedge and then subjected to the reversal process described below. Processing process

【table】

[Table] First developing water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water to 1000ml Invert water 700ml Nitrilo-N-N-N-trimethylenephosphonic acid 6Na salt 3g Stannous chloride (dihydrate) 1g P-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Add water 1000ml Color developing water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 7g Sodium triphosphate (dihydrate) 36g Potassium bromide 1g Potassium iodide ( 0.1% solution) 90ml Sodium hydroxide 3g Citrazic acid 1.5g N-methyl-N-(β-methanesulfamidoethyl)-3-methyl-4-aminoaniline sulfate 11g Ethylenediamine 3g Add water to 1000ml Conditioned water 700ml Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water to 1000ml Bleach water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Iron()ammonium ethylenediaminetetraacetate (dihydrate) ) 120.0g Potassium bromide 100.0g Add water to 1.0 Stability Water landing 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water to 1000ml Stable water 800ml Formalin (37% by weight) 5.0ml Fuji Dry well 5.0ml Add water 1.0 The maximum concentration (Dmax) and gradation (γ) of each sample thus obtained were measured, and the results shown in Table 5 were obtained. As a result, it was found that the effects of the additive of the present invention were also observed in reversal photosensitive materials.

[Table] Example 5 When preparing the emulsified dispersion in the preparation of Sample 1 of Example 1, the compound of the present invention was added to the same layer as shown in Table 6, and the magenta coupler was added at a coupler coating amount of 330 mg/m ² Samples 40 to 45 were prepared using the same method except that the following changes were made. These samples were treated and evaluated in the same manner as in Example 1. The results are shown in Table 6.

【table】

[Table] Table 6 shows that, as in Example 1, the additive of the present invention has the effect of increasing the color density and increasing the contrast of the pyrazoloazole coupler.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic material having at least one silver halide photographic light-sensitive layer on a support, at least one of the pyrazoloazole couplers represented by the following general formulas [] to []. 1
1. A silver halide color photographic material, characterized in that it contains a species and at least one compound represented by the following general formula []. General formula [] (A represents [Formula] [Formula] [Formula] [Formula], and R ₁ represents an alkyl group, an aryl group, an alkoxy group, an alkylamino group, an anilino group, or a heterocyclic group. R ₂ represents an alkyl group,
It represents an alkoxy group, a hydroxyl group, or a halogen atom, and m is an integer from 0 to 4. ) General formula [] [Formula] General formula [] [Formula] General formula [] [Formula] (R ² , R ³ and R ⁴ represent a hydrogen atom or a substituent, X is a hydrogen atom or a primary aromatic Represents a group that can be separated by a coupling reaction with a medicated amino developer.It also includes cases where R ² , R ³ , R ⁴ or X forms a dimer or more multimer.) However, the pyra The zoroazole coupler is a magenta coupler represented by the following general formula (A), or a magenta dye-forming polymer coupler having a repeating unit represented by the following general formula (B) and/or general formula (C). Sometimes, the compound represented by the general formula () is not the compound represented by the following general formula [']. General formula (A) (In the formula, R _a and R _b represent an alkyl group or an aryl group, and Z _a represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidation product of a color developing agent.) General formula (B) General formula (C) (In the formula, R _c represents a hydrogen atom, a halogen atom, or an alkyl group, R _d represents an alkyl group, an aryl group, or an alkylthio group, J represents a divalent organic group, and Z _b represents a hydrogen atom or a color developing Represents a group that can be separated by a coupling reaction with the oxide of the active ingredient.) General formula (') (In the formula, R _e represents an alkyl group, an alkoxy group, an aryl group, an alkylamino group, or an anilino group, R _f represents an alkyl group, an alkoxy group, or a halogen atom, and s represents an integer from 0 to 2,
R _f may be the same or different when s is 2. )