JPH0473939B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material in which a dye image is stable against heat and light and stain generation is prevented. [Background of the Invention] Conventionally, aromatic primary
The oxidized product of the amine-based color developing agent and the coloring agent undergo a coupling reaction to produce, for example, indophenol, indoaniline, indamine, azomethine,
It is well known that phenoxane, phenazine, and similar dyes are produced to form dye images. In this type of photography, a subtractive color method is usually used to reproduce colors, and blue sensitivity,
A silver halide color photographic light-sensitive material is used in which green-sensitive and red-sensitive light-sensitive silver halide emulsion layers contain color formers that are related to extra colors, that is, couplers that develop yellow, magenta, and cyan colors. . Couplers used to form the yellow image include, for example, acylacetanilide couplers, and couplers for forming magenta dye images include, for example, pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, or indazolone couplers. Furthermore, as a coupler for forming a cyan dye image, for example, a phenol or naphthol coupler is generally used. It is desirable that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity. Further, it is desirable that the uncolored areas of the silver halide color photographic light-sensitive material do not turn yellow (hereinafter referred to as Y-stain) due to light or moist heat. However, with conventional magenta couplers, Y-stain occurs due to light and moist heat in uncolored areas, and browning due to light in dye image areas is extremely large compared to yellow couplers and cyan couplers, resulting in poor color reproduction.
It is often a problem. 5-pyrazolones are widely used to form magenta dyes. The dye formed from this magenta coupler of 5-pyrazolones has a wavelength of 550 nm.
In addition to the main absorption near 430 nm, the presence of sub-absorption near 430 nm is a major problem in color reproduction, and various studies have been conducted to solve this problem. Magenta couplers having an anilino group at the 3-position of 5-pyrazolones have small side absorption, and are particularly useful for obtaining color images for printing. For these techniques, see e.g. US Patent 2343703
No. 1,059,994. However, the above-mentioned magenta coupler has the disadvantage that the image storage stability, especially the fastness of the dye image to light, is extremely poor, and moreover, the Y-stain in the uncolored area is large. As another means to reduce the sub-absorption around 430nm of the above magenta coupler, a British patent
Pyrazolobenzimidazoles described in US Patent No. 1047612, indazolones described in US Patent No. 3770447, and US Pat.
1H-pyrazolo [5,1
-c]-1,2,4-triazole type coupler,
Research Disclosure
1H-pyrazolo[1,5-b]-1,2,4-triazole couplers described in Research Disclosure 24531 (1984);
1H-pyrazolo[1,5-c]-1,2,3-triazole type coupler, JP-A-59-162548, Research Disclosure
1H-imidazo[1,2-b]-pyrazole couplers described in Research Disclosure 24531 (above), Research Disclosure 24531 (above).
1H-pyrazolo[1,5-b]pyrazole couplers described in Research Disclosure 24230 (1984), Research Disclosure 24230 (1984).
The use of magenta couplers such as the 1H-pyrazolo[1,5-d]tetrazole type couplers described in J.D. Disclosure 24220 (1984) has been proposed. Among these, 1H-pyrazolo[5,1-c]-1,2,4
-triazole coupler, 1H-pyrazolo[1,
5-b]-1,2,4-triazole type coupler,
1H-pyrazolo[1,5-c]-1,2,3-triazole coupler, 1H-imidazo[1,2-
b] Pyrazole type coupler, 1H-pyrazolo [1.5
-b]-pyrazole type couplers and 1H-pyrazolo[1,5-d]tetrazole type couplers, the subabsorption around 430 nm is
It is a coupler that is significantly smaller than dyes formed from 5-pyrazolones having an anilino group in the position, and is preferable for color reproduction.Additionally, it has the advantage that it produces very little Y-stain in uncolored areas when exposed to light, heat, and humidity. It has the following. However, the fastness of azomethine dyes formed from these couplers to light is extremely low, and in addition, the dyes are easily discolored by light, which significantly impairs the performance of color photographic light-sensitive materials, especially for printing. It has not been put to practical use in color photographic materials. Furthermore, JP-A-59-125732 discloses that when a 1H-pyrazolo[5,1-c]-1,2,4-triazole type magenta coupler is used in combination with a phenol compound or a phenyl ether compound,
It has been shown that the light fastness of magenta dye images obtained from 1H-pyrazolo[5,1-c]-1,2,4-triazole type magenta couplers is improved. However, the above Japanese Patent Application Publication No. 59-125732
Many of the phenolic compounds or phenyl ether compounds disclosed in this issue are 1H-
Even when combined with a pyrazolo[5,1-c]-1,2,4-triazole type magenta coupler, it is still not sufficient to prevent fading of the magenta dye image obtained from the coupler due to light. It was found that the effect of preventing color change of the dye image due to light was very small. In view of the above-mentioned problems, the present inventors conducted extensive research and found that among phenol compounds or phenyl ether compounds, a compound represented by the general formula [XII] of the present invention has a specific structure, 1H- When used in combination with a pyrazolo[5,1-c]-1,2,4-triazole type magenta coupler, it has a uniquely large effect not only in preventing fading of the magenta dye image obtained from the coupler but also in preventing discoloration due to light. I have come to discover that I can make the most of it. Furthermore, the compound represented by the general formula [XII] of the present invention is 1H-pyrazolo[5,1-c]-1,2,4-
Not only the magenta dye image obtained from the triazole type magenta coupler but also the general formula of the present invention []
It has been recognized that the magenta coupler according to the invention exhibits a remarkable effect in preventing the magenta dye image obtained from fading due to light. The compound represented by the general formula [XII] of the present invention includes a part of the compound shown in JP-A-59-125732; , 1H-pyrazolo[5,1-c]-1,
There is no specific description of the fact that when used in combination with a 2,4-triazole type magenta coupler, the effect of preventing discoloration and fading of dye images is particularly great. [Object of the Invention] A first object of the present invention is to provide a silver halide photographic material which has excellent color reproducibility and which has significantly improved light fastness of magenta dye images. A second object of the present invention is to provide a silver halide photographic material having a magenta dye image with little discoloration due to light. A third object of the present invention is to provide a silver halide photographic material that is prevented from producing Y-stain in uncolored areas due to light, heat, and humidity. [Structure of the Invention] The above object of the present invention is to satisfy the following general formula [ ] ~
This is achieved by a silver halide photographic material containing a magenta dye-forming coupler represented by [] and a compound represented by the following general formula [XII]. General formula [] General formula [] General formula [] General formula [] General formula [] General formula [] [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and
R ₈ represents a hydrogen atom or 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. ] General formula [XII] [In the formula, R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R ₁₄ and R ₁₅ are
Each represents a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acylamino group, a sulfonyl group, a sulfonamido group, or a hydroxy group. m and n each represent an integer of 0 to 4, and when m is an integer of 2 to 4, R ₁₄ is
They may be the same or different. Also, n is 2
When it is an integer of ˜4, R ₁₅ may be the same or different. A has 1 carbon in the straight chain part
~6 alkylene group. ] Hereinafter, unless otherwise specified, the compound represented by the general formula [XII] according to the present invention will be referred to as a magenta dye image stabilizer. [Specific Configuration of the Invention] Next, the present invention will be specifically explained. In the magenta dye image-forming couplers represented by the above general formulas [] to [], R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ , R ₆ , R ₇ and R ₈ represent a hydrogen atom or a substituent, and examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group. , aryl group, heterocyclic group, acyl group, 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 an arylthio group and a 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 ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ has 1 to 32 carbon atoms, and the alkenyl group and alkynyl group has 2 carbon atoms. -32, cycloalkyl groups, and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl groups, alkenyl groups, and 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 atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a hetero atom {specifically, hydroxy, alkoxy, aryloxy, heterocycles substituted via an oxygen atom such as oxy, siloxy, acyloxy, carbamoyloxy;
Nitro, amino (including dialkylamino, etc.),
Those substituted through a nitrogen atom such as sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, alkylthio,
Those substituted via a sulfur atom such as arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl, and those substituted via a phosphorus atom such as phosphonyl. Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1-hexylnonyl group, 1,1'-dipentylnonyl group, 2-chloro-t-butyl group,
Trifluoromethyl group, 1-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3- m-butanesulfonaminophenoxypropyl group, 3-4'-{α-[4″(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylpropyl group, 3-{4′-[α-
(2″,4″-di-t-amylphenoxy)butanamide]phenyl}-propyl group, 4-[α-(o-
chlorophenoxy) tetradecaneamide phenoxy] propyl group, allyl group, cyclopentyl group,
Examples include cyclohexyl group. The aryl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is preferably a phenyl group, and substituents (for example, 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. R ₁ , R ₂ , R ₃ , R ₄ , The heterocyclic groups represented by R ₅ , R ₆ , R ₇ and R ₈ are preferably 5- to 7-membered, and may be substituted or fused. Specifically, 2- Examples include furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc. Acyl represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ Examples of the group include acetyl group, phenylacetyl group, dodecanoyl group, α-2,4
Examples include alkylcarbonyl groups such as -di-t-amylphenoxybutanoyl group, arylcarbonyl groups such as benzoyl group, 3-pentadecyloxybenzoyl group, and p-chlorobenzoyl group. The sulfonyl groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ include methylsulfonyl group, alkylsulfonyl group such as dodecylsulfonyl group, benzenesulfonyl group, p- Examples include arylsulfonyl groups such as toluenesulfonyl groups. The sulfinyl groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ include ethyl sulfinyl group, octylsulfinyl group, 3-phenoxybutyl group. Examples include an alkylsulfinyl group such as a rufinyl group, a phenylsulfinyl group, and an arylsulfinyl group such as a m-pentadecyl phenylsulfinyl group. Phosphonyl groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ include alkylphosphonyl groups such as butyloctylphosphonyl group, and octyloxyphosphonyl group. Examples include alkoxyphosphonyl groups, aryloxyphosphonyl groups such as phenoxyphosphonyl groups, and arylphosphonyl groups such as phenylphosphonyl groups. A carbamoyl group, an alkyl group, an aryl group (preferably a phenyl group), etc. represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be substituted, For example, N-methylcarbamoyl group, N,N-
Dibutylcarbamoyl group, 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 groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-propylsulfamoyl group, N,
N-diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-
Examples include ethyl-N-dodecylsulfamoyl group and N-phenylsulfamoyl group. Examples of spiro compound residues represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ include spiro[3.3]heptan-1-yl. Examples of the bridged carbonized compound residues represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ include bicyclo[2.2.1]heptan-1-yl, tricyclo[ 3.3.1.1 ^3,7 ]decane-1-yl, 7,7-dimethyl-bicyclo[2.2.1]heptan-1-yl, and the like. The alkoxy groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be further substituted with the substituents listed above for the alkyl group. ,
Examples include methoxy group, propoxy group, 2-ethoxyethoxy group, pentadecyloxy group, 2-dodecyloxyethoxy group, phenethyloxyethoxy group, and the like. The aryloxy group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is preferably phenyloxy, and the aryl nucleus is further used as a substituent or atom for the aryl group. may be substituted with the ones listed above, such as phenoxy group, pt-butylphenoxy group, m-pentadecylphenoxy group, and the like. The heterocyclic oxy groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ preferably have a 5- to 7-membered heterocycle, and the heterocycle further includes It may have a substituent, for example, 3, 4, 5,
6-tetrahydropyranyl-2-oxy group, 1-
A phenyltetrazole-5-oxy group is mentioned. The siloxy groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be further substituted with an alkyl group, etc., such as trimethylsiloxy group, triethyl Examples include siloxy group and dimethylbutylsiloxy group. Examples of the acyloxy group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ include an alkylcarbonyloxy group, an arylcarbonyloxy group, and further substituents. Specific examples thereof include an acetyloxy group, an α-chloroacetyloxy group, a benzoyloxy group, and the like. The carbamoyloxy groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be substituted with an alkyl group, an aryl group, etc., such as N-ethyl Examples include carbamoyloxy group, N,N-diethylcarbamoyloxy group, and N-phenylcarbamoyloxy group. The amino groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
Examples include ethylamino group, anilino group, m-chloroanilino group, 3-pentadecyloxycarbonylanilino group, and 2-chloro-5-hexadecaneamideanilino group. The acylamino group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group) etc., which may further have a substituent, specifically an acetamido group, an α-ethylpropanamide group, an N-
Phenylacetamide group, dodecanamide group,
Examples include 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group, and the like. Examples of the sulfonamide group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ include an alkylsulfonylamino group, an arylsulfonylamino group, and further substituents. It may have. Specifically, methylsulfonylamino group, pentadecylsulfonylamino group, benzenesulfonamide group,
p-toluenesulfonamide group, 2-methoxy-
Examples include 5-t-amylbenzenesulfonamide group. The imide groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be open-chain or cyclic, and may have a substituent. For example, a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutarimide group, etc. may be mentioned. The ureido groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc. Examples include N-ethylureido group, N-methyl-N-decylureido group, N-phenylureido group, N-p-tolylureido group, and the like. The sulfamoylamino group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, N-phenylsulfamoylamino group, etc. It will be done. The alkoxycarbonylamino groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ include:
It 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 ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may have a substituent, for example, phenoxycarbonylamino group, 4-methylphenoxycarbonylamino group. The alkoxycarbonyl groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may further have a substituent, such as a methoxycarbonyl group,
Examples include butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benzyloxycarbonyl group, and the like. The aryloxycarbonyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may further have a substituent, such as a phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-
Examples include pentadecyloxyphenoxycarbonyl group. The alkylthio groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may further have a substituent, for example, an ethylthio group, a dodecylthio group, Octadecylthio group, Fenerthio group, 3-
Examples include phenoxypropylthio group. The arylthio groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are preferably phenylthio groups and may further have a substituent, such as phenylthio group, p- Methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, p-
Examples include acetaminophenylthio group. The heterocyclic thio group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is preferably a 5- to 7-membered heterocyclic thio group, and further includes a fused ring. or may have a substituent. For example, 2-pyridylthio group, 2-benzothiazolylthio group,
A 2,4-diphenoxy-1,3,5-triazole-6-thio group is mentioned. 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 the carboxyl group, examples of groups substituted via a carbon atom include the general formula (R ₁ ' has the same meaning as R ₁ above, and Z' represents a group of nonmetallic atoms necessary to form the nitrogen-containing heterocycle of the magenta dye image-forming coupler represented by the general formulas [] to []. , R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group, or a heterocycle), a hydroxymethyl group, and a triphenylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups,
Examples include alkoxyoxalyloxy groups. The alkoxy group may further have a substituent,
For example, ethoxy group, 2-phenoxyethoxy group,
2-cyanoethoxy group, phenethyloxy group, p
-chlorobenzyloxy group and the like. The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-dodecylphenoxy group, 4
-methanesulfonamidophenoxy group, 4-[α
-(3′-pentadecylphenoxy)butanamide]
Phenoxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p
-methoxyphenoxy group and the like. The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a condensed ring or may have a substituent. in particular,
Examples include 1-phenyltetrazolyloxy group and 2-benzothiazolyloxy group. Examples of the acyloxy group include acetoxy groups, alkylcarbonyloxy groups such as butanoloxy groups, alkenylcarbonyloxy groups such as cinnamoyloxy groups, and arylcarbonyloxy groups such as benzoyloxy groups. Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group. As the alkylthio group, butylthio group, 2
-cyanoethylthio group, phenethylthio group, benzylthio group, etc. The arylthio group includes phenylthio group, 4
-Methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butylphenylthio group, etc. can be mentioned. Examples of the heterocyclic thio group include 1-phenyl-1,2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. Examples of the group substituted via the nitrogen atom include the general formula

Examples include those represented by the formula. Here, R ₄ ′ and R ₅ ′ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group,
It represents an aryloxycarbonyl group or an alkoxycarbonyl group, and R ₄ ' and R ₅ ' may be combined to form a heterocycle. However, R ₄ ′ and R ₅ ′ are not both hydrogen atoms. The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an acylamino group, and a sulfonamide group. group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamino group, aryloxycarbonylamino group, hydroxyl group, carboxyl group, cyano group, and a halogen atom.
Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-ethylhexyl group.
-chloroethyl group. The aryl group represented by R ₄ ' or R ₅ ' has 6 to 32 carbon atoms, particularly preferably a phenyl group or a naphthyl group, and the aryl group may have a substituent,
Examples of the substituent include those listed above for substituting the alkyl group represented by R ₄ ' or R ₅ ' 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-cyanophenylcarbamoyl group, and Np-tolylcarbamoyl group. Examples of the acyl group represented by R ₄ ′ or R ₅ ′ include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. You may do so. Specific examples of the acyl group include hexafluorobutanoyl group,
2,3,4,5,6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthoyl group,
Examples include 2-furylcarbonyl group. The sulfonyl group represented by R ₄ ′ or R ₅ ′ is
Alkylsulfonyl group, arylsulfonyl group,
A heterocyclic sulfonyl group may be mentioned, which may have a substituent, and specific examples include an ethanesulfonyl group, a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, a p-chlorobenzenesulfonyl group, etc. . The aryloxycarbonyl group represented by R ₄ ' or R ₅ ' may have a substituent such as those listed for the aryl group, and specific examples thereof include a phenoxycarbonyl group. The alkoxy carbonyl 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. Examples include groups. 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. Substituents on the heterocycle (for example, R ₁ to R ₈ ) in the general formulas [] to [] described below are moiety (here R″ represents a hydrogen atom or 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, and Z″ represents a nonmetallic atomic group necessary to form the nitrogen-containing heterocycle of the general formula [] to [] ), it forms a so-called bis-type coupler, which is, of course, included in the present invention. You can leave it there. For example, in the general formula [], R ₅
and R ₆ , but in the general formula [], R ₇ and R ₈ are
They may be bonded to each other to form a ring (eg, 5- to 7-membered cycloalkene, benzene). Among the magenta couplers represented by the general formulas [] to [], particularly preferred are those represented by the general formula []
It is a magenta coupler represented by . Furthermore, in general formulas [] to [], it is preferable that R ₁ satisfies the following condition 1, more preferably the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1, 2 and 3 are satisfied. This is a case of satisfaction. 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 substituent R ₁ on the heterocycle is one 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 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 substituent that may have the group include the general Specific examples and substituents of the group represented by R ₁ in formulas [] to [] 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 and cycloalkenyl represented by R ₁ in the above general formulas [] to []. , specific examples of bridged hydrocarbon compound residues with heterocyclic groups and substituents thereof. Among the general formulas [], (i) two of R ₉ to R ₁₁ are alkyl groups, (ii) one of R ₉ to R ₁₁ , for example R ₁₁ , is a hydrogen atom and , when the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom. Further, in (i), two of R ₉ to _{R 11} are preferable.
One is an alkyl group and the other is a hydrogen atom or an alkyl group. Herein, the alkyl and cycloalkyl may further have a substituent. Specific examples of the alkyl, cycloalkyl and the substituent thereof include R ₁ in the above general formulas [] to [], but alkyl, cyclo Specific examples of alkyl and its substituents are listed. Furthermore, R ₂ to _{R 8} in the general formulas [] to [] are preferably those represented by the following general formula []. 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 R ¹ preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms.
It does not matter whether it is straight chain or branched. Further, this alkylene may have a substituent. Examples of the substituent include the general formulas [] to
When R ₁ in [] is an alkyl group, the substituents that the alkyl group may have include those shown below. Preferred substituents include phenyl. Preferred specific examples of alkylene represented by R ¹ are shown below. −CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

[Formula] − 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, octadacil, 2-hexidecyl, 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 [], particularly preferred are those represented by the following general formula [XI]. General formula [XI] In the formula, R ₁ and X are R ₁ and X in the general formula []
and R ¹ and R ² are the same as in the general formula []
It is synonymous with R ¹ and R ² . Moreover, the synthesis of the coupler is carried out in the Journal of
Journal of the Chemical Society
Chemical Society), Perkin I
(1977), 2047-2052, U.S. Patent No. 3725067, JP-A-59-99437, JP-A-58-42045, JP-A-59-
No. 162548, JP-A-59-171956, JP-A-60-33552
The synthesis was carried out with reference to No. 60-43659 and JP-A-60-43659. The couplers of the present invention are usually 1 x 10 ^-3 mol to 1 mol, preferably 1 x 10 ^-2 mol per mol of silver halide.
It can be used in a range of mol to 8×10 ^-1 mol. The couplers of the present invention can also be used in combination with other types of magenta couplers. The magenta dye image stabilizer used in combination with the magenta dye image-forming coupler represented by the above general formula [] to [] (hereinafter referred to as the coupler according to the present invention) prevents the magenta dye image from fading due to light. It is a compound represented by the general formula [XII] that not only has an effect but also has an effect of preventing discoloration due to light. In the general formula [XII], specific examples of the alkyl group, cycloalkyl group, alkenyl group, and aryl group represented by R ₁₂ and R ₁₃ include:
Examples include the groups detailed in R ₁ of the general formulas [] to []. A halogen atom, an _alkyl group, a _cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acylamino group, a sulfonyl group, and
Specific examples of sulfonamide groups are also represented by the general formula [] ~
Examples include the groups detailed in R ₁ in []. The groups listed above may each be substituted with other substituents. For example, halogen atom, alkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylamino group, arylamino group, acylamino group, carbamoyl group, sulfonamide group, sulfamoyl group etc. A represents an alkylene group in which the straight chain portion has 1 to 6 carbon atoms; however, even if this alkylene group is straight chain,
A branched version is also acceptable. Further, this alkylene group may have one or more substituents, and examples of the substituents include an aryl group, a cyano group, a halogen atom,
heterocyclic group, cycloalkyl group, alkoxy group,
Examples include hydroxy group and aryloxy group. In addition, this alkylene group is

【formula】

The alkylene chain itself may constitute a cycloalkyl ring as shown in [Formula]. Among the compounds represented by the general formula [XII], compounds particularly useful in the present invention are such that R ₁₂ and R ₁₃ are each a hydrogen atom, an alkyl group, or a cycloalkyl group, and R ₁₄ and R ₁₅ are each a hydrogen atom. , alkyl group, alkoxy group or hydroxy group, m
and n are each an integer of 0 to 2, and A is a substituted or unsubstituted methylene group. Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby. The compound according to the general formula [XII] of the present invention is
-31625, JP-A-48-26133, JP-A-51-124926
It can be produced according to the synthetic method described. However, the above-mentioned publications state that the compound included in the general formula [XII] of the present invention has the property of improving the light fastness of coloring dyes obtained from photographic couplers, particularly pyrazolone magenta couplers. However, the general formula of the present invention []
There is no description whatsoever regarding the effect of preventing discoloration and fading of magenta dye images obtained from magenta dye image-forming couplers represented by ~[] against light. As a result of intensive study, the inventors of the present invention found that the general formula []
It has been discovered that the compound represented by the general formula [XII] exerts an unexpected and specific effect on the preservation of magenta dye images obtained from the magenta couplers represented by ~[]. The amount of the magenta dye image stabilizer represented by the general formula [XII] of the present invention to be used is 5 to 5 to
It is preferably 300 mol%, more preferably 10 to 200 mol%. In the silver halide photographic light-sensitive material of the present invention, in addition to the magenta dye image stabilizer according to the present invention, other magenta dye image stabilizers represented by the following general formula [], namely, phenolic compounds and phenyl Ether compounds can also be used in combination. General formula [] In the formula, R ₁₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group,
R ₁₇ , R ₁₈ , R ₂₀ , and R ₂₁ each represent 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, and R ₁₉ represents an alkyl group, a hydroxy group, or an aryl group. Or represents an alkoxy group. Further, R ₁₆ and R ₁₇ may be ring-closed with each other to form a 5- or 6-membered ring, in which case R ₁₉ represents a hydroxy group or an alkoxy group. Further, R ₁₆ and R ₁₇ may be ring-closed with each other to form a methylenedioxy ring. Furthermore, R ₁₈ and R ₁₉ may be ring-closed with each other to form a 5-membered hydrocarbon ring, in which case R ₁₆ represents an alkyl group, an aryl group, or a heterocyclic group. However, the case where R ₁₆ is a hydrogen atom and R ₁₉ is a hydroxy group is excluded. In the general formula [], R ₁₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group,
Straight chain or branched alkyl groups such as n-octyl group, tert-octyl group, benzyl group, and hexadecyl group can be mentioned. Moreover, this alkyl group may have a substituent. Also _R16
Examples of the alkenyl group represented by include allyl, hexenyl, and octenyl groups.
Furthermore, as the aryl group of R ₁₆ , phenyl,
Each group of naphthyl is mentioned. This aryl group can have a substituent, and specific examples include a methoxyphenyl group and a chlorophenyl group. Further, specific examples of the heterocyclic group represented by R ₁₆ include a tetrahydropyranyl group and a pyrimidyl group. In the general formula [], R ₁₇ , R ₁₈ , R ₂₀ and
R ₂₁ is a hydrogen atom, a halogen atom, a hydroxy group,
It represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamino group, and among these, the alkyl group, alkenyl group, and aryl group are the same as the alkyl group, alkenyl group, and aryl group mentioned above for _R16 . can be mentioned. Examples of the halogen atom include atoms such as fluorine, chlorine, and bromine.
Further, the alkoxy group includes a methoxy group,
Specific examples include ethoxy group and benzyloxy group. Furthermore, the acylamino group is
R'NHCO-, where 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.), an aryl group (eg, phenyl, methoxyphenyl, naphthyl, etc.), or a heterocyclic group (eg, pyridyl, pyrimidyl, etc.). In the above general formula [], R ₁₉ represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group, and among these, the alkyl group and aryl group include the alkyl group represented by R ₁₆ above,
Specific examples include the same groups as the aryl group. Regarding the alkoxy group of R ₁₉ ,
The same alkoxy groups mentioned for R ₁₇ , R ₁₈ , R ₂₀ and R ₂₁ can be mentioned. Among the phenol compounds or phenyl ether compounds represented by the general formula [] that are used in combination with the magenta coupler of the present invention, particularly preferred are tetraalkoxybiindane compounds, which are represented by the following general formula []. be able to. General formula [] In the formula, R ₂₅ is an alkyl group (e.g. methyl, ethyl, propyl, n-octyl, tert-octyl,
(benzyl, hexadecyl), an alkenyl group (eg, allyl, octenyl, oleyl), an aryl group (eg, phenyl, naphthyl), or a heterocyclic group (eg, tetrahydropyranyl, pyrimidyl). R ₂₂ and R ₂₃ are each a hydrogen atom, a halogen atom, (e.g. fluorine,
chlorine, bromine), an alkyl group (e.g. methyl, ethyl, n-butyl, benzyl), an alkenyl group (e.g. allyl, hexenyl, octenyl) or an alkoxy group (e.g. methoxy, ethoxy, benzyloxy), and R ₂₄ is a hydrogen atom. , an alkyl group (eg methyl, ethyl, n-butyl, benzyl), an alkenyl group (eg 2-propenyl, hexenyl, octenyl) or an aryl group (eg phenyl, methoxyphenyl, chlorphenyl, naphthyl). The compound represented by the general formula [] is disclosed in U.S. Patent No. 3935016, U.S. Patent No. 3982944, U.S. Patent No. 4254216,
JP 55-21004, JP 54-145530, UK Patent 2077455, JP 2062888, US Patent 3764337
No. 3432300, No. 3574627, No. 3573050,
JP-A No. 52-152225, No. 53-20327, No. 53-
No. 17729, No. 55-6321, British Patent No. 1347556, Publication No. 2066975, Special Publication No. 12337, No. 1977, No. 48-
It also includes compounds described in No. 31625, US Pat. No. 3,700,455, and the like. Typical specific examples of the compound represented by the general formula [] according to the present invention are shown below, but the present invention is not limited thereto. The phenol compound or phenyl ether compound represented by the general formula [] is preferably 200 mol% or less based on the magenta dye image stabilizer represented by the general formula [XII] of the present invention,
More preferably, it can be used in an amount of 140 mol% or less. Although many of the phenol compounds and phenyl ether compounds have the effect of preventing fading of the magenta dye image obtained from the magenta coupler of the present invention, they often have little effect of preventing discoloration. Therefore, it is not preferable to use an excessive amount of the phenol compound and phenyl ether compound in the magenta dye image stabilizer of the present invention. Generally speaking, the magenta dye image obtained from the magenta coupler not only fades when exposed to light, but also undergoes significant discoloration due to light, and the color tone of the dye image changes from magenta to yellowish. The magenta dye image stabilizer represented by the general formula [XII] of the present invention can prevent fading and discoloration of the magenta dye image obtained from the magenta coupler due to light. It has an effect that cannot be achieved with magenta dye image stabilizers of phenolic compounds and phenyl ether compounds. Therefore, when using the conventional magenta dye image stabilizers of phenol compounds and phenyl ether compounds in combination with the magenta dye image stabilizer represented by the general formula [XII] of the present invention,
The amount of the magenta dye image stabilizer of the conventional phenol compound and phenyl ether compound must be selected to such an extent that discoloration caused by light is not noticeable. When an appropriate amount of the conventional magenta dye image stabilizer of the phenolic compound and phenyl ether compound represented by the above [] is used in combination with the magenta dye image stabilizer of the present invention represented by the above general formula [XII], , additive effects may be observed when used together. Although it is preferred that the magenta couplers of the invention and the magenta dye image stabilizers of the invention are used in the same layer, the stabilizers may be used in layers adjacent to the layer in which the couplers are present. The silver halide photographic light-sensitive material of the present invention can be applied to, for example, color negative and positive films, color photographic paper, etc., but the present invention particularly applies when applied to color photographic paper used for direct viewing. The effect of the method is 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,
Usually, it has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. The number and order of layers may be changed as appropriate depending on the important performance and purpose of use. 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 halide,
Any material used in conventional silver halide emulsions can be used, such as silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. 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, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. Alternatively, growth may be carried out by adding halide ions and silver ions sequentially or simultaneously while controlling the pH and pAg in the mixing pot, taking into account the critical growth rate of silver halide crystals. After growth, a conversion method may be used to change the silver halide composition of the grains. When producing the silver halide emulsion used in 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 prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. Metal ions can be added to the inside of the particles and/or on the surface of the particles using iron salts or complex salts, and can be reduced inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can provide sensitizing nuclei. 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. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643. 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. Sensing methods and the like can be used alone or in combination. The silver halide emulsion of the present invention uses 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 is used during chemical ripening and/or at the end of chemical ripening for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or maintaining stable photographic performance. Time,
and/or after chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers may 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, sugar derivatives, and cellulose derivatives may also be used. Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as monopolymers or copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Ru. 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 the silver halide photographic material of the present invention. The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. The emulsion layer of the silver halide photographic light-sensitive material of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing. A dye-forming coupler is used that forms a dye. The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler in the blue light-sensitive emulsion layer. , a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, a silver halide photographic material may be produced using a method different from the above combination. Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides); examples of magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, and pyrazones. Examples include triazole, open-chain acylacetonitrile couplers, and cyan dye-forming couplers include naphthol couplers and phenol couplers. It is desirable that these dye-forming coupler molecules contain a group called a ballast group, which makes the coupler non-diffusive and has a carbon number of 8 or more. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. Either equivalence is fine. Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the surface of silver halide crystals can be prepared using solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc.
Various methods can be used, and can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsification dispersion method is
It can be applied by conventionally known methods of dispersing hydrophobic additives such as couplers, and is usually dissolved in a high boiling point organic solvent with a boiling point of about 150°C or higher, if necessary in combination with a low boiling point and/or water-soluble organic solvent. After emulsifying and dispersing a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, the desired hydrophilicity is obtained. It may be added to the colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion. Examples of high-boiling organic solvents include phenol derivatives, phthalates, phosphates, citric esters, benzoic esters, alkylamides, fatty acid esters, which do not react with the oxidized form of the developing agent;
An organic solvent with a boiling point of 150°C or higher, such as trimesic acid ester, is used. When a hydrophobic compound is dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using a machine or ultrasound, anionic surfactants, nonionic surfactants, and cationic surfactants are used as dispersion residues. A surfactant can be used. The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the silver halide photographic light-sensitive material of the present invention, causing color turbidity or sharpness. Color antifogging agents are used to prevent deterioration in quality and noticeable graininess. The antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers. A protective layer of the silver halide photographic material of the present invention,
A hydrophilic colloid layer such as an intermediate layer may contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. The silver halide photographic material of the present invention may be provided with a filter layer, an antihalation layer, and/or an auxiliary layer for the 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. In the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention, increasing the addibility to reduce the gloss of the light-sensitive material;
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other. A lubricant can be added to reduce the sliding friction of the silver halide photographic material of the present invention. An antistatic agent for the purpose of preventing static electricity can be added to the silver halide photographic material 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 the silver halide photographic light-sensitive material of the present invention has the following properties: improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and (accelerating development, increasing contrast, Various surfactants are used for the purpose of improving photographic properties (such as sensitization). The photographic emulsion layer and other layers of the silver halide photographic light-sensitive material of the present invention are flexible reflective supports such as paper laminated with a baryta layer or an α-olefin polymer, synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, etc. It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics. The silver halide photographic material of the present invention can be improved in adhesion, antistatic properties, and dimensional stability directly or on the surface of the support after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. , abrasion resistance, hardness,
It may be applied through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties. When coating the silver halide photographic material 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 silver halide photographic material of the present invention can be exposed to electromagnetic waves in a spectral region to which the emulsion layer constituting the silver halide photographic material of the present invention is sensitive. As a light source, natural light (sunlight),
Tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp,
Cathode ray tube flying spot, various laser beams,
Light emitted from a phosphor excited by light emitting diode light, electron beams, X-rays, γ-rays, α-rays, etc.
Any known light source can be used. 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, because they are more stable than in the free state. Additionally, these compounds are generally present in a concentration of about 0.1 g to about 30 g per color developer, preferably about 1 g per color developer.
Use at a concentration of ~15g. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxytoluene, 2-amino-3
-oxytoluene, 2-oxy-3-amino-
Includes 1,-dimethylbenzene and the like. A particularly useful aromatic primary amine 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, particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, 2-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 contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate,
An alkaline 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, a thickening agent, and the like can be optionally contained. 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 develops color in the uncolored areas of the color former, and its composition consists of 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 salts 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 Acetate 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 fixer and bleach-fixer contain ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, sulfite, boric acid, borax, etc. , sodium hydroxide, potassium hydroxide,
A PH buffer consisting of various salts such as sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. can be contained alone or in combination with two or more types. 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 Effects of the Invention] In the present invention, a silver halide containing a magenta dye image-forming coupler represented by the above general formulas [] to [] and a magenta dye image stabilizer represented by the above general formula [XII] According to photographic light-sensitive materials, the fastness of magenta dye images, which conventionally have low fastness to light, heat, and humidity, can be improved. This effectively prevents Y-stain from forming on the parts. Furthermore, by using a dye image stabilizer represented by the general formula [] in combination, the light resistance of the dye image is improved. [Examples] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 On a paper support laminated on both sides with polyethylene, gelatin (15.0 mg/100 cm ² ) and comparative magenta coupler a (6.0 mg/100 cm ² ) were added to 2,5-di-
tert-octylhydroquinone (0.8mg/ ^100cm2 )
After emulsifying and dispersing tricresyl phosphate with silver chlorobromide emulsion (silver bromide 80 mol%,
Sample 1 was obtained by mixing with a coated silver amount of 3.8 mg/100 cm ² ), coating, and drying. A sample 2 was obtained by adding the above PH-13 as a magenta dye image stabilizer to the above sample 1 in an equimolar amount as the magenta coupler. Samples 3, 7, and 11 were obtained in the same manner except that the magenta coupler in Sample 1 was replaced with magenta couplers 1, 44, and 130 according to the present invention, respectively. In the above Samples 3, 7, and 11, the magenta dye image stabilizer PH-13 was added in an equimolar amount to the coupler to obtain Samples 4, 8, and 12, respectively, and further, in place of PH-13, samples related to the present invention were added. Magenta image stabilizer A-
4 was added in equimolar amounts as the coupler to prepare samples 5, 9, and
Got 13. In addition, in the samples 3, 7, and 11, the
Samples 6, 10, and 14 were prepared by adding PH-13 and A-4 in a total ratio of 1:2 and adding the same molar amount as the coupler. Comparison magenta coupler a The sample obtained above was exposed to light through an optical wedge according to a conventional method, and then processed in the following steps. [Processing process] Processing temperature Processing time Color development 33°C 3 minutes 30 seconds Bleach-fixing 33°C 1 minute 30 seconds Washing 33°C 3 minutes Drying 50-80°C 2 minutes The components of each processing solution are as follows. [Color developer] Benzyl alcohol 12ml Diethylene glycol 10ml Potassium carbonate 25g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Hydroxyamine sulfate 2.5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate
Add 4.5g water to make 1, and adjust the pH to 10.2 with NaOH. [Bleach-fix solution] Ammonium thiosulfate 120g Sodium metabisulfite 15g Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to 1 and adjust the pH to 6.7-6.8. The concentrations of Samples 1 to 14 treated above were measured using a densitometer (model KD-7R manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions. Each of the above-treated samples was exposed to a xenon fade meter for 10 days, and the light resistance of the dye image was examined for Y-stain in the uncolored area.
It was left in a high temperature, high humidity atmosphere of RH for 14 days, and the moisture resistance of the dye image and the Y-stain in the uncolored area were examined. The results obtained are shown in Table 1. However, the evaluation of each item of light fastness and moisture fastness of the dye image is as follows. [Residual rate] Percentage of dye remaining after light and moisture resistance tests at an initial density of 1.0. [Y-stain] From the concentration of Y-stain after light resistance and moisture resistance tests,
Value obtained by subtracting the concentration of Y-stain before light and moisture resistance tests. [Degree of discoloration] The value obtained by subtracting (yellow density)/(magenta density) before the light fastness test from (yellow density)/(magenta density) after the light fastness test at an initial density of 1.0.The larger this value is, the more yellow the color becomes. This means that the color tone tends to change easily.

[Table] As is clear from Table 1, Samples 3, 7, and 11 made using the coupler of the present invention are different from the conventional 4
Equivalent form of 3-anilino-1,2-pyrazolo-5-
Compared to Sample 1, which was created using an on-type coupler, it is clear that Y-stain is extremely unlikely to occur in the light fastness and humidity tests. It can be seen that the color changes and fades easily. Samples 4, 8, 12
is a sample prepared by using the coupler of the present invention in combination with the well-known magenta dye image stabilizer PH-13, which certainly greatly improves the fading of the dye image due to light. cannot improve discoloration. On the other hand, in samples 5, 9, and 13 prepared using the coupler of the present invention and the dye image stabilizer of the present invention,
Resistance tests against light, heat, and humidity show that the dye image shows little discoloration or fading, and almost no Y-stain occurs in uncolored areas. This is the conventional 4-equivalent type 3-anilino-1,2-pyrazolo-5
- This was not possible with the combination of the on-type coupler and the dye image stabilizer PH-13 (Sample 2). Furthermore, in addition to the coupler and magenta dye image stabilizer according to the present invention, a conventional magenta dye image stabilizer was added, and samples 6, 10, and 14 had further improved dye persistence in the light fastness test. I understand that. Example 2 Samples 15-46 were prepared using the coupler and magenta dye image stabilizer combinations shown in Table 2, coated in exactly the same manner as in Example 1. Samples 15-46 were processed as described in Example 1. Furthermore, these samples were subjected to a light resistance test and a moisture resistance test in the same manner as in Example 1, and the results shown in Table 2 were obtained. Note that the comparative magenta coupler b in the table has the following structure. Comparison magenta coupler b

【table】

[Table] As is clear from Table 2, the magenta dye image stabilizer of the present invention is used in combination with the conventionally used 4-equivalent type 3-anilino-1,2-pyrazolo-5-one type coupler. (Samples -15, 16)
When the coupler of the present invention was used in combination with a magenta dye image stabilizer commonly used in the past (Samples-19, 20, 21, and 22), there was no discoloration, fading, or Y-stain in the uncolored area in the light fastness test. and Y in humidity test
It can be seen that it is not possible to improve all of the stains, and that all of the above-mentioned improvements can only be achieved by using the coupler of the present invention in combination with the magenta dye image stabilizer of the present invention. Example 3 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic light-sensitive material, and Sample 31 was obtained. 1st layer: blue-sensitive silver halide emulsion layer α-pivaloyl-α- as a yellow coupler
(2,4-dioxo-1-benzylimidazolidin-3-yl)-2-chloro-5-[γ-(2,4
-di-t-amylphenoxy)butyramide] acetanilide at 6.8 mg/1000 cm ² , blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver: 3.2
mg/100cm ² , dibutyl phthalate 3.5mg/100
cm ² and gelatin were coated at a coating amount of 13.5 mg/100 cm ² . 2nd layer: middle layer 2,5-di-t-octylhydroquinone
0.5mg/ ^100cm2 , dibutyl phthalate 0.5mg/100cm2
100cm ² and gelatin was coated at 9.0mg/100cm ² . 3rd layer: green-sensitive silver halide emulsion layer The magenta coupler 18 was 3.5 mg/100 cm ² , the green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) was 2.5 mg/100 cm ² in terms of silver, dibutyl phthalate
3.0mg/100cm ² and gelatin were coated at 12.0mg/100cm ² . 4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-sec
-butyl-5-t-butylphenyl)benzotriazole 7.0 mg/100 cm ² , di-butyl phthalate 6.0 mg/100 cm ² , 2,5-di-t-octylhydroquinone 0.5 mg/100 cm ² and gelatin 12.0 mg/100 cm 2
It was painted so that it was ^100cm2 . 5th layer: Red-sensitive silver halide emulsion layer 2-[α-(2,4-di-
t-pentylphenoxy)butanamide]-4,
4.2mg/6-dichloro-5-ethylphenol
100cm ² , red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver: 3.0mg/100cm ² , tricresyl phosphate 3.5mg/100cm ² and gelatin.
The coating was applied at a concentration of 11.5mg/ ^100cm2 . 6th layer: Protective layer Gelatin was coated at 8.0 mg/100 cm ² . In the above sample 47, the magenta dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3 to create multilayer samples 48 to 56, which were exposed and processed in the same manner as in Example 1. After that, a light resistance test (15 days of exposure to xenon fademeter) was conducted. The results are also shown in Table 3.

[Table] From the results, the magenta dye image stabilizer of the present invention is effective in stabilizing the dye image of the magenta coupler related to the present invention, and the results increase as the amount added increases. Further, samples 48 to 56 showed extremely small discoloration of the dye images in the light fastness test compared to sample 47. Furthermore, in the sample of the present invention, the discoloration and fading of the magenta dye are extremely small, and after the light fastness test, the overall color balance with the yellow and cyan couplers as a silver halide color photographic light-sensitive material is good, and the color reproducibility is extremely good. It was maintained in good condition.

Claims (1)

[Scope of Claims] 1. A halogenated compound characterized by containing at least one magenta dye image-forming coupler represented by the following general formulas [] to [] and a compound represented by the following general formula [XII] Silver photosensitive material. General formula [] General formula [] General formula [] General formula [] General formula [] General formula [] [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and
R ₈ represents a hydrogen atom or 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. ] General formula [XII] [In the formula, R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. R ₁₄ and R ₁₅ are a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acylamino group, a sulfonyl group, and a sulfonamido group, respectively. Or represents a hydroxy group. m and n each represent an integer of 0 to 4, and when m is an integer of 2 to 4, R ₁₄ may be the same or different. Also, n is 2~
When it is an integer of 4, R ₁₅ may be the same or different. A has 1 to 1 carbon atoms in the straight chain part.
6 represents an alkylene group. ]