JPH0549211B2 - - 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 that can be rapidly developed, has improved processing stability, has high sensitivity, and can save silver. In general, silver halide color photographic light-sensitive materials have three types of photographic silver halide emulsion layers selectively sensitized to have sensitivity to blue light, green light, and red light, coated on a support. ing. For example, in silver halide photographic optical materials for color negatives, generally a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are coated in this order from the exposed side. A bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer to absorb the blue light that passes through the blue-sensitive silver halide emulsion layer. is provided. Furthermore, each emulsion layer is provided with other intermediate layers and a protective layer as the outermost layer for various special purposes. Furthermore, for example, in a silver halide photographic light-sensitive material for color photographic paper, generally from the side to be exposed, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are formed. Similar to silver halide photographic materials for color negatives, interlayers including an ultraviolet absorbing layer, protective layers, etc. are provided for special purposes. It is also known that each of these silver halide emulsion layers is provided in a different arrangement from the above, and each silver halide emulsion layer has substantially the same wavelength or photosensitivity to each color light. It is also known to use a photosensitive silver halide emulsion layer consisting of two layers. In these silver halide color photographic light-sensitive materials, for example, aromatic monomers are used as color developing agents.
The exposed silver halide grains are developed using a grade amine color developing agent, and a dye image is formed by the reaction between the oxidation product of the color developing agent and the dye-forming coupler. In this method,
Typically, phenolic or naphthol based cyan couplers, 5-prazolone based, pyrazolinobenzimidazole based, pyrazolotriazole based, indazolone based or cyanoacetyl based magenta couplers and An acylacetamide or benzoylmethane yellow coupler is used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developer. The present invention relates to a silver halide color photographic light-sensitive material in which these couplers are preliminarily contained in the photographic constituent layers and rendered non-diffusive.

[Prior Art] In recent years, those skilled in the art have desired silver halide color photographic materials that can be processed quickly, have high image quality, high sensitivity, excellent processing stability, and are low cost. In particular, silver halide color photographic materials that can be rapidly processed are desired. In other words, silver halide color photographic light-sensitive materials are subjected to running processing in automatic processing machines installed in each laboratory, but as part of an effort to improve service to users, processing is carried out on the same day that the development is received. In recent years, there has been a demand for the product to be returned to the user within a few hours of receipt, and the development of silver halide color photographic materials that can be processed even more quickly is becoming increasingly urgent. ing. Additionally, in running processing, there is a problem in that photographic properties vary greatly between laboratories or even within the same laboratory due to changes in the composition of the processing solution and fluctuations in conditions, making it impossible to obtain stable photographic performance. . These changes in the composition of the processing solution and fluctuations in conditions are caused by the elution and elution of photographically active substances from the light-sensitive material during the development process (running).
This is thought to be due to accumulation or other causes. Therefore, in order to respond to variations in processing conditions, it is necessary to highly control the development time, the temperature and pH of the developer, and the halogen concentration, especially the bromine ion concentration, in the developer. However, it is difficult to highly control these conditions in distributed processing, particularly in small-scale minilabs, which have become popular in recent years. Therefore, it is particularly necessary to develop a silver halide color photographic light-sensitive material whose photographic performance is less dependent on processing conditions and whose processing is highly stabilized. Processing stability is a problem even with current processing times, but processing stability becomes more of a problem in rapid processing. Furthermore, it is required that such process-stabilized silver halide color photographic materials be provided economically at low cost. Therefore, regarding silver halide color photographic light-sensitive materials that can be rapidly processed, conventional techniques include, for example, silver halide fine graining technology described in JP-A-51-77223, JP-A-58-184142, Technology for reducing the silver bromide of silver halide as described in Japanese Patent Publication No. 56-418939 Cyan coloring can be achieved by reducing the amount of silver in silver halide emulsion layers other than the cyan coloring layer as described in JP-A-56-165145. Technology to improve color development by leucoization of layers, and use of color development accelerators when developing exposed silver halide color photographic materials using aromatic primary amine color developing agents. The technique is also known. For example, such color development accelerators include U.S. Pat.
No. 2496903, No. 4038075, No. 4119462, British Patent No. 1430998, British Patent No. 1455413, Japanese Patent Application Publication No. 15831/1983,
No. 55-62450, No. 55-62451, No. 55-62452,
No. 55-62453, No. 51-12422, No. 55-62453,
There are compounds described in Japanese Patent Publication No. 51-12422, Japanese Patent Publication No. 55-49728, etc. However, when using these conventional techniques, processing time is shortened, but processing stability is poor.
Additionally, there are problems with fogging and storage stability in same-day performance. When the low silver bromide emulsion described above is used, fewer bromide ions are eluted into the processing solution from the silver halide color photographic light-sensitive material containing the low silver bromide emulsion, and the concentration of bromide ions in the processing solution is set low. However, when a silver halide color photographic material containing a low silver bromide emulsion is processed using a processing solution with a low bromine ion concentration, processing stability is poor. Processing stability here refers to the degree of variation in sensitometry with respect to variations in processing solution composition, pH, temperature, bromide ion concentration, etc., and to contamination of other compounds other than the processing solution composition. Furthermore, when the above-mentioned fine grain silver halide is used, it has the disadvantage of poor processing stability;
Another drawback is that the finer the particles, the lower the sensitivity. On the other hand, when using this method, the yellow and magenta color-forming layers have a drawback that the color-forming properties are not sufficient.

[Object of the present invention]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic material which can be rapidly processed and has improved processing stability. Another object of the present invention is to provide a silver halide color photographic material that provides high sensitivity and high image quality. Still another object of the present invention is to provide a silver halide color photographic material that can save silver.

[Structure of the invention]

The present inventors have conducted various studies on the average grain size of silver halide, the silver halide composition, and the amount of silver in the silver halide emulsion layer. I couldn't find anyone. However, as a result of further intensive research by the present inventors, the object of the present invention is to provide a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. In a silver halide color photographic light-sensitive material having an emulsion layer, the average grain size of silver halide in the blue-sensitive silver halide emulsion layer is 0.8 μm or less, and the odor of silver halide in the blue-sensitive silver halide emulsion layer is The silver halide content is 50 to 75 mol%, the silver bromide content of silver halide in the green-sensitive silver halide emulsion layer is 30 to 60 mol%, and the silver bromide content in the silver halide emulsion layer is 30 to 60 mol%. The total amount of silver in the silver emulsion layer is 0.55 g/m ² or less, and at least one yellow coupler represented by the following general formula (1) and at least one magenta coupler represented by the following general formula (2) It has been found that the present invention can be achieved by a silver halide color photographic light-sensitive material containing one type of silver halide. General formula (1) In the formula, Coup represents a yellow dye-forming coupler residue from which one hydrogen atom at the coupling position has been removed, and X represents a group of nonmetallic atoms necessary to complete the benzene nucleus or naphthalene nucleus. R is a hydrogen atom, a halogen atom, a nitro atom, a cyano atom, a carboxyl group, or an alkyl group that may each have a substituent, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, alkylcarbonyl group,
Arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, alkylcarbamonylamino group, arylcarbonylamino group, sulfonamide tree, alkyl Sulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, amino group, alkylsulfinyl group, arylsulfinyl group, phosphinyl group,
N-acylcarboimidoyl group, N-alkylcarboimidoyl group, N-arylcarboimidoyl group, heterocyclic group, ureido group, alkylcarbonyloxy group or arylcarbonyloxy group, or represented by the following general formula (3) represents a group, n
represents an integer from 0 to 4, and when n is 2 or more, each R
may be the same or different. General formula (3) In the formula, R ₁ is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, each of which may have a substituent. , alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonamide group, arylsulfonamide group,
Alkylsulfamoyl group, arylsulfamoyl group, alkylcarbonylamino group, arylcarbonylamino group, amino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbonyl group or arylcarbonyl group represent. X ₁ represents a divalent organic linking group, l represents 0 or 1, m represents 0, 1, 2, 3 or 4, m is 2
In the above case, each R ₁ may be the same or different. General formula [2] In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X' represents a hydrogen atom or a substituent that can be eliminated by reaction with an oxidized product of a color developing agent. Further, R' represents a hydrogen atom or a substituent. That is, the present invention specifies the average grain size of silver halide in the blue-sensitive silver halide emulsion layer described above, as well as the silver halide composition and silver amount of a specific silver halide emulsion layer, and further specifies the silver halide composition and silver amount of a specific yellow It has been discovered that the above objects of the present invention can be achieved when a coupler and a magenta coupler are used. With such a configuration, it is possible to achieve both rapid processing performance and processing stability, and furthermore, high sensitivity and high It was surprising that the image quality could be achieved, which could not have been expected from conventional techniques and their combinations. The present invention will be explained in detail below. The above general formula [1] will be explained. The halogen atom represented by R includes, for example, a chlorine atom, a fluorine atom, etc., and the alkyl group includes, for example, a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, a sec-butyl group, and a tert-butyl group. group, pentyl group, octyl group, dodecyl group,
Cycloalkyl groups such as octadecyl group include cyclopentyl group, cyclohexyl group, and norbornyl group; alkenyl groups include allyl group; aralkyl groups include benzyl group and β-phenylethyl group; and aryl groups include phenyl group. , naphthyl group, etc.; examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, iso-propoxy group, butoxy group,
tert-butoxy group, hexyloxy group, octyloxy group, dodecyloxy group, hexadecyloxy group, etc.; aryloxy groups include phenoxy group, tolyloxy group, etc.; alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, etc. , tert-butoxycarbonyl group, dodecyloxycarbonyl group, 2-ethoxyethyloxycarbonyl group, 1-dodecyloxycarbonyl ethoxycarbonyl group, 1-(2,4
-di-tert-amylphenoxycarbonyl)ethoxycarbonyl group, etc., the aryloxycarbonyl group includes, for example, a phenoxycarbonyl group,
m-dodecyloxyphenoxycarbonyl group, p
-dodecyloxyphenoxycarbonyl group, p-
tert-octylphenoxycarbonyl group, 2,4
-di-tert-amylphenoxycarbonyl group, m
- lauroylamide phenoxycarbonyl group, etc.
Examples of the alkylcarbonylamino group include an acetamide group, a pivaloylamide group, a lauroylamide group, an α-(2,4-di-tert-amylphenoxy)butanamide group, and a γ-(2,4-di-tert-amylphenoxy)butanamide group.
-amylphenoxy)butanamide group, α-(m
-dodecyloxyphenoxy)butanamide group,
Examples of the arylcarbonylamino group include α-(m-butanesulfonamidophenoxy)tetradecanamide group, α-(p-dimethylaminosulfonamidophenoxy)tetradecanamide group, etc. Benzamide group, m-dodecylbenzenesulfonamide benzamide group, 3-chloro-4-dodecyloxybenzamide group, m-(2,4-di-tert-aminophenoxy)carbonylbenzamide group, p
-Hexadecyloxycarbonylbenzamide group, alkylsulfonamide group, such as methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group, octanesulfonamide group, dodecanesulfonamide group, hexadecanesulfonamide group, ethoxyethanesulfonamide group γ-(2,4-di-tert-amylphenoxy)propanesulfonamide group, etc.; examples of the arylsulfonamide group include benzenesulfonamide group, m-chlorobenzenesulfonamide group, m-butoxybenzenesulfonamide group,
p-lauroylamide benzenesulfonamide group, p-dodecylbenzenesulfonamide group, p
-dodecyloxybenzenesulfonamide group, etc.
Examples of alkylcarbonyl groups include acetyl group, ethylcarbonyl group, t-butylcarbonyl group, and dodecylcarbonyl group; examples of arylcarbonyl groups include benzoyl group, tolyl group,
Examples of the alkylcarbamoyl group and arylcarbamoyl group such as naphthoyl group include ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl, and N-phenylcarbamoyl group; examples of the alkylsulfamoyl group and arylsulfamoyl group include naphthoyl group, etc.; For example, N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N
-alkyl-N-arylsulfamoyl group,
N,N-diarylsulfamoyl group, etc.; examples of alkylsulfonyl groups include methylsulfonyl group, ethylsulfonyl group, t-butylsulfonyl group, and dodecylsulfonyl group; examples of arylsulfonyl groups include phenylsulfonyl group, p-
benzyloxyphenylsulfonyl group, etc.; examples of alkylsulfinyl groups include methylsulfinyl group, ethylsulfinyl group, t-butylsulfinyl group, dodecylsulfinyl group; examples of arylsulfinyl group include Examples of the phosphinyl group include phenylsulfenyl group, p-benzyloxyphenylsulfinyl group, p-tolylsulfenyl group, etc.

A group represented by [Formula] (where R' is an alkyl group, an alkoxy group,
Represents an aryl group or an aryloxy group. )N
-As the acylcarboimidoyl group, for example, N-
N-alkyl or N-arylcarboimidoyl groups such as acetocarboimidoyl group, N-bivaloylcarboimidoyl group, N-benzoylcarboimidoyl group, etc. include N-methylcarboimidoyl group, N-ethylcarboimidoyl group, etc. imidoyl group,
Examples of heterocyclic groups such as N-phenylcarboimidoyl groups include 5- or 6-membered heterocyclic groups containing nitrogen, oxygen, and sulfur atoms as heteroatoms, fused heterocyclic groups, and pyridyl and quinolyl groups. ,
furyl group, benzothiazolyl group, oxazolyl group, imidazolyl group, naphthoxazolyl group, etc.
Examples of amino groups include alkylamino groups (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), arylamino groups (e.g. phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group, 2
-chloro-5-tetradecanamide anilino group, etc.), cycloamino group (e.g. piperidino group, pyrrolidino group, etc.), heterocyclic amino group (e.g. 4-
pyridylamino group, 2-benzoxazolylamino group, etc.), ureido groups such as methylureido group, phenylureido group, tolylureido group, etc., and alkylcarbonyloxy groups such as acetoxy group, ethylcarbonyloxy group, t-
Examples of the arylcarbonyloxy group include a butylcarbonyloxy group, a dodecylcarbonyloxy group, and a benzoyloxy group, a tolyloxy group, a naphthylcarbonyloxy group, and the like. Examples of substituents that the alkyl group or arylcarbonyloxy group represented by R may have include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, Aryl group, alkoxy group, aryloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocycle group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N
-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxyl group, mercapto group, etc., and the substituent may have one or more. In the general formula [3], 2 represented by X ₁
Examples of valent organic linking groups include alkylene groups, -
O- group,

[Formula] group,

[Formula] group,

[Formula] group,

[Formula] group,

[Formula] Group -,

[Formula] group,

[Formula] group,

[Formula] Groups, etc. may be mentioned. Examples of the halogen atom for R ₁ include a chlorine atom,
Examples of alkyl groups such as fluorine atoms include methyl group, ethyl group, propyl group, iso-propyl group,
Butyl group, sec-butyl group, tert-butyl group, pentyl group, octyl group, dodecyl group, octadodecyl group, etc.; cycloalkyl groups include cyclopentyl group, cyclohexyl group, norbornyl group; examples of aralkyl groups include benzyl group. ,
β-phenylethyl group, etc., aryl groups such as phenylnaphthyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group, iso-propoxy group, butoxy group, tert-butoxy group, hexyloxy group, octyloxy group , dodecyloxy group, hexadecyloxy group, etc.; examples of aryloxy groups include phenoxy group, tolyloxy group, etc.; examples of alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, dodecyloxycarbonyl group , 2-ethoxyethyloxycarbonyl group, 1-dodecyloxycarbonylethoxycarbonyl group, 1-(2,4
-di-tert-amylphenoxycarbonyl)ethoxycarbonyl group, etc., the aryloxycarbonyl group includes, for example, a phenoxycarbonyl group,
m-dodecyloxyphenoxycarbonyl group, p
-dodecyloxyphenoxycarbonyl group, p-
tert-octylphenoxycarbonyl group, 2,4
-di-tert-amylphenoxycarbonyl group, m
- lauroylamide phenoxycarbonyl group, etc.
Examples of the alkylcarbonylamino group include an acetamido group, a piparoylamide group, a lauroylamide group, an α-(2,4-di-tert-amylphenoxy)butanamide group, and a γ-(2,4-di-tert-amylphenoxy)butanamide group.
-amylphenoxy)butanamide group, α-(m
-dodecyloxyphenoxy)butanamide group,
α-(m-butanesulfonamidophenoxy)tetradecanamide group, α-(p-dimethylaminosulfonamidophenoxy)tetradecanamide group, etc. Arylcarbonylamino includes, for example, benzamide group, m-dodecyloxybenzamide group, m-dodecylbenzenesulfonamide benzamide group, 3-chloro-4-dodecyloxybenzamide group, m-(2,4-di-tert-amylphenoxy)carbonylbenzamide group, p-hexadecyloxycarbonylbenzamide group Ki et al.
Examples of the alkylsulfonamide group include methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group, octanesulfonamide group, dodecanesulfonamide group, hexadecanesulfonamide group, ethoxyethanesulfonamide group, γ-(2,4- di-tert-amylphenoxy)
Arylsulfonamide groups such as propanesulfonamide groups include, for example, benzenesulfonamide groups, m-chlorobenzenesulfonamide groups, p-
-butoxybenzenesulfonamide group, m-lauroylamide benzenesulfonamide group, p-dodecylbenzenesulfonamide group, p-dodecyloxybenzenesulfonamide group, etc. Examples of alkylcarbonyl groups include acetyl group, ethylcarbonyl group, t-butyl Carbonyl group, dodecylcarbonyl group, etc.; examples of arylcarbonyl group include benzoyl group, tolyl group, naphthoy group, etc.; examples of alkylcarbamoyl group and arylcarbamoyl group include ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl group, Examples of the alkylsulfamoyl group and arylsulfamoyl group such as N-phenylcarbamoyl group include N-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, and N-alkyl group. -N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.; examples of alkylsulfonyl groups include methylsulfonyl group, ethylsulfonyl group, t-butylsulfonyl group, dodecylsulfonyl group, etc.; For example, phenylsulfonyl group, p-benzyloxyphenylsulfonyl group, etc. Amino groups include, for example, alkylamino groups (e.g. n-butylamino, methylamino group, cyclohexylamino, etc.), arylamino groups (e.g. phenylamino, N -methylanilino, diphenylamino, N
-acetylanilino, 2-chloro-5-tetradecanamideanilino, etc.), cycloamino groups (e.g. piperidino, pyrrolidino, etc.), heterocyclic amino groups (e.g. 4-pyridylamino, 2-benzoxolyl amino, etc.), etc. be able to. Examples of substituents that the alkyl group or arylcarbonyl group represented by R ₁ may have include an alkyl group, an alkenyl group, a cyclic alkyl group,
Aralkyl group, cyclic alkenyl group, halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, Diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N
-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxyl group, mercapto group, etc., and may have one or more of these substituents. In general formula [1], more preferable R is a cyano group, a nitro group, a carboxyl group, a halogen atom, (for example, a chlorine atom, a fluorine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an iso group, etc.). -propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, octyl group,
dodecyl group, octadecyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, propoxy group, iso-propoxy group, butoxy group, tert-butoxy group, hexyloxy group, octyloxy group, dodecyloxy group, hexadecyloxy group) groups), alkoxycarbonyl groups (e.g., methoxycarbonyl groups, ethoxycarbonyl groups, tert-
butoxycarbonyl group, dodecyloxycarbonyl group, 2-ethoxyethyloxycarbonyl group,
1-dodecyloxycarbonyl ethoxycarbonyl group, 1-(2,4,-di-tert-aminophenoxycarbonyl)ethoxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, m-dodecyloxy Phenoxycarbonyl group, p-dodecyloxyphenoxycarbonyl group, p-tert-octylphenoxycarbonyl group, 2,4-di-tert-amylphenoxycarbonyl group, m-lauroylamide phenoxycarbonyl group groups), alkylcarbonylamino groups {e.g. acetamido group, pivaloylamide group, lauroylamide group, α-(2,4-di-tert-amylphenoxy)butanamide group, γ-(2,4-
di-tert-amylphenoxy)butanamide group,
α-(m-dodecyloxyphenoxy)butanamide group, α-(m-butanesulfonamidophenoxy)tetradecanamide group, α-(p-dimethylaminosulfonamidophenoxy)tetradecanamide group}, arylcarbonyl Amino group {e.g. benzamide group, m-dodecyloxybenzamide group, m-dodecylbenzenesulfonamidobenzamide group, 3-chloro-4-dodecyloxybenzamide group, m-(2,4-di-tert- amylphenoxy) carbonylbenzamide group, p
-hexadecyloxycarbonylbenzamide group, etc.}, alkylsulfonamide group {e.g., methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group, octanesulfonamide group, dodecanesulfonamide group, hexadecanesulfonamide group, ethoxyethanesulfone group Amido group, γ-(2,4-di-tert-amylphenoxy)
propanesulfonamide group, etc.}, arylsulfonamide group (e.g., benzenesulfonamide group, m-chlorobenzenesulfonamide group, p-
Butoxybenzenesulfonamide group, m-lauroylamide benzenesulfonamide group, p-dodecylbenzenesulfonamide group, p-dodecyloxybenzenesulfonamide group, etc., alkylcarbonyl groups (e.g. acetyl group, ethylcarbonyl group, t-butylcarbonyl group, dodecylcarbonyl group, etc.), arylcarbonyl group (e.g., benzoyl group, toluyl group, naphthoy group, etc.), carbamoyl group (e.g., ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl group, N-phenylcarbamoyl group, etc.) ), sulfamoyl groups (e.g. N-alkylsulfamoyl, N,N-dialkylsulfamoyl groups, N-
Arylsulfamoyl group, N-alkyl-N-
arylsulfonyl group, N,N-diarylsulfamoyl group, etc.), alkylsulfonyl group (e.g. methylsulfonyl group, ethylsulfonyl group, t-butylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (e.g. phenyl sulfonyl group, p-benzyloxyphenylsulfonyl group, etc.),

【formula】

【formula】

【formula】

【formula】 【formula】

【formula】

【formula】

【Formula】Also teeth

[Formula]. In the above formula, _R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₃ is a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, propyl group, iso-propyl group,
butyl group, sec-butyl group, tert-butyl group, pentyl group, octyl group, dodecyl group, octadecyl group, etc.), cycloalkyl group (e.g. cyclopentyl group, cyclohexyl group, norbornyl group, etc.),
Alternatively, it represents an aryl group (eg, phenyl group, naphthyl group, etc.). R ₄ and R ₅ are each a hydrogen atom (e.g., methyl group, ethyl group, propyl group, iso-propyl group,
butyl group, sec-butyl group, tert-butyl group, pentyl group, octyl group, dodecyl group, octadecyl group, etc.), cycloalkyl group (e.g. cyclopentyl group, cyclohexyl group, norbornyl group, etc.), alkenyl group (e.g. allyl group, etc.) ), an aralkyl group (eg, benzyl, β-phenylethyl group, etc.), or an aryl group (eg, phenylnaphthyl group, etc.), and R ₄ and R ₅ may form a 5- or 6-membered ring. R ₆ is an alkyl group (e.g. methyl group, ethyl group, propyl group, iso-propyl group, butyl group,
sec-butyl group, tert-butyl group, pentyl group,
octyl group, dodecyl group, octadecyl group, etc.),
Cycloalkyl groups (e.g. cyclobentyl group, cyclohexyl group, norbornyl group, etc.), aryl groups (e.g. phenylnaphthyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, propoxy group, iso-propoxy group, butoxy group, tert
-butoxy group, hexyloxy group, octyloxy group, dodecyloxy group, hexadecyloxy group, etc.) or an aryloxy group (eg, phenoxy group, tolyloxy group, etc.). In general formula [1], examples of the yellow coupler residue of Coup include pivaloylacetanilide type,
Benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type,
Benzothiazolylacetamide type, malone ester monoamide type, benzothiazolylacetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, benzimidazolylacetamide type or benziminodazolylacetate type coupler residue, USA Coupler residues derived from heterocycle-substituted acetamides or heterocycle-substituted acetates included in Patent No. 3841880, or U.S. Patent No. 3770446, British Patent No. 1459171, West German Patent (OLS) No. 2503099, JP-A-50-139738, or Research Disk Examples include coupler residues derived from acylacetamides described in Rosier No. 15737 and heterocyclic coupler residues described in US Pat. No. 4,046,574. Further, in the present invention, Coup in the general formula [1] is preferably a coupler residue represented by the following general formula [4] or [5]. General formula [4] General formula [5] In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group. In the above formula, if R ₇ , R ₈ or R ₉ contain a diffusion-resistant group, it is selected such that the total number of carbon atoms is 8 to 32, preferably 10 to 22; The total number is preferably 15 or less. Next, R ₇ to _{R 9} in the general formulas [4] and [5]
I will explain about it. R ₇ represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R ₈ and R ₉ each represent an aromatic group or a heterocyclic group. The aliphatic group represented by R ₇ preferably has 1 carbon number
~22, and may be substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group are an alkoxy group, an aryloxy group,
Amino groups, acylamino groups, halogen atoms, etc. may themselves have further substituents.
Specific examples of aliphatic groups useful as _R7 are: isopropyl, isobutyl, tert-butyl, isoamyl, tert-amyl, 1,1-dimethylbutyl, 1,1-dimethylhexyl group, 1,1-diethylhexyl group,
dodecyl group, hexadecyl group, octadecyl group,
Cyclohexyl group, 2-methoxyisopropyl group, 2-phenoxyisopropyl group, 2-p-
tert-butylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinimide)isopropyl group, α-(phthalimido)isopropyl group,
α-(benzenesulfonamido)isopropyl group, etc. R ₇ , R ₈ or R ₉ is an aromatic group (especially phenyl group)
In this case, the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups. , an alkyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. It may be substituted with a phenyl group, an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group of these substituents The moieties may be further substituted with one or more alkyl groups having a total of 1 to 22 carbon atoms. The phenyl group represented by R ₇ , R ₈ or R ₉ further includes an amino group, including one substituted with a lower alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group, a cyano group, It may be substituted with a thiocyano group or a halogen atom. Furthermore, R ₇ , R ₈ or R ₉ may represent a substituent in which a phenyl group is bonded to another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, and the like.
These substituents themselves may have further substituents. When R ₇ represents an alkoxy group, the alkyl portion has 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.
represents a straight-chain or branched-chain alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group, which may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like. When R ₇ , R ₈ or R ₉ represents a heterocyclic group,
Each heterocyclic group is bonded to the carbon number of the carbonyl group of the acyl group in alpha acylacetamide or the nitrogen atom of the amide group via one of the carbon atoms forming the ring. Examples of such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine. These may further have a substituent on the ring. Representative couplers that can be used in the present invention are described below. :

【table】

【table】

【table】

【table】

【table】

【table】
\

_CH3

【table】

【table】

【table】

【table】 The coupler represented by the general formula [1] can be synthesized by combining known methods. Synthesis of an acylacetamide type coupler having an aryloxy group as a leaving group is carried out by halogenating the coupling position of a four-equivalent coupler and reacting it with a phenolic compound in the presence of a base. Synthesis methods for these two-equivalent couplers are described in the following known documents. U.S. Patent No. 3894875, U.S. Patent No. 3933501
No. 4296199, No. 3277554, No. 3476563,
Same No. 4296200, No. 4234678, No. 4228233, Same No.
No. 4351897, No. 4264723, No. 4366237, No.
3408194, Japanese Patent Publication No. 57-70871, Japanese Patent Publication No. 57-
These include No. 96343 and No. 53-52423. Generally speaking, it is advantageous to synthesize the coupler core and then introduce a leaving group, but it is also advantageous to first synthesize the two-equivalent coupling group of the coupler and generate an active group such as an amino group by reduction. A method of later introducing a diffusion-resistant group can also be used. Next, a typical synthesis example of the coupler of the present invention will be specifically shown. Synthesis Example (1) Synthesis of Exemplary Coupler 27 α-chloro-α-pivaloyl-2-chloro-5
-(n-hexadecanesulfonamide)acetanilide 41.4g, 4-acetylamino-2-cyanophenol 12.8g dimethylacetamide 150ml
and dissolved in 100 ml of acetonitrile under reflux. 11.7 ml of triethylamine was added dropwise over 30 minutes, followed by reaction under reflux for 1 hour. After cooling, the reaction mixture was poured into ice water (containing 10 ml of concentrated acid). Ethyl acetate 200% of oil
ml, washed twice with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 50 g of residue. This residue was subjected to silica gel chromatography,
The product-containing portion was concentrated under reduced pressure, and the residue was
Crystallization from hexane/isopropanol gave 28 g of exemplified coupler 27. (Melting point 85-93°C) Synthesis example (2) Synthesis of exemplary coupler 37 α-chloro-α-pivaloyl-2-chloro-5
-(n-dodecyloxycarbonyl)acetanilide 35g, 2-chloro-4-ethylsulfamoylphenol 17.3g dimethylacetamide 200g
ml and 100 ml of acetonitrile were dissolved under reflux. 10.7 ml of triethylamine was added dropwise to this mixture, followed by a reflux reaction for 2 hours. After cooling, the reaction mixture was poured into ice water (containing approximately 10 ml of concentrated hydrochloric acid) and the oily substance ethyl acetate was dissolved.
Extracted with 200ml. The ethyl acetate layer was washed twice with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 46 g of residue. This residue was subjected to silica gel chromatography, the product-containing portion was concentrated under reduced pressure, and the residue was crystallized from n-hexane/ethanol to obtain 32 g of Exemplary Coupler 37. (Melting point 82-89°C) Synthesis example (3) Synthesis of exemplary coupler 12 18.2g (0.03mol) of a and 5.1g (0.03mol)
b , i.e., 7.0 g (0.06
mol) of tetramethylguanidine (TMG) was added. The reaction mixture was stirred at 20°C for 15 hours. The precipitated salts were collected, washed with cold ethyl acetate, and then methanol was added to 200ml. This solution was gradually poured into an ice water/hydrochloric acid mixture to decompose the salt, thus obtaining a coupler.
10.0g (45%) recrystallized from ethyl acetate
A white solid product was obtained, melting point 177-181°C. Synthesis Example (4) Synthesis of Exemplary Coupler 24 To a solution of 19.5 g (0.033 mol) a and 6.7 g (0.064 mol) triethylamine in 150 ml acetonitrile, while stirring, 8.1 g
(0.033 mol) of b , methyl-3-methanesulfonamide-4-hydroxybenzoate, was added. The mixture was heated on a steam bath with stirring for 3 hours. After cooling, the mixture was poured into ice water (containing 5 ml of concentrated hydrochloric acid). The gummy solid was collected, triturated with water, and dried. The crude product was chromatographed through a silica gel column (eluting with dichloromethane). Fractions containing pure product were collected and the solvent was removed under reduced pressure. A white residue was obtained. Recrystallization from isopropyl alcohol yielded 16 g (61%) white solid, mp 96-97.
℃ was obtained. Synthesis Example (5) Synthesis of Exemplary Coupler 52 α-chloro-α-pivaloyl-2-chloro-5
44 g of -(n-hexadecanesulfonamide)acetanilide and 112 g of 3,3'-dichloro-4,4'-dihydroxydiphenylsulfone were dissolved in 240 ml of dimethylacetamide and 210 ml of acetonitrile under reflux. Slowly drop 9.7ml of triethylamine,
Afterwards, the mixture was reacted under reflux for 5 hours. The reaction mixture was diluted with 5% aqueous sodium solution.
ml and extracted with 300 ml of ethyl acetate. After washing the oil layer twice with water, it was dried over magnesium sulfate and concentrated under reduced pressure to obtain 60 g of residue. This residue was subjected to silica gel chromatography, the product-containing portion was concentrated under reduced pressure, and the residue was crystallized from n-hexane/ethanol (10/1 volume ratio) to obtain 45 g of Exemplary Coupler 52. (Melting point 91-96
°C) Synthesis Example (6) Synthesis of Exemplary Coupler 53 α-Chloro-α-pivaloyl-2-chloro-5
33 g of -(n-dodecyloxycarbonyl)acetanilide and 112 g of 3.3'-dichloro-4,4'-dihydroxydiphenylsulfone were dissolved in 300 ml of dimethylacetamide and 150 ml of acetonitrile under reflux. Add 15ml of triethylamine dropwise to this mixture,
Afterwards, the mixture was reacted under reflux for 3 hours. The reaction mixture was diluted with 5% sodium hydroxide solution.
ml and extracted with 300 ml of ethyl acetate. The oil layer was washed with water three times, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 58 g of residue. This residue was subjected to silica gel chromatography, the product-containing portion was concentrated under reduced pressure, and the residue was crystallized from n-hexane/isopropanol to obtain 38 g of Exemplary Coupler 53. (Melting point 88-92°C) Synthesis example (7) Synthesis of exemplary coupler 64 α-chloro-α-pivaloyl-2-chloro-5
-(n-hexadecanesulfonamide)acetanilide 35.5g, 8-acetylamino-4-diethylsulfamoyl-1-naphthol 22.2g dimethylacetamide 200ml and acetonitrile 100ml
ml, and 14 g of tetramethylguanidine was added at 80°C to 85°C with stirring. This reaction mixture was allowed to react at the same temperature for 5 hours. After the reaction was completed, the mixture was poured into ice water (containing 10 ml of concentrated hydrochloric acid), and the precipitated oily substance was extracted with ethyl acetate. The oil layer was washed twice with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 52 g of residue. This residue was subjected to silica gel chromatography, the product-containing portion was concentrated under reduced pressure, and the residue was crystallized from ethyl acetate/n-hexane to obtain 23 g of Exemplary Coupler 64. (Melting point 126-139°C) Synthesis example (8) Synthesis of exemplary coupler 75 α-chloro-α-pivaloyl-2-chloro-5
- Add 30.0 g of (n-dodecyloxycarbonyl)acetanilide and 18.9 g of 2-chloro-8-dimethylsulfamoyl-1-naphthol to 150 ml of dimethylformamide and 150 ml of acetonitrile,
Tetramethylguanidine 14 at 80℃ with stirring
g was added. This reaction mixture was allowed to react at the same temperature for 5 hours. Thereafter, the reaction mixture was poured into ice water (containing 10 ml of concentrated hydrochloric acid), and the precipitated oily substance was extracted with ethyl acetate. The oil layer was washed twice with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 43 g of residue. This residue was subjected to silica gel chromatography, the product-containing portion was concentrated under reduced pressure, and the residue was crystallized from n-hexane/ethanol to obtain 18 g of Exemplary Coupler 75. (Melting point 115-123°C) In the silver halide color photographic light-sensitive material of the present invention, the photographic constituent layer to which the yellow coupler represented by the general formula [1] is added is preferably a silver halide emulsion layer and/or a silver halide emulsion layer. It is a non-photosensitive layer adjacent to the silver halide emulsion layer, and more preferably both are contained in the silver halide emulsion layer. In the present invention, the photographic constituent layers include a photosensitive layer containing a photosensitive silver halide emulsion, and non-photosensitive layers such as an intermediate layer, a filter layer, an undercoat layer, and a protective layer. The amount of the yellow coupler added is not limited, but is preferably 1 x 10 ^-3 to 5 mol per mol of silver.
More preferably, it is 1×10 ⁻² to 5×10 ⁻¹ mol. Next, the above general formula [2] according to the present invention will be explained. Examples of the substituent represented by R' include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, and a carbamoyl group. basis,
Sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group , imide group, ureido group, sulfamoylamino group,
alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group,
Aryloxycarbonyl group, alkylthio group,
Examples include arylthio group and heterocyclic thio group. Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred. The alkyl group represented by R′ has 1 carbon number
~32, alkenyl groups, alkynyl groups with 2 to 32 carbon atoms, cycloalkyl groups, cycloalkenyl groups with 3 to 12 carbon atoms, especially 5 to 32 carbon atoms.
7 is preferable, and the alkyl group, alkenyl group, and alkynyl group may be linear or branched. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a hetero atom {specifically, hydroxy, alkoxy, aryloxy, heterocycles substituted via an oxygen atom such as oxy, siloxy, acyloxy, carbamoyloxy;
Nitro, amino (including dialkylamino, etc.),
Those substituted through a nitrogen atom such as sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, alkylthio,
Those substituted via a sulfur atom such as arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl, and those substituted via a phosphorus atom such as phosphonyl. Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1-hexylnonyl group, 1,1'-dipentylnonyl group, 2-chloro-t-butyl group,
Trifluoromethyl group, 1-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3- m-butanesulfonaminophenoxypropyl group, 3-4'-{α-[4″(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylpropyl group, 3-{4′-[α-
(2″,4″-di-t-amylphenoxy)butanamide]phenyl}-propyl group, 4-[α(o-chlorophenoxy)tetradecanamidephenoxy]propyl group, allyl group, cyclopentyl group,
Examples include cyclohexyl group. The aryl group represented by R' is preferably a phenyl group, which may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.). Specifically, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4
-tetradecanamide phenyl group, hexadecyloxyphenyl group, 4'-[α-(4''-t-butylphenoxy)tetradecanamide] phenyl group, etc. The heterocyclic group represented by R' is 5 -7-membered ones are preferred, and may be substituted or fused.Specifically, 2-furyl group, 2-
Examples include thienyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group. Examples of the acyl group represented by R′ include acetyl group, phenylacetyl group, dodecanoyl group,
Alkylcarbonyl groups such as α-2,4-di-t-amylphenoxybutanoyl group, benzoyl group,
Examples include arylcarbonyl groups such as 3-pentadecyloxybenzoyl group and p-chlorobenzoyl group. Examples of the sulfonyl group represented by R' include a methylsulfonyl group, an alkylsulfonyl group such as a dodecylsulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group, and a p-toluenesulfonyl group. Examples of the sulfinyl group represented by R' include ethylsulfinyl group, octylsulfinyl group, 3
- an alkylsulfinyl group such as a phenoxybutylsulfinyl group, a phenylsulfinyl group, m
Examples include arylsulfinyl groups such as -pentadecyl phenylsulfinyl group. Examples of the phosphonyl group represented by R' include an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and a phenyl group. Examples include arylphosphonyl groups such as phosphonyl groups. The carbamoyl group represented by R' is an alkyl group,
Aryl groups (preferably phenyl groups) may be substituted, for example, N-methylcarbamoyl groups, N,N-dibutylcarbamoyl groups, N-(2
-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group,
N-{3-(2,4-di-t-amylphenoxy)
propyl}carbamoyl group, and the like. The sulfamoyl group represented by R′ is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-
Examples include (2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, and N-phenylsulfamoyl group. Examples of the spiro compound residue represented by R' include spiro[3.3]heptan-1-yl. Examples of the bridged carbonized compound residue represented by R′ include bicyclo[2.2.1]heptane-1-yl, tricyclo[3.3.1.1 ^3,7 ]decane-1-yl, 7,7
-dimethyl-bicyclo[2.2.1]heptane-1-
Ile et al. The alkoxy group represented by R' may be further substituted with the substituents listed above for the alkyl group, such as methoxy group, propoxy group,
-ethoxyethoxy group, pentadecyloxy group,
Examples include 2-dodecyloxyethoxy group and phenethyloxyethoxy group. The aryloxy group represented by R' is preferably phenyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, such as phenoxy group, p
Examples include -t-butylphenoxy group and m-pentadecylphenoxy group. The heterocyclic oxy group represented by R' is 5-
Those having a 7-membered heterocycle are preferred, and the heterocycle may further have a substituent, for example,
Examples include 3,4,5,6-tetrahydropyranyl-2-oxy group and 1-phenyltetrazol-5-oxy group. The siloxy group represented by R' may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like. Examples of the acyloxy group represented by R' include an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-
Examples include chloroacetyloxy group and benzoyloxy group. The carbamoyloxy group represented by R' may be substituted with an alkyl group, an aryl group, etc., such as N-ethylcarbamoyloxy group, N,N-
Examples include diethylcarbamoyloxy group and N-phenylcarbamoyloxy group. The amino group represented by R' may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, an anilino group,
Examples include m-chloroanilino group, 3-pentadecyloxycarbonylanilino group, and 2-chloro-5-hexadecaneamideanilino group. Examples of the acylamino group represented by R' include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent, specifically an acetamido group, α-ethylpropanamide group, N-phenylacetamide group, dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group, etc. can be mentioned. Examples of the sulfonamide group represented by R' include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specifically, methylsulfonylamino group, pentadecylsulfonylamino group, benzenesulfonamide group, p-toluenesulfonamide group, 2-
Examples include methoxy-5-t-amylbenzenesulfonamide group. The imide group represented by R′ can be an open-chain one,
It may be cyclic and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutarimide group, and the like. The ureido group represented by R' may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group. , N-p-tolylureido group, and the like. The sulfamoylamino group represented by R′ is an alkyl group, an aryl group (preferably a phenyl group)
For example, N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, N-phenylsulfamoylamino group, etc. may be substituted. The alkoxycarbonylamino group represented by R' may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like. The aryloxycarbonylamino group represented by R' may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group. The alkoxycarbonyl group represented by R′ may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group,
Examples include benzyloxycarbonyl group. The aryloxycarbonyl group represented by R' may further have a substituent, such as a phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, etc. Can be mentioned. The alkylthio group represented by R' may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group, and a 3-phenoxypropylthio group. The arylthio group represented by R' is preferably a phenylthio group and may further have a substituent, such as a phenylthio group, a p-methoxyphenylthio group,
Examples thereof include a 2-t-octylphenylthio group, a 3-octadecylphenylthio group, a 2-carboxyphenylthio group, and a p-acetaminophenylthio group. The heterocyclic thio group represented by R' is 5-
A 7-membered heterocyclic thio group is preferred, and may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group. Substituents that can be separated by reaction with the oxidized product of the color developing agent represented by Examples include groups substituted via. In addition to carboxyl groups, examples of groups substituted via a carbon atom include, for example, the general formula (R ₁ ' has the same meaning as the above R, Z' has the same meaning as the above Z, R ₂ ' and R ₃ ' are hydrogen atoms, aryl groups,
Represents an alkyl group or a heterocyclic group. ), a hydroxymethyl group, and a triphenylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups,
Examples include alkoxyoxalyloxy groups. The alkoxy group may further have a substituent,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, phenethyloxy group, p-chlorobenzyloxy group, and the like. The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-dodecylphenoxy group, 4
-methanesulfonamidophenoxy group, 4-[α
-(3′-pentadecylphenoxy)butanamide]
Phenoxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p
-methoxyphenoxy group and the like. The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a condensed ring or may have a substituent. in particular,
Examples include 1-phenyltetrazolyloxy group and 2-benzothiazolyloxy group. Examples of the acyloxy group include acetoxy groups, alkylcarbonyloxy groups such as butanoloxy groups, alkenylcarbonyloxy groups such as cinnamoyloxy groups, and arylcarbonyloxy groups such as benzoyloxy groups. Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group. As the alkylthio group, butylthio group, 2
-cyanoethylthio group, phenethylthio group, benzylthio group, etc. The arylthio group includes phenylthio group, 4
-Methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butylphenylthio group, etc. can be mentioned. Examples of the heterocyclic thio group include 1-phenyl-1,2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. Examples of the group substituting via the nitrogen atom include the general formula

Examples include those represented by the formula. Here, R ₄ ′ and R ₅ ′ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, an albamoyl group, an acyl group, a sulfonyl group,
It represents an aryloxycarbonyl group or an alkoxycarbonyl group, and R ₄ ' and R ₅ ' may be combined to form a heterocycle. However, R ₄ ' and R ₅ are not both hydrogen atoms. The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an acylamino group, and a sulfonamide group. group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamino group, aryloxycarbonylamino group, hydroxyl group, carboxyl group, cyano group, and a halogen atom.
Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-ethylhexyl group.
-chloroethyl group. The aryl group represented by R ₄ ′ or R ₅ ′ is
A phenyl group or a naphthyl group having 6 to 32 carbon atoms is particularly preferable, and the aryl group may have a substituent, such as a substituent for the alkyl group represented by R ₄ ' or R ₅ ' above. and alkyl groups. Specific examples of the aryl group include phenyl group, 1-naphthyl group, and 4-methylsulfonylphenyl group. The heterocyclic group represented by R ₄ ′ or R ₅ ′ is 5
It is preferably 6-membered, may be a condensed ring, and may have a substituent. As a specific example, 2
-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, 2-pyridyl group and the like. The sulfamoyl group represented by R ₄ ' or R ₅ ' includes N-alkylsulfamoyl group, N,N-
Examples include dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc., and these alkyl groups and aryl groups have the substituents listed for the alkyl groups and aryl groups. You can leave it there. Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group,
Examples include N-dodecylsulfamoyl group and N-p-tolylsulfamoyl group. Examples of the carbamoyl group represented by R ₄ ' or R ₅ ' include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc. The alkyl group and aryl group may have the substituents listed for the alkyl group and aryl group. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, Np-cyanophenylcarbamoyl group, and Np-tolylcarbamoyl group. Examples of the acyl group represented by R ₄ ′ or R ₅ ′ include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. You may do so. Specific examples of the acyl group include hexafluorobutanoyl group,
2,3,4,5,6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthoyl group,
Examples include 2-furylcarbonyl group. The sulfonyl group represented by R ₄ ′ or R ₅ ′ is
Alkylsulfonyl group, arylsulfonyl group,
A heterocyclic sulfonyl group may be mentioned, which may have a substituent, and specific examples include an ethanesulfonyl group, a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, a p-chlorobenzenesulfonyl group, etc. . The aryloxycarbonyl group represented by R ₄ ' or R ₅ ' may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like. The alkoxycarbonyl group represented by R ₄ ' or R ₅ ' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a benzyloxycarbonyl group. etc. The heterocycle formed by combining R ₄ ' and R ₅ ' is preferably a 5- to 6-membered ring, and may be saturated or unsaturated, and may or may not have aromaticity. It may also be a fused ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxaoxazolidinyl group, 2- N-1,1-dioxo-3-
(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group,
1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl group, 1-(1,
2,4-triazolyl) group, 1-(1,2,3-
triazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,
3,4-tetrahydroquinolyl group, 2-oxo-
Examples include 1-pyrrolidinyl group, 2-1H-pyridone group, phthaladione group, 2-oxo-1-piperidinyl group, and these heterocyclic groups include alkyl groups,
Aryl group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkylamino group, arylamino group, acylamino group, sulfonamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group , an aryloxycarbonyl group, an imide group, a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like. Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned. In addition, general formula [2] and general formula [4] to be described later
Substituents on the heterocycle in [10] (for example, R′,
R ₁ ~ R ₈ ) is When it has a part (here R'', X and Z'' are synonymous with R', X' and Z in general formula [2]),
Although it forms a so-called screw-type coupler, it is of course included in the present invention. Further, the ring formed by Z, Z', Z'' and Z ₁ described below may be further fused with another ring (for example, a 5- to 7-membered cycloalkene). For example, in the general formula [7] is the general formula [8] where R ₅ and R ₆ are
In the formula, R ₇ and R ₈ may be bonded to each other to form a ring (eg, 5- to 7-membered cycloalkene, benzene). More specifically, what is represented by general formula [2] is represented by, for example, the following general formulas [4] to [10]. General formula [4] General formula [5] General formula [6] General formula [7] General formula [8] general formula

[9] The general formula [4] ~

In [9], R ₁ to R ₈ and X have the same meanings as R' and X' above. Moreover, among the general formulas [2], those represented by the following general formula [10] are preferable. General formula [10] In the formula, R ₁ , X' and Z ₁ are R' in general formula [2],
Synonymous with X' and Z. The general formula [4] ~

Among the magenta couplers represented by [9], particularly preferred are the magenta couplers represented by the general formula [4]. Regarding the substituents on the heterocycle in general formulas [2] to [10], R in general formula [2] and R ₁ in general formulas [4] to [10]
It is preferable that the following condition 1 is satisfied, more preferable is the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1, 2 and 3 are satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds. The most preferred substituents R' and R ₁ on the heterocycle are those represented by the following general formula [11]. General formula [11] In the formula, R ₉ , R ₁₀ and R ₁₁ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group , phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group , acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group represents,
At least two of R ₉ , R ₁₀ and R ₁₁ are not hydrogen atoms. Also, two of the above R ₉ , R ₁₀ and R ₁₁ , for example R ₉
and R ₁₀ may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R ₁₁ may be further bonded to the ring to form a bridged hydrocarbon compound residue. You may. The group represented by R ₉ to _{R 11} may have a substituent, and specific examples of the group represented by R ₉ to R ₁₁ and the substituents that the group may have are the same as those mentioned above. Specific examples of the group represented by R' in formula [2] and substituents are listed. Also, for example, a ring formed by combining R ₉ and R ₁₀ and
Specific examples of the bridged hydrocarbon compound residue formed by R ₉ to R ₁₁ and the substituents it may have include cycloalkyl, cycloalkenyl, represented by R' in the above general formula [2], Specific examples of the bridged hydrocarbon compound residue with a heterocyclic group and its substituents are listed. Among the general formulas [11], (i) two of R ₉ to _{R 11} are alkyl groups, and (ii) one of R ₉ to R ₁₁ , for example R ₁₁ , is a hydrogen atom. Then, when the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom, then. Furthermore, it is preferable among () that two of R ₉ to _{R 11} are alkyl groups and the other one is a hydrogen atom or an alkyl group. Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substituent represented by R′ in the general formula [2]. Specific examples of substituents are listed. In addition, substituents that the ring formed by Z in general formula [2] and the ring formed by Z ₁ in general formula [10] may have, and general formulas [4] to
R ₂ to _{R 8} in [8] are the following general formula [12]
The one represented by is preferable. General formula [12] -R ¹ -SO ₂ -R ² In the formula, R ¹ represents alkylene, and R ² represents alkyl, cycloalkyl or aryl. The alkylene represented by R ¹ preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms.
It does not matter whether it is straight chain or branched. Moreover, this alkylene may have a substituent. Examples of the substituent include those shown as substituents that the alkyl group may have when R' in the above-mentioned general formula [2] is an alkyl group. Preferred substituents include phenyl. Preferred specific examples of alkylene represented by R ¹ are shown below. −CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

【formula】

[Formula] −CH ₂ CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

[Formula] The alkyl group represented by R ² may be linear or branched. Specifically, methyl, ethyl, propyl, iso
-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl,
Examples include octadacil and 2-hexyldecyl. The cycloalkyl group represented by R ² is 5-
A 6-membered one is preferred, such as cyclohexyl. The alkyl and cycloalkyl represented by R ² may have a substituent, examples of which include the above-mentioned substituents.
Examples of substituents for R ¹ include those exemplified. Specifically, the aryl represented by R ² is:
Examples include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as those exemplified as the substituent for R ¹ above. Moreover, when there are two or more substituents, those substituents may be the same or different. Among the compounds represented by the general formula [2], particularly preferred are those represented by the following general formula [13]. General formula [13] In the formula, R′ and X′ are R′ in general formula [2],
R ¹ and R ² which are synonymous with X' are synonymous with R ¹ and R ² in general formula [12]. Specific examples of the compound represented by general formula [2] are shown below. The synthesis of the above couplers is a journal of the
Chemical Society (Journal of the
Chemical Society), Perkin I
(1977), 2047-2051, U.S. Patent No. 3725067, JP-A-59-99437, JP-A-58-42045, JP-A-59-
No. 162548, JP-A-59-171956, JP-A-60-33552
Synthesis can be carried out with reference to No. 60-43659 and JP-A No. 60-43659. The coupler represented by the general formula [2] can be used generally in an amount of 1.times.10.sup.- ³ mol to 1 mol, preferably 1.times.10.sup.- ² mol to 8.times.10.sup. ^-1 mol per mol of silver halide. Further, the coupler represented by the general formula [2] can also be used in combination with other types of magenta couplers. The average grain size of the silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention is
It is 0.8 μm or less, preferably 0.2 to 0.6 μm. If the average particle size exceeds 0.8 μm, desilvering properties will be poor, processing will take time, and processing stability will deteriorate. On the other hand, the average grain size is preferably 0.2 μm or more in view of the sensitivity of the blue-sensitive silver halide emulsion layer. The blue-sensitive silver halide emulsion layer in the present invention may consist of two or more layers, and in this case, the above average grain size is the average grain size of all of these layers. The average grain size of the silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention is determined by one method arbitrarily selected from various methods commonly used in the technical field for the above purpose. It is sufficient if it is within the above range when measured. Loveland's "particle size analysis method" AS is used to measure the average particle size.
TM Symposium on Light Microcopy, 1955, pp. 94-122 and "Theory of the Photographic Process" by Mies and James, 3rd edition,
Includes those listed in Chapter 2 of McClammin Publishing (1966). The particle size is measured using the projected area or approximate diameter of the particle. The silver halide used in the photographic material of the present invention may be a polydisperse emulsion in which the average grain size is distributed over a wide range, but a monodisperse emulsion is preferred. A monodisperse emulsion is one in which most of the silver halide grains appear to have the same shape when the emulsion is observed using an electron microscope, have uniform grain sizes, and have a grain size distribution defined by the following formula. It is something. That is, when the standard deviation s of particle size distribution is divided by the average particle size, the value is 0.20 or less. In the case of spherical silver halide grains, the average grain size referred to here refers to the diameter of the grains, and in the case of grains with shapes other than spherical, the average diameter when the projected image is converted to a circular image of the same area. A value defined by the following formula, where the individual grain size is ri and the number is ni. = Σni ri/Σni The relationship between particle size distribution is described in "Empirical relationship between sensitometric distribution and particle size distribution in photography" The Photographic Journal, Volume LXXIX (1949)
This can be determined using the method described in the paper by Tribel and Smith, pp. 330-338. The silver halide contained in the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer of the present invention may be silver chlorobromide, silver chloroiodobromide, or a mixture thereof. The contents are 50-75 mol% and 30-60 mol%, respectively. In the present invention, one or both of the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer may be composed of two or more layers. In the present invention, the silver bromide content refers to the total bromide content of each layer in the total silver halide contained in each of the total blue-sensitive silver halide emulsion layer and the total green-sensitive silver halide emulsion layer. Refers to the silver content. When the silver bromide content exceeds 75 mol % in the blue-sensitive layer and 60 mol % in the green-sensitive layer, processing stability deteriorates, color turbidity occurs, and image quality deteriorates. On the other hand, if the silver bromide content is less than 50 mol % in the blue-sensitive layer and 30 mol % in the green-sensitive layer, processing stability deteriorates. When the silver halide contained in the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer of the present invention is silver chloroiodobromide, the silver iodide content does not exceed 2 mol%. Preferably. The silver bromide content of the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer is 50 to 75 mol% for the former and 30 to 60 mol% for the latter. The silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention is also monodisperse like the silver halide contained in the blue-sensitive silver halide emulsion layer. Preferably. The composition of the silver halide contained in the red-sensitive silver halide emulsion layer is not particularly limited, and may be silver bromide, silver chlorobromide, silver chloroiodobromide, or a mixture thereof. However, silver chlorobromide is preferred, with a silver bromide content of 30 to 95 mol%. Furthermore, the red-sensitive silver halide emulsion layer in the present invention may consist of two or more layers. The average grain size of the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is not particularly limited, but is generally 0.1 to 2 μm, more preferably 0.2 to 1 μm, particularly preferably 0.25 μm. ~
It is 0.8μm. The total amount of silver contained in the silver halide emulsion layers other than the red-sensitive silver halide emulsion layer (silver coating amount) in the silver halide color photographic light-sensitive material of the present invention is
It is 0.55g/ ^m2 or less. If the amount of silver exceeds 0.55 g/m ² , the color development of the red-sensitive silver halide emulsion layer will decrease and the image quality will deteriorate. On the other hand, from the viewpoint of maximum density and sensitivity, the amount of silver is preferably 0.15/m ² or more. In the present invention, the amount of silver is particularly preferably 0.2 to 0.5 g/m ² . Silver halide compositions preferably used in the present invention include silver chlorobromide and silver chloroiodobromide. Furthermore, it may be a combination mixture such as a mixture of silver chloride and silver bromide. That is, when the silver halide photosensitive material according to the present invention is used for color photographic paper, particularly fast developability is required, so it is preferable that the halogen composition of the silver halide contains a chlorine atom, and at least 1 mol. Particular preference is given to silver chlorobromide or silver chloroiodobromide containing % silver chloride. The monodisperse silver halide grains preferably used in the present invention may be obtained by any conventionally known preparation method such as an acidic method, a neutral method, or an ammonia method. Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. PH and pAg in the reaction vessel when growing silver halide grains
It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains, for example, as described in JP-A No. 54-48521. The silver halide emulsion in the light-sensitive material of the present invention includes activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; selenium sensitizers; reduction sensitizers such as 1 tin salt;
Thiourea dioxide, polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc., or such as ruthenium, palladium, platinum , water-soluble salt sensitizers such as rhodium and iridium, specifically ammonium chloroparadate,
Potassium chloroplatinate and sodium chloroparadate (some of these act as sensitizers or fog suppressants depending on the amount), alone or in combination as appropriate (for example, gold sensitizers) Chemical sensitization may be carried out by using a combination of a gold sensitizer and a sulfur sensitizer, a gold sensitizer and a selenium sensitizer, etc. The silver halide emulsion is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing heterocyclic compound having at least one hydroxytetrazaindene and mercapto group is added. At least one kind may be contained. The silver halide in the photosensitive material of the present invention is
In order to impart photosensitivity to each desired wavelength range, optical sensitization may be carried out by adding an appropriate sensitizing dye in an amount of 5 x 10 ^-8 to 3 x 10 ^-3 mol per 1 mol of silver halide. good. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following. That is, as sensitizing dyes used in the blue-sensitive silver halide emulsion layer, for example, West German Patent No. 929080,
U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No. 2503776,
Same No. 2519001, No. 2912329, No. 3656959, Same No.
No. 3672897, No. 3694217, No. 4025349, No. 3672897, No. 3694217, No. 4025349, No.
No. 4046572, British Patent No. 1242588, Special Publication No. 1977-
Examples include those described in No. 14030 and No. 52-24844. In addition, as sensitizing dyes used in green-sensitive silver halide emulsions, for example,
No. 1939201, No. 2072908, No. 2739149, No.
Representative examples thereof include cyanine dyes, merocyanine dyes, complex cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in No. 2945763, British Patent No. 505979, and the like. Furthermore, as sensitizing dyes used in red-sensitive silver halide emulsions, for example,
No. 2269234, No. 2270378, No. 2442710, No. 2269234, No. 2270378, No. 2442710, No.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2454629, No. 2776280, and the like. Furthermore, U.S. Patent No. 2,213,995;
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 2493748, No. 2519001, West German Patent No. 929080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions. . These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.
Typical examples are U.S. Patent No. 2688545, U.S. Patent No. 2977229,
3397060, 3522052, 3527641, 3527641, 3522052, 3527641,
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
No. 110618 and No. 52-109925. Each silver halide emulsion layer in the light-sensitive material of the present invention may contain a coupler other than the present invention. In the present invention, conventionally known yellow couplers, magenta couplers, and cyan couplers can be used in combination as couplers other than the above-mentioned couplers of the present invention. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and it is also possible to use a diffusible dye-releasing coupler or the like in combination with these couplers. Furthermore, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent couplers but also 2-equivalent couplers. Specific examples of cyan couplers include U.S. Patent No. 2369929;
Same No. 2434272, No. 2474293, No. 2521908, Same No.
No. 2895826, No. 3034892, No. 3311476, No. 3311476, No.
No. 3458315, No. 3476563, No. 3583971, No.
3591383, 3767411, 4004928, West German Patent Application (OLS) 2414830, 2454329, JP 48-59838, 51-26034, 48-5055,
No. 51-146827, No. 52-69624, No. 52-90932
No. 58-95346. The photographic material of the present invention may contain various photographic additives in addition to the above. For example, AI dyes, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, and hardening films described in Research Disclosure No. 17643. Agents, surfactants, plasticizers, wetting agents, etc. can be used. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. Supports for the silver halide color photographic light-sensitive material of the present invention include, for example, rosette paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or with a reflector, such as glass plates, cellulose acetate, etc. , polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and transparent supports thereof, and these supports are appropriately selected depending on the intended use of the photosensitive material. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers in the light-sensitive material of the present invention. Also US patent
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 2761791 and No. 2941898. In the light-sensitive material of the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer from the support side. . In the light-sensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and various layers such as a filter layer, anti-curl layer, protective layer, anti-halation layer, etc. may also be provided as constituent layers. They can be used in appropriate combinations. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included. There are no particular limitations on the method of processing the photosensitive material according to the present invention, and any processing method can be applied. For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment as necessary, and a method in which bleaching and fixing are performed separately after color development, followed by further washing with water if necessary. and/or methods of stabilizing; or prehardening, neutralization, color development, stop-fixing, washing, bleaching,
Method of fixing, washing with water, post hardening, washing with water, color development, washing with water, supplementary color development, stopping, bleaching, fixing,
Processing using any of the following methods: washing with water and stabilization in that order, or halogenation bleaching of the developed silver produced by color development, and then color development again to increase the amount of dye produced. You may. In the color development of the silver halide color photographic light-sensitive material of the present invention, the processing temperature of various processing steps such as bleach-fixing (or bleaching, fixing), and further washing, stabilization, drying, etc., which are carried out as necessary, is determined from the viewpoint of rapid processing. It is preferable to carry out at a temperature of 30°C or higher. The silver halide color photographic light-sensitive material of the present invention is disclosed in JP-A-51-14834, JP-A-58-105145, and JP-A-58-58.
No. 134634 and No. 58-18631 and patent application No. 1983-
Stabilization treatment as an alternative to washing may be performed as shown in No. 2709 and No. 59-89288.

【Effect of the invention】

(1) According to the silver halide color photographic light-sensitive material of the present invention, rapid color development processing is possible, and images with excellent processing stability and high quality can be obtained. (2) The silver halide color photographic light-sensitive material of the present invention has high sensitivity. (3) According to the present invention, it is possible to save silver in silver halide color photographic light-sensitive materials.

【Example】

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 On a paper support laminated with polyethylene,
The following layers were sequentially coated from the support side to prepare silver halide color photographic material samples No. 1 to 5. Layer 1...1.2g/ ^m2 gelatin, 0.22g/ ^m2
Blue-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), 0.50
0.80 dissolved in g/m ² dioctyl phthalate
Layer containing g/m ² of the yellow coupler of the invention (Example 82). Layer 2...0.7g/ ^m2 gelatin, 10mg/ ^m2 erasion dye (AI-1), 5mg/ ^m2 (AI
-2) the middle layer consisting of; Layer 3...1.25 g/m ² gelatin, 0.22 g/m ² green-sensitive silver chlorobromide emulsion (silver bromide content and average particle size are shown in Table 1), 0.30 g/m ² dioctyl phthalate A layer containing 0.62 g/m ² of the magenta coupler of the invention (Example 44) dissolved in . Layer 4: Intermediate layer consisting of 1.2 g/m ² of gelatin. Layer 5...1.4 g/m ² gelatin, 0.20 g/m ² red-sensitive silver chlorobromide emulsion (silver bromide content and average particle size are shown in Table 1), 0.20 g/m ² dioctyl phthalate A layer containing 0.45 g/m ² of cyan coupler (C-1) dissolved in . Layer 6...1.0g/ ^m2 gelatin and 0.20g/ ^m2
A layer containing 0.30 g/m ² Tinuvin 328 (manufactured by Ciba Geigy, ultraviolet absorber) dissolved in dioctyl phthalate. Layer 7: A layer containing 0.5 g/m ² of gelatin. C-1 AI-1 AI-2 In addition, as a hardening agent, 2,4-dichloro-6-
Sodium hydroxy-s-triazine layer 2,
0.017 per gram of gelatin in 4 and 7, respectively.
g.

[Table] Each of the photosensitive material samples Nos. 1 to 5 was exposed through an optical wedge and then processed in the following steps. Processing steps (38°C) Color development 3 minutes Bleach-fixing 1 minute Washing with water 1 minute Drying 60-80°C 2 minutes The composition of each processing solution is as follows. [Color developer] Pure water 800ml Benzyl alcohol 15ml Hydroxylamine sulfate 2.0g Potassium bromide 1.5g Sodium chloride 1.0g Potassium sulfite 2.0g Triethanolamine 2.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl -4-aminoaniline sulfate
4.5g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5ml Potassium carbonate 32g Whitex BB (50% aqueous solution) 2ml (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make 1. , adjust the pH to 10.1 with 20% potassium hydroxide or 10% dilute sulfuric acid. [Bleach-fix solution] Pure water 550ml Iron () ammonium ethylenediaminetetraacetate
65g Ammonium thiosulfate 85g Sodium bisulfite 10g Sodium metabisulfite 2g Disodium ethylenediaminetetraacetic acid 20g Sodium bromide 10g Add pure water to make 1, and adjust to PH = 7.0 with aqueous ammonia or dilute sulfuric acid. Separately, potassium bromide 0.5 of the above color developer,
The same samples Nos. 1 to 5 as above were each developed using color developing solutions with the only difference being 1.0, 2.0, and 2.5. Sensitometry was performed on each of the obtained samples by a conventional method. Potassium bromide concentration 1.5g/
The sensitivity of each sample at that time is set as 100, and Table 2 shows the change in sensitivity when the potassium bromide concentration is varied, and the gamma value at each potassium bromide concentration. Also, add 0.1 bleach-fix solution to 1 part color developer.
Table 3 shows the gamma values when 0.2, 0.3 and 0.4 ml were added.

【table】

【table】

[Table] represents the gamma value.
As is clear from Table 2, sample No. 1 of the present invention
It can be seen that Samples No. 5 and No. 5 exhibit less gamma movement when the potassium bromide concentration fluctuates, and have excellent processing stability. Comparing Samples No. 1 and No. 3, although the silver halide grains in the blue-sensitive silver halide emulsion are the same, the gamma variation of the blue-sensitive silver halide emulsion is different; This shows that processing stability (particularly with respect to potassium bromide) varies depending on the composition of silver halide grains in a photosensitive silver halide emulsion. In addition, from Samples No. 2 and No. 3, when the silver bromide content of the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer was low outside the range of the present invention, the gamma fluctuation was large. Sample No. 4 shows that the large-grain blue-sensitive silver halide emulsion exhibits large variations in sensitivity. Furthermore, as is clear from the results in Table 3, the samples of the present invention show less variation in gamma when the bleach-fix solution is mixed into the color developer, indicating that they have excellent processing stability. Example 2 Samples Nos. 1 and 5 were tested for rapid processability. That is, using each processing solution of Example 1 (however, the potassium bromide concentration of the color developer was 1.0 g/
It was set to ) Color development time: 2 minutes, 2 minutes 30 seconds,
Sensitivity (S), gamma (γ) and maximum density (Dm) at 3 minutes were investigated. The results are shown in Table 4.

【table】

[Table] As is clear from the results in Table 4, the sample of the present invention
It can be seen that No. 5 has sufficient photographic performance in terms of sensitivity, gamma, maximum density, etc. even with a color development time of 2 minutes, and is excellent in rapid processing performance. Example 3 Sample No. 6 was prepared in the same manner as in Example 1, except that the yellow coupler in layer 1 was changed to Example 83, the magenta coupler in layer 3 was changed to Example 165, and the amount of silver coating was changed to the amount shown in Table 5. I created No.7.

[Table] Using these samples No. 6, No. 7 and sample No. 5 of Example 1, the processing stability (against fluctuations in potassium bromide) and the maximum red-sensitive silver halide emulsion layer were evaluated as in Example 1. The concentration (Dm) was investigated. The results are shown in Table 6.

【table】

[Table] As is clear from Table 7, when the total silver amount of the silver halide emulsion layers other than the red-sensitive silver halide emulsion layer is outside the range of the present invention, as in Samples No. 6 and No. 7, the red The maximum density of the photosensitive silver halide emulsion layer is lower than Sample No. 1 according to the present invention, and the present invention can save silver, has less color turbidity, has high image quality, high sensitivity,
It also has excellent processing stability. Example 4 Regarding Sample No. 5 of Example 1, the silver bromide content of the blue-sensitive silver halide emulsion and the green-sensitive silver halide emulsion was changed as shown in Table 7 without changing the average grain size. Samples Nos. 8 to 19 were prepared. The same evaluations as in Example 1 were performed on Samples Nos. 8 to 19. The results are shown in Table 8.

【table】

【table】

【table】

[Table] As is clear from Table 8, the silver bromide content of the blue-sensitive silver halide emulsion is 50 to 75 mol%,
and the silver bromide content of the green-sensitive silver halide emulsion is
The effect of the present invention can be obtained only when the content is 30 to 60 mol%. Example 5 Regarding Sample No. 5 of Example 1, the yellow coupler in the blue-sensitive silver halide emulsion layer and the magenta coupler in the green-sensitive silver halide emulsion layer were changed to couplers shown in Table 9 with the same molar content, respectively. Sample No.20～
Created 23. The same evaluation as in Example 1 was performed on Samples Nos. 20 to 23. The results are shown in Table 10.

[Table] YY-1: YY-2: α-pivaloyl-α-(2,4-dioxo-5,5′-dimethyloxazolidine-3-
yl)-2-chloro-5-[α-(2,4-di-
tert-pentylphenoxy)butanamide]acetanilide MM-1: MM-2:

[Table] As is clear from Table 10, samples Nos. 20 and 21, which used yellow couplers other than the present invention, both had large variations in the blue-sensitive layer, and samples Nos. 21 and 21, which used yellow couplers other than the present invention, both had large variations in the blue-sensitive layer. Samples Nos. 22 and 23 both have large processing fluctuations in the green-sensitive layer. That is, the effect of the present invention is observed only when both the yellow coupler and the magenta coupler are the couplers of the present invention. Example 6 Regarding Sample No. 5 of Example 1, the magenta couplers in the green-sensitive silver halide emulsion layer were changed to the couplers shown in Table 11 with the same molar content, and Samples Nos. 24 to 31 were prepared.
It was created. The same evaluation as in Example 1 was performed for Samples Nos. 24 to 31. The results are shown in Table 12.

【table】

[Table] As is clear from Table 12, the general formula of the present invention
Samples Nos. 24 to 31 using magenta couplers represented by (5), (7), (8), and (9), respectively, had small processing fluctuation ranges, and the effects of the present invention were recognized.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. The average grain size of the silver halide in the silver halide emulsion layer is 0.8 μm or less, the silver bromide content of the silver halide in the blue-sensitive silver halide emulsion layer is 50 to 75 mol%, and the silver bromide content of the silver halide in the blue-sensitive silver halide emulsion layer is 50 to 75 mol %. The silver bromide content of silver halide in the silver emulsion layer is 30 to 60 mol%, and the total amount of silver in silver halide emulsion layers other than the red-sensitive silver halide emulsion layer is 0.55 g/m ² or less A silver halide color photograph characterized in that it contains at least one yellow coupler represented by the following general formula [1] and at least one magenta coupler represented by the following general formula [2] photosensitive material. General formula [1] [In the formula, Coup represents a yellow dye-forming coupler residue from which one hydrogen atom at the cut ring position has been removed, and X represents a group of nonmetallic atoms necessary to complete the benzene nucleus or naphthalene nucleus. R is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxyl group, or an alkyl group that may each have a substituent, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group,
Aryloxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, alkylcarbonylamino group, arylcarbonylamino group, Sulfonamide group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, amino group, alkylsulfinyl group, arylsulfinyl group, phosphinyl group, N-acylcarboimidoyl group, N-alkylcarboimidoyl group, N-arylcarboimidoyl group, heterocyclic group, ureido group, alkylcarbonyloxy group or arylcarbonyloxy group, or a group represented by the following general formula (3), n represents an integer of 0 to 4, and when n is 2 or more, each R may be the same or different. ] General formula (3) [In the formula, R ₁ is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, or an alkyl group that may have a substituent, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, or an aryloxy group. group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylcarbonylamino group, arylcarbonylamino group, amino group, alkylcarbamoyl group, Represents an arylcarbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, or an arylcarbonyl group. X ₁ represents a divalent organic linking group, l represents 0 or 1, m represents 0, 1, 2, 3 or 4, m
When is 2 or more, each R ₁ may be the same or different. ] General formula [2] [In the formula, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X' represents a hydrogen atom or a substituent that can be eliminated by reaction with an oxidized product of a color developing agent. Further, R' represents a hydrogen atom or a substituent. ]