JPH0427536B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to silver halide photographic light-sensitive materials, and more specifically, silver halide color photographs that have excellent fastness to light, do not impair the whiteness of white areas, and have excellent sharpness. Regarding photosensitive materials. [Background of the Invention] A method of forming a dye image using a silver halide color photographic light-sensitive material includes a method of forming a dye image by a reaction between a photographic coupler and an oxidized color developing agent. Magenta, yellow, and cyan couplers are used as photographic couplers for color reproduction, and aromatic primary amine color developing agents are used as color developing agents. A dye such as an azomethine dye is formed by the reaction of each coupler with an oxidized form of an aromatic primary amine color developing agent, and a reaction between a cyan coupler and an oxidized form of an aromatic primary amine color developing agent forms a dye such as an azomethine dye. , dyes such as indoaniline dyes are formed. Among these, in order to form a magenta image, 5-pyrazolone, cyanoacetophenone,
Indazolone, pyrazolobenzimidazole, pyrazolotriazole couplers, etc. are used. Most of the magenta color image forming couplers that have been used in practice have been 5-pyrazolone couplers. Color images formed from 5-pyrazolone couplers have excellent fastness to light and heat, but the color tone of this dye is not sufficient;
Unnecessary absorption with a yellow component exists near 430 nm, and the absorption spectrum of visible light near 550 nm is also broad, causing color turbidity and resulting in photographic images lacking in vividness. The U.S. patent for this coupler without unnecessary absorption
No. 3725067, JP-A-59-162548, JP-A-59-
1H-pyrazolo [3,
2-c]-s-triazole coupler, 1H-imidazo[1,2-b]-pyrazole coupler,
1H-b pyrazolo[1,5-b]-pyrazole coupler or 1H-b pyrazolo(1,5-d]
Tetrazole couplers are particularly good. However, the light fastness of magenta dye images formed from these couplers is significantly lower. When these couplers are used in photosensitive materials, especially photosensitive materials suitable for direct viewing,
This impairs the essential requirement for photographic materials to record and preserve images, making it difficult to put them into practical use. Many methods have been proposed to improve the light fastness of these dye images.
Typical methods include a method in which the dye itself formed from the coupler is made fast, and a method in which various antifading agents are added to improve the fastness. The method of adding an anti-fading agent is an effective means of preventing fading and is widely used. Examples of compounds that improve the fastness of dye images to light include hydroquinone derivatives described in U.S. Patent No. 2360290, U.S. Patent No. 2418613, U.S. Pat. , No. 3573050, No. 3574627,
Same No. 3764337, Same No. 3574626, Same No. 3698909,
Derivatives such as chroman and malan described in U.S. Patent No. 4015990, U.S. Patent No. 3457079,
p described in No. 3069262, Special Publication No. 13496, etc.
-alkoxyphenols, etc. However, these compounds did not have sufficient effects. On the other hand, JP-A-56-99340
No. 56-168652 and No. 60-51834 describe techniques for improving light fastness using metal complexes. Although these metal complexes are effective as light-fastening agents, some of the metal complexes themselves are highly colored, and have the disadvantage that the white parts of photographic images appear yellow, yellow-green, or green. . Therefore, we used metal complexes in combination to improve light fastness.
In addition, it was desired to improve the whiteness of the white part.
Conventionally, two types of methods have been used to improve whiteness. One is a method of improving the whiteness of the base paper support itself, which is described in JP-A-53-19021, etc., and the other is a method of improving the whiteness of the base paper support itself, which is described in JP-A-53-19021.
This method uses oil-soluble dyes as described in No. 93150. Improvement in the whiteness of the base paper itself is determined by the properties of the titanium oxide contained in the base paper, and it is difficult to significantly improve the whiteness. Improving whiteness by using oil-soluble dyes is more effective in that it can be easily used in silver halide photographic materials, and the range of improvement in whiteness is large. As a result of various studies, the present inventors surprisingly found that at least one particular magenta coupler, at least one particular metal complex, and at least one oil-soluble dye can be used in combination. It has been found that the light fastness of dye images can be improved without impairing the whiteness of the white parts of photographic images, and the sharpness of dye images can also be improved. In particular, the lightfastness and sharpness improvement effects on dye images obtained from the particular magenta couplers used in the above combinations of the present invention are significantly greater than expected improvements in dye images when used in combination with conventional couplers. This could not have been predicted from any of the prior art techniques. [Object of the Invention] Therefore, the first object of the present invention is to provide a dye image with excellent light fastness without impairing the whiteness of the white part.
Another object of the present invention is to provide a silver halide photographic material with excellent sharpness. A second object of the present invention is to provide a silver halide photographic material that has excellent color reproducibility of magenta dye images and improved light fastness of magenta dye images. [Structure of the Invention] The above object of the present invention is to provide at least one magenta coupler represented by the following general formula [] and a metal complex having a singlet oxygen quenching rate constant of 3×10 ⁷ M ^-1 ·sec ^-1 or more. and at least one oil-soluble dye. General formula [] [Wherein, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle represented by the following general formulas [] to [], and the ring formed by Z may have a substituent. . X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ] General formula [] General formula [] General formula [] General formula [] General formula [] General formula [] (In the general formulas [] to [], R ₂ to _{R 8} have the same meaning as R above.) [Specific structure of the invention] Next, the present invention will be specifically explained. The above general formula according to the present invention [] General formula [] In the magenta coupler represented by, 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 separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. 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,
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,
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 to 1 carbon atoms.
32, alkenyl groups, alkynyl groups with 2 to 32 carbon atoms, cycloalkyl groups, cycloalkenyl groups with 3 to 12 carbon atoms, especially 5 to 7 carbon atoms
Preferred are alkyl groups, alkenyl groups,
Alkynyl groups 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 atom, heterocycle, cycloalkyl group, cycloalkenyl, spiro compound residue, bridged hydrocarbon In addition to compound residues, acyl, carboxy, carbamoyl,
Those substituted via a carbonyl group such as alkoxycarbonyl and aryloxycarbonyl, and those substituted via a hetero atom {specifically, hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, etc. substituted through the oxygen atom, nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino,
Those substituted via a nitrogen atom such as acylamino, sulfonamide, imide, and ureido; those substituted via a sulfur atom such as alkylthio, 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)tetradecanamidophenoxy]
Examples include propyl group, allyl group, cyclopentyl group, and cyclohexyl group. The aryl group represented by R is preferably a phenyl group, and 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- A 7-membered group is preferable, and may be substituted or condensed. Specific examples thereof include 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group. Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, α
-2,4-di-t-amylphenoxybutanoyl group and other alkylcarbonyl groups, benzoyl groups, 3
Examples include arylcarbonyl groups such as -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-toenesulfonyl group. The sulfinyl group represented by R includes ethylsulfinyl group, octylsulfinyl group, 3-
Alkylsulfinyl group such as phenoxybutylsulfinyl group, phenylsulfinyl group, m-
Examples include arylsulfinyl groups such as pentadecyl phenylsulfinyl groups. The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group,
Examples include alkoxyphosphonyl groups such as octyloxyphosphonyl groups, aryloxysulfonyl groups such as phenoxyphosphonyl groups, and arylsulfonyl groups such as phenylphosphonyl 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]heptan-1-yl, tricyclo[3.3.1.1 ³ ' ⁷ ]decane-1-yl, 7,7-
1-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, 2-
Ethoxyethoxy group, pentadecyloxy group, 2
-dodecyloxyethoxy group, phenethyloxyethoxy group and the like. The aryloxy group represented by R is preferably a phenyloxy group, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, such as a phenoxy group, p
Examples include -t-butylphenoxy group and m-pentadecylphenoxy group. The heterocyclic oxy group represented by R is 5 to 7
Preferably, the heterocycle has a substituent, for example, 3,
Examples include 4,5,6-tetrahydropyranyl-2-oxy group and 1-phenyltetrazole-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. The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-chloroacetyloxy group, etc. , benzoyloxy group, etc. The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, an N-phenylcarbamoyloxy group, etc. Can be mentioned. 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, anilino group, m
-chloroanilino group, 3-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecaneamideanilino group, and the like. As the acylamino group represented by R, an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group)
etc., which may further have a substituent, specifically an acetamide group, an α-ethylpropanamide group, an N-phenylacetamide group, a dodecanamide group, a 2,4-di-t-amylphenoxylene group, etc. Examples include cyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group, and the like. 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 may 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,
Examples include N-methyl-N-decylureido group, N-phenylureido group, and Np-tolylureido group. The sulfamoylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoyl Examples include an amino group and an N-phenylsulfamoylamino group. 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, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc. The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, etc. It will be done. 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, p-methoxyphenylthio group, 2
-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, p-acetaminophenylthio group and the like. The heterocyclic thio group represented by R is 5 to 7
A membered heterocyclic thio group is preferable, 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. Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by and substituent groups. 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, and R ₂ ' and R ₃ ' represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) ,
Examples include hydroxymethyl group and 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, hexadecylcarbamoylmethoxy 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 aryloxycarbonyloxy 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 substituted via the nitrogen atom include the general formula Examples include those shown in . Here R ₄ ′ and
R ₅ ′ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and R ₄ ′ and
R ₅ ' may be combined to form a heterocycle. however
R ₄ ′ and R ₅ ′ cannot both be 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, octyl group, 2-ethylhexyl group, and 2-ethylhexyl group.
-chloroethyl group. The aryl group represented by R ₄ ' or R ₅ ' has 6 to 32 carbon atoms, and is preferably a phenyl group or a naphthyl group, and the aryl group may have a substituent. Examples of substituents for the alkyl group represented by ₄ ' or _R5 ' include those listed above and an alkyl group. Specific examples of the aryl group include phenyl group, 1-naphthyl group, 4
-methylsulfonylphenyl group. The heterocyclic group represented by R ₄ ′ or R ₅ ′ is 5 to
A 6-membered ring is preferred, and may be a fused ring,
It may have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-furyl group, 2-quinolyl group, 2-pyrimidyl group,
-benzothiazolyl group, 2-biridyl group, etc. The sulfamoyl group represented by R ₄ ' or R ₅ ' includes N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, These alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group, 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-dianophenylcarbamoyl 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 one, 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-dioxoxazolidinyl 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, the general formula [] and the general formula [] ~
Substituents on the heterocycle in [] (for example, R,
R ₁ ~ R ₈ ) is When it has a moiety (R″, X, and Z″ are synonymous with R, X, and Z in the general formula []),
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 [], R ₅ and R ₆ are the general formula []
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 the general formula [] is represented by, for example, the following general formulas [] to []. General formula [] General formula [] General formula [] General formula [] General formula [] General formula [] In the general formulas [] to [], R ₁ to R ₈ and X have the same meanings as R and X described above. Also, preferred among the general formulas [] are those represented by the following general formula []. General formula [] In the formula, R ₁ , X and Z ₁ are R in the general formula [],
Synonymous with X and Z. Among the magenta couplers represented by the general formulas [] to [], particularly preferred are the magenta couplers represented by the general formula []. Regarding the substituents on the heterocycle in the general formulas [] to [], R in the general formula [] and R ₁ in the general formulas [] to []
preferably satisfies Condition 1 below, more preferably satisfies Conditions 1 and 2 below, and particularly preferably satisfies Conditions 1, 2 and 3 below. 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 []. General formula [] 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, and 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 [] 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, and heterocyclic groups represented by R in the above general formula []. Specific examples of bridged hydrocarbon compound residues and their substituents are listed. Among the general formulas [], it is preferable that () two of R ₉ to _{R 11} are alkyl groups, () one of R ₉ to R ₁₁ , for example R ₁₁ , is a hydrogen atom, and the other When two of 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, cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and the substituent thereof represented by R in the general formula []. Here are some specific examples. In addition, substituents that the ring formed by Z in general formula [] and the ring formed by Z ₁ in general formula [] may have, and general formulas [] ~
R ₂ to _{R 8} in [] are the following general formula []
The one represented by is preferable. General formula [] -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 R1 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 general formula [] above is an alkyl group. Preferred substituents include phenyl. Preferred specific examples of alkylene represented by R ¹ are shown below. _{−CH2CH2CH2-} ^, _{_ _}

【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, octadecyl, 2-hexyldecyl, and the like. 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 [], those represented by the following general formula [] are particularly preferred. General formula [XI] In the formula, R and X are synonymous with R and X in the general formula [], and R ¹ and R ² are R ¹ in the general formula [],
Synonymous with R ² . Moreover, the synthesis of the coupler is carried out in the Journal of
Journal of the Chemical Society, Perkin
) (1977), 2047-2052, U.S. Patent No. 3725067,
The synthesis was carried out with reference to JP-A-59-99437 and JP-A-58-42045. The coupler of the present invention 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. The couplers of the present invention can also be used in combination with other types of magenta couplers. Furthermore, when the silver halide photographic material according to the present invention is used as a multicolor photographic material, in addition to the coupler of the present invention, yellow couplers and cyan couplers commonly used in this industry are used in the usual manner. be able to. Furthermore, if necessary, a colored coupler having a color correction effect or a coupler (DIR coupler) that releases a development inhibitor during development may be used. Two or more of the above couplers can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. As the cyan coupler and yellow coupler used in the present invention, a phenol-based or naphthol-based cyan coupler and an acylacetamide-based or benzoylmethane-based yellow coupler are used, respectively. These yellow couplers include, for example, U.S. Patent Nos. 2778658, 2875057, 2908573,
3277155, 3227550, 3253924, 3277155, 3227550, 3253924,
No. 3265506, No. 3277155, No. 3341331, No. 3265506, No. 3277155, No. 3341331, No.
No. 3369895, No. 3384657, No. 3408194, No. 3369895, No. 3384657, No. 3408194, No.
No. 3415652, No. 3447928, No. 3551155, No.
3582322, 3725072, 3894875, etc., German Patent Publication No. 1547868, 2057941, 2162899
No. 2163812, No. 2218461, No. 2219917,
No. 2261361, No. 2263875, Special Publication No. 1973-13576,
JP-A-48-29432, JP-A No. 48-66834, JP-A No. 49-
No. 10736, No. 49-122335, No. 50-28834 and No.
It is described in No. 50-132926, etc. As a cyan coupler, for example, the US patent
No. 2369929, No. 2423730, No. 2434272, No.
No. 2474293, No. 2698794, No. 2706684, No.
No. 2772162, No. 2801171, No. 2895826, No. 2895826, No. 2801171, No. 2895826, No.
No. 2908573, No. 3034892, No. 3046129, No. 3046129, No.
No. 3227550, No. 3253294, No. 3311476, No. 3227550, No. 3253294, No. 3311476, No.
No. 3386301, No. 3419390, No. 3458315, No. 3458315, No. 3419390, No. 3458315, No.
No. 3476563, No. 3516831, No. 3560212, No. 3560212, No. 3516831, No. 3560212, No.
No. 3582322, No. 3583971, No. 3591383, No. 3582322, No. 3583971, No. 3591383, No.
No. 3619196, No. 3632347, No. 3652286, No. 3619196, No. 3632347, No. 3652286, No.
No. 3737326, No. 3758308, No. 3779763, No.
No. 3839044, No. 3880661, German patent publication
No. 2163811, No. 2207468, Special Publication No. 39-27563,
45-28836, JP-A No. 47-37425, 50-
No. 10135, No. 50-25228, No. 50-112038, No. 50
−117422, No. 50-130441, No. 53-109630,
No. 56-65134, No. 56-99341 and Research Disclosure 14853
(1976) etc. The metal complex according to the present invention is a metal complex having a singlet oxygen quenching rate constant of 3×10 ⁷ M ⁻¹ ·sec ⁻¹ or more. The above quenching rate constant of singlet oxygen is the journal
Journal of Physical Chemistry
Physical Chemistry) 83 , 591 (1979), etc., and is determined by the method of measuring photobleaching of rubrene. That is, a chloroform solution of rubrene and a chloroform solution containing a mixture of rubrene and the compound to be measured are irradiated with light of equal energy. The initial capacity of rubrene at this time is [R], the concentration of the compound to be measured is [Q], the concentration of rubrene in the solution of rubrene alone after the test is [R] ^O _F , and the concentration of rubrene after the test and the compound to be measured are When the concentration of rubrene in a mixed solution of compounds is [R] ^Q _F , the quenching rate constant (kq) of singlet oxygen is kq = 5.3 × 10 ⁷ ([R] ^Q / _F - [R] ^O / _F ) + 1 .7×10 ⁴
ln([R] ^Q / _F / [R] ^O / _F / [Q]ln([R] / [R
] ^Q / _F ). The metal complex according to the present invention has a singlet oxygen quenching rate constant defined by the above formula of 3×10 ⁷ M ^-1 ·sec ^-1 or more, preferably 1×10 ⁸ M ^-1 ·sec ^- A compound with a quenching rate constant of ¹ or more. The central metal of the metal complex is preferably a transition metal, more preferably a metal atom of Fe, Co, Ni, Pd, or Pt, and particularly preferably a Ni metal atom. The quenching rate constant of singlet oxygen according to the present invention is 3
As the metal complex of ×10 ⁷ M ⁻¹ ·sec ⁻¹ or more, those represented by the following general formulas [XII] to [ ] are preferable. General formula [XII] General formula [] General formula [] [In general formula [], general formula [] and general formula [], M represents a metal atom. X ¹ and X ² are each an oxygen atom, a sulfur atom or -NR ⁷ - (R ⁷ is a hydrogen atom, an alkyl group,
represents an aryl group or a hydroxyl group). X ³ represents a hydroxyl group or a mercapto group. Y represents an oxygen atom or a sulfur atom. R ³ , R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom, a halogen atom, a cyano group, or an alkyl group, aryl group, cycloalkyl group or heterocyclic ring bonded to a carbon atom directly or via a divalent linking group. represents a group. Further, at least one of the combinations of R ³ and R ⁴ and R ⁵ and R ⁶ may form a 5- or 6-membered ring together with the carbon atoms connected to each other. Z ⁰ represents a compound capable of coordinating with M or a residue thereof. General formula [] [In the formula, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each bonded to a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, or a carbon atom on the benzene ring directly or indirectly via a divalent linking group. Represents an alkyl group, aryl group, cycloalkyl group or heterocyclic group. Also R ₂₁ and R ₂₂ , R ₂₂ and R ₂₃ or R ₂₃
R ₂₄ may be combined with each other to form a 6-membered ring. R ₂₅ represents a hydrogen atom, an alkyl group or an aryl group. A represents a hydrogen atom, an alkyl group, an aryl group or a hydroxy group. M represents a metal atom. ] In the general formula [XII], general formula [] and general formula [], X ¹ and X ² may be the same or different, but each represents an oxygen atom, a sulfur atom or -NR ⁷ -(R ⁷ is a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, benzyl group, etc.), an aryl group (e.g. phenyl group) , tolyl group, naphthyl group, etc.) or hydroxyl group), preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom. X ³ in the general formula [] represents a hydroxyl group or a mercapto group, preferably a hydroxyl group. Y in general formula [XII], general formula [] and general formula [] represents an oxygen atom or a sulfur atom (in general formula [], the two Y's may be the same or different from each other). , preferably a sulfur atom. R ³ , R ⁴ , R ⁵ and R ⁶ in general formula [], general formula [] and general formula [] may be the same or different, and hydrogen atoms, halogen atoms (fluorine, chlorine, , bromine, iodine), cyano group,
Direct or divalent linking groups [e.g. -O-, -S-,
-NH-, ^-NR7'- , { ^R7 ' is a hydroxyl group, an alkyl group (e.g. methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i- (butyl group, etc.), aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.). }, -OCO-, -CO-, -NHCO-,
−CONH−, −COO−, −SO ₂ NH−, −NHSO ₂
-, -SO ₂ -, etc.] to a carbon atom (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, dodecyl group, hexadecyl group, etc.), and these alkyl groups The group may be a straight-chain alkyl group or a branched alkyl group), an aryl group (e.g., phenyl group, naphthyl group, etc.), a cycloalkyl group (e.g., cyclopentyl group, cyclohexyl group), or a heterocyclic group (e.g., pyridyl group, imidazolyl group). group, frill group,
thienyl group, pyrrolyl group, pyrrolidinyl group, quinolyl group, morpholinyl group, etc.). Among these, examples of groups formed by an alkyl group, aryl group, cycloalkyl group or heterocyclic group bonded to a carbon atom via a divalent linking group include an alkoxy group (e.g. methoxy group, ethoxy group, n-butyloxy group, straight chain or branched alkyloxy group such as octyloxy group), alkoxycarbonyl group (straight chain or branched alkyloxy group such as methoxycarbonyl group, ethoxycarbonyl group, n-hexadecyloxycarbonyl group) branched alkyloxycarbonyl group), alkylcarbonyl group (e.g. straight chain or branched alkylcarbonyl group such as acetyl group, valeryl group, stearoyl group, etc.), arylcarbonyl group (e.g. benzoyl group etc.), alkylamino group (e.g. N- n-
butylamino group, N,N-di-n-butylamino group, straight chain or branched alkylamino group such as N,N-di-n-octylamino group), alkylcarbamoyl group (e.g. n-butylcarbamoyl group,
straight-chain or branched alkylcarbamoyl groups such as n-dodecylcarbamoyl group), alkylsulfamoyl groups (e.g. n-butylsulfamoyl group,
(straight chain or branched alkylsulfamoyl group such as n-dodecylsulfamoyl group), alkylacylamino group (straight chain or branched alkylcarbonylamino group such as acetylamino group, palmitoylamino group), aryloxy group (e.g., phenoxy group, naphthoxy group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group,
naphthoxycarbonyl group, etc.), arylamino group (e.g. N-phenylamino group, N-phenyl-
N-methylamino group, etc.), arylcarbamoyl group (e.g., phenylcarbamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), arylacylamino group (e.g., benzoylamino group, etc.). be able to. Furthermore, R ³ , R ⁴ , R ⁵ and R ⁶ in general formula [XII], general formula [] and general formula [] are R ³ and R ⁴
and at least one of the combinations of R ⁵ and R ⁶ is 5- or 6-membered with the carbon atoms connected and bonded to each other.
It may form a ring of members. In this case, examples of the 5- or 6-membered ring formed by at least one of the combinations of R ³ and R ⁴ and R ⁵ and R ⁶ together with the carbon atoms to which they are bonded include a cyclopentene ring, a cyclohexene ring, and a benzene ring. ring (however, this benzene ring includes a fused benzene ring, that is, for example, a naphthalene ring, an anthracene ring), a hydrocarbon ring having at least one saturated bond, a heterocycle (for example, a nitrogen-containing 5- or 6-membered heterocycle) ), etc. When these 5- or 6-membered rings have a substituent, examples of the substituent include a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, an alkyl group (such as a methyl group, an ethyl group,
Straight chain or branched alkyl groups having 1 to 20 carbon atoms such as n-propyl group, n-butyl group, n-octyl group, t-octyl group, n-hexadecyl group), aryl group (e.g. phenyl group, naphthyl group, etc.), alkoxy group (e.g. methoxy group, n-
butoxy group, t-butoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), alkoxycarbonyl group (e.g., n-pentyloxycarbonyl group, t-
(linear or branched alkyloxycarbonyl groups such as pentyloxycarbonyl group, n-octyloxycarbonyl group, t-octyloxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group, etc.), acyl group (e.g. acetyl group), group, straight-chain or branched alkylcarbonyl group such as stearoyl group), acylamino group (for example, straight-chain or branched alkylcarbonylamino group such as acetamido group, arylcarbonylamino group such as benzoylamino group), arylamino group ( For example, N-phenylamino group, etc.), alkylamino group (for example, N-n-butylamino group, N,
(straight chain or branched alkylamino group such as N-diethylamino group), carbamoyl group (for example straight chain or branched alkylcarbamoyl group such as n-butylcarbamoyl group), sulfamoyl group (for example N,N-di-n- Butylsulfamoyl group, N
- straight chain or branched alkylsulfamoyl groups such as -n-dodecylsulfamoyl group), sulfonamide groups (straight chain or branched alkylsulfonylamino groups such as methylsulfonylamino group, etc.),
arylsulfonylamino groups such as phenylsulfonylamino groups), sulfonyl groups (e.g. linear or branched alkylsulfonyl groups such as mesyl groups, arylsulfonyl groups such as tosyl groups), cycloalkyl groups (e.g. cyclohexyl groups, etc.), etc. can be mentioned. General formula [XII], general formula [] and general formula [] are preferably alkyl groups or aryl groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ or R ³ and R ⁴ and R ⁵ and R ⁶ It is selected from the cases where at least one of the combinations forms a 5- or 6-membered ring with the carbon atoms connected to each other, and more preferably, the combinations of R ³ and R ⁴ and R ⁵ and R ⁶ are This is the case where a six-membered ring, particularly preferably a benzene ring, is formed together with the carbon atoms that are connected to each other. Further, M in general formula [XII], general formula [] and general formula [] represents a metal atom, preferably a transition metal atom, more preferably a nickel atom, a copper atom, an iron atom, a cobalt atom, a palladium atom, A platinum atom, most preferably a nickel atom. The compound capable of coordinating with M represented by Z ⁰ in the general formula [] is preferably an alkylamine having a linear or branched alkyl group, and particularly preferably the total number of carbon atoms in the alkyl group is 2 to 2. 36
dialkylamines and trialkylamines having 3 to 24 atoms, specific examples of which include butylamine, octylamine (e.g. t-octylamine), dodecylamine (e.g. n-dodecylamine), hexadecylamine. , monoalkylamines such as diethylamine, dibutylamine, dioctylamine, didodecylamine, diethanolamine, dibutanolamine, and dialkylamines such as triethylamine, tributylamine, trioctylamine, triethanolamine, tributanolamine, tributanolamine, etc. Examples include trialkylamines such as octanolamine. More preferred metal complexes according to the present invention represented by general formula [XII], general formula [] and general formula [] are represented by the following general formula [XIIa], general formula [a] and general formula [a]. It is a metal complex. General formula [XIIa] General formula [a] General formula [a] In the general formula [XIIa], the general formula [a] and the general formula [a], M, X ¹ , X ² , X ³ Y and Z ⁰ have the same meanings as above, respectively. In general formula [XIIa], general formula [a], and general formula [a], R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each an alkyl group (e.g., methyl group, ethyl group, n-propyl group, n-butyl group). group, linear or branched alkyl group having 1 to 20 carbon atoms such as n-octyl group, t-octyl group, n-hexadecyl group), aryl group (e.g. phenyl group, naphthyl group, etc.), alkoxy group ( For example, methoxy group, n-
butoxy group, t-butoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), alkoxycarbonyl group (e.g., n-pentyloxycarbonyl group, t-
(linear or branched alkyloxycarbonyl groups such as pentyloxycarbonyl group, n-octyloxycarbonyl group, t-octyloxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group, etc.), acyl group (e.g. acetyl group), group, straight-chain or branched alkylcarbonyl group such as stearoyl group), acylamino group (for example, straight-chain or branched alkylcarbonylamino group such as acetamido group, arylcarbonylamino group such as benzoylamino group), arylamino group ( For example, N-phenylamino group, etc.), alkylamino group (for example, N-n-butylamino group, N,
straight-chain or branched alkylamino groups such as N-diethylamino group), carbamoyl groups (e.g. straight-chain or branched alkylcarbamoyl groups such as n-butylcarbamoyl group), sulfamoyl groups (e.g. N,N-di-n-butyl Sulfamoyl group, N
- straight chain or branched alkylsulfamoyl groups such as -n-dodecylsulfamoyl group), sulfonamide groups (straight chain or branched alkylsulfonylamino groups such as methylsulfonylamino group, etc.),
represents an arylsulfonylamino group such as a phenylsulfonylamino group), a sulfonyl group (e.g. a linear or branched alkylsulfonyl group such as a mesyl group, an arylsulfonyl group such as a tosyl group), or a cycloalkyl group (e.g. a cyclohexyl group, etc.) . m and n each represent an integer of 0 to 4. A more preferred compound among general formulas [XIIa], [a], and [a] is a compound represented by general formula [a]. The most preferred compound among the compounds represented by the general formula [a] is the general formula [b]
It is indicated by. General formula [b] In general formula [b], M, X ¹ , X ² , Y,
R ¹¹ , R ¹² , m, and n are the same as above, and R ¹⁵ ,
R ¹⁶ and R ¹⁷ represent a hydrogen atom, an alkyl group (eg, butyl group, octyl group, stearyl group, etc.) or an aryl group (eg, phenyl group, naphthyl group, etc.). However, at least two of R ¹⁵ , R ¹⁶ and R ¹⁷ represent an alkyl group or an aryl group. In the general formula [], R ₂₁ , R ₂₂ , R ₂₃
Examples of the halogen atom represented by _R24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ is preferably an alkyl group having 1 to 19 carbon atoms, and may be either a straight-chain alkyl group or a branched alkyl group, and a substituent It may have. The aryl group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ preferably has 6 to 14 carbon atoms and may have a substituent. The heterocyclic group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ is preferably a 5-membered ring or a 6-membered ring, and may have a substituent. The cycloalkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ is preferably a 5-membered ring group or a 6-membered ring group, and may have a substituent. A 6-membered ring formed by combining R ₂₁ and R ₂₂ with each other is, for example,

【formula】

[expression] or

[Formula] etc. The 6-membered ring formed by R ₂₂ and R ₂₃ or R ₂₃ and R ₂₄ bonding to each other is preferably a benzene ring, and this benzene ring may have a substituent, and the bonded ring may be a benzene ring. It may be. Examples of the alkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ include methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, decyl group, dodecyl group, Examples include a tetradecyl group, a hexadecyl group, and an octadecyl group. Examples of the aryl group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ include a phenyl group and a naphthyl group. The heterocyclic group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ is preferably a 5- to 6-membered heterocyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom in the ring as a hetero atom. Examples thereof include a furyl group, a hydrofuryl group, a thienyl group, a pyrrolyl group, a pyrrolidyl group, a pyridyl group, an imidazolyl group, a pyrazolyl group, a quinolyl group, an indolyl group, an oxazolyl group, and a thiazolyl group. Examples of the cycloalkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ include a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, and a cyclohexadienyl group. Examples of the 6-membered ring formed by combining R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ include a benzene ring,
Examples include a naphthalene ring, an isobenzothiophene ring, an isobenzofuran ring, and an isoindone ring. The alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ above has two linking groups, such as oxy group (-o-), thio group (- s-), amino group, oxycarbonyl group, carbonyl group, carbamoyl group,
It may be bonded to a carbon atom on the benzene ring via a sulfamoyl group, carbonylamino group, sulfonylamino group, sulfonyl group, carbonyloxy group, or the like. Examples of the alkyl groups represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ bonded to carbon atoms on the benzene ring via the divalent linking group include alkoxy groups (for example, methoxy groups, ethoxy group, butoxy group, propoxy group, 2-ethylhexyloxy group, n-decyloxy group, n-dodecyloxy group, or n-hexadecyloxy group), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, butoxy carbonyl group, n-decyloxycarbonyl group or n
-hexadecyloxycarbonyl group), acyl group (e.g. acetyl, valeryl, stearoyl, benzoyl or toluoyl group), acyloxy group (e.g. acetoxy or hexadecylcarbonyloxy group), alkylamino group (e.g. For example, n-butylamino group, N,N-diethylamino group, or N,N-didecylamino group), alkylcarbamoyl group (such as butylcarbamoyl group, N,N-diethylcarbamoyl group, or n-dodecylcarbamoyl group) , alkylsulfamoyl group (e.g., butylsulfamoyl group, N,N-
diethylsulfamoyl group or n-dodecylsulfamoyl group), sulfonylamino group (for example, methylsulfonylamino group or butylsulfonylamino group, etc.), sulfonyl group (for example, mesyl group, ethanesulfonyl group, etc.), or an acylamino group (for example, an acetylamino group, a valerylamino group, a palmitoylamino group, a benzoylamino group, or a toluoylamino group). Examples in which the cycloalkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are bonded to a carbon atom on the ring via the above-mentioned divalent linking group include a cyclohexyloxy group, a cyclohexylcarbonyl group, Examples include a cyclohexyloxycarbonyl group, a cyclohexylamino group, a cyclohexenylcarbonyl group, and a cyclohexenyloxy group. Examples of aryl groups represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ bonded to carbon atoms on the ring via the above divalent linking group include aryloxy groups (e.g. phenoxy group or naphthoxy group), aryloxycarbonyl group (e.g.
phenoxycarbonyl group or naphthoxycarbonyl group), acyl group (such as benzoyl group or naphthoyl group), anilino group (such as phenylamino group, N-methylanilino group or N-acetylanilino group), acyloxy group (such as phenylamino group, N-methylanilino group or N-acetylanilino group), (e.g., benzoyloxy or toluoyloxy), arylcarbamoyl (e.g., phenylcarbamoyl), arylsulfamoyl (e.g., phenylsulfamoyl), arylsulfonylamino (e.g., phenyl), Sulfonylamino group, p-
tolylsulfonylamino group, etc.), an arylsulfonyl group (eg, benzenesulfonyl group, tosyl group, etc.), or an acylamino group (eg, benzoylamino group, etc.). The alkyl group, aryl group, heterocyclic group, cycloalkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ above, or R ₂₁ and R ₂₂ , R ₂₂ and R ₂₃ or R ₂₃
The 6-membered ring formed by bonding with R ₂₄ is a halogen atom (for example, a chlorine atom, a bromine atom, or a fluorine atom), a cyano group, an alkyl group (for example, a methyl group, an ethyl group, an i-propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group, or methoxyethoxyethyl group), aryl group (e.g. phenyl group, tolyl group, naphthyl group, chlorophenyl group) , methoxyphenyl or acetylphenyl), alkoxy groups (such as methoxy, ethoxy, butoxy, propoxy or methoxyethoxy), aryloxy groups (such as phenoxy, triloxy, naphthoxy or methoxyphenoxy group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, butoxycarbonyl group, or phenoxymethoxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group,
triloxycarbonyl group or methoxyphenoxycarbonyl group), acyl group (e.g. formyl group, acetyl group, valeryl group, stearoyl group, benzoyl group, toluoyl group, naphthoyl group or p-methoxybenzoyl group), acyloxy group (e.g., acetoxy or acyloxy groups), acylamino groups (e.g.,
acetamido group, benzamide group, or methoxyacetamido group), anilino group, such as (phenylamino group, N-methylanilino group, N
-phenylanilino group or N-acetylanilino group), alkylamino group (e.g. n-
Butylamino group, N,N-diethylamino group, 4
-methoxy-n-butylamino group, etc.), carbamoyl group (e.g., n-butylcarbamoyl group, N,N-diethylcarbamoyl group, n-butylsulfamoyl group, N,N-diethylsulfamoyl group, n- dodecylsulfamoyl group or N-(4-methoxy-n-butyl)sulfamoyl group), sulfonylamino group (e.g.
methylsulfonylamino group, phenylsulfonylamino group, or methoxymethylsulfonylamino group), or a sulfonyl group (for example, mesyl group, tosyl group, or methoxymethanesulfonyl group). The alkyl group represented by R ₂₅ and A may have a substituent and may be linear or branched. These alkyl groups preferably have 1 to 20 carbon atoms, excluding the carbon atoms in the substituent moiety, such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, etc. group, dodecyl group, tetradecyl group,
Examples include hexadecyl group, heptadecyl group, and octadecyl group. The aryl group represented by _R25 and A may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms excluding the carbon atoms in the substituent part, such as phenyl group, tolyl group, etc. Alternatively, a naphthyl group can be mentioned. Furthermore, two ligands may be linked via A. In the formula, M represents a metal atom. Preferably it is a transition metal atom. More preferably Cu, Co, Ni,
Pd, Fe or Pt, particularly preferably Ni. A preferred group for A is a hydroxy group. Furthermore, among the complexes represented by the above general formula [], those in which R ₂₁ is an oxy group, a thio group, an alkyl group via a carbonyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, is a hydroxy group or fluorine, R ₂₂ ,
At least one of the groups represented by R ₂₃ or R ₂₄ is a hydrogen atom, a hydroxy group, an alkyl group, or an alkoxy group. More preferred among these are those in which R ₂₅ is a hydrogen atom, R ₂₁ ,
It is a complex in which the total number of carbon atoms in the groups represented by R ₂₂ , R ₂₃ or R ₂₄ is at least 4 or more. Specific examples of metal complexes according to the present invention are shown below, but the present invention is not limited to these compounds. The metal complexes represented by the general formulas [XII] to [] are disclosed in British Patent No. 858890 and German Patent Application Publication No.
It can be synthesized by the method described in No. 2042652 and the like. The metal complex represented by the general formula [] is
EGCox.FWPinkard, W.Wa-rdlaw and K.C. Webster, Journal of Chemical Society (EGCox.FWPinkard, W.Wa-rdlaw)
and KC Webster, J.Chem.Soc., 1935, 459. The metal complex according to the present invention is preferably used in a coating amount of approximately 20 mg/m ² to 500 mg/m ² , although it varies depending on the type of metal complex used and the type of coupler used. m ² to 300
More preferably, a coating weight of mg/m ² is used. The metal complex according to the present invention can be prepared using an oil-in-water dispersion method,
The metal complex according to the present invention is added to the coupler-added layer and/or the layer adjacent to the coupler-added layer of a silver halide photographic light-sensitive material by a latex dispersion method or the like, but it is preferable that the metal complex according to the present invention is added to the same layer as the coupler-added layer. . Furthermore, it is preferable to add it into the same oil droplet as the coupler. Note that JP-A-55-93150 cites copper phthalocyanine compounds, but these compounds are used in very small amounts to adjust the whiteness of the white area, and they do not affect the fastness of dye images. The metal complex according to the present invention used for oxidation is characterized by its physical properties (quenching rate constant of single-term oxygen), amount used, method of use,
Their purpose is completely different. The oil-soluble dye according to the present invention refers to an organic dye whose solubility in water [g/100g of water] (heaviness of a substance soluble in 100g of water) at 20°C is 1×10 ^-2 or less, and typical Examples of the compounds include anthraquinone compounds and azo compounds. The oil-soluble dye according to the present invention preferably has a molecular extinction coefficient of maximum absorption wavelength (solvent chloroform) of 5000 or more at a wavelength of 400 nm or more,
More preferably, it is 20,000 or more. The oil-soluble dye according to the present invention ranges from 0.01 mg/m ² to
The coating amount is preferably 10 mg/m ² , more preferably 0.05 mg/m ² to 5 mg/m ² . The oil-soluble dye according to the present invention can be used in any photographic emulsion layer, but it is more preferable to add it to a non-photosensitive layer other than the coupler-containing layer. A particularly preferred method of using the oil-soluble dye according to the present invention is to use an oil-soluble dye having a molecular extinction coefficient of 20,000 or more at a maximum absorption wavelength of 400 nm or more.
It is included in a non-photosensitive layer other than the coupler addition layer at a coating amount of 0.05 mg/m ² to 5 mg/m ² . Preferred oil-soluble dyes in the present invention include:
It is a compound represented by the following general formula [] or []. General formula [] In the formula, R ₁ to _{R 8} each represent a hydrogen atom, a hydroxy group, an amino group or a halogen atom. General formula [] In the formula, R ₉ to _{R 20} are each a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, an alkyl group,
It represents an alkoxy group, an aminocarbonyl group, an amino group or a -N=NR group (where R is an aryl group). Examples of the halogen atom represented by R ₁ to _{R 8} in the general formula [ ] include a chlorine atom, a bromine atom, and the like. In addition, the amino group represented by R ₁ to _{R 8} may have a substituent, and this substituent is
Examples include alkyl groups (eg, methyl group, butyl group, etc.), aryl groups (eg, phenyl group, etc.), acyl groups (eg, methoxy group, benzoyl group, etc.). Examples of the halogen atom represented by R ₉ to _{R 20} in the general formula [] include a chlorine atom, a bromine atom, etc. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an alkoxy group. Examples of the carbonyl group include a methoxy group, an ethoxy group, and a propoxy group, and examples of the aminocarbonyl group include a methylaminocarbonyl group and a phenylaminocarbonyl group. Further, the amino group represented by R ₉ to _{R 20} may have the same substituent as in the general formula []. Typical examples of oil-soluble dyes used in the present invention are listed below, but the invention is not limited thereto. As a method of using a metal complex and an oil-soluble dye in combination according to the present invention, a metal complex with a singlet oxygen quenching rate constant of 3×10 ⁷ M ^-1 ·sec ^-1 or more is used.
It is preferable to use a coating amount of 200 mg/m ² to 500 mg/m ² and use an oil-soluble dye in a coating amount of 0.01 mg/m ² to 10 mg/m ² . Furthermore, the quenching rate constant of singlet oxygen is 3×
10 ⁷ M ^-1・sec ^-1 or higher metal complex from 20 mg/m ² to
used in the coupler-containing layer at a coating weight of 500mg/ ^m2 ,
More preferably, an oil-soluble dye is used in a non-photosensitive layer other than the coupler-containing layer in a coating amount of 0.01 mg/m ² to 10 mg/m ² . Methods for dispersing the coupler represented by the general formula [], the metal complex according to the present invention, and the oil-soluble dye used in the present invention include the so-called aqueous alkali dispersion method, solid dispersion method, latex dispersion method, and oil-in-water type. Various methods can be used, such as an emulsion dispersion method, and can be appropriately selected depending on the chemical structures of the coupler, metal complex, and oil-soluble dye. In the present invention, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. These dispersion methods have been well known for a long time, and the latex dispersion method and its effects are described in Japanese Patent Application Laid-open Nos. 49-74538 and 51-51.
Publications No. 59943 and No. 54-32552, Research Disclosure magazine, 1976
August, No. 14850, pages 77-79. Suitable latexes used in the latex dispersion process include, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-
(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxybentyl)]acrylamide, 2-acrylamide-2
- Homopolymers, copolymers and terpolymers of monomers such as methylpropanesulfonic acid and the like. As an oil-in-water emulsification dispersion method,
Conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, usually using a high boiling point organic solvent with a boiling point of about 150°C or higher, if necessary, a low boiling point and/or water-soluble organic solvent, The metal complex, oil-soluble dye, and coupler are dissolved and dispersed in a hydrophilic binder such as gelatin using a surfactant and dispersing means such as a stirrer, homogenizer, colloid mill, flow mixer, and ultrasonic device. make use of,
After being emulsified and dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion. The high boiling point organic solvent that can be preferably used in the present invention is a compound with a dielectric constant of less than 6.0,
The lower limit is not particularly limited, but the dielectric constant is
1.9 or more is preferable. Examples include esters such as phthalic esters and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds with a dielectric constant of less than 6.0. Further, in the present invention, a high boiling point organic solvent having a vapor pressure of 0.5 mmHg or less at 100° C. is preferable. Even more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent. Note that the organic solvent may be a mixture of two or more types, and in this case, the dielectric constant of the mixture may be less than 6.0. Note that the dielectric constant indicates the dielectric constant at 30°C. Phthalic acid esters advantageously used in the present invention include those represented by the following general formula []. General formula [] In the formula, R ₃₀ and R ₃₁ are each an alkyl group,
Represents an alkenyl group or an aryl group. however,
The total number of carbon atoms in the groups represented by R ₃₀ and R ₃₁ is 9 to 32. More preferably, the total number of carbon atoms is 16 to 24. In the present invention, the alkyl group represented by R ₃₀ and R ₃₁ in the general formula [] may be linear or branched, such as a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group,
These include hexadecyl group, heptadecyl group, octadecyl group, etc. The aryl group represented by R ₃₀ and R ₃₁ is, for example, a phenyl group, a naphthyl group, etc., and the alkenyl group is, for example, a hexenyl group, a heptenyl group, an octadecenyl group, etc. These alkyl groups, alkenyl groups and aryl groups are
May have single or multiple substituents,
Examples of substituents for alkyl and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, and alkoxycarbonyl groups. Examples of substituents for aryl groups include halogen atoms and alkyl groups. , an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkoxycarbonyl group, and the like. Phosphate esters advantageously used in the present invention include those represented by the following general formula []. General formula [] In the formula, R ₃₂ , R ₃₃ and R ₃₄ each represent an alkyl group, an alkenyl group or an aryl group.
However, the total number of carbon atoms represented by R ₃₂ , R ₃₃ and R ₃₄ is 24 to 54. The alkyl group represented by R ₃₂ , R ₃₃ and R ₃₄ in the general formula [] is, for example, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group. , tetradecyl group, pentadecyl group,
These include hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and the like. These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably R ₃₂ , R ₃₃ and R ₃₄ are alkyl groups, such as 2-ethylhexyl group,
Examples include n-octyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, sec-decyl group, sec-dodecyl group, t-octyl group, and the like. Specific examples of organic solvents preferably used in the present invention are shown below. The silver halide photographic light-sensitive material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but in particular, when color photographic paper intended for direct viewing is used, the method of the present invention can be used. The effects of this will be effectively demonstrated. The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-photosensitive silver halide emulsion layer are usually used. It has a structure in which the sexual layers are laminated on a support in an appropriate number and order of layers,
The number of layers and the order of layers may be changed as appropriate depending on the important performance and purpose of use. When the silver halide photographic light-sensitive material of the present invention is a multicolor light-sensitive material, the specific layer structure includes, on the support, a yellow dye image forming layer, an intermediate layer, a magenta dye image forming layer of the present invention, and a dye image forming layer, an intermediate layer containing an ultraviolet absorber, a cyan dye image forming layer, an intermediate layer containing an ultraviolet absorber,
Particularly preferred are those arranged with a protective layer. The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the silver halide emulsion of the present invention) includes silver bromide, silver iodobromide, silver iodochloride, and chloride. Any of those used in conventional silver halide emulsions, such as silver chloride and silver chloride, can be used. The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion of the present invention, halide ions and silver ions may be mixed at the same time, or one may be mixed in the presence of the other. In addition, by sequentially and simultaneously adding halide ions and silver ions while controlling the PH and pAg in the mixing pot, taking into account the critical growth rate of silver halide crystals,
It may be generated. After growth, a convergence method may be used to change the halogen composition of the particles. When producing the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary. The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt,
Metal ions can be added using thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts or complex salts to be included inside the particles and/or on the surface of the particles, and placed in an appropriate reducing atmosphere. In some cases, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, the method described in Research Disclosure No. 17643 can be used. The silver halide grains used in the silver halide emulsion of the present invention may consist of uniform layers inside and on the surface, or may consist of different layers. The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains. The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of {100} planes to {111} planes can be used. or,
The particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions. The silver halide emulsion of the present invention is chemically sensitized by a conventional method. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensation methods can be used alone or in combination. The silver halide emulsion of the present invention is produced using a dye known as a sensitizing dye in the photographic industry.
Can be optically sensitized to a desired wavelength range. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good. The silver halide emulsion of the present invention includes chemical heat treatment and/or chemical ripening for the purpose of preventing fog and/or maintaining stable photographic performance during the manufacturing process, storage, or photographic processing of light-sensitive materials. At the end of the process and/or after chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added. As the binder (or protective colloid) for the silver halide emulsion of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins,
Hydrophilic colloids such as sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances such as monopolymers or copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion of the present invention can be formed by using a hardening agent alone or in combination to crosslink binder (or protective colloid) molecules and increase film strength. It is hardened. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution. A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention. A dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer may be included in the photographic emulsion layer or other hydrophilic colloid layer of a photosensitive material using the silver halide emulsion of the present invention for the purpose of improving dimensional stability. I can do it. Anionic surfactants, nonionic surfactants, Cationic surfactants can be used. Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers),
Color antifoggants are used to prevent color turbidity, deterioration of sharpness, and noticeable graininess due to migration of oxidized products of developing agents or electron transfer agents. The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers. In the color light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image. Image stabilizers preferably used in the present invention include the following general formulas [A] to [H] and [J],
[K] can be mentioned. General formula [A] In the formula, R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R ₂ ,
R ₃ , R ₅ , and R ₆ are hydrogen atoms, halogen atoms, and
It represents a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamino group, and R ₄ represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group. Further, R ₁ and R ₂ may be ring-closed with each other to form a 5- or 6-membered ring, in which case R ₄ represents a hydroxy group or an alkoxy group. Further, R ₃ and R ₄ may be ring-closed to form a 5-membered hydrocarbon ring, in which case R ₁ represents an alkyl group, an aryl group, or a heterocyclic group. However, this excludes the case where R ₁ is a hydrogen atom and R ₄ is a hydroxy group. In the general formula [A], R ₁ is a hydrogen atom,
It represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group,
Straight chain or branched alkyl groups such as n-octyl group, tert-octyl group, and hexadecyl group can be mentioned. Examples of the alkenyl group represented by R ₁ include allyl, hexenyl, and octenyl groups. Furthermore, examples of the aryl group for R ₁ include phenyl and naphthyl groups. Furthermore, specific examples of the heterocyclic group represented by R ₁ include a tetrahydropyranyl group and a pyrimidyl group. Each of these groups can have a substituent, for example, the alkyl group having a substituent is a benzyl group, an ethoxymethyl group, and the aryl group having a substituent is a methoxyphenyl group, a chlorophenyl group, a 4-hydroxy-
Examples include 3,5-dibutylphenyl group. In general formula [A], R ₂ , R ₃ , R ₅ and R ₆
represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or _an acylamino group; Examples include the same groups as alkenyl and aryl groups. Examples of the halogen atoms include fluorine, chlorine, and bromine. Further, specific examples of the alkoxy group include a methoxy group and an ethoxy group. Furthermore, the acylamino group is represented by R'CONH-,
Here, R′ is an alkyl group (e.g. methyl,
ethyl, n-propyl, n-butyl, n-octyl, tert-octyl, benzyl, etc.), alkenyl groups (e.g. allyl, octynyl, oleyl, etc.), aryl groups (e.g. phenyl,
methoxyphenyl, naphthyl, etc.), or heterocyclic groups (eg, pyridyl, pyrimidyl, etc.). In the general formula [A], R ₄ represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group, and among these, the alkyl group and aryl group are the same as the alkyl group and aryl group shown in R ₁ above. The following can be specifically mentioned. Regarding the alkenyl group of R ₄ , the above R ₂ ,
The same alkoxy groups mentioned for R ₃ , R ₅ and R ₆ can be mentioned. R ₁ and R ₂ are mutually closed to form a benzene ring, such as chroman, coumaran,
Examples include methylenedioxybenzene. Furthermore, examples of the ring formed by R ₃ and R ₄ together with a benzene ring include indane. These rings may have substituents (eg alkyl, alkoxy, aryl). In addition, a spiro compound may be formed by using the atom in the ring formed by R ₁ and R ₂ or R ₃ and R ₄ by ring closure as a spiro atom, or by using R ₂ , R ₄ , etc. as a linking group,
A screw body may also be formed. Among the phenol compounds or phenyl ether compounds represented by the general formula [A], preferred are RO- groups (R represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group).
It is a biindane compound having four compounds, and is particularly preferably represented by the following general formula [A-1]. General formula [A-1] In the formula, R is an alkyl group (e.g. methyl, ethyl,
propyl, n-octyl, tert-octyl, benzyl, hexadecyl), alkenyl groups (e.g.
represents a group represented by an aryl group (eg, phenyl, naphthyl), or a heterocyclic group (eg, tetrahydropyranyl, pyrimidyl). R ₉ and R ₁₀ are each a hydrogen atom, a halogen atom, (e.g., fluorine,
R ₁₁ is hydrogen atoms, alkyl groups (e.g. methyl, ethyl, n-butyl, benzyl), alkenyl groups (e.g. 2-propenyl,
hexenyl, octenyl) or an aryl group (eg phenyl, methoxyphenyl, chlorophenyl, naphthyl). The compound represented by the general formula [A] is disclosed in U.S. Patent Nos. 3935016, 3982944, 4254216,
JP 55-21004, JP 54-145530, UK Patent Publication No. 2077455, JP 2062, 888, US Patent No.
3764337, same No. 3432300, same No. 3574627, same No.
No. 3573050, Japanese Patent Publication No. 52-152225, No. 53-20327
No. 53-17729, No. 55-6321, British Patent No.
No. 1347556, Publication No. 2066975, Special Publication No. 54-12337
No. 48-31625, US Pat. No. 3,700,455, and the like. The amount of the compound represented by the general formula [A] used is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the magenta coupler. Typical specific examples of the compound represented by the general formula [A] are shown below.

【table】

【table】

【table】 General formula [B] (In the formula, R ₁ and R ₄ are hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, alkenyloxy group, hydroxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide, respectively) _R2 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and _R3 represents a hydrogen atom, a halogen atom, or an alkyl group. , represents an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acyloxy group, a sulfonamido group, a cycloalkyl group, or an alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents. For example, Alkyl group, alkenyl group,
alkoxy group, aryl group, aryloxy group,
Hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, acyloxy group, carbamoyl group, sulfonamide group,
Examples include sulfamoyl group. Further, R ₂ and R ₃ may be ring-closed with each other to form a 5- or 6-membered ring. Examples of the ring formed by R ₂ and R ₃ together with a benzene ring include a chroman ring and a methylene dioxybenzene ring. Y represents an atomic group necessary to form a chroman or coumaran ring. The chroman or coumaran ring is a halogen atom,
Alkyl group, cycloalkyl group, alkoxy group,
It may be substituted with an alkenyl group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, or a heterocycle, and may further form a spiro ring. Among the compounds represented by general formula [B], compounds particularly useful in the present invention are general formulas [B-1] and [B-
2], [B-3], [B-4], and [B-5]. General formula [B-1] General formula [B-2] General formula [B-3] General formula [B-4] General formula [B-5] General formula [B-1], [B-2], [B-3], [B-
R ₁ , R ₂ , R ₃ and R ₄ in [4] and [B-5] have the same meanings as in the above general formula [B], and R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or a heterocyclic group. Furthermore, R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ , and R ₉ and R ₁₀ may be cyclized with each other to form a carbocycle; It may be substituted with an alkyl group. The general formula [B-1], [B-2], [B-3],
R ₁ and R ₄ in [B-4] and [B-5]
is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group or a cycloalkyl group, R ₅ , R ₆ , R ₇ ,
Particularly useful are compounds in which R ₈ , R ₉ and R ₁₀ are hydrogen atoms, alkyl groups, or cycloalkyl groups. The compound represented by the general formula [B] is Tetrahedron, 1970, vol26, 4743-4751
Page, Journal of the Chemical Society of Japan, 1972, No. 10, pp. 1987-1990,
Chemistry Letters (chem.Lett.), 1972(4)
It represents, contains, and can be synthesized according to the methods described therein, pages 315-316, JP-A-55-139383. The amount of the compound represented by the general formula [B] used is preferably 5 to 300 mol%, more preferably
It is 10 to 200 mol%. Typical specific examples of these compounds are shown below.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] General formula [C] General formula [D] In the formula, R ₁ and R ₂ are hydrogen atoms, halogen atoms,
It represents an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamido group, or an alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents. For example, halogen atoms, alkyl groups,
Examples include alkenyl groups, alkoxy groups, aryloxy groups, hydroxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acylamino groups, carbamoyl groups, sulfonamide groups, and sulfamoyl groups. Y represents an atomic group necessary to form a dichroman or dicoumaran ring together with a benzene ring. The chroman or coumaran ring is a halogen atom,
Alkyl group, cycloalkyl group, alkoxy group,
It may be substituted with an alkenyl group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, or a heterocyclic group, and may further form a spiro ring. Among the compounds represented by the general formulas [C] and [D], the compounds particularly useful in the present invention are the compounds represented by the general formula [C-
1], [C-2], [D-1] and [D-2]. General formula [C-1] General formula [C-2] General formula [D-1] General formula [D-2] R ₁ and R ₂ in the general formulas [C-1], [C-2], [D-1] and [D-2] have the same meanings as in the general formulas [C] and [D],
R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, hydroxy groups, alkenyl groups, alkenyloxy groups, aryl groups, aryloxy groups or heterocyclic groups represents. Furthermore, R ₃ and R ₄ , R ₄ and R ₅ , R ₅ and R ₆ , R ₆
and R ₇ and R ₇ and R ₈ may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group. In the general formulas [C-1], [C-2], [D-1] and [D-2], R ₁ and R ₂ are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups or cycloalkyl Particularly useful are compounds in which the groups R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are hydrogen atoms, alkyl groups or cycloalkyl groups. Compounds represented by general formulas [C] and [D] are described in Journal of the Chemical Society (J.Chem.Soc.C) 1968 (14), pp. 1837-1843, Journal of the Society of Organic Synthetic Chemistry 1970, 28(1), pp. 60-65, Tetrahedron 1973.(29), 2707-2710
and can be synthesized according to the methods described therein. The amount of the compound represented by the general formula [C] or [D] used is preferably 5 to 300 mol%, more preferably
It is 10 to 200 mol%. Specific representative examples of these compounds are shown below.

【table】

【table】

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[Table] General formula [E] In the formula, R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R ³ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, or an aryloxy group. group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group. R ² and R ⁴ are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, aryl groups, acyl groups,
It represents an acylamino group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents. Examples include alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acylamino groups, carbamoyl groups, sulfonamide groups, and sulfamoyl groups. Further, R ¹ and R ² may be ring-closed with each other to form a 5- or 6-membered ring. At that time, R ³ and R ⁴ are hydrogen atoms, halogen atoms,
It represents an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamido group, or an alkoxycarbonyl group. Y represents an atomic group necessary to form a chroman or coumaran ring. The chroman or coumaran ring is a halogen atom,
Alkyl group, cycloalkyl group, alkoxy group,
It may be substituted with an alkenyl group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group, and may further form a spiro ring. Among the compounds represented by the general formula [E], compounds particularly useful in the present invention are those represented by the general formula [E-1] and [E-
2], [E-3], [E-4] and [E-5]. General formula [E-1] General formula [E-2] General formula [E-3] General formula [E-4] General formula [E-5] R ¹ in general formulas [E-1] to [E-5],
R ² , R ³ and R ⁴ have the same meanings as in the above general formula [E], and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and
R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or a heterocyclic group. Furthermore, R ⁵ and R ⁶ ,
R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group. good. In the general formulas [E-1] to [E-5],
R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, alkyl groups,
or cycloalkyl group, the above general formula [E-5]
, R ³ and R ⁴ are hydrogen atoms, alkyl groups,
an alkoxy group, a hydroxy group or a cycloalkyl group, and the above general formulas [E-1] to [E-5]
Particularly useful are compounds in which R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are hydrogen atoms, alkyl groups, or cycloalkyl groups. The compound represented by the general formula [E] is described in Tetrahedron Letters 1965.
(8), pp. 457-460, Journal of the Chemical Society (J.Chem.Soc.C)
1966. (22), pp. 2013-2016, Zh.Org.Khim 1970,
(6), pages 1230 to 1237, and can be synthesized according to the methods described therein. The amount of the compound represented by the general formula [E] used is preferably 5 to 300 mol%, more preferably 10 to 300 mol%, based on the magenta coupler according to the present invention.
It is 200 mol%. Specific representative examples of these compounds are shown below.

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【table】

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[Table] General formula [F] In the formula, R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R ₂ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, or an aryloxy group. group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group, or alkoxycarbonyl group. R ₃ is a hydrogen atom, a halogen atom, an alkyl group,
Represents an alkenyl group, aryl group, acyl group, acylamino group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group. R ₄ is a hydrogen atom, a halogen atom, an alkyl group,
Represents an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, or an alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents. For example, alkyl groups, alkenyl groups,
alkoxy group, aryl group, aryloxy group,
Examples include a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group. Furthermore, R ₁ and R ₂ may be ring-closed with each other to form a 5- or 6-membered ring. At that time, R ₃ and R ₄ are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups,
Alkoxy group, alkenyloxy group, hydroxy group, aryl group, aryloxy group, acyl group,
Represents an acylamino group, acyloxy group, sulfonamide group, or alkoxycarbonyl group. Y represents an atomic group necessary to form a chroman or coumaran ring. The chroman or coumaran ring is a halogen atom,
Alkyl group, cycloalkyl group, alkoxy group,
It may be substituted with an alkenyl group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group, and may further form a spiro ring. Among the compounds represented by general formula [F], compounds particularly useful in the present invention are general formulas [F-1] and [F-
2], [F-3], [F-4] and [F-5]. General formula [F-1] General formula [F-2] General formula [F-3] General formula [F-4] General formula [F-5] In general formulas [F-1] and [F-5]
R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as in the above general formula [F], and R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are hydrogen atoms, halogen atoms, Represents an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or a heterocyclic group. Furthermore, R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ , and R ₉ and R ₁₀ may be cyclized with each other to form a carbocycle; It may be substituted with an alkyl group. Further, in [F-3], [F-4] and [F-5], two R ₁ to R ₁₀ may be the same or different. The general formula [F-1], [F-2], [F-3],
In [F-4] and [F-5], R ₁ , R ₂ , and R ₃ are hydrogen atoms, alkyl groups, cycloalkyl groups, and R ₄ is hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups, or cycloalkyl groups. , further R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are hydrogen atoms,
Particularly useful are compounds that are alkyl or cycloalkyl groups. The compound represented by the general formula [F] is Tetrahedron 1970, Vol26, 4743~
4751 pages, Journal of the Chemical Society of Japan 1972, No. 10, 1987-1990
Page, Synthesis 1975, Vol6, 392
~393 pages, Bul Soc, Chim,
Belg) 1975, Vol 84(7), pages 747-759, and can be synthesized according to the methods described therein. The amount of the compound represented by the general formula [F] used is preferably 5 to 300 mol%, more preferably 10 to 300 mol%, based on the magenta coupler according to the present invention.
It is 200 mol%. Specific representative examples of the compound represented by the general formula [F] are shown below.

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【table】

[Table] General formula [G] In the formula, R ¹ and R ³ are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, and a cycloalkyl group, respectively. group or an alkoxycarbonyl group. R ² is a hydrogen atom, a halogen atom, an alkyl group,
Represents an alkenyl group, hydroxy group, aryl group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group, alkoxycarbonyl group. The groups listed above may each be substituted with other substituents. As a substituent, for example, an alkyl group,
Examples include an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group. Further, R ² and R ³ may be ring-closed with each other to form a 5- or 6-membered hydrocarbon ring. This 5- or 6-membered hydrocarbon ring is a halogen atom, an alkyl group,
It may be substituted with a cycloalkyl group, an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, or the like. Y represents an atomic group necessary to form an indane ring. The indane ring is a halogen atom, an alkyl group,
It may be substituted with an alkenyl group, an alkoxy group, a cycloalkyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, or the like, and may further form a spiro ring. Among the compounds represented by general formula [G], compounds particularly useful in the present invention are represented by general formulas [G-1] to [G-
3]. General formula [G-1] General formula [G-2] General formula [G-3] R ¹ in general formulas [G-1] to [G-3],
R ² and R ³ have the same meaning as in general formula [G], and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, Represents an alkenyl group, hydroxy group, aryl group, aryloxy group or heterocyclic group.
R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ and R ⁸ and R ⁹
may be closed together to form a hydrocarbon ring,
Furthermore, the hydrocarbon ring may be substituted with an alkyl group. In the general formulas [G-1] to [G-3],
R ¹ and R ³ are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups or cycloalkyl groups, R ²
Particularly useful are compounds in which R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen, alkyl, hydroxy or cycloalkyl. The amount of the compound represented by the general formula [G] used is 5 to 300 mol% based on the magenta coupler.
is preferable, and more preferably 10 to 200 mol%. Typical specific examples of the compound represented by the general formula [G] are shown below.

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[Table] General formula [H] In the formula, R ¹ and R ² each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group. R ³ is a hydrogen atom, a halogen atom, an alkyl group,
alkenyl group, alkoxy group, hydroxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group,
Represents a cycloalkyl group or an alkoxycarbonyl group. The groups listed above may each be substituted with other substituents, such as alkyl groups, alkenyl groups,
alkoxy group, aryl group, aryloxy group,
Examples include a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group. Further, R ¹ and R ² and R ² and R ³ may be ring-closed with each other to form a 5- or 6-membered hydrocarbon ring, and the hydrocarbon ring may be a halogen atom, an alkyl group, a cycloalkyl group, or an alkoxy group. , an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, etc. Y represents an atomic group necessary to form an indane ring, and the indane ring may be substituted with a substituent capable of substituting the above hydrocarbon ring, and may further form a spiro ring. Among the compounds represented by the general formula [H], compounds particularly useful in the present invention are represented by the general formulas [H-1] to [H-
2]. General formula [H-1] General formula [H-2] General formula [H-3] R ¹ in general formulas [H-1] to [H-3],
R ² and R ³ have the same meaning as in general formula [H], and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, Represents a hydroxy group, alkenyl group, aryl group, aryloxy group or heterocyclic group.
Also R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ and R ⁸
and R ⁹ may be ring-closed with each other to form a hydrocarbon ring, and the hydrocarbon ring may be further substituted with an alkyl group. In the general formulas [H-1] to [H-3],
R ¹ and R ² are each a hydrogen atom, an alkyl group or a cycloalkyl group, R ³ is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy cycloalkyl group, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and Particularly useful are compounds in which R ⁹ is each a hydrogen atom, an alkyl group or a cycloalkyl group. Methods for synthesizing the compound represented by the general formula [H] are known, and are disclosed in U.S. Pat. No. 3,057,929, Chem.
2574 pages, Journal of the American Chemical Society (J.Am.Chem.Soc.)
1973, 95(5), pp. 1673-1674; Chemistry Letters, 1980, pp. 739-742. It is preferably mol%, more preferably 10 to 200 mol%.Specific representative examples represented by general formula [H] are shown below.

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【table】

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[Table] General formula [J] [In the formula, R ¹ represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y together with a nitrogen atom represents 5 to 7
Represents a group of nonmetallic atoms necessary to form a membered heterocycle. However, when there are two or more heteroatoms among the nonmetallic atoms containing nitrogen atoms forming the heterocycle, at least two heteroatoms are not adjacent to each other. ] Examples of the aliphatic group represented by R include a saturated alkyl group that may have a substituent and an unsaturated alkyl group that may have a substituent. Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc., and examples of unsaturated alkyl groups include ethenyl group, propenyl group, etc. It will be done. The cycloalkyl group represented by R ¹ is a 5- to 7-membered cycloalkyl group that may have a substituent, such as a cyclopentyl group and a cyclohexyl group. The aryl group represented by R ¹ represents a phenyl group or a naphthyl group, each of which may have a substituent. Aliphatic group, cycloalkyl group represented by R ¹ ,
Substituents for aryl groups include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, acylamino groups, sulfamoyl groups, sulfonamide groups, carbonyloxy groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy groups, and heterocycles. group, alkylthio group, arylthio group, etc., and these substituents may further have a substituent. In the general formula [J], Y represents a nonmetallic atomic group necessary to form a 5- to 7-membered heterocycle together with a nitrogen atom; At least two of the heteroatoms must be heteroatoms, and the at least two heteroatoms must not be adjacent to each other. In the heterocycle of the compound represented by the general formula [J], it is not preferable if all the heteroatoms are adjacent to each other because the function as a magenta dye image stabilizer cannot be exhibited. The above 5- of the compound represented by the general formula [J]
The 7-membered heterocycle may have a substituent, and examples of the substituent include an alkyl group, an aryl group, an acyl group,
These include a carbamoyl group, an alkoxycarbonyl group, a sulfonyl group, a sulfamoyl group, and may further have a substituent. Further, the 5- to 7-membered heterocycle may be saturated, but a saturated heterocycle is preferred. Further, a benzene ring or the like may be fused to the heterocycle, or a spiro ring may be formed. The amount of the compound represented by the general formula [J] of the present invention used is preferably 5 to 300 mol%, more preferably 10 to 300 mol%, based on the magenta coupler represented by the general formula [I] of the present invention. It is 200 mol%. Typical specific examples represented by general formula [J] are shown below.

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Among the compounds represented by the general formula [J], piperazine compounds and homopiperazine compounds are particularly preferred, and compounds represented by the following general formula [J-1] or [J-2] are particularly preferred. It is. General formula [J-1] General formula [J-2] In the formula, R ² and R ³ each represent a hydrogen atom, an alkyl group or an aryl group. However, R ² and R ³
cannot become hydrogen at the same time. R ⁴ to ^{R 13} each represent a hydrogen atom, an alkyl group, or an aryl group. In the above general formulas [J-1] and [J-2]
R ² and R ³ each represent a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group represented by R ² or R ³ include a methyl group, an ethyl group, a butyl group, an octyl group, and a dodecyl group. , tetradecyl group, hexadecyl group, octadecyl group, etc. The aryl group represented by R ² or R ³ includes a phenyl group and the like. The alkyl group and aryl group represented by R ² or R ³ may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group,
Examples include aryloxy groups and heterocyclic groups. The total number of carbon atoms in R ² and R ³ (including substituents) is 6
~40 is preferred. In the general formula [J-1] or [J-2], R ⁴ to ^{R 13} each represent a hydrogen atom, an alkyl group, or an aryl group, but the alkyl group represented by R ⁴ to ^{R 13} is Examples include methyl group, ethyl group, and the like. Examples of the aryl group represented by R ⁴ to R ¹³ include a phenyl group. Specific examples of the compound represented by the general formula [J-1] or [J-2] include the above-mentioned exemplary piperazine compounds (J-1) to (J-30) and exemplary homopiperazine compounds (J- 51) to (J-62). Next, a synthesis example of a typical magenta dye image stabilizer of the present invention represented by the general formula [J] will be shown. Synthesis Example 1 (Synthesis of Compound J-2) Piperazine 9.0g and myristyl bromide 55
15 g of anhydrous potassium carbonate was added to 100 ml of acetone in which g was dissolved, and the mixture was boiled and refluxed for 10 hours to react. After the reaction, the reaction solution was poured into 500 ml of water, and then extracted with 500 ml of ethyl acetate. After drying the ethyl acetate layer over magnesium sulfate, the ethyl acetate was distilled off to obtain the desired product as white crystals. acetone 300
ml to give 34 g of white scaly crystals (yield: 70
%) was obtained. Melting point: 55-58°C Synthesis example 2 (Synthesis of compound J-34) 18 g of 4-morpholinoaniline was mixed with 100 g of ethyl acetate.
ml, 12 ml of acetic anhydride was added little by little while stirring and keeping the reaction solution at 20°C. After adding acetic anhydride, the mixture was cooled on ice, and the precipitated crystals were collected by filtration and then recrystallized from ethyl acetate to obtain 16.5 g of white powdery crystals (yield: 75%). Melting point 207-210℃ General formula [K] In the formula, R ¹ represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y together with a nitrogen atom represents 5 to 7
Represents other simple bonds or divalent hydrocarbon groups necessary to form a membered heterocycle. ^R2 , ^R3 ,
R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom, an aliphatic group, a cycloalkyl group or an aryl group.
However, R2 and R4 and R3 and ^R6 may be bonded to each other to form a simple bond to form an unsaturated 5- to 7-membered heterocycle together with the nitrogen atom and Y. Also, Y
When is a simple bond, R ⁵ and R ⁷ may combine with each other to form a simple bond, and together with the nitrogen atom and Y, form an unsaturated 5-membered heterocycle. Also, when Y is not just a bond, R ⁵ and Y,
R ⁷ and Y or Y itself may form an unsaturated bond to form an unsaturated 6- or 7-membered heterocycle together with the nitrogen atom and Y. Examples of the aliphatic group represented by R ¹ include a saturated alkyl group that may have a substituent and an unsaturated alkyl group that may have a substituent. Examples of saturated alkyl groups include methyl group, ethyl group,
Examples include a butyl group, an octyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and examples of the unsaturated alkyl group include an ethenyl group and a propenyl group. The cycloalkyl group represented by R ¹ is a 5- to 7-membered cycloalkyl group that may have a substituent, and examples thereof include a cyclopentyl group and a cyclohexyl group. The aryl group represented by R ¹ represents a phenyl group or a naphthyl group which may have a substituent. Aliphatic group, cycloalkyl group represented by R ¹ ,
Substituents for aryl groups include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, acylamino groups, sulfamoyl groups, sulfonamide groups, carbonyloxy groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy groups, and heterocycles. group, alkylthio group, arylthio group, etc., and these substituents may further have a substituent. In the above general formula [K], Y represents a simple bond or a divalent hydrocarbon group necessary to form a 5- to 7-membered heterocycle with a nitrogen atom, but when Y is a simple bond, , Furthermore, R ⁵ and R ⁷ may combine with each other to form a simple bond to form an unsaturated 5-membered heterocycle, and when Y is a divalent monovalent hydrogen group, that is, methylene In the case of groups,
R ⁵ and Y or R ⁷ and Y form an unsaturated bond,
An unsaturated 6-membered heterocycle may be formed, and in the case of an ethylene group, R ⁵ and Y, R ⁷ and Y, or Y itself may form an unsaturated bond, forming an unsaturated 7-membered ring. may form a heterocycle. 2 further represented by Y
The valent hydrocarbon group may have a substituent, and the substituent includes an alkyl group, a carbamoyl group, an alkyloxycarbonyl group, an acylamino group, a sulfonamide group, a sulfamoyl group, an aryl group, a heterocyclic group, etc. Can be mentioned. In the general formula [K], R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, an aliphatic group,
Represents a cycloalkyl group or an aryl group,
Examples of the aliphatic group represented by R ² to ^{R 7} include a saturated alkyl group that may have a substituent and an unsaturated alkyl group that may have a substituent. Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc., and examples of unsaturated alkyl groups include ethenyl group, propenyl group, etc. It will be done. As the cycloalkyl group represented by R ² to R ⁷ ,
A 5- to 7-membered cycloalkyl group which may have a substituent, such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group represented by R ² to ^{R 7} include a phenyl group and a naphthyl group which may have a substituent. Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by ^R2 to ^R7 above include alkyl group, aryl group, alkoxy group, carbonyl group,
Carbamoyl group, acylamino group, sulfamoyl group, sulfonamide group, carbonyloxy group,
Alkylsulfonyl group, arylsulfonyl group,
Examples include hydroxy group, heterocyclic group, alkylthio group, and the like. The compound represented by the general formula [K] has 5 to 7
It is preferable to have a saturated heterocycle as a member ring than to have an unsaturated ring. The amount of the compound represented by the general formula [K] used below is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the magenta coupler represented by the general formula [I] of the present invention. It is mole%. Representative specific examples of the compound represented by the above general formula [K] are shown below.

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Next, a typical synthesis example of the compound represented by the above general formula [K] will be shown. Synthesis Example 1 (Synthesis of Compound K-14) Piperazine 9.0g and myristyl bromide 28
6.0 g of anhydrous potassium carbonate was added to 60 ml of acetone in which g was dissolved, and the mixture was boiled and refluxed for 20 hours to react. After the reaction, pour the reaction solution into 300ml of water,
Extracted with 300ml of ethyl acetate. After drying the ethyl acetate layer over magnesium sulfate, the ethyl acetate was distilled off to obtain the desired product as white crystals. acetone 100
ml to give 12 g of white flaky crystals (yield: 43
%) was obtained. Melting point: 175 to 180°C To prevent fogging due to discharge caused by electrostatic charging of the photosensitive material in the protective layer, intermediate layer, etc. of the photosensitive material of the present invention due to friction, etc., and to prevent image deterioration due to UV light. may contain an ultraviolet absorber. A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development. The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide light-sensitive material using the silver halide emulsion of the present invention reduces the gloss of the light-sensitive material, increases the ease of writing, and makes the light-sensitive materials intertwined with each other. A matting agent can be added for prevention purposes. A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention. An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer. The photographic emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention may be used to improve coating properties, prevent static electricity, improve slipperiness, emulsification dispersion, prevent adhesion, and (promote development, improve high contrast). Various surfactants are used for the purpose of improving photographic properties (such as oxidation, sensitization, etc.). A photographic material using the silver halide emulsion of the present invention has a photographic emulsion layer and other layers on a flexible reflective support such as baryta paper or paper laminated with α-olefin polymer, synthetic paper, cellulose acetate, nitric acid, etc. It can be applied to films made of semi-synthetic or synthetic polymers such as cellulose, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics. The silver halide material of the present invention can be used directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. The coating may be applied via one or more subbing layers (to improve wear resistance, hardness, antihalation, frictional properties and/or other properties). When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously. The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten lamps, fluorescent lamps, mercury lamps,
Xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser lights, light emitting diode lights, electron beams, X-rays, γ
Any known light source can be used, such as light emitted from a phosphor excited by rays, alpha rays, or the like. Exposure times include not only exposure times of 1 millisecond to 1 second, which are normally used in cameras, but also exposure times shorter than 1 microsecond, such as those using cathode ray tubes or xenon flash lamps.
Exposures of 100 microseconds to 1 microsecond can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently. The silver halide photographic material of the present invention can be used to form an image by color development as known in the art. The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds generally have a concentration of about 0.1 g to about 30 g per color developer,
Preferably from about 1 g to about 15 per color developer
Use at a concentration of g. As the aminophenol developer, for example, o
-aminophenol, p-aminophenol, 5
-amino-2-oxytoluene, 2-amino-3
-oxytoluene, 2-oxy-3-amino-
Includes 1,4-dimethylbenzene and the like. A particularly useful primary aromatic amino color developer is an N,N'-dialkyl-p-phenylenediamine compound, in which the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride,
p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β- Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,
N'-diethylaniline, 4-amino-N-(2-
(methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate and the like. In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention further contains various components that are normally added to color developers, such as sodium hydroxide and sodium carbonate. , an alkali agent such as potassium carbonate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener and a thickening agent. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. As the bleaching agent used in the bleaching process, a metal complex salt of an organic acid is used, and the metal complex salt is
It has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. Its composition is aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. Coordinated with metal ions such as iron, cobalt, and copper. The most preferred organic acids used to form such metal complexes of organic acids include:
Mention may be made of polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid sodium salt The bleaching agent used contains a metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.
In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . Furthermore, the fixing solution and bleach-fixing solution contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, and borax. , sodium hydroxide, potassium hydroxide,
It may contain one or more PH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent may be added. For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. [Specific Examples of the Invention] The present invention will be explained in further detail by showing specific examples below. Example 1 On a support made of polyethylene-coated paper, 4 mg/dm ² of exemplary magenta coupler 2, 2 mg/dm ² of green-sensitive silver chlorobromide emulsion, 4 mg/dm ² of dioctyl phthalate, and gelatin were added. 16mg/ ^dm2
The coating was applied so that the coating amount was as follows. Furthermore, gelatin was coated on the top layer at a coating amount of 9 mg/dm ² . The sample thus prepared is referred to as sample 1 (comparison). Next, Samples 2 to 16 were prepared which were the same as Sample 1 except that a coupler, a metal complex, and an oil-soluble dye were added to the coupler-containing layer of Sample 1 in the combinations shown in Table 1. A sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.,
KS-7 model) was used to perform wedge exposure of green light, and then the following processing was performed. Standard processing steps (processing temperature and processing time) [1] Color development 38℃ 3 minutes 30 seconds [2] Bleach fixing 33℃ 1 minute 30 seconds [3] Washing process 25-30℃ 3 minutes [4] Drying 75-80 ℃ Approximately 2 minutes [Color developer] Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-methyl-4 -Amino-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total amount to 1 and adjust the pH to 10.20. [Bleach-fix solution] Ethylenediaminetetraacetic acid diammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water. In addition, the total amount is set to 1. After the treatment, the resulting samples were subjected to a light fastness test, a whiteness measurement, and a sharpness measurement in the following manner. [Lightfastness test] Fading rate (Do-D)/(Do) x 100 when each dye image formed on each sample is exposed to sunlight for 30 days using an underglass outdoor exposure table, where Do represents the initial density (1.0) and D represents the density after fading). [Measurement of whiteness] The white part (unexposed part) of each sample obtained was
Hitachi Color Analyzer calculates the a*b* values based on the object color measurement method specified in JISZ8722 and Z8727.
Measured using Model 607. As the a* value increases, the redness increases, and as the a* value decreases, the greenness increases. Further, as the b* value increases, the yellowish tinge increases, and as the b* value decreases, the bluish tinge increases. In addition, visual judgment of whiteness was performed. [Sharpness test] MTF (Modulation Transfer Function) of the photosensitive silver halide emulsion layer
tion) was determined using a microdensitometer, and the MTF values at a spatial frequency of 5 lines/mm were compared. In addition,
Determination of image sharpness by MTF is well known to those skilled in the art, but the theory of
The Theory of the Potographic Process, 3rd edition
3rdeddition). The results of these measurements are shown in Table 1.

【table】

[Table] However, the structural formula of the comparative magenta coupler used in Table 1 is shown below. Comparison magenta coupler As is clear from Table 1, the samples containing couplers alone (1, 7, 9, 11, 13) had poor light resistance and poor sharpness. Sample 2 using only the metal complex according to the present invention
In this case, the light resistance is improved, but the whiteness of the white part deteriorates. Samples of the present invention (3-6, 8, 10,
12, 14), there is no deterioration in whiteness and not only light fastness is improved, but also sharpness is improved. In addition, in the sample of the present invention, the degree of improvement in light resistance and sharpness is greater than that in sample (16) using the comparative magenta coupler. Example 2 Samples 17 to 32 were prepared in the same manner as Sample 1, except that a metal complex and an oil-soluble dye were added to the coupler-containing layer of Sample 1 in the combinations shown in Table 2. The sample thus prepared was subjected to the same exposure treatment as in Example 1. For each sample obtained after processing, the light fastness, whiteness, and sharpness of the magenta dye image were measured in the same manner as in Example 1. The results are shown in Table 2.

【table】

[Table] However, the structural formulas of the comparative metal complexes used in Table 2 are as follows. comparative metal complexes From Table 2, it is clear that the samples (2, 17, 19, 21,
23, 25, 27, 29), deterioration of color chromaticity occurs.
Samples of the present invention (3, 18, 20, 22, 24, 26,
28, 30), images with no deterioration in whiteness and good light fastness and sharpness were obtained. Moreover, this effect was not observed in samples using comparative metal complexes. Example 3 A multicolor silver halide photographic light-sensitive material was prepared by sequentially coating the following layers on a support made of polyethylene-coated paper from the support side. 1st layer: blue-sensitive silver halide emulsion layer α-pivalyl-α- as a yellow coupler
(1-benzyl-2,4-dioxo-imidaridin-3-yl)-2-chloro-5-[γ-(2,4
-di-t-amylphenoxy)butyramide]-
Acetanilide: 8 mg/dm ² , blue-sensitive silver chlorobromide emulsion: 3 mg/dm ² (calculated as silver), 2,4-di-t-
Butylphenol-3',5'-di-t-amyl-
3 mg/dm 2 of 4'-hydroxybenzoate, 3 mg/dm ² of dioctyl phthalate and 3 mg/dm ² of gelatin.
The coating was applied so that the coating amount was 16 mg/dm ² . 2nd layer: Intermediate layer Gelatin was coated at a coating amount of 4 mg/dm ² . Third layer: Green-sensitive silver chlorobromide emulsion layer: 4 mg/d of the above-mentioned magenta coupler (57)
m ² , 2 mg/d of green-sensitive silver chlorobromide emulsion converted to silver
m ² , 4 mg/dm ² of dioctyl phthalate and 16 mg/dm ² of gelatin were coated. 4th layer: Intermediate layer UV absorber 2-hydroxy-3',5'-di-t
-amylphenol)-benzotriazole 3
mg/dm, 2-(2'-hydroxy-3',5'-di-t
-butylphenol)-benzotriazole 3
mg/dm ² , 4 mg/dm ² of dioctyl phthalate, and 14 mg/dm ² of gelatin. 5th layer: Red-sensitive silver chlorobromide emulsion layer 2,4-dichloro-3- as cyan coupler
1 mg/d of methyl-6-[α-(2,4-di-t-amylphenoxy)butyramide]-phenol
m ² , 2-(2,3,4,5,6-pentafluorophenyl)acylamino-4-chloro-5-[α
-(2,4-di-tert-amylphenoxy)pentylamide] was coated at a coating amount of 3 mg/dm ² and the red-sensitive silver chlorobromide emulsion was coated at a coating amount of 3 mg/dm ² in terms of silver. 6th layer: Intermediate layer 2-(2'-hydroxy-3',
2 mg/dm ² of 5'-di-5-amylphenol)-benzotriazole, 2-(2'-hydroxy-3',
2 mg/dm 2 of 5'-di-t-butylphenol)-benzotriazole and 2 mg/dm ² of dioctyl phthalate.
mg/dm ² and gelatin was coated at a coating amount of 6 mg/dm ² . 7th layer: Protective layer Gelatin was coated at a coating amount of 9 mg/dm ² . The sample thus prepared is designated as sample 33. Next, a metal complex (applied at a ratio of 0.5 mol to the coupler) and an antioxidant (applied at a ratio of 0.5 mol to the coupler) were added to the third layer of Sample 33, and an oil-soluble dye was added to the fourth layer as shown in Table 3. Samples 34 to 46, which were the same as sample 33, were prepared except that the combinations shown were added. The sample thus prepared was subjected to the same exposure treatment as in Example 1. For each sample obtained after processing, the light fastness, whiteness, and sharpness of the magenta image were measured in the same manner as in Example 1. The results are shown in Table 3.

[Table] As is clear from Table 3, Sample 33 using only the coupler of the present invention has poor light resistance and sharpness.
In addition, a sample in which a metal complex was added to the coupler of the present invention
34, the whiteness deteriorates and the sharpness is not improved. Samples (35 to 46) of the present invention in which a metal complex and an oil-soluble dye were used in combination with the coupler of the present invention had good light fastness and sharpness, and clear images were obtained without deterioration of whiteness. In addition, samples containing antioxidants (39 to 46)
The lightfastness was further improved and more robust dye images were obtained. Example 4 Samples 47 to 52 were prepared in the same manner as Sample 35 of Example 3, except that the metal complex of the third layer and the high boiling point organic solvent were used in the combinations shown in Table 4. These samples were exposed to light in the same manner as in Example 3, and the light fastness, whiteness, and sharpness of magenta images were measured. The results are shown in Table 4.

[Table] As is clear from Table 4, in the sample of the present invention,
Lightfastness, whiteness, and sharpness are all good. In addition, samples 35, 47, 50, and 51 using DOP and TNP, which have a low dielectric constant, have a particularly large improvement in light resistance and are more effective than samples 48 and 52, which use DEP, which has a high dielectric constant. Example 5 Samples 53 to 62 were prepared in the same manner as Sample 1, except that a coupler, a metal complex, and an oil-soluble dye were added to the coupler-containing layer of Sample 1 in the combinations shown in Table 5. The thus prepared samples were subjected to the same exposure treatment as in Example 1, and the light fastness, whiteness, and sharpness of the magenta dye images were measured in the same manner as in Example 1 for each sample obtained after the treatment. The results are shown in Table 5.

[Table] As is clear from Table 5, data of the present invention in which the coupler of the present invention is combined with a metal complex and an oil-soluble dye.
Samples No. 54, 56, 58, 60, and 62 had good light fastness and sharpness, and no deterioration of whiteness occurred, and clear images were obtained.

Claims (1)

[Claims] 1. At least one magenta coupler represented by the following general formula []; and at least one metal complex having a singlet oxygen quenching rate constant of 3×10 ⁷ M ^-1 ·sec ^-1 or more; A silver halide photographic material comprising at least one oil-soluble dye. General formula [] [Wherein, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle represented by the following general formulas [] to [], and the ring formed by Z may have a substituent. . X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ] General formula [] General formula [] General formula [] General formula [] General formula [] General formula [] [In general formulas [] to [], R ₂ to R ₈ have the same meanings as R above. ]