JPH1172887A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve sharpness, to produce a significant interlayer effect and to improve the shelf stability of a sensitive material over a long period of time by incorporating a specified compd. SOLUTION: A compd. represented by the formula is incorporated. In the formula, Y is the residue of a yellow coupler capable of coupling with the oxidized body of a color developing agent, T is a 1,2,4- or 1,2,3-triazole skeleton bonded to the coupling position of Y through a nitrogen atom, the skeleton may have a substituent, S is a sulfur atom bonded to a carbon atom of T, R1 is a hydrogen atom, alkyl which may have a substituent or aryl which may have a substituent, R2 is alkyl which may have a substituent or aryl which may have a substituent, R3 is alkyl which may have a substituent or aryl which may have a substituent, R4 is an arbitrary substituent which may be substd. on the benzene ring, (n) is an integer of 0-4, and in the case of n>=2, R4 's may be the same or different.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having improved photographic characteristics and storage stability with time.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand for the development of color light-sensitive materials having high sensitivity and excellent sharpness and color reproducibility.

[0003] As a means for improving sharpness, DIR compounds which react with an oxidized form of a color developing agent to release a development inhibitor are known. It is well known that by including this in an emulsion, sharpness is improved by the edge effect. However, these DIR compounds have the disadvantage that the development inhibitor released during color development diffuses into the processing solution from the photosensitive material and accumulates, resulting in the processing solution exhibiting development inhibiting properties.

[0004] Couplers for solving such problems are disclosed in JP-A-57-151944 and JP-A-58-20515.
No. 0, No. 60-218644, No. 60-221750
No. 61-11743 and U.S. Pat.
No. 12 has been proposed.

When these couplers are separated from the coupling position of the coupler, they exhibit a development inhibiting property, and after flowing out into a processing solution, have a property of being decomposed into a compound which does not affect photographic properties. It is a coupler having a leaving group. Certainly, even when a large amount of light-sensitive material was subjected to running processing by this coupler, the decrease in sensitivity was small and the contamination of the developing solution was considerably reduced.

However, the light-sensitive material containing the coupler has a change in photographic characteristics during storage, sharpness, and deterioration of color reproduction. Further, considering the compatibility of the coupler itself with the edge effect and the layering effect, it is still not considered. Not enough.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material having good sharpness, a large overlay effect, and improved storage stability over time. To provide.

[0008]

The above objects of the present invention have been attained by the following constitutions.

(1) A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (101).

[0010]

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[In the formula, Y represents a yellow coupler residue capable of performing a coupling reaction with an oxidized form of a color developing agent, and T may have a substituent bonded to the coupling position of Y with a nitrogen atom. It represents a 1,2,4-triazole skeleton or a 1,2,3-triazole skeleton which may have a substituent.
S represents a sulfur atom bonded on the carbon atom of T. R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ₂ represents an alkyl group which may have a substituent or a substituent. Represents an optionally substituted aryl group. R ₃ represents an optionally having an alkyl group or a substituent an optionally substituted aryl group, R ₄
Represents an arbitrary substituent which can be substituted on the benzene ring, and n represents 0, 1, 2, 3, or 4. When n is 2 or more, each R ₄
May be the same or different. (2) A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (201).

[0012]

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[Wherein, Y represents a yellow coupler residue capable of undergoing a coupling reaction with an oxidized form of a color developing agent, and T may have a substituent bonded to the coupling position of Y with a nitrogen atom. It represents a 1,2,4-triazole skeleton or a 1,2,3-triazole skeleton which may have a substituent.
S represents a sulfur atom bonded on the carbon atom of T. R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ₂ represents an alkyl group which may have a substituent or a substituent. Represents an optionally substituted aryl group. R ₅ represents an arbitrary substituent that can be substituted on the benzene ring, and m represents 0, 1, 2, 3, 4 or 5. When m is 2 or more, each R ₄ may be the same or different. (3) A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (301).

[0014]

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[Wherein, Y represents a yellow coupler residue capable of undergoing a coupling reaction with an oxidized form of a color developing agent, and T may have a substituent bonded to the coupling position of Y with a nitrogen atom. It represents a 1,2,4-triazole skeleton or a 1,2,3-triazole skeleton which may have a substituent.
S represents a sulfur atom bonded on the carbon atom of T. R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ₂ represents an alkyl group which may have a substituent or a substituent. Represents an optionally substituted aryl group. R ₆ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ₇ represents an alkyl group which may have a substituent or a substituent. Represents an optionally substituted aryl group. X represents an oxycarbonyl group, a carbamoyl group, or a carbonyl group. (4) A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (401).

[0016]

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[Wherein, Y represents a yellow coupler residue capable of performing a coupling reaction with an oxidized form of a color developing agent, and T may have a substituent bonded to the coupling position of Y with a nitrogen atom. It represents a 1,2,4-triazole skeleton or a 1,2,3-triazole skeleton which may have a substituent.
S represents a sulfur atom bonded on the carbon atom of T. R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ₂ represents an alkyl group which may have a substituent or a substituent. Represents an optionally substituted aryl group. W represents an aryloxy group which may have a substituent, an arylthio group which may have a substituent, or a sulfonyl group which may have a substituent. In the general formula (101), examples of the yellow coupler residue represented by Y include a malondiamide type, a malonester monoamide type, a malondiester type, a benzoylacetanilide type, a cycloalkanoylacetamide type, a pivaloylacetanilide type, and dibenzoyl. Examples include a methane type, a benzothiazolylacetamide type, a benzoxazolylacetamide type, and a benzimidazolylacetamide type. Representative is U.S. Pat. No. 2,298,4.
No.43, No.2,407,210, No.2,875,05
No. 7, 3,048, 194, 3, 265, 506
No. 3,447,928. Nos. 5,021,332 and 5,021,33
0 or a coupler residue described in EP 421,221A.

In the general formula (101), a compound having the following structure is particularly preferable as the yellow coupler residue represented by Y (* indicates a position where the group is bonded to a group of T or less).

[0019]

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The group represented by T in the general formula (101) is specifically the following general formula (102) or the following general formulas (103), (104), (105), (106),
It is represented by (107).

[0021]

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In the general formulas (102) to (107), an asterisk (*) indicates a position bonding to the yellow coupler residue Y, and an asterisk (**) indicates a substituent of S or less in the general formula (101). Represents the position to join. From the general formulas (102) to (1
In 07), Z represents a hydrogen atom or a substituent.
Examples of the substituent represented by Z include an alkyl group (eg, methyl group, isopropyl group, cyclopropyl group, etc.), an aryl group (eg, phenyl group, tolyl group, etc.), a heterocyclic residue (eg, furyl group, thienyl group, Pyridyl group, etc.), alkylthio group (eg, methylthio group, t-octylthio group, etc.), arylthio group (eg, phenylthio group, etc.), oxycarbonyl group (eg, methoxycarbonyl group, cyclohexyloxycarbonyl group, etc., alkoxycarbonyl group, phenoxycarbonyl And an aryloxycarbonyl group such as a group and a heterocyclic oxycarbonyl group such as a 2-pyridyloxycarbonyl group).

In the general formula (101), R ₁ represents a hydrogen atom, an alkyl group which may have a substituent (for example, methyl, isopropyl, cyclopropyl, 2-chloroethyl, etc.), or a substituent. Aryl group (eg, phenyl group, tolyl group, p-methoxyphenyl group, etc.)
Represents R ₁ is preferably a hydrogen atom.

In the general formula (101), R ₂ represents an alkyl group which may have a substituent (eg, a methyl group, an isopropyl group, a cyclopropyl group, a t-butyl group, a 2-chloroethyl group), or a substituent Aryl group (e.g., phenyl group, tolyl group, p-methoxyphenyl group, etc.)
Represents R ₂ is preferably an alkyl group, particularly preferably an alkyl group having a total carbon number of 4 or less.

In the general formula (101), R ₃ is an alkyl group which may have a substituent (for example, methyl group, isopropyl group, cyclopropyl group, t-butyl group, 2-chloroethyl, etc.), or a substituent Aryl group (e.g., phenyl group, tolyl group, p-methoxyphenyl group, etc.)
Represents R ₃ is preferably an alkyl group having 8 or less carbon atoms, particularly an alkyl group having 4 or less carbon atoms.

In the general formula (101), R ₄ represents an arbitrary substituent which can be substituted on the benzene ring. The substituent alkyl group shown by R ₁ and R _2, R _3, in addition to, a Hajime Tamaki (e.g., 2-tetrahydrofuryl group of aryl group, 4-
Imidazolyl group, indoline-1-yl group, and 2-
A carbonyl group (eg, an acetyl group, an alkylcarbonyl group such as a trifluoroacetylpivaloyl group, a benzoyl group, a pentafluorobenzoyl group,
Arylcarbonyl groups such as 3,5-di-t-butyl-4-hydroxybenzoyl group, etc.), oxycarbonyl groups (e.g., alkoxycarbonyl groups such as methoxycarbonyl group, cyclohexyloxycarbonyl group, n-dodecyloxycarbonyl group, etc.), and phenoxy Carbonyl group, 2,
Aryloxycarbonyl groups such as 4-di-t-amylphenoxycarbonyl group and 1-naphthyloxycarbonyl group; and heterocyclic oxycarbonyl groups such as 2-pyridyloxycarbonyl group and 1-phenylpyrazolyl-5-oxycarbonyl group ), A carbamoyl group (for example, an alkylcarbamoyl group such as a dimethylcarbamoyl group and a 4- (2,4-di-t-amylphenoxy) butylaminocarbonyl group, an arylcarbamoyl group such as a phenylcarbamoyl group and a 1-naphthylcarbamoyl group), A sulfonyl group (for example, an alkylsulfonyl group such as a methanesulfonyl group and a trifluoromethanesulfonyl group, and an arylsulfonyl group such as a p-toluenesulfonyl group), a sulfamoyl group (for example, a dimethylsulfamoyl group,
(2,4-di-t-amylphenoxy) alkylsulfamoyl group such as butylaminosulfonyl group, arylsulfamoyl group such as phenylsulfamoyl group), halogen atom (eg, chlorine atom, bromine atom, etc.), Cyano group,
Nitro group, alkenyl group (eg, 2-propylene group, oleyl group, etc.), hydroxy group, alkoxy group (eg, methoxy group, 2-ethoxyethoxy group, etc.), aryloxy group (eg, phenoxy group, 2,4-di-t -Amylphenoxy group, 4- (4-hydroxyphenylsulfonyl) phenoxy group, etc.), heterocyclic oxy group (eg, 4-pyridyloxy group, 2-hexahydropyranyloxy group, etc.), carbonyloxy group (eg, acetyloxy group) ,
Trifluoroacetyloxy group, alkylcarbonyloxy group such as pivaloyloxy group, benzoyloxy group,
Aryl carbonyloxy group such as pentafluorobenzoyloxy group, etc., urethane group (eg, alkyl urethane group such as N, N-dimethyl urethane group, N-phenyl urethane group, aryl such as N- (p-cyanophenyl) urethane group) Urethane group), sulfonyloxy group (for example, alkylsulfonyloxy group such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group, n-dodecanesulfonyloxy group, benzenesulfonyloxy group, and arylsulfonyloxy group such as p-toluenesulfonyloxy group) ), An amino group (eg, an alkylamino group such as a dimethylamino group, a cyclohexylamino group, or an n-dodecylamino group, an arylamino group such as an anilino group, a pt-octylanilino group, etc.), a sulfonylamino group (eg, methanesulfur Alkylsulfonylamino groups such as nilamino group, heptafluoropropanesulfonylamino group, n-hexadecylsulfonylamino group, arylsulfonylamino groups such as p-toluenesulfonylamino group and pentafluorobenzenesulfonylamino), sulfamoylamino group ( For example, an alkylsulfamoylamino group such as N, N-dimethylsulfamoylamino group, an arylsulfamoylamino group such as N-phenylsulfamoylamino group, an acylamino group (eg, acetylamino group, myristoylamino group, etc.) An arylcarbonylamino group such as an alkylcarbonylamino group or a benzoylamino group), a ureido group (for example, an alkylureido group such as an N, N-dimethylureido group, an N-phenylureido group, an N- (p-cyanophenyl)) Arylureido groups such as id group), an alkylthio group (e.g. methylthio group, t-octylthio group), such as an arylthio group (e.g., phenylthio group, etc.).

R ₄ is an alkyl group or an aryl group;
A heterocyclic group, an alkoxy group, an aryloxy group, and an acylamino group are preferred, and an alkyl group having 8 or less carbon atoms, particularly 4 or less carbon atoms is particularly preferred. The substitution position of R ₄ is 6
The position (o-position) is preferred.

In the general formula (101), the group of atoms including T other than Y represents a development inhibitor residue released from Y by a coupling reaction with an oxidized color developing agent.
Particularly preferred is a development inhibitor having the following structure (indicated by a hydrogen atom attached to the development inhibitor residue represented by the structural formula of an atom group including T other than Y).

[0029]

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In the general formula (201), Y, T, R
_1, R ₂ is Y and T of the general formula (101) include the groups exemplified in R _1, R _2.

In the general formula (201), R ₅ represents an arbitrary substituent which can be substituted on the benzene ring, and the general formula (10)
The substituents exemplified as R _{4 in} 1) are exemplified. In formula (201), preferred R ₅ is a halogen atom, a carbonyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, a cyano group, or a nitro group. Particularly preferred are a halogen atom and an alkoxycarbonyl group. In formula (201), the most preferred R ₅ is an alkoxycarbonyl group having a total carbon number of 6 or less.

In the general formula (201), atoms other than Y, including T, represent development inhibitor residues released from Y by a coupling reaction with an oxidized color developing agent.
Particularly preferred is a development inhibitor having the following structure (indicated by a hydrogen atom attached to the development inhibitor residue represented by the structural formula of an atom group including T other than Y).

[0033]

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In the general formula (301), Y, T and R
_1, R ₂ is Y and T of the general formula (101) include the groups exemplified in R _1, R _2.

In the general formula (301), R ₆ is a hydrogen atom or an alkyl group which may have a substituent (for example, methyl group, isopropyl group, cyclopropyl group, 2-chloroethyl and the like), and an aryl group (for example, phenyl group). Group, tolyl group, p-methoxyphenyl group, etc.). R ₆ is preferably a hydrogen atom.

In the general formula (301), R ₇ represents an alkyl group which may have a substituent (for example, a methyl group, an isopropyl group, a cyclopropyl group, a t-butyl group, a 2-chloroethyl group, etc.), and an aryl group ( For example, phenyl group, tolyl group,
p-methoxyphenyl group etc.). R ₇ is preferably an alkyl group, particularly preferably an alkyl group having a total carbon number of 4 or less.

In the general formula (301), X represents an oxycarbonyl group (for example, an alkoxycarbonyl group such as methoxycarbonyl group, cyclohexyloxycarbonyl group, n-dodecyloxycarbonyl group, phenoxycarbonyl group, 2,4-di-t -Amylphenoxycarbonyl group,
An aryloxycarbonyl group such as a 1-naphthyloxycarbonyl group, and a 2-pyridyloxycarbonyl group,
A heterocyclic oxycarbonyl group such as a 1-phenylpyrazolyl-5-oxycarbonyl group and the like, a carbamoyl group (for example, a dimethylcarbamoyl group, a 4- (2,4-di-t-
Amylphenoxy) alkylcarbamoyl group such as butylaminocarbonyl group, arylcarbamoyl group such as phenylcarbamoyl group, 1-naphthylcarbamoyl group),
Carbonyl group (for example, alkylcarbonyl group such as acetyl group, trifluoroacetylpivaloyl group, etc., arylcarbonyl group such as benzoyl group, pentafluorobenzoyl group, 3,5-di-t-butyl-4-hydroxybenzoyl group, etc.) Represents Preferably X is an oxycarbonyl group, particularly preferably an alkoxycarbonyl group having a total carbon number of 7 or less.

In the general formula (301), atoms other than Y, including T, represent a development inhibitor residue released from Y by a coupling reaction with an oxidized color developing agent.
Particularly preferred is a development inhibitor having the following structure (indicated by a hydrogen atom attached to the development inhibitor residue represented by the structural formula of an atom group including T other than Y).

[0039]

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In the general formula (401), Y, T, R
_1, R ₂ is Y and T of the general formula (101) include the groups exemplified in R _1, R _2.

In the general formula (401), W is an aryloxy group which may have a substituent (for example, phenoxy group, p
-Ethoxycarbonylphenoxy group, 2,4-di-t-
Alkyl such as amylphenoxy group, 4- (4-hydroxyphenylsulfonyl) phenoxy group, arylthio group (eg, phenylthio group, p-ethoxycarbonylphenylthio group), sulfonyl group (eg, methanesulfonyl group, trifluoromethanesulfonyl group) A sulfonyl group and an arylsulfonyl group such as a p-toluenesulfonyl group). Preferably W is an aryloxy group, and a substituted phenoxy group is particularly preferred.

In the general formula (401), atoms other than Y, including T, represent development inhibitor residues released from Y by a coupling reaction with an oxidized color developing agent.
Particularly preferred is a development inhibitor having the following structure (indicated by a hydrogen atom attached to the development inhibitor residue represented by the structural formula of an atom group including T other than Y).

[0043]

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Next, typical compounds represented by the general formula (101) of the present invention are shown, but the present invention is not limited thereto.

[0045]

[Table 1]

Similarly, the general formulas (201) and (3)
Representative compounds represented by (01) and (401) are shown in Tables 2, 3, and 4, respectively, but the present invention is not limited thereto.

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

The following are representative examples of the synthesis of the compounds of the present invention.

[Synthesis Example 1] <Synthesis of Exemplified Compound 101>

[0052]

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5.55 g of INH-101 was added to 50 ml of chloroform, and triethylamine 2.02 was added at room temperature.
g was added. Then, 8.27 g of the compound (A) dissolved in 100 ml of chloroform was added dropwise. After completion of the dropwise addition, stirring was further continued at room temperature for 5 hours. After completion of the reaction, the reaction solution was washed successively with saturated saline, dilute hydrochloric acid, and water. After drying over magnesium sulfate, chloroform was distilled off under reduced pressure. The resulting corn-like concentrated residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / hexane as a developing solution to give 4.50 g of Exemplified Compound 101.
was gotten. The structure was confirmed by NMR and MS spectra.

[Synthesis Example 2] <Synthesis of Exemplified Compound 207>

[0055]

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5.32 g of compound (B) and 6.71 g
Of INH-202 was added to 100 ml of DMF, and then 2.30 g of tetramethylguanidine was added. Then, stirring was continued at room temperature for 5 hours. After completion of the reaction, the reaction solution is
It was poured into 0 ml and extracted with ethyl acetate. Further, the extract was washed successively with saturated saline, dilute hydrochloric acid and water. After drying over magnesium sulfate, ethyl acetate was distilled off under reduced pressure. The resulting candy-like concentrated residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / hexane as a developing solution to obtain 4.32 g of Exemplified Compound 207. The structure was confirmed by NMR and MS spectra.

[Synthesis Example 3] <Synthesis of Exemplified Compound 301>

[0058]

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6.59 g of INH-301 was added to 50 ml of chloroform, and 2.0 ml of triethylamine was added at room temperature.
g was added. Then, 8.27 g of the compound (A) dissolved in 100 ml of chloroform was added dropwise. After completion of the dropwise addition, stirring was further continued at room temperature for 8 hours. After completion of the reaction, the reaction solution was washed successively with saturated saline, dilute hydrochloric acid, and water. After drying over magnesium sulfate, chloroform was distilled off under reduced pressure. The resulting corn-like concentrated residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / hexane as a developing solution to give 4.52 g of Exemplified Compound 301.
was gotten. The structure was confirmed by NMR and MS spectra.

[Synthesis Example 4] <Synthesis of Exemplified Compound 401>

[0061]

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7.31 g of INH-401 was added to 50 ml of chloroform, and triethylamine 2.02 was added at room temperature.
g was added. Then, 8.27 g of the compound (A) dissolved in 100 ml of chloroform was added dropwise. After completion of the dropwise addition, stirring was further continued at room temperature for 4 hours. After completion of the reaction, the reaction solution was washed successively with saturated saline, dilute hydrochloric acid, and water. After drying over magnesium sulfate, chloroform was distilled off under reduced pressure. The resulting corn-like concentrated residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / hexane as a developing solution to give 4.88 g of Exemplified Compound 401.
was gotten. The structure was confirmed by NMR and MS spectra.

The general formulas (101), (201),
The compounds represented by (301) and (401) (hereinafter also referred to as the DIR coupler according to the present invention) can be added to any layer in a photographic material, for example, a silver halide emulsion layer and / or a non-photosensitive hydrophilic colloid layer. Although it can be contained, it is preferably used in the silver halide emulsion layer. More preferably, it is used for a blue-sensitive silver halide emulsion layer and / or a green-sensitive silver halide emulsion layer.

In order to incorporate the DIR coupler according to the present invention into the hydrophilic colloid layer of the color light-sensitive material, for example, a solvent having a high boiling point such as known dibutyl phthalate, tricresyl phosphate, dinonylphenol or the like and ethyl acetate, The DIR coupler according to the present invention is dissolved alone or in combination with a mixed solution with a low boiling point solvent such as ethyl propionate, and then mixed with a gelatin aqueous solution containing a surfactant, and then rotated at a high speed. After emulsifying and dispersing using a mixer, a colloid mill or an ultrasonic dispersing machine, directly add to the emulsion, or set the emulsified dispersion, shred and wash with water, and then add this to the emulsion. Can be used.

The amount of the DIR coupler according to the present invention is as follows:
The amount is preferably 0.0005 to 5.0 mol, more preferably 0.002 to 1.0 mol, per mol of silver halide.

The DIR couplers according to the present invention may be used alone or in combination of two or more.

As the silver halide emulsion used in the light-sensitive material of the present invention, any conventional silver halide emulsion can be used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region using a sensitizing dye.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or hardly soluble synthetic polymer.

A coupler is used in the emulsion layer of the silver halide color photographic light-sensitive material of the present invention.

Further, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, and a hardening agent are obtained by coupling with a colored coupler having a color correcting effect, a competitive coupler, and an oxidized form of a developing agent. Compounds which release photographically useful fragments such as filming agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

The light-sensitive material can be provided with an auxiliary layer such as a filter layer, an antihalation layer, and an anti-irradiation layer. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained.

The light-sensitive material can contain a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder and a bleaching accelerator.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain a dye image using the silver halide color photographic light-sensitive material of the present invention, for example, T.I. H. Theory of the Photographic by James
Process 4th edition (The Theory of The
PhotographicProcess Forth
Edition, pages 291-334 and Journal of the American Chemical Society (Journal of the American)
Chemical Society) Vol. 73, No. 3,
RD (Research Disclosure) 17 by using a p-phenylenediamine-based color developing agent known per se described on page 100 (1951).
Development can be carried out by a usual method described in pages 643 to 28-29, RD18716 615 and RD308119XIX.

[0076]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to prepare a silver halide color photographic light-sensitive material sample 1.

The amount of addition is expressed in grams per m ² .
However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.044 OIL-1 0.044 Gelatin 1.33 Second Layer (Intermediate Layer) AS-10 .160 OIL-1 0.20 Gelatin 1.40 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.12 Silver iodobromide b 0.50 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 SD-4 3.0 × 10 ^-6 C-1 0.51 CC-1 0.047 OIL-2 0.45 AS- 2 0.005 Gelatin 1.40.

Fourth layer (medium-speed red-sensitive layer) Silver iodobromide c 0.64 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-2 0.22 CC-1 0.028 DI-1 0.002 OIL-2 0.21 AS-3 0.006 Gelatin 0.87 Fifth layer (high-sensitivity red-sensitive layer) Silver bromide c 0.13 Silver iodobromide d 1.14 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-30. 17 CC-1 0.029 DI-1 0.027 OIL-2 0.23 AS-3 0.013 gelatin 1.23 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 gelatin 1 .00.

Seventh layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0.245 Silver iodobromide b 0.105 SD-4 5.0 × 10 ^-4 SD-5 5.0 × 10 ^{− 4} M-1 0.21 CM-2 0.039 OIL-1 0.25 AS-2 0.003 AS-4 0.063 Gelatin 0.98 8th layer (intermediate layer) M-1 0.03 CM- 2 0.005 OIL-1 0.16 AS-1 0.11 Gelatin 0.80 Ninth layer (medium-speed green-sensitive layer) Silver iodobromide e 0.87 SD-6 3.0 × 10 ^-4 SD-7 6.0 × 10 ^-5 SD-8 4.0 × 10 ^-5 M-1 0.17 CM-2 0.048 CM-3 0.059 DI-2 0.012 OIL-1 0.29 AS-4 0.05 AS-2 0.005 Gelatin 1.43.

Tenth layer (high-sensitivity green color-sensitive layer) Silver iodobromide f 1.19 SD-6 4.0 × 10 ^-4 SD-7 8.0 × 10 ^-5 SD-8 5.0 × 10 ^-5 M-1 0.09 CM-3 0.020 DI-3 0.005 OIL-1 0.11 AS-4 0.026 AS-5 0.014 AS-6 0.006 Gelatin 0.78 11th layer (yellow filter layer) Yellow colloidal silver 0.05 OIL-1 0.18 AS-7 0.16 gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide g 0.29 iodine Silver bromide h 0.19 SD-9 8.0 × 10 ^-4 SD-10 3.1 × 10 ^-4 Ya-1 0.91 DI-4 0.022 OIL-1 0.37 AS-20. 002 Gelatin 1.29.

Thirteenth layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.13 Silver iodobromide i 1.00 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^{− 4} Ya-1 0.48 DI-4 0.019 OIL-1 0.21 AS-2 0.004 Gelatin 1.55 Fourteenth layer (first protective layer) Silver iodobromide j 0.30 UV-10 0.055 UV-2 0.110 OIL-2 0.63 Gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 001 Gelatin 0.55 The characteristics of the above silver iodobromide are shown below (the average particle size is one side length of a cube of the same volume).

Emulsion No. Average particle size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 b 0.40 8.0 1.4 c 0.60 7.0 3.0. 1 d 0.74 7.0 5.0 e 0.60 7.0 4.1 f 0.65 8.7 6.5 g 0.40 2.0 4.0 h 0.65 8.0 1. 4 i 1.00 8.0 2.0 j 0.05 2.0 1.0 In addition to the above composition, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizers ST-1, ST-2, antifoggant AF-1, weight average molecular weight: 10,000 and weight average molecular weight: 1,
100,000 two types of polyvinylpyrrolidone (AF-
2), inhibitors AF-3, AF-4, AF-5, hardener H
-1, H-2 and the preservative Ase-1 were added.

The structure of the compound used in the above sample is shown below.

[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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Further, the DIR compound (DI-4) of the twelfth layer and the thirteenth layer of the sample 1 was compared with an equimolar amount of the comparative DIR compound (DI-4).
R-1, 2 and compounds 101, 102, 10 of the present invention
Except for changing to 5, 106, and 110, the same as Sample 1,
Samples 2 to 8 were obtained. The compound 101 of the present invention used in the above sample is actually a mixture of the following three types of positional isomers.

[0096]

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Similarly, each of the compounds 102, 105, 106, and 110 of the present invention used in the above sample is a mixture of three kinds of positional isomers.

[0098]

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A part of each of the samples 1 to 8 thus prepared was left to stand at 55 ° C. and 20% RH for 7 days.
Untreated sample and the above treatment (hereinafter referred to as 55 ° C. treatment)
The sample thus obtained was subjected to wedge exposure using blue light, color-developed by the following processing steps, and the sensitivity and gamma of the blue photosensitive layer were measured. The sensitivity is shown as a relative value when the sensitivity of Sample 1 is set to 100, and the gamma is shown as a relative value when the gamma of Sample 1 is set to 1.0.

At the same time, the measurement of image sharpness was also performed. The sharpness was determined by measuring the MTF of the dye image and indicating the relative value of the MTF of 30 lines / mm (sample 1 was taken as 100). Table 5 shows the results
Shown in

<< Color development processing >> (Processing step) Process Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 minutes 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 60 seconds 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

<Preparation of processing agent> (Composition of color developing solution) Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Finish to 2.0 liters and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Composition of color developing replenisher) Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make up to 1.0 liter, and potassium hydroxide or 20% sulfuric acid was used. Adjust to pH 10.18.

(Composition of bleaching solution) Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Adjust to pH 4.4 with water or glacial acetic acid.

(Composition of bleaching replenisher) Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust to pH 4.4 using aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Solution) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.2 using aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.5 with aqueous ammonia or glacial acetic acid. .

(Preparation of Stabilizing Solution and Stabilizing Replenishing Solution) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Add water to make up to 1.0 liter, and adjust to pH 8.5 using ammonia water or 50% sulfuric acid.

[0109]

[Table 5]

As is clear from Table 5, Comparative Sample No.
No. 1 has a large decrease in sensitivity and a decrease in gamma during storage. Comparative sample No. Samples Nos. 2 and 3 show a large decrease in sensitivity and gamma during storage and a small effect of improving sharpness. On the other hand, the sample Nos. 4 to No. 4. 8, it can be seen that the sharpness improving effect is large, and the decrease in sensitivity and the decrease in gamma during storage are small.

Example 2 Further, the twelfth layer and the thirteenth layer of Sample 1 produced in Example 1 were prepared.
The DIR compound (DI-4) in the layer
Samples 2 and 9 to 14 were obtained in the same manner as Sample 1 except that IR-1 and DIR-3 (structures are described in Chemical formula 29) and Compounds 201, 202, 207, 212, and 213 of the present invention were used. Was. The compound 20 of the present invention used in the above sample was used.
1 is actually a mixture of the three regioisomers shown below.

[0112]

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Similarly, the compounds 202, 207, 212, and 213 of the present invention used in the above samples are each a mixture of three kinds of positional isomers.

Each sample thus prepared was subjected to the same operation as in Example 1 to obtain photographic characteristic values. Table 6 shows the results.

[0115]

[Table 6]

As is clear from Table 6, Comparative Sample No.
No. 1 has a large decrease in sensitivity and a decrease in gamma during storage. Comparative sample No. In Nos. 2 and 9, sensitivity and gamma decrease during storage are large and the sharpness improving effect is small. On the other hand, the sample Nos. 10 to No. 14, it can be seen that the sharpness improving effect is large, and the decrease in sensitivity and the decrease in gamma are small even during storage.

Example 3 The D and D of the twelfth and thirteenth layers of the sample 1 manufactured in the first example were obtained.
An IR compound (DI-4) was equimolar to this comparative DIR-
Samples 15 to 20 were obtained in the same manner as in Sample 1, except that Compound No. 4 (the structure is described in Chemical formula 29), DIR-5 and Compounds 301, 303, 304, and 305 of the present invention were used. The compound 301 of the present invention used in the above sample is actually a mixture of the following three types of positional isomers.

[0118]

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Similarly, the compounds 303, 304, and 305 of the present invention used in the above samples are each a mixture of three types of positional isomers.

[0120]

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Each sample thus prepared was subjected to the same operation as in Example 1 to obtain photographic characteristic values. Table 7 shows the results.

[0122]

[Table 7]

As is clear from Table 7, the comparative sample No.
No. 1 has a large decrease in sensitivity and a decrease in gamma during storage. Comparative sample No. Nos. 15 and 16 have a large decrease in sensitivity and gamma during storage, and have little effect of improving sharpness. On the other hand, the sample Nos. No. 17 to No. 17 20 shows that the sharpness improving effect is large, and that the reduction in sensitivity and the reduction in gamma are small even during storage.

Example 4 The D and H of the twelfth and thirteenth layers of Sample 1 produced in Example 1 were obtained.
An IR compound (DI-4) was equimolar to this comparative DIR-
6 (structure is described in Chemical Formula 32) and compound 401 of the present invention;
Samples 21 to 25 were obtained in the same manner as in Sample 1, except that the samples were changed to 402, 406, and 407. The compound 401 of the present invention used in the above sample is actually a mixture of the following three types of positional isomers.

[0125]

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Similarly, the compounds 402, 406 and 407 of the present invention used in the above samples are each a mixture of three kinds of positional isomers.

Each sample thus prepared was subjected to the same operation as in Example 1 to obtain photographic characteristic values. Table 8 shows the results.

[0128]

[Table 8]

As is clear from Table 8, the comparative sample No.
No. 1 has a large decrease in sensitivity and a decrease in gamma during storage. Comparative sample No. No. 21 has a large decrease in sensitivity and gamma during storage, and has little sharpness improving effect. On the other hand, the sample Nos. No. 22 to No. 22. 25, the sharpness improving effect is large, and it can be seen that sensitivity reduction and gamma reduction are small even during storage.

Example 5 The following layers were coated on a triacetate base in the following order to prepare a basic sample.

(1) As a cyan coupler, C.I.
Red-sensitive silver iodobromide emulsion layer containing 5 g / m ² , gelatin 2.4 g / m ² and silver halide 1.6 g / m ² (2) Gelatin 0.5 g / m ² and 2,5-di A gelatin interlayer containing 0.1 g / m ² of -t-octyl hydroquinone (3) 1.70 g / Ya-1 of a yellow coupler as a yellow coupler
m ² , gelatin 2.4 g / m ² and silver halide 1.6 g
/ M ² blue-sensitive silver iodobromide emulsion layer (4) A protective layer comprising 0.8 g / m ^{2 of} gelatin.

Samples 26 to 32 were prepared by adding 3.0 × 10 ⁻⁴ mol / m ^{2 of the} DIR compound shown in Table 9 to the third layer containing the yellow coupler among the constituent layers of the basic sample. (The structures of DIR-7 and 8 are described in Chemical Formula 32).

Each sample was divided into two parts, one of which was subjected to wedge exposure with white light, and the other to wedge exposure with red light. Next, the same processing as in Example 1 was performed. For each sample, a gamma value is obtained from a characteristic curve of a cyan dye obtained by color development, and gamma (gR) by red exposure is changed to gamma (gW) by white exposure.
Table 9 shows the values (gR / gW) divided by.

[0134]

[Table 9]

As is clear from Table 9, the compound of the present invention has a large gR / gW, and shows a larger overlay effect than when a conventional DIR coupler is used, and is effective in improving color reproducibility. It turned out to be a DIR coupler.

Example 6 Of the constituent layers of the basic sample prepared in Example 5, the DIR compound shown in Table 10 was added to the third layer containing the yellow coupler at 3.0 × 10 ⁻⁴ mol / m ^2. , Samples 33 to 36
Was prepared.

Each sample was divided into two parts, one of which was subjected to wedge exposure with white light, and the other was subjected to wedge exposure with red light. Next, the same processing as in Example 1 was performed.

For each sample, the gamma value was determined from the characteristic curve of the cyan dye obtained by color development, and the gamma (gR) by red exposure was changed to the gamma (gR) by white exposure.
Table 10 shows the values (gR / gW) divided by W).

[0139]

[Table 10]

As is clear from Table 10, the compounds of the present invention have a large gR / gW, exhibit a larger overlay effect than when a conventional DIR coupler is used, and are effective in improving color reproducibility. It turned out to be a DIR coupler.

Example 7 Of the constituent layers of the basic sample prepared in Example 5, the DIR compound shown in Table 11 was added to the third layer containing the yellow coupler at 3.0 × 10 ⁻⁴ mol / m ^2. , Samples 37-40
Was prepared.

Each sample was divided into two parts. One of the samples was subjected to wedge exposure with white light, and the other was subjected to wedge exposure with red light. Next, the same processing as in Example 1 was performed.

For each sample, the gamma value was determined from the characteristic curve of the cyan dye obtained by color development, and the gamma (gR) due to red exposure was changed to the gamma (gR) due to white exposure.
Table 11 shows the values (gR / gW) divided by W).

[0144]

[Table 11]

As is clear from Table 11, the compounds of the present invention have a large gR / gW, exhibit a larger layering effect than when a conventional DIR coupler is used, and are effective in improving color reproducibility. It turned out to be a DIR coupler.

Example 8 Of the constituent layers of the basic sample prepared in Example 5, the DIR compound shown in Table 12 was added to the third layer containing the yellow coupler at 3.0 × 10 ⁻⁴ mol / m ^2. , Samples 41 to 44
Was prepared.

Each sample was divided into two parts, one of which was subjected to wedge exposure with white light, and the other was subjected to wedge exposure with red light. Next, the same processing as in Example 1 was performed.

For each sample, a gamma value was determined from the characteristic curve of the cyan dye obtained by color development, and the gamma (gR) due to red exposure was changed to the gamma (gR) due to white exposure.
Table 12 shows the values (gR / gW) divided by W).

[0149]

[Table 12]

As is clear from Table 12, the compounds of the present invention have a large gR / gW, exhibit a larger overlay effect than when a conventional DIR coupler is used, and are effective in improving color reproducibility. It turned out to be a DIR coupler.

[0151]

According to the present invention, a color light-sensitive material having good sharpness, a large overlay effect, and improved storage stability of the light-sensitive material over time can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Naoki Sato 1 Konica Corporation, Sakuracho, Hino-shi, Tokyo

Claims (4)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (101). Embedded image [In the formula, Y represents a yellow coupler residue capable of performing a coupling reaction with an oxidized form of a color developing agent, and T represents a 1,2, which may have a substituent bonded to the coupling position of Y with a nitrogen atom. , 4-triazole skeleton or a 1,2,3-triazole skeleton which may have a substituent. S represents a sulfur atom bonded on the carbon atom of T. R ₁ is a hydrogen atom,
R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent Represents R ₃ represents an alkyl group which may have a substituent or an aryl group which may have a substituent; R ₄ represents an arbitrary substituent which can be substituted on a benzene ring;
Represents 2, 3 or 4. When n is 2 or more, each R ₄ may be the same or different. ] 2. A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (201). Embedded image [In the formula, Y represents a yellow coupler residue capable of performing a coupling reaction with an oxidized form of a color developing agent, and T represents a 1,2, which may have a substituent bonded to the coupling position of Y with a nitrogen atom. , 4-triazole skeleton or a 1,2,3-triazole skeleton which may have a substituent. S represents a sulfur atom bonded on the carbon atom of T. R ₁ is a hydrogen atom,
R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent Represents R ₅ represents an arbitrary substituent that can be substituted on the benzene ring, and m represents 0, 1, 2, 3, 4 or 5. m is 2
At this time, each R ₄ may be the same or different. ] 3. A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (301). Embedded image [In the formula, Y represents a yellow coupler residue capable of performing a coupling reaction with an oxidized form of a color developing agent, and T represents a 1,2, which may have a substituent bonded to the coupling position of Y with a nitrogen atom. , 4-triazole skeleton or a 1,2,3-triazole skeleton which may have a substituent. S represents a sulfur atom bonded on the carbon atom of T. R ₁ is a hydrogen atom,
R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent Represents R ₆ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ₇ represents an alkyl group which may have a substituent or a substituent. Represents an optionally substituted aryl group. X represents an oxycarbonyl group, a carbamoyl group, or a carbonyl group. ] 4. A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (401). Embedded image [In the formula, Y represents a yellow coupler residue capable of performing a coupling reaction with an oxidized form of a color developing agent, and T represents a 1,2, which may have a substituent bonded to the coupling position of Y with a nitrogen atom. , 4-triazole skeleton or a 1,2,3-triazole skeleton which may have a substituent. S represents a sulfur atom bonded on the carbon atom of T. R ₁ is a hydrogen atom,
R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent Represents W is an aryloxy group optionally having a substituent,
Represents an arylthio group which may have a substituent, or a sulfonyl group which may have a substituent. ]