JPH0562972B2 - - 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 specifically to a silver halide color photographic light-sensitive material with improved color development, color image fastness to light, and color reproducibility. be. (Prior art) Compared to conventional 5-pyrazolones, pyrazoloazole couplers have lower spectral absorption of dyes obtained by coupling with oxidized paraphenyl diamines.
Since there is little unnecessary absorption around 430 nm, various proposals have been made to improve the color reproduction of color photosensitive materials. Pyrazolobenzimidazole skeleton, previously known from U.S. Patent No. 3061432 and U.S. Patent No. 3369897, U.S. Patent No.
1H-pyrazolo [3,2-
c] [1,2,4] triazole skeleton, recently known from US Pat. No. 4,500,630, 1H-imidazo[1,2-b] pyrazole skeleton, US patent
1H-pyrazolo [1,5-
b] [1,2,4] Triazole skeleton, JP-A-1989-1999
1H-pyrazolo [1,5-
d] A tetrazole skeleton has been proposed. However, a light-sensitive material in which this pyrazoloazole magenta coupler is dispersed in a silver halide emulsion layer using a high-boiling organic solvent has low color development, and the transmission or reflection absorption spectrum of the film or photographic paper does not necessarily have a tail on the long wavelength side. The problems were that the sharpness was not good, the color reproducibility was not sufficiently improved, and the light fastness of the color image was not sufficient. (Problems to be Solved by the Invention) The azomethine dyes derived from the pyrazoloazole couplers with these skeletons certainly have no unnecessary absorption near 430 nm, and have sharp edges on the long wavelength side, which is favorable for color reproduction. However, they do not necessarily cut well on the long wavelength side, the coupling rate with the oxidized form of the developing agent is slow, and the light fastness of the resulting color image is low, making them unsuitable for use in color photographic materials. was still unsatisfactory. (Objective of the present invention) Therefore, the object of the present invention is to improve color development by increasing the rate of coupling with the oxidized form of a developing agent, to improve the fastness of the produced color image, especially the fastness to light, and to further improve the sensitivity. The object of the present invention is to provide a silver halide color light-sensitive material using a pyrazoloazole coupler that enables the formation of a silver halide color. (Means for Solving the Problem) The object of the above is to provide a silver halide color photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a support. , a silver halide color characterized in that at least one pyrazoloazole magenta coupler represented by the following general formula [] is co-dispersed with at least one high-boiling point solvent represented by the following general formula [] This was achieved using photographic materials. General formula [] In the formula, R ₁ and R ₂ 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 amine developer. R ₁ , R ₂ or X may form a dimer or more multimer. Here, R ₁
and at least one of R ₂ represents a group bonded to the pyrazoloazole ring via a secondary or tertiary carbon atom, and furthermore, at least one of R ₁ and R ₂ has one -NHSO ₂ - group. It is a group having the above. However, when R ₁ is a tertiary alkyl group, or when R ₂ is bonded to the pyrazolotriazole ring through a secondary carbon atom, R ₂ is not a substituted aralkyl group. In the general formula [], a multimer means 2 molecules in one molecule.
It means a group having three or more groups represented by the general formula [ ], and includes bis-forms and polymer couplers. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by the general formula [] (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 non-chromogenic ethylene-like monomers that do not couple with the oxidation products. General formula [] In the formula, R ₃ , R ₄ and R ₅ each represent an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group.
However, the total number of carbon atoms in the groups represented by R ₃ , R ₄ and R ₅ is 12 to 60. Here, R ₃ ,
R ₄ and R ₅ are never both tolyl groups. The pyrazolotriazole coupler represented by the general formula [] will be explained in detail below. In the general formula [], substituents, R ₁ and R ₂ are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group,
represents an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, At least one of R ₁ or R ₂ represents a group bonded to the pyrazoloazole ring via a secondary or tertiary carbon atom, and furthermore, at least one of R ₁ or R ₂
is a group having one or more _-NHSO2- groups.
However, when R ₁ is a tertiary alkyl group, or R ₂
is attached to the pyrazolotriazole ring through a secondary carbon atom, R ₂ is not a substituted aralkyl group. In the general formula [], X represents a hydrogen atom, a halogen atom, a carboxy group, or a group that can be decoupled by bonding to the carbon at the coupling position via an oxygen atom, nitrogen atom, sulfur atom, or the like. The case where R ₁ , R ₂ or X becomes a divalent group and forms a bis body is also included. Also,
When the moiety represented by the general formula [] is present in the vinyl monomer, R ₁ or R ₂ represents a simple bond or a connecting group, and the moiety represented by the general formula [] and the vinyl group are connected via this. Join. More specifically, R ₁ and R ₂ are hydrogen atoms, halogen atoms (e.g., chlorine atoms, bromine atoms, etc.),
Alkyl groups (e.g. methyl, propyl, hexyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-amylphenoxy)
Propyl group, 2-dodecyloxyethyl group, 3-
phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group,
etc.), aryl groups (e.g. phenyl group, 4-t
-butylphenyl group, 2,4-di-t-amyl phenyl group, 4-tetradecanamidophenyl group,
etc.), heterocyclic groups (e.g., 2-furyl group, 2-
thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.) ), aryloxy groups (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.),
Carbamoyloxy group (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., acetamide group, benzamide group, tetradecanamide 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-benzylhydantoynyl group, 4-(2-ethylhexanoylamino)
phthalimide group, etc.), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (e.g., methylthio group, octylthio group, tetratecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio 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-tetradecanamidophenylthio group,
), heterocyclic thio groups (e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonylamino groups (e.g., methoxycarbonylamino groups,
tetradecyloxycarbonylamino group, etc.),
Aryloxycarbonylamino group, 2,4-di-tert-butylphenoxycarbonylamino group,
etc.), sulfonamide group, (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-
Ethylcarcamoyl 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.), and an aryloxycarbonyl group (e.g., phenyloxycarbonyl group, 3-pentadecyphenyloxycarbonyl group, etc.). At least one of R ₁ or R ₂ represents a group bonded to the pyrazoloazole ring via a secondary or tertiary carbon atom. If these groups are explained in detail, isopropyl group, t-butyl group, t-hexyl group, cyclohexyl group, adamantyl group,
1-ethoxyisopropyl group, 1-phenoxy-
1,1-dimethylmethyl group, α,α-dimethylbenzyl group, α,α-dimethylphenylethyl group,
α-ethylbenzyl group, 1-ethyl-1-[4-
(2-butoxy-5-tert-octylbenzenesulfonamido)phenyl]methyl group, 1-methyl-2-[4-(4-dodecyloxybenzenesulfonamido)phenyl]ethyl group, 1-methyl-2
-(2-octyloxy-5-tert-octylbenzenesulfonamido)ethyl group, 1,1-dimethyl-2-(2-octyloxy-5-tert-octylbenzenesulfonamido)ethyl group, 1-
Methyl-2-[2-octyloxy-5-(2-octyloxy-5-tert-octylbenzenesulfonamide)benzenesulfonamide]ethyl group, 1-ethyl-2-(2-dodecyloxy-5
-tert-octylbenzenesulfonamido)ethyl group, 1-(2-hydroxyethyl)-2-{α-
[3-(2-octyloxy-5-tert-octylbenzenesulfonamido)phenoxy]dodecanamide}ethyl group, etc. To explain in detail about X, group, 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, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxy group Siethoxy group, 5-
phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), groups linked via a nitrogen atom (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.). When R ₁ , R ₂ or -ethylethylene group, 1,10-decylene group, -CH ₂ CH ₂ -O-
CH ₂ CH ₂ -, etc.), substituted or unsubstituted phenylene groups (e.g. 1,4-phenylene group, 1,3-
phenylene group,

【formula】

[Formula], etc.), -NHCO-R ⁷ -CONH- group (R ⁷ represents a substituted or unsubstituted alkylene group or phenylene group), and the like. When the compound represented by the general formula [] is present in the vinyl monomer, the linking group represented by R ₁ or R ₂ is an alkylene group (a substituted or unsubstituted alkylene group, such as a methylene group, an ethylene group, etc.). ,1
-Methylethylene group, 1,10-decylene group, -
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 aralkylene groups (e.g.

【formula】

[Formula], etc.) and groups formed by combining those selected from these. Note that the vinyl group in the vinyl monomer may have a substituent other than those represented by the general formula []. 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-alkyl acrylic acid (such as methacrylic acid), and derivatives of these acrylic acids. ester or amide (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide,
diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate,
n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate,
n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylate lonitrile,
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 ester, N-vinyl-2-
Examples include pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together. Examples of couplers included in the present invention are shown below,
It is not limited to this. (M-1) (M-2) (M-3) (M-4) (M-5) (M-6) (M-7) (M-8) (M-9) (M-10) (M-11) (M-12) (M-13) (M-14) (M-15) (M-16) (M-17) (M-18) (M-19) (M-20) (M-21) (M-22) (M-23) (M-24) (M-25) (M-26) (M-27) (M-28) (M-29) (M-30) (M-31) The reason why the total number of carbon atoms of the substituents represented by R ₃ , R ₄ and R ₅ in the general formula [] is 12 to 60 is that if it is outside this range, the improvement effect aimed at by the present invention will decrease. This is to do so. Also, the total number of carbon
If it exceeds 60, the ability to dissolve the coupler decreases and the coupler may precipitate, which is not preferable. In the general formula [], R ₃ , R ₄ or
The alkyl group represented by R ₅ may be a straight chain alkyl group or a branched alkyl group, such as a methyl group,
Ethyl group, propyl group, butyl group, pentyl group,
Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc., and R ₃ ,
The cycloalkyl group represented by R ₄ or R ₅ is, for example, a cyclopentyl group or a cyclohexyl group. The aryl group represented by R ₃ , R ₄ or R ₅ is a phenyl group, naphthyl group, etc., and the alkenyl group is a butenyl group, a pentenyl group, a hexenyl group,
These include heptenyl group, octenyl group, decenyl group, dodecenyl group, octadecenyl group, and the like. These alkyl groups, cycloalkyl groups, aryl groups and alkenyl groups may have one or more substituents, and examples of substituents for the alkyl groups, cycloalkyl groups and alkenyl groups include halogen atoms (e.g. elementary atoms, chlorine atoms, etc.), alkoxy groups (e.g., methoxy, ethoxy, butoxy, etc.), aryl groups (e.g., phenyl, naphthyl, etc.), aryloxy groups (e.g., phenoxy, etc.), alkenyl groups, alkoxycarbonyl Examples of substituents for the aryl group include alkyl groups in addition to those listed as substituents for the alkyl group, cycloalkyl group, and alkenyl group. Preferably R ₃ , R ₄ and
R ₅ is a 2-ethylhexyl group, a 7-methyloctyl group, a cyclohexyl group, a phenyl group, an isopropylphenyl group, a straight-chain alkyl group having 8 to 18 carbon atoms, and the like. Further, R ₃ , R ₄ and R ₅ are never all tolyl groups. In the present invention, a high boiling point organic solvent refers to an organic solvent having a boiling point of 175° C. or higher at 1 atmosphere. In the present invention, the amount of the high boiling point organic solvent represented by the general formula [] may be any amount depending on the type and usage amount of the magenta coupler represented by the general formula []. It is preferred that the boiling point organic solvent/magenta coupler ratio is 0.05 to 20. Further, the high boiling point organic solvent according to the present invention represented by the general formula [] can be used in combination with other conventionally known high boiling point organic solvents within the range that can achieve the object of the present invention. Examples of these high boiling point organic solvents include phthalate ester solvents such as dibutyl phthalate and di-2-ethylhexyl phthalate, amide solvents such as N,N-diethyldodecanamide, fatty acid ester solvents, and benzoate esters. Examples include phenolic solvents such as 2,5-di-tert-amylphenol, and ether solvents such as dihexadecyl ether. Specific examples of the high boiling point organic solvent represented by the general formula [] are shown below, but the invention is not limited thereto.

【table】

【table】

【table】

[Table] The magenta coupler and the high-boiling organic solvent according to the present invention can be dispersed and contained in at least one hydrophilic organic colloid layer constituting the photographic light-sensitive layer. As a method for introducing a coupler into a silver halide emulsion layer, a known method such as that described in US Pat. No. 2,322,027 is generally used. The high boiling point organic solvent used in the present invention generally has very good solubility for the coupler of the present invention, but there are cases where the coupler is insufficiently dissolved due to the small coupler solvent/coupler ratio. can be used in combination with other coupler solvents such as phthalate coupler solvents. In the present invention, before dissolving the coupler in the coupler solvent, an organic solvent having a boiling point of about 30 to 150°C, such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, or methyl isobutyl is used. Ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. may also be present. Even when a coupler dissolved in a coupler solvent is introduced into a silver halide emulsion layer by these methods, for example, the method described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943, A dispersion method using a polymer can also be used in combination. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it can also be introduced into the hydrophilic colloid as an alkaline aqueous solution. As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. For more information on how to make gelatin, see The Macromolecular Chemistry of Gelatin (Academic Press) by Arthur Vuis.
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. A preferred silver halide is silver chlorobromide.
Particularly preferred is silver chlorobromide containing from 20 mol % to 100 mol % silver bromide. 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 it is preferably 2μ or less. The particle size may be narrow or wide. The silver halide grains in the photographic emulsion layer are cubic,
It may have a regular crystalline structure such as an octagonal shape, or may have an irregular crystalline structure such as a spherical shape or a plate shape, or a composite shape of these crystalline 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 from P. Grafkide's "Chemistry and Physics of Photography" (published by Paul Montell),
(1967), “Photographic Emulsion Chemistry” (Focal Press, 1966) by G. F. Daafin, “Manufacture and Coating of Photographic Emulsions” (Focal Press, 1964) by V. L. Zelikman et al. (P. Glafkides, “Chimie et
Physique Photographique” {(Paul Montel,
(1967)}, GFDlffin, “Photographic Emulsion
Chemistry” {(Focal Press, (1966)}, VL
Zelikman et al., “Making and Coating
Photographic Emulsion” {(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).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can 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 present. Silver halide emulsions are usually chemically sensitized. For chemical sensitization, see H. Frieser, “Basic Silver Halide Photographic Processing” (ed. Academia Verlag, 1968) (H. Frieser, “Die
Grundlagender Photograpischen Prozessemit
Silver-halogeniden” (Akademische
Varlagsgesellshaft, 1968), pages 675-734, can be used. That is, sulfur-containing compounds that can react with activated gelatin and silver (e.g. thiosulfates, thioureas,
Sulfur sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds): Noble metal compounds (e.g. , gold 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. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.; thioketo compounds such as oxadorinthion; azaindenes, e.g. Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,
3,3a,7) tetraazaindene), pentaazaindene, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic 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 contains 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, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, 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 enhanced with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Contains 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 a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus,
A naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. 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 5-6 page heterocyclic 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, aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat.
Nos. 2933390 and 3635721), aromatic organic acid formaldehyde compounds (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. The present invention
Multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support can also be produced. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the 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 prepared using the present invention, in addition to the coupler represented by the above general formula [], other dye-forming couplers may be used in the color development process. 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 coupler, pyrazolonebenzimidazole coupler, pyrazolo[5,1-
C] [1,2,4] Triazole couplers, pyrazolopyrazole couplers, pyrazolotetrazole couplers, open chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc.,
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are desirably 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 the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. Further, the photosensitive material may contain a coupler or a compound that releases a development accelerator 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 you can. 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 image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include hydroquinone derivatives, gallic 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 higher than 50°C. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiasulfates 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 phenylene diamines (e.g. 4-amino-N,N-dinitylaniline, 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-methoxyethylaniline, etc.) can be used. In addition, LFA Mason, "Photo Processing Chemistry" (Focal Press) (1966) {(LFMason
“Photograhic Processing Chemistry (Focal
Press) (1966), pages 226-229, U.S. Patent
Those described in No. 2193015, No. 2592364, JP-A-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. Also, if necessary, water softener,
Preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol,
Polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines, dye-forming couplers,
Competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, tackifying agents, polycarboxylic acid chelating agents, antioxidants, and the like may also be included. 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 a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper (), peracids, quinones, nitrone compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Complex salts of aminobocarboxylic acids such as 1,3-diamino-2-probanoltetraacetic 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() complexes are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. The color photographic emulsion layer forming the dye image layer according to the present invention is coated on a flexible support such as plastic film, paper or cloth which is commonly used in photographic light-sensitive materials. Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polycarbonate, baryta layers or α-olefin polymers (e.g. polyethylene, polypropylene), etc. Paper coated or laminated with The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. When using these supports for reflective materials, it is preferable to add a white pigment to the support or laminate layer. Examples of white pigments include titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, and titanium phosphate, but titanium dioxide, barium sulfate, and zinc oxide are Particularly useful. The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsions and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. When these supports are used in reflective materials, a hydrophilic colloid layer containing a white pigment at high density can be further provided between the support and the emulsion layer to improve the whiteness and sharpness of photographic images. . In the reflective material having the magenta coupler of the present invention, a paper support laminated with a polymer is often used as the support, but if a synthetic resin film kneaded with a white pigment is used, smoothness, gloss, and sharpness can be achieved. In addition to improving the accuracy, photographic images with particularly excellent sharpness and depiction of dark areas can be obtained, which is particularly preferable. In this case, polyethylene terephthalate and cellulose acetate are particularly useful as raw materials for the synthetic resin film, and barium sulfate and titanium oxide are particularly useful as white pigments. After development and drying, the photographic material of the present invention can be laminated with a plastic film on the front and back sides. Plastic films for lamination include polyolefin, polyester, polyacrylate, polyvinyl acetate, polystyrene,
There are butadiene-styrene copolymers, polycarbonates, etc., especially polyethylene terephthalate,
Copolymers of vinyl alcohol and ethylene, polyethylene, etc. are useful. (Effects of the Invention) According to the present invention, it is possible to obtain a silver halide photographic material with enhanced development activity using a pyrazoloazole magenta coupler. Furthermore, according to the present invention, a silver halide color photographic light-sensitive material is obtained which forms a magenta color image of an excellent hue with a sharp edge of absorption on the long wavelength side and has improved reproducibility and color image fastness. (Example) The present invention will be described below with reference to Examples, but the present invention is not limited thereto. Example 1 An exemplary coupler (M-
10), add 13.2 g of exemplified compound (P-5) and 20 ml of ethyl acetate to 6.62 g of this coupler, and heat at 60°C.
The mixture was dissolved by heating and added to 100 ml of an aqueous solution containing 10 g of gelatin and 1.0 g of sodium dodecylbenzenesulfonate to obtain a fine emulsified dispersion using a mechanical method. The entire amount of this emulsified dispersion was added to 100 g of silver chlorobromide emulsion (containing 6.55 g of Ag) consisting of 80 mol% of Br, and 2% of 2,4-dihydroxy-
10 ml of 6-chloro-s-triazine sodium salt was added and coated on a paper support laminated with polyethylene on both sides so that the coated silver amount was 180 mg/ ^m2 , and a gelatin layer was provided on top of this coated layer. A sample was prepared. This is designated as sample 1. Next, in place of the above-mentioned exemplified compound (P-5), exemplified compounds (P-8), (P-12), (P-25), (P-
Samples were prepared in the same manner using 32, n=1), (P-40) and (P-42). These samples are designated as Samples 2, 3, 4, 5, 6, and 7. Furthermore, Sample 8 was prepared by using dibutyl phthalate as a comparative high-boiling organic solvent in place of Exemplified Compound (P-5). On the other hand, as a magenta coupler, the following comparative coupler was used in place of the previous exemplary coupler (M-10), and sample 9 was used with exemplary compound (P-5) as the solvent.
It was created. Comparison coupler (A) These samples 1 to 9 were subjected to wet exposure of 1000 CMS and treated with the following processing 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 Developer: 33°C, 3 minutes and 30 seconds Bleach-fix: 33°C, 1 minute and 30 seconds Washing: 28-35°C, 3 minutes The results obtained by carrying out the above treatment are shown in the following table.

[Table] From the above results, the combination of the coupler and high boiling point organic solvent of the present invention has high sensitivity and density near the maximum density (shoulder density) in terms of photographic properties, whereas conventional photographic properties are poor and use is prohibited. It was found that what had been difficult to achieve was dramatically improved, and it also showed excellent performance with no fogging. In addition, it was found that the color image obtained by color development had a clear magenta hue due to the characteristics of the coupler of the present invention and the use of the high boiling point organic solvent of the present invention, with a lower absorption density on the long wavelength side. . Next, these samples were subjected to a 20-day fading test using a fluorescent lamp bleaching device (15,000 lux), and the results shown in the table below were obtained.

【table】

[Table] Concentrations.
The above results indicate that the combination of the coupler and high-boiling solvent of the present invention has excellent color image fastness to light, and also exhibits excellent performance without staining, which is said to be caused by decomposition of the coupler. Recognize. Example 2 A coating solution was prepared according to the method described in Example 1 using 6.62 g of the exemplified coupler (M-10), 13.2 g of the exemplified compound (P-6) as a high-boiling organic solvent, and 25 ml of ethyl acetate. did. Next, 9.56 g of exemplary coupler (M-11), 19.1 g of (P-36), and ethyl acetate.
A coating solution was prepared in the same manner as above using 30 ml. Furthermore, the comparative coupler (A) shown in Example 1 was
A coating solution was prepared in the same manner as in Example 1 using 6.45 g of dibutyl phthalate and 12.9 g of dibutyl phthalate as the high-boiling organic solvent. Using these coating solutions prepared above, the first layer (lowest layer) to the seventh layer (top layer) as shown in the attached table were coated on a support whose both sides were laminated with polyethylene, and color photographic exposure was performed. Materials 11, 12, and
Created 13. The coating solution for each emulsion layer was prepared according to the method of the example. A B-G-R3 color separation filter was attached to these three types (11 to 13) of color photographic materials, and Example 1
It was exposed and processed in the same manner as above. Of each sample obtained in this way, (P-
The color images of Samples 11 and 12 using 6) and (P-36) have higher sensitivity than Sample 13, and as shown in Example 1, the density and gradation of the shoulders in the high density area are high and there is no fog. The density of the parts was low, and the hue was vivid and highly saturated.

【table】

【table】

[Table] Example 3 As a coupler, exemplary coupler (M-1) 7.61
g is exemplified compound (P-8) 15.2 g, ethyl acetate 20
ml and heated to 60°C to dissolve. This was added to 100 ml of an aqueous solution containing 10 g of gelatin and 1.0 g of sodium dodecylbenzenesulfonate to obtain a fine emulsified dispersion by a mechanical method. The entire amount of this emulsified dispersion was added to 100 g of a silver chlorobromide emulsion (containing 6.55 Ag) consisting of 90 mol% Br, and 2% sodium 2,4-dihydroxy-6-chloro-s-triazine was added as a hardener. A sample was prepared by adding 10 ml of salt and coating it on a triacetate clear base so that the coated silver amount was 600 mg/m ² .A gelatin layer was provided as a protective layer on top of this coated layer to prepare a sample. This is designated as sample 21. Next, the exemplified compound (P-8) was added to the exemplified compound (P-8).
-39), samples were prepared in the same manner.
This is designated as sample 22. Also, an exemplary coupler (M-
Replace 1) with (M-29), add 19.4 g of the exemplified compound (P-8) and 19.4 g of (p-39) to this 9.71 g, add 20 ml of ethyl acetate to each, and proceed in the same manner as above. A sample was prepared using the method. These are designated as samples 23 and 24. Furthermore, a sample was prepared in exactly the same manner as described above using the comparative coupler (A) used in Example 1 as the magenta coupler and the exemplified compound (P-8) as the high boiling point organic solvent. . This is designated as sample 25. These samples 21 to 25 were subjected to wet exposure of 200 CMS and treated with the following processing solution. 1 Color development 36.7℃ 3 minutes 00 seconds 2 Stop 27℃ 40 seconds 3 Washing with water 27℃ 40 seconds 4 First fixing 27℃ 40 seconds 5 Washing with water 27℃ 40 seconds 6 Acceleration 27℃ 40 seconds 7 Bleaching 27 °C 40 seconds 8 Water washing 27 °C 40 seconds 9 Second fixing 27 °C 40 seconds 10 Water washing 27 °C 1 minute 00 seconds 11 Stable 27 °C 10 seconds Color developer composition Sodium sulfite 4.35 g 4-amino-3-methyl- N,N-diethylaniline 2.95g Sodium carbonate 17.10g Potassium bromide 1.72g Add water 1 PH10.5 Stop solution composition Sulfuric acid (6N) 50ml Add water 1 PH1.0 First and second fixer composition Thio Ammonium sulfate 60g Sodium sulfite 2.5g Sodium bisulfite 10.3g Potassium iodide 0.5g Add water 1 PH5.8 Accelerator composition Sodium pyrosulfite 3.3g Glacial acetic acid 5.0ml PBA-1 (KODAK persulfate bleach accelerator) 3.3g EDTA・Add 4 sodium salt 0.5g water 1 PH4.0 Bleach solution composition Sodium persulfate 33.0g Sodium chloride 15.0g Sodium dihydrogen phosphate 7.0g Phosphoric acid (85%) 2.5ml Add water 1 PH2.3 Stable Liquid composition Formalin (37%) 15.0ml Add water 1 The results obtained are shown in Table 3.

[Processing process]

First development (black and white development) 38℃ 1′15″ Water washing 38℃ 1′30″ Reverse exposure 100Lux or more 1″ or more Color development 38℃ 2′15″ Water washing 38℃ 45″ Bleach fixing 38℃ 2′00″ Washing with water 38℃ 2′15″ [Processing solution composition] First developer Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt 0.6g Diethylenetriaminepentaacetic acid, pentasodium salt
4.0g Potassium sulfite 30.0g Potassium thiocyanate 1.2g Potassium carbonate 35.0g Hydroquinone monosulfonate potassium salt
25.0g diethylene glycol 15.0ml 1-phenyl 4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0g potassium bromide 0.5g potassium iodide 5.0mg Add water 1 (PH9.70) Color developer benzyl alcohol 15.0ml diethylene glycol 12.0ml 3,6-dithia-1,8-octanediol
0.2g Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt 0.5g Diethylenetriaminepentaacetic acid, pentasodium salt
2.0g Sodium sulfite 2.0g Potassium carbonate 25.0g Hydroxylamine sulfate 3.0g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate
5.0g Potassium bromide 0.5g Potassium iodide 1.0mg Add water 1 (PH10.40) Bleach-fix solution 2-mercapto-1,3,4-triazole
1.0g Ethylenediaminetetraacetic acid, disodium, dihydrate
5.0g Ethylenediaminetetraacetic acid/Fe()/ammonium hydrate 80.0g Sodium sulfite 15.0g Sodium thiosulfate (700g/liquid) 160.0ml Glacial acetic acid 5.0ml Add water 1 (PH6.50)

[Table] As can be seen from the above table, Sample 33, which used the coupler of the present invention and the high boiling point organic solvent of the present invention, exhibited excellent color density, excellent color image stability, and improved image quality. It is clear that the occurrence of damaging stains is also low. Moreover, the obtained color image showed a bright magenta color with high color saturation. Example 5 Sample 41 was then prepared by coating the first to twelfth layers on the triacetate film base in the following order. 1st layer; antihalation layer UV absorber 5-chloro-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H
-benzotriazole 15g, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole 30g, 2-(2-hydroxy-3
-sec-butyl-5-t-butylphenyl)-
35 g of 2H-benzotriazole and dodecyl 5-(N,N-diethylamino)-2-benzenesulfonyl-2,4-bentadienoate
An emulsion obtained by stirring 100 g of tricresyl phosphate, 200 ml of tricresyl phosphate, 200 ml of ethyl acetate, 20 g of sodium dodecylbenzenesulfonate, and a 10% aqueous gelatin solution at high speed (hereinafter referred to as emulsion (a))
was mixed with 10% gelatin, black colloidal silver, water, and coating aids and coated to a dry film thickness of 2μ. 2nd layer; gelatin middle layer 2,5-di-t-octylhydroquinone, dibutyl phthalate 100c.c. and ethyl acetate
An emulsion (hereinafter referred to as emulsion (b)) obtained by dissolving 100 c.c.
) 2 kg with 1.5 kg of 10% gelatin,
It was applied to a dry film thickness of 1μ. 3rd layer; low-sensitivity red-sensitive emulsion layer cyan coupler 2-(heptafluorobutyramide)-5-{2′-(2″,4″-di-t-
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% gelatin aqueous solution (hereinafter referred to as emulsion) c)), 1 kg of red-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin,
The iodine content is 4 mol%) and the dry film thickness is
It was applied to a thickness of 1μ. (Amount of silver: 0.5 g/m ² ) 4th layer: Highly sensitive red-sensitive emulsion layer Emulsion (c) is mixed with 1 kg of red-sensitive silver iodobromide emulsion (silver 70
(60 g of gelatin, iodine content: 2.5 mol%) and coated to a dry film thickness of 2.5 μm. (Silver amount: 0.8 g/m ² ) Fifth layer: Intermediate layer 1 kg of emulsion (b) was mixed with 1 kg of 10% gelatin and coated to a dry film thickness of 1 μm. 6th layer: low-sensitivity green-sensitivity emulsion layer, magenta coupler instead of cyan coupler 300 g of an emulsion obtained in the same manner as the emulsion of the third layer (hereinafter referred to as emulsion (d)) except that di-2-ethylhexyl phthalate was used.
Green-sensitive silver iodobromide emulsion 1 kg (70 g silver, gelatin)
(60 g, iodine content: 3 mol %) and coated to a dry film thickness of 2.0 μm. (Amount of silver: 0.7 g/m ² ) 7th layer: Highly sensitive green-sensitive emulsion layer 1000 g of emulsion (d) was mixed with green-sensitive silver iodobromide emulsion 1.
Kg (containing 70 g of silver, 60 g of gelatin, and iodine content of 2.5 mol%) was mixed and coated to a dry film thickness of 2.0 μm. (Amount of silver: 0.7 g/m ² ) 8th layer: Gelatin intermediate layer Mix 1 kg of emulsion (b) with 1 kg of 10% gelatin,
It was applied to a dry film thickness of 0.5μ. 9th layer; Yellow filter layer: An emulsion containing yellow colloidal silver is coated with a dry film thickness of 1 μm.
It was applied so that 10th layer; low-sensitivity blue-sensitivity emulsion layer α-(pivaloyl)-α-(1-benzyl-5-ethoxy-3-hydantoinyl)-2- which is a yellow coupler instead of cyan coupler
An emulsion (hereinafter referred to as emulsion (e)) obtained in the same manner as the third layer emulsion except that chloro-5-dodecyloxycarbonylacetanilide was used.
1000g of blue-sensitive silver iodobromide emulsion (1kg of silver 70
(60 g of gelatin, iodine content: 2.5 mol%) and coated to a dry film thickness of 1.5 μm. (Amount of silver 0.6 g/m ² ) 11th layer; Highly sensitive blue-sensitive emulsion layer 1000 g of emulsion (e) was mixed with blue-sensitive silver iodobromide emulsion 1.
Kg (containing 70 g of silver, 60 g of gelatin, and iodine content of 2.5 mol%) was mixed and applied to a dry film thickness of 3 μm. (Amount of silver: 1.1 g/m ² ) 12th layer; 2nd protective layer Emulsion (a) was mixed with 10% gelatin, water, and a coating aid, and coated to a dry film thickness of 2 μm. 13th layer; 1st protective layer Fine-grain emulsion with a covered surface (grain size
A 10% gelatin aqueous solution containing 0.06μ, 1 mol% silver iodobromide emulsion) was applied at a silver coating amount of 0.1 g/m ² and a dry film thickness.
It was applied to a thickness of 0.8μ. Each layer contains a gelatin hardening agent of 1,4-
Bis(vinylsulfonylacetamido)ethane and surfactant were added. Next, the magenta coupler of the present invention (M-28)
Sample 42 was prepared in the same manner as Sample 41, except that the following was used for the sixth layer with low green sensitivity and the seventh layer with high green sensitivity. 6th layer; low green sensitivity layer An emulsion obtained in the same manner as the emulsion for the third layer (hereinafter referred to as emulsion (f)) was emulsified except that the magenta coupler (M-28) of the present invention was used. It was mixed with 500 g of a silver iodobromide emulsion (containing 35 g of silver and 30 g of gelatin, and the iodine content was 3 mol %) for the green-sensitive layer in an amount equal to the mole of substance (d), and coated to give a dry film thickness of 2.0 μm.
(Amount of silver: 0.35 g/m ² ) 7th layer: Highly green-sensitive layer Emulsion (d) and emulsion (f) in equimolar amounts were mixed into a green-sensitive silver iodobromide emulsion (500 g) (containing 35 g of silver and 30 g of gelatin). ,
Iodine content is 2.5 mol%) and dry film thickness
It was applied to a thickness of 2.0μ. (Amount of silver: 0.35 g/m ² ) Next, the same process as the emulsion of the third layer was carried out except that the magenta coupler (M-28) of the present invention and the high boiling point organic solvent (P-8) of the present invention were used. A sample was prepared in which the obtained emulsion (hereinafter referred to as emulsion (g)) was used in place of emulsion (f) of sample 42, and designated as sample 43. These samples 41 to 43 were subjected to wedge exposure according to the conventional method and then subjected to the following development treatment.The results are shown below.
5. Concentration measurement was performed using Fuji FSD-103. Processing process Time Temperature First development 6 minutes 38℃ Water washing 2 minutes Inversion 2 minutes Color development 6 minutes Adjustment 2 minutes Bleaching 6 minutes Fixing 4 minutes Water washing 4 minutes Stability 1 Dry at room temperature. The composition of the treatment solution used is as follows. First developer water 700ml Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone 2g Potassium silver bromide 2.5g Potassium thiocyanate 1.2g Potassium silver iodide (0.1% solution) 2ml Add water to 1000ml Reverse liquid water 700ml Nitrilo-N,N,N-trimethylenephosphonic acid・Pentasodium salt 3g Stannous chloride (dihydrate) 1g p-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Add water 1000ml Color developer water 700ml Nitrilo-N,N,N-trimethylenephosphonic acid・Pentasodium salt 3g Sodium sulfite 7g Sodium phosphate (12 hydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazine acid 1.5g N-ethyl-N-(β-methane) Sulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11g 3,6-dithiaoctane-1,8-diol 1g Add water to 1000ml Adjustment water 700ml Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) )
8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water to 1000ml Bleach solution water 800g Sodium ethylenediaminetetraacetate (dihydrate)
2g Ethylenediaminetetraacetate iron () ammonium (dihydrate) 120g Potassium bromide 100g Add water 1000ml Fixer water 800ml Sodium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water 1000ml Stable solution water 800ml Formalin (37% by weight) 5.0ml Fuji Drywell (surfactant manufactured by Fujifilm Corporation) 5.0ml Add water to 1000ml

【table】

〔Effect of the invention〕

As described above, according to the present invention, color density, color image fastness, and color reproducibility are improved, the amount of silver can be reduced, and a silver halide color photographic material with less staining can be obtained. .

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer provided on a support, wherein the silver halide emulsion layer contains a compound having the following general formula []. 1. A silver halide color photographic light-sensitive material, characterized in that at least one magenta coupler represented by the following formula is co-dispersed with at least one high-boiling point organic solvent represented by the following general formula []. General formula [] [In the formula, R ₁ and R ₂ 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 amine developer. R ₁ , R ₂ or X may form a dimer or more multimer. Here, R ₁
and at least one of R ₂ represents a group bonded to the pyrazoloazole ring via a secondary or tertiary carbon atom, and furthermore, at least one of R ₁ and R ₂ has one -NHSO ₂ - group. It is a group having the above. However, when R ₁ is a tertiary alkyl group, or when R ₂ is bonded to the pyrazolotriazole ring through a secondary carbon atom, R ₂ is not a substituted aralkyl group. ] General formula [ ] [In the formula, R ₃ , R ₄ and R ₅ each represent an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group.
However, the total number of carbon atoms in the groups represented by R ₃ , R ₄ and R ₅ is 12 to 60. Here, R ₃ ,
R ₄ and R ₅ are never both tolyl groups. ]