JPH0366652B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] 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. [Prior Art] Conventionally, aromatic primary
The oxidized product of the grade amine color developing agent and the color forming agent perform a coupling reaction to produce, for example, indophenol, indolinine, indamine, azomethine,
It is well known that phenoxazine, phenazine, and similar pigments are produced to form color images. In such photographic systems, a subtractive color reproduction method is usually adopted, and color forming agents having additional colors, namely yellow and magenta, are added to blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver halide emulsion layers, respectively. A silver halide color photographic light-sensitive material containing a coupler that develops a cyan color is also used. Examples of couplers used to form the yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, and indazolone couplers. Furthermore, as a coupler for forming a cyan image, for example, a phenol or naphthol coupler is generally used. It is desired 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. Also, silver halide photographic materials (hereinafter referred to as color photographic materials)
It is desired that the uncolored portion of the material does not turn yellow (hereinafter referred to as Y-stain) due to light or moist heat. However, in the case of magenta couplers, Y-staining due to moist heat in uncolored areas and fading due to light in dye image areas are extremely large compared to yellow couplers and cyan couplers, and often pose a problem. Couplers commonly used to form magenta dyes are 1,2-pyrazolo-5-ones. A major problem with the dye formed from this 1,2-pyrazolo-5-one magenta coupler is that in addition to the main absorption near 550 nm, it also has a secondary absorption near 430 nm. Various studies have been conducted. A magenta coupler having an anilino group at the 3-position of a 1,2-pyrazolo-5-one has a small side absorption and is particularly useful for obtaining a color image for printing. These techniques are described in, for example, US Pat. No. 2,343,703 and British Patent No. 1,059,994. However, the above-mentioned magenta coupler has the disadvantage that the image storage property, especially the fastness of the dye image to light, is extremely poor, and 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, as well as US Pat.
1H-pyrazolo [5,1-
c]-1,2,4-triazole type coupler, 1H-pyrazolo[1,5-b]-1,2,4-triazole type coupler described in Research Disc. No. 24531 (1984), Research Disc. 1H-pyrazolo [1,
5-c]-1,2,3-triazole type coupler,
Japanese Patent Publication No. 59-162548, Research Disclosure
1H-imidazo [1,
2-b]-pyrazole type coupler, described in Research Disclosure No. 24230 (1984) 1H-pyrazolo[1,5-b] pyrazole type coupler, described in Research Disclosure No. 24220 (1984)
Magenta couplers such as 1H-pyrazolo[1,5-d]tetrazole type couplers have been proposed.
Among these, 1H-pyrazolo[5,1-c]-1,
2,4-triazole coupler, 1H-pyrazolo[1,5-b]-1,2,4-triazole coupler, 1H-pyrazolo[1,5-c]-1,
2,3-triazole coupler, 1H-imidazo[1,2-b]pyrazole coupler, 1H-
The dye formed from the pyrazolo[1,5-b] pyrazole type coupler and the 1H-pyrazolo[1,5-d] tetrazole type coupler has a sub-absorption near 430 nm of the 1,2 type having an anilino group at the above-mentioned 3-position.
- It is significantly smaller than dyes formed from pyrazol-5-ones and is preferred for color reproduction;
It has the advantage that the generation of Y-stain in uncolored areas is extremely small when exposed to light, heat, and humidity. 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 materials, especially printed color photographic materials. , it has not been put to practical use in printed color photographic materials. In addition, JP-A-59-125732 discloses that a 1,2,4-triazole type magenta coupler is used in combination with a phenol compound or a phenyl ether compound for 1H-pyrazolo[5,1-c]. 1H-pyrazolo[5,1-c]-1,2,4
- Techniques have been proposed to improve the light fastness of magenta dye images obtained from triazole type magenta couplers. However, it has been recognized that even the above techniques are still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light. In view of this problem, the inventors of the present invention have conducted extensive studies and found that
The above 1H-pyrazolo[5,1-c]-1,2,4
- Triazole couplers, 1H-pyrazolo[1,5-b]-1,2,4-triazole couplers, 1H-pyrazolo[1,5-c]-1,
2,3-triazole coupler, 1H-imidazo[1,2-b]-pyrazole coupler, 1H-
The compound represented by the general formula [] of the present invention has a remarkable effect on preventing discoloration and fading of pyrazolo[1,5-b]pyrazole couplers and 1H-pyrazolo[1,5-d]-tetrazole couplers against light. I found that it works. This technique is disclosed in Japanese Patent Application No. 60-31297. However, there is expected to be room for further improvement. [Object of the invention] The present invention has been made in view of the above problems.
A first object of the present invention is to provide a color photographic material with excellent color reproducibility and significantly improved light fastness of magenta dye images. A second object of the present invention is to provide a color photographic material having a magenta dye image that is less discolored by light. A third object of the present invention is to provide a color photographic material in which the generation of Y-sterene in uncolored areas is prevented from being exposed to light and humidity. [Structure of the Invention] As a result of further studies on improvements, the present inventors found that among the couplers listed above, there is a 1H-pyrazolo[5,1-c]-1,2,4-triazole type coupler. When a compound represented by the general formula [] of the present invention is used in combination with a coupler having a specific structure, a particularly significant effect, which was unexpected at first, has been discovered. The above purpose is to obtain 1H-pyrazolo[5,1-c]-1,2,4 whose 3-position is substituted with the following general formula []
This is achieved by a silver halide photographic material containing at least one of the -triazohel type magenta couplers and at least one of the compounds represented by the following general formula []. General formula [] -R ¹ -SO ₂ -R ² In the formula, R ¹ is 1H-pyrazolo[5,1-c]-1,
An alkylene group in which the straight chain part connecting the 3-position carbon of 2,4-triazole and -SO ₂ has 3 or more carbon atoms,
R ² represents an alkyl group, a cycloalkyl group or an aryl group. General formula [] In the formula, R ¹¹ and R ¹⁴ are a hydrogen atom, a halogen atom, 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, and a sulfonamide group, respectively. , represents a cycloalkyl or alkoxycarbonyl group, R ¹² is a hydrogen atom, an alkyl group, an aryl group,
R13 represents an acyl group, cycloalkyl group, or heterocyclic group, and ^R13 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, or a cycloalkyl group. group or an alkoxycarbonyl group. Also with R ¹²
R ¹³ may be ring-closed with each other to form a 5- or 6-membered ring. Y represents an atomic group necessary to form a chroman or coumaran ring. Hereinafter, unless otherwise specified, the compound represented by the general formula [] according to the present invention will be referred to as a magenta dye image stabilizer. The magenta coupler according to the present invention is a 1H-pyrazolo[5,
1-C]-1,2,4-triazole type magenta coupler, in the general formula []-R ¹ -SO ₂ -R ² , R ¹ is 1H-pyrazolo[5,1-C]-1 ，
R2 represents an alkylene group in which the linear part of the carbon chain connecting the 3-position carbon of the 2,4-triazole and _-SO2- has 3 or more carbon atoms, and ^R2 represents an alkyl group, a cycloalkyl group, or an aryl group. The alkylene group represented by R ¹ has a straight chain portion having 3 or more carbon atoms, preferably 3 to 6 carbon atoms, and this alkylene group may have a substituent. Examples of the substituent include aryl, cyano, halogen atom, heterocycle, cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, as well as acyl, carboxy, carbamoyl, alkoxycarbonyl, aryloxy. Those substituted via a carbonyl group such as carbonyl, and those substituted via a hetero atom {specifically, hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy,
Those substituted via an oxygen atom such as carbamoyloxy, nitrogen atoms such as nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, etc. substitution through a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc., and substitution through a phosphorus atom such as phosphonyl}. Preferred substituents include phenyl. Preferred specific examples of alkylene represented by R ¹ are shown below. −CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

【formula】

[Formula] −CH ₂ CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

[Formula] The alkyl group represented by R ² may be linear or branched. Specifically, methyl, ethyl, propyl, iso-
Propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadacil, 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. 1H-pyrazolo[5,1-C]-1 of the present invention,
Among the 2,4-triazole type magenta couplers, preferred ones are represented by the following general formula []. General formula [] In the above general formula [], R ¹ and R ² have the same meaning as R ¹ and R ² in the general formula [], R represents a hydrogen atom or a substituent, and X represents a hydrogen atom or an oxidized product of a color developing agent. Represents a substituent that can be removed by reaction with. 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,
Examples include an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, 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 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 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, anyloxycarbonyl, 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 free atom such as phosphonyl, etc.}]. 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'-{a-[4''(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylpropyl group, 3-{4'-[a-
(2″,4″-di-t-amylphenoxy)butanamide]phenyl}-propyl group, 4-[a-(o-
chlorophenoxy) tetradecaneamide phenoxy] propyl group, allyl group, cyclopentyl group,
Examples include 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
-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'-[a-(4''-t-butylphenoxy)tetradecanamido]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, a
-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-toluenesulfonyl group. Examples of the sulfinyl group represented by R include 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 thereof include alkoxyphosphonyl groups such as octyloxyphosphonyl groups, aryloxyphosphonyl groups such as phenoxyphosphonyl groups, and arylphosphonyl groups such as phenylphosphonyl groups. The carbamoyl group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N6 (2-
pentadecyl octylethyl) carbamoyl group,
N-ethyl-N-dodecylcarbamoyl group, N-
Examples include {3-(2,4-di-t-amylphenoxy)propyl}carbamoyl group. 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 ^3,7 ]decane-1-yl, and 7,7-yl.
Examples include dimethyl-bicyclo[2.2.1]heptane-1-yl. 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 phenyloxy, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group, such as phenoxy group, p-
Examples include t-butylphenoxy group and m-pentadecylphenoxy group. The heterocyclic oxy group represented by R is 5 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 a-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 and an N-phenylcarbamoyloxy group. The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, 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 a-ethylpropanamide group, an N-phenylacetamide group, a dodecanamide group, and a 2,4-di-t-amylphenoxylene group. Examples include cyacetamide group, a-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. Specific examples include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesphonamide group, and a 2-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 thereof include an amino group, an N-phenylsulfamoylamino group, and the like. 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 phenoxylcarbonylamino 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. 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 ′, R ¹ ′, and R ² ′ have the same meanings as R, R ^{1 ,} and R ² above, and R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) A group represented by
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-[a
-(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 methanecarbonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyl group. Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group. As the alkylthio group, butylthio group, 2
-cyanoethylthio group, phenethylthio group, benzylthio group, etc. The arylthio group includes phenylthio group, 4
-Methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butylphenylthio group, etc. can be mentioned. Examples of the heterocyclic thio group include 1-phenyl-1,2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. Examples of the group substituting via the nitrogen atom include the general formula

[Specific effects of the invention]

In the present invention, 1H-pyrazolo[5,1-c]-1,2,4 whose 3-position is substituted with the above general formula []
- According to a color photographic material containing a triazole type magenta coupler and a magenta dye image stabilizer represented by the general formula [], it has been known that
The fastness of magenta dye images, which have low fastness to heat and humidity, specifically, changes in color, fading, and
The generation of Y-stain in uncolored areas due to light, heat, and humidity can be effectively prevented. Furthermore, by using a dye image stabilizer represented by the general formula [XI] in combination, the light resistance of the dye image is significantly improved. [Specific Examples of the Invention] 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 Gelatin (15.0 mg/100 cm ² ), comparative magenta coupler a (6.0 mg/100 cm ² ) below, and 2,5-di-tert-octylhydroquinone (0.8 mg) were placed on a paper support laminated on both sides with polyethylene. /100
cm ² ) along with tricresyl phosphate (silver bromide)
Sample 1 was obtained by mixing with 80 mol % and coating amount of silver 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 equal molar amount to that of the magenta coupler. Samples 5, 9, and 13 were obtained in the same manner except that the magenta coupler in Sample 1 was replaced with magenta couplers (1), (7), and (25) according to the present invention, respectively. Samples 5, 9, and 13 were obtained in the same manner. Samples 2, 6, 10, and 14 were prepared by adding PH-13 as the magenta dye image stabilizer in an equimolar amount to the coupler in Sample 13.
I got it. Furthermore, instead of PH-13, the magenta image stabilizer B-35 according to the present invention was added in an amount equal to the coupler in moles to obtain Samples 3, 7, 11, and 15, respectively. Furthermore, in the samples 1, 5, 9, and 13, the PH
Samples 4, 8, 12, and 16 were prepared by adding a total of -13 and B-35 at a ratio of 1:2 and equimolar amounts to the coupler. Comparative magenta coupler a (Patent Application No. 59-280486,
Coupler used in Example-1) 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 with water 33°C 3 minutes Drying 50-80°C 2 minutes The components of each processing solution are as follows. [Color developer] Benzyl alcohol 12m Diethylene glycol 10m Potassium carbonate 25g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Hydroxylamine 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-mentioned processed samples was exposed to a xenon fade meter for 12 days to examine the light resistance of the dye image. The results obtained are shown in Table 1. However, the evaluation of the light fastness of the dye image is as follows. [Residual rate] Percentage of dye remaining after light fastness test for initial density 1.0. [Degree of color change] 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 changes from magenta to yellow. This means that the color tone tends to change easily.

[Table] As is clear from Table 1, comparative coupler a and couplers A-(1), (7), and (25) of the present invention alone (samples 1, 5, 9, and 13) showed no resistance in the light resistance test. It can be seen from the residual rate and degree of discoloration of the dye image area that it easily discolors and fades due to light. In addition, the conventionally well-known magenta dye image stabilizer for the above couplers.
Samples 2, 6, 10, created using PH-13
14 does considerably improve the fading of the dye image, but cannot improve the discoloration. On the other hand, in sample 3, which was prepared by using comparative coupler a in combination with the magenta dye image stabilizer of the present invention, it can be seen that discoloration and fading of the dye image were greatly improved. It can be seen that Samples 7, 11, and 15, which were prepared by using the magenta dye image stabilizer of the present invention in combination, were further improved in discoloration and fading of the dye images compared to Sample 3. It can also be seen that in samples 8, 12, and 16, which were created by using the coupler of the present invention in combination with two types of magenta dye image stabilizers, the light fastness of the dye images was improved over that of samples 7, 11, and 15. . Example 2 Samples 17 to 32 were prepared by applying couplers and magenta dye image stabilizers in combinations shown in Table 2 in exactly the same manner as in Example 1. Samples 17-32 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. Comparative magenta coupler b (Patent Application No. 1983-25793,
Coupler used in Example-2)

[Table] As is clear from Table 2, the combination of the coupler of the present invention and the magenta dye image stabilizer of the present invention increases the stability of the magenta dye image against light. It can be seen that this has been greatly improved. 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 material, and sample 33 was obtained. 1st layer: blue-sensitive silver halide emulsion layer α-vivaloyl-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/100 cm ² and blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted into silver.
3.2mg/100cm ² , 3.5mg/dibutyl phthalate
100cm ² and gelatin was coated at a coating amount of 13.5mg/100cm ² . 2nd layer: middle layer 2,5-di-octylhydroquinone
0.5mg/ ^100cm2 , dibutyl phthalate 0.5mg/100cm2
100cm ² and gelatin was coated at 9.0mg/100cm ² . Third layer: green-sensitive silver halide emulsion layer containing 3.5 mg/magenta coupler A-7 of the present invention.
100cm ² , 2.5mg/100cm ² of green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver, 3.0mg/100cm ² of dibutyl phthalate, and gelatin.
The coating was applied so that the amount was 12.0mg/ ^100cm2 . 4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-sec
-butyl-5-t-butylphenyl)benzotriazole at 7.0 mg/100 cm ² , di-butyl phthalate at 6.0 mg/100 cm ² , 2,5-di-t-octylhydroquinone at 0.5 mg/100 cm ² and gelatin
The coating was applied so that the amount was 12.0mg/ ^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 bromide emulsion (containing 80 mol% silver bromide)
3.0 mg/100 cm ² in terms of silver, 3.5 mg/100 cm ² in tricresyl phosphate 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 33, the dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3,
Multilayer samples 34 to 42 were prepared, exposed and treated in the same manner as in Example 1, and then subjected to a light resistance test (irradiated with a xenon fademeter for 15 days). The results are also shown in Table 3.

【table】

[Table] From this result, the dye image stabilizer of the present invention is
It is effective as a dye image stabilizer for magenta couplers related to the present invention, and the results become greater as the amount added increases. Further, Samples 34 to 42 showed extremely small discoloration of the dye images in the light fastness test compared to Sample 33. Furthermore, in the sample of the present invention, discoloration and fading of the magenta dye were extremely small, and even after the light fastness test, the overall color balance with the yellow and cyan couplers as a color photographic material was good, and extremely good color reproducibility was maintained. .

Claims (1)

[Claims] 1H- in which the 1-3rd position is substituted with the following general formula []
A silver halide photographic material comprising a pyrazolo[5,1-c}-1,2,4-triazole type magenta coupler and at least one compound represented by the following general formula []. General formula [] -R ¹ -SO ₂ -R ² [wherein R ¹ is 1H-pyrazolo[5,1-c]-
The linear moiety connecting the 3-position carbon of the 1,2,4-triazole and _-SO2 represents an alkylene group having 3 or more carbon atoms, and ^R2 represents an alkyl group, a cycloalkyl group, or an aryl group. ] General formula [ ] [In the formula, R ¹¹ and R ¹⁴ 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. basis,
Represents a cycloalkyl or alkoxycarbonyl group, R ¹² 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 ¹³ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group. group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamido group, cycloalkyl group, or alkoxycarbonyl group. Further, R ¹² and R ¹³ may be ring-closed with each other to form a 5- or 6-membered ring. Y represents an atomic group necessary to form a chroman or coumaran ring. ]