JPS62273532A - Silver halide photographic sensitive material containing new magenta coupler - Google Patents

Abstract

PURPOSE:To obtain the titled material having excellent light fastness and formalin-resistance and a high coloring property by incorporating a specific magenta coupler into at least one layer of the silver halide emulsion layers. CONSTITUTION:The magenta coupler which is substituted with a substituent shown by the formula (Ar-s-) at 6 position of 1H-pyrazolo[3,2-C]-s-triazole type magenta coupler is incorporated into at least one layer of the silver halide emulsion layers. The 1H-pyrazolo[3,2-C]-s-triazole type magenta coupler is shown by the formula wherein Ar is aryl or a hetero aromatic group, R is hydrogen atom or a substituent, X is hydrogen atom or a group capable of releasing by coupling reaction of an oxidant of the color developing agent. The used amount of the magenta coupler is preferably a range of 1.5X10<-3>-7.5X10<-1>mol per 1mol of silver. Thus, the titled material having good light fastness and formalin-resistance and high coloring property is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a magenta coupler that is free from undesirable side absorption, has high color development, and forms magenta dye images with improved storage stability, especially light fastness. The present invention relates to a silver halide photographic light-sensitive material containing the present invention. More specifically, the present invention relates to a silver halide color photographic material containing a novel magenta coupler.

[Conventional technology]

In general, in silver halide color photographic materials, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and the oxidized products of the color developing agent produced at this time are combined with yellow, magenta and A dye image can be obtained by coupling with a coupler forming each cyan dye.

In order to form the magenta dye, the coupler that has been used in practice has traditionally been the pyrazolone type coupler,
This has problems in that it has undesirable side absorption and is poor in storage stability, particularly in resistance to formalin gas (formalin resistance).

In order to improve the above problems, various 1H-pyrazolo(3,2-C)-s-triazole magenta couplers have been proposed.For example, U.S. Pat.
．． 067, British Patent No. 1,252,418, British Patent No. 1
, No. 334,515. The compounds described in both patents are, of course, superior to pyrazolone magenta couplers in terms of side absorption, but improvements in formalin resistance are insufficient, and little improvement has been shown in terms of color development and light fastness of images. do not have.

Research Disclosure
The compound described in 12443 cannot be put to practical use at all in terms of color development.
1H-pyrazolo(3,2-C) - described in No. 2045
Although s'-) lyazole type magenta couplers have been significantly improved in terms of formalin resistance and color development, there has been little improvement in light resistance.

Further, although the coupler described in JP-A-59-125732 has been improved in color forming properties, no improvements have been made in terms of the light resistance of dye images based on the described coupler.

In the technique described in JP-A No. 59-125732, the light resistance of the image is simply improved by the additive used in combination. Although the light resistance has been slightly improved, it is still not sufficient.

In other words, 1H-pyrazolo (3
, 2-C) -5-) It can be said that little improvement has been made in the light resistance of dye images of lyazole magenta couplers.

[Purpose of the invention]

An object of the present invention is to provide a silver halide color photographic material that is free from undesirable side absorption, has good light resistance and formalin resistance, and has high color development.

[Structure of the invention]

The object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers contains 1H-pyrazolo[3,2-C ) This is achieved by a silver halide photographic material containing a magenta coupler in which the 6-position of the -s-triazole type magenta coupler is substituted with a substituent represented by the following general formula [I].

The 1H-pyrazolo(3,2-C)-s-triazole type magenta coupler mentioned here has the general formula % Formula % General formula (1) Ar-3- General formula (Il) However, General formula (1), ( In II), Ar represents an aryl group or a heteroaromatic group, and in the general formula CI+),
R represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a coupling reaction with an oxidized color developing agent,
Represents a group that can leave.

Examples of the aryl group represented by Ar in the general formulas (13 and CI+) include a phenyl group and a naphthyl group. this? The phenyl group and naphthyl group may further have a substituent. The heteroaromatic group represented by Ar is preferably a 5- to 6-membered ring, such as a chenyl group, a furyl group, a pyrrolyl group, an imidazolyl group, Examples include a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxasilyl group, an isoxazolyl group, a benzthiazolyl group, a benzimidazolyl group, a benzoxasyl group, a pyridyl group, a pyrimidyl group, and a pyrazolyl group. These heteroaromatic groups may further have a substituent. Examples of substituents that can be substituted on the aryl group and heteroaromatic group represented by Ar include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms), alkyl groups, aryl groups, heterocyclic groups, nitro groups, and cyano groups. , an alkoxy group, an aryloxy group, an alkylthio group, an alkylthio group, an alkylcarbonyl group, an alkylcarbonyl group, an alkylsulfonamide group,
Arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, acylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonyl group, irisulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkylcarbonyloxy Examples include a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxy group, a carboxy group, an amino group, and a secondary amino group.

Further, R in general formula (n) represents a hydrogen atom or a substituent, and specific examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an aryl group. groups, heteroaromatic groups, etc., those substituted via carbonyl groups such as acyl, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via heteroatoms, specifically sulfonyl and sulfinyl. , sulfamoyl, alkylthio, oliruthio, or those substituted through a sulfur atom such as heteroaromatic ring groups, alkoxy, aryloxy, heteroaromatic ring groups, acyloxy,
Those substituted via an oxygen atom such as carbamoyloxy, amino, acylamino, sulfonamide, imide,
Represents those substituted via a nitrogen atom such as ureido, sulfamoylamino, alkoxycarbonylamino, and aryloxycarbonylamino.

R will be explained in more detail.

That is, the alkyl group represented by R has 1 carbon number.
-32, preferably alkenyl groups and alkynyl groups have 2 to 32 carbon atoms, cycloalkyl groups,
The cycloalkenyl group preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms, and the alkyl group, alkenyl group, or alkynyl group may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups include substituted S (for example, aryl, cyano, halogen atom, heterocycle, cycloalkyl, cycloalkenyl, spiro compound residue, organic hydrocarbon compound residue) In addition to groups, those substituted through a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryoloxycarbonyl, and those substituted through a hetero atom, specifically hydroxy, alkoxy, aryloxy, heterocyclic oxy,
fl of siloxy, acyloxy, carbamoyloxy, etc.
& Those that substitute via a nitrogen atom, such as nitro, amine (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, etc. What to replace, alkylthio? +J-ruthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc., which are substituted via a sulfur atom, etc.).

Specifically, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a pentadecyl group, a heptadecyl group,
1-hexylnonyl group, 1,1'-dipentylnonyl group, 2-chloro-t-butyl group, trifluoromethyl group,
l-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2.4-di-t-amylphenoxymethyl group, anilino group, ■-phenylisopropyl 5.3-m-butanesulfonaminophenoxypropyl group , 3-4'-(α-[4" (p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino)phenylpropyl group, 3-+4'-[α-(2",
Examples include 4'-di-t-amylphenoxy)butanamido]phenyl)-propyl group, 4-[α-(O-chlorophenoxy)tetradecanamidophenoquine]propyl group, allyl group, cyclopentyl group, and cyclohexyl group.

The aryl group represented by R is preferably a phenyl group, and this aryl group may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, phenyl group, 4-t-butylphenyl group,
Examples include 2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'-[α-(4'-t-butylphenoxy)tetradecanamido]phenyl group, and the like.

The heterocyclic group represented by R is preferably 5-7R, which may be substituted or fused, specifically 2-furyl group, 2-chenyl group, Examples include 2-pyrimidinyl group and 2-benzothiazolyl group.

Examples of the acyl group represented by R include acetyl group,
Alkylcarbonyl groups such as phenylacetyl group, dodecanoyl group, α-2,4-di-t-amylphenoxybutanoyl group, verdiyl group, 3-pentadecyloxybenzoyl group, p-chlorohendiyl group, etc. carbonyl group, etc.

Examples of the sulfonyl group represented by R include alkylsulfonyl groups such as methylsulfonyl group and dodecylsulfonyl group, and arylsulfonyl groups such as benzenesulfonyl group and p-toluenesulfonyl group.

Examples of the sulfinyl group represented by R include ethylsulfinyl group, octylsulfinyl group, alkylsulfinyl group such as 3-phenoxybutylsulfinyl group, phenylsulfinyl group, arylsulfinyl group such as m-pentadecylphenylsulfinino, etc. .

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group,
Examples include arylphosphonyl groups such as phenylphosphonyl groups.

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pentadecyl group), etc. Examples thereof include octylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, and N-(3-(2,4-di-t-amylphenoxy)proyl)carbamoyl group.

The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, N, N-
Examples include diethylsulfamoyl group, N-(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)hebutan-1-yl and the like.

Examples of the organic carbonized compound residue represented by R include bicyclo(2,2,1)hebutan-1-yl, tricyclo(3,3,1,1)decane-1-yl, 7,7-dimethyl- Examples include bicyclo(2,2°1)hebutan-1-yl.

The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group, a propoxy group, a 2-ethoxyethoxy group, a pentadecyloxy group, and a 2-dodecyloxy group. Examples include ethoxy group and phenethyloxyethoxy group.

The aryloxy group represented by R is preferably phenyloxy A, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, such as phenoxy group, pt-butylphenoxy group, m-pentadecylphenoxy group, and the like.

The peterocyclic oxy group represented by R preferably has a 5- to 7-membered heterocycle, and the cough heterocycle may further have a substituent, for example, 3.4.5.6 -tetrahydrobilanyl-2-oxy group and 1-phenyltetrazole-5-oxy group.

Examples of the acyloxy group represented by R include an alkylcarbonyloxy group and an arylcarbonyloxy group, which may further have a substituent, specifically an acyloquine group, α-chloroacetyloxy, etc. and benzoyl group, benzoyl group, and benzoyl group.

The carbamoyloxy group represented by R is an alkyl group,
It may be substituted with an aryl group, and examples thereof include N-ethylcarbamoyloxy group, N,N-diethylcarbamoyloxy group, N-phenylcarbamoyloxy group, and the like.

The amino group represented by R is an alkyl group, an aryl group (
(preferably phenyl group), etc., such as ethylamino group, anilino group, m~dichlornylino group, 3-pentadecyloxycarbonylanilino group, 2
-chloro-5-hexadecaneamide anilide group and the like.

Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have one substituent, specifically an acetamido group,
Examples include α-ethylpropanamide group, N-phenylacetamide group, dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl-4-hydroxyphenoxybutanamide group, and the like.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group, an alkylsulfonylamino group, etc., which may further have a substituent, specifically a methylsulfonylamino group, a pentadecylsulfonylamino group, etc. group, benzenesulfonamide group, p-toluenesulfonamide group, 2-methoxy-5-t-amylbenzenesulfonamide group, and the like.

The imide group represented by R may be open-chain or cyclic, and may have a substituent, such as succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarinide group, etc. Examples include imide groups.

The ureido group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group, Examples include N-p-tolylureido group.

The sulfamoylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc. (e.g., N, N-dibutylsulfamoylamino group, N-methyl Examples include sulfamoylamino group and N-phenylsulfamoylamino group.

The alkoxycarbonylamino group represented by R may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like.

The -ruoxycarponylamino group represented by R is
It may have a substituent, such as a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc.

The oxycarbonyl group represented by R may further have a substituent, such as phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, and the like.

The alkylthio group represented by R may further have a substituent, for example, an ethylthio group, a dodecylthio group,
Examples include octadecylthio group, phenethylthio group, and 3-phenoxypropylthio group.

The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group, a p-methoxyphenylthio group, a 2-t-octylphenylthio group, a 3-octadecylphenylthio group, 2
-carboxyphenylthio group, p-acetaminophenylthio group, etc.

The heterocyclic thio group represented by R is preferably a 5- to 7-membered heterocyclic thio group, and may further have a fused ring,
Moreover, it may have a substituent.

Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Groups that can be separated by the coupling reaction with the oxidized color developing agent represented by groups (e.g. acylamino group, diacylamino group, alkylamino group, arylamino group, etc.), azo group, aryloxy group (e.g. phenoxy group, p-methoxyphenoxy group, p-butanesulfonamidophenoxy group, p- carboxyphenoxy group, etc.)
, alkoxy groups (e.g. methoxy group, ethoxy group, 2-
methoxyethyloxy group, etc.), alkylthio group (e.g., phenylthio group, p-carboxyphenylthio group, etc.), alkylthio group (e.g., methylthio group, 2-hydroxyethylthio group, etc.), heterocyclic thio group (e.g., 1-ethylthio group, etc.), (tetrazole-5-thioyl group, 2-pyridylthio group, etc.)
, heterocyclic groups (e.g. 1-pyrazolyl group, l-imidazolyl group, 2,5-pyrazolinedione-1-yl group, etc.),
Examples include a carboxyl group, a sulfo group, an alkoxycarbonyl group, an alkoxycarbonyl group, and an aralkoxycarbonyl group.

Next, specific examples of the compound represented by the general formula (I[) are shown below in (1) to (30). Naturally, the present invention is not limited to these exemplified compounds.

Exemplary compound +11 CH.

CI! .

C@H+7 ■ CHs C, H5 ■ C8゜)lt+ Jin CsL+ CH.

LL; @1117 Hs Next, a general method for synthesizing the compound of the present invention will be described below. References are as follows.

R, Gomper, W, Topfl: Hemisorani Berichte (CheIII.

Ber, ), 95.2861 (1962) R, Gomp.
perJ, Topfl: Hemisorani Berichte (Che
Il.

Ber, ), 95.2881 (1962) J, Ba1l
ey: Journal of the Chemical Society, Parkin 1 (J, Chem, Soc,.

Perkin I), 2047 (1977)l
H(A) HH Ha 12 o.

(However, in the above reaction formula, Ar, R, and X have the same meanings as in general formulas (1) and (I[), and Ha7!o represents a halogen atom.) This can be achieved by the method described in No. 43947 and the like.

In addition to the above synthesis method, it is also possible to synthesize intermediate (A) by diazotization, reduction, acylation, ring closure, hydrolysis, and decarboxylation without hydrolyzing the intermediate (A).

H2) Reduction H (8) Xll Specific synthesis examples will be described in the Examples section below.

The silver halide photographic material of the present invention comprises a support and a hydrophilic colloid layer containing at least one silver halide emulsion layer coated on the support. This hydrophilic colloid layer is coated on at least one side of the support. The above-mentioned silver halide emulsion is coated directly on the support or coated via a hydrophilic colloid layer that does not contain the silver halide emulsion, and a hydrophilic protective layer is further formed on the silver halide emulsion layer. A sex colloid layer may be applied.
In addition, the silver halide emulsion layer may be divided into silver halide emulsion layers of different sensitivities, for example high sensitivity and low sensitivity. In this case, the silver halide emulsion layers of different sensitivities may have a hydrophilic An intermediate layer of sexual colloid layer may be provided,
Further, an intermediate layer may be provided between the silver halide emulsion layer and the protective layer.

The magenta coupler represented by the general formula (n) used in the present invention may be contained in a hydrophilic colloid layer coated on at least one side of the support, but it may not be contained in at least one of the silver halide emulsion layers. It is preferable that

The amount of the magenta coupler according to the present invention to be added to the photographic material of the present invention is preferably in the range of 1.5 x 10"3 mol to 7.5 ~5X10-' moles.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film, a positive film, or a color photographic paper, but the present invention particularly applies when a color photographic paper intended for direct viewing is used. The effects of this will be effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be for monochrome use or for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a photographic coupler is usually used.
It has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers and a non-photosensitive layer are laminated on at least one side of the 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 includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The method for creating and growing the zero-species particles may be the same or different.

In the silver halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to P in the mixing pot.
The halogen composition of the particles may be changed by sequentially and simultaneously adding H and pAg while controlling, or by using a converge run method after growth.

By using a silver halide solvent as necessary during the production of the silver halide emulsion according to the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled.

The silver halide grains used in the silver halide emulsion according to the present invention are cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or Complex salts, iron salts, or complex salts can be used to add metal ions and encapsulate them inside the particles and/or on the surface of the particles. Can provide reduction-sensitized nuclei.

In the silver halide emulsion according to the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or
Alternatively, it may be left as is.

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 according to 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 according to 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 according to 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. , (1°0.03 plane and (i, 1.1)
Any surface ratio can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion according to the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion according to the present invention can be chemically sensitized by a conventional method. In other words, sulfur-containing compounds that can react with silver ions, sulfur sensitization using activated gelatin,
A selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal compound using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion according to the present invention is used in the photographic industry.
Optical sensitization can be achieved to a desired wavelength range using dyes known as sensitizing dyes. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it may be a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. In addition, a supersensitizer that enhances the sensitizing action of the sensitizing dye may be included in the emulsion.

The silver halide emulsion according to the present invention is useful for preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials.
Or, for the purpose of keeping photographic performance stable, antifoggants or Compounds known as stabilizers can be added.

Binder (or protective colloid) for silver halide emulsions
It is advantageous to use gelatin, but other synthetic hydrophilic polymers such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, W derivatives, cellulose derivatives, single or copolymers, etc. Hydrophilic colloids such as substances can also be used.

For photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion according to the present invention, a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength may be used alone or in combination. It is hardened by. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion according to the present invention.

It can contain a dispersion (latex) of a photosensitive synthetic polymer using the silver halide emulsion according to the present invention.

In the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a camping reaction with an oxidized product of p-phenylenediamine derivatives, aminophenol derivatives, etc.). The dye-forming couplers are typically selected such that for each H emulsion layer a dye is formed which absorbs light in the light sensitive spectrum of the emulsion layer, and a yellow dye is formed in the blue light sensitive emulsion layer. As for the forming couplers, 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, silver halide color photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides, etc.); examples of magenta dye-forming couplers include, in addition to the couplers according to the present invention, 5-pyrazolone couplers, pyrazolobenzimidazole couplers,
Examples include pyrazolotriazole and open-chain acylacetonitrile couplers, and examples of cyan dye-forming couplers include naphthol couplers and phenol couplers.

It is desirable that these dye-forming couplers have a group called a ballast group in the molecule having 8 or more carbon atoms to make the coupler non-diffusive;
It can be either 4-equivalent, in which 4 molecules of silver ions need to be reduced to form a molecular dye, or 2-equivalent, in which only 2 molecules of silver ions need to be reduced. .

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. Various methods for dispersing hydrophobic additives such as couplers can be applied to the oil-in-water emulsion dispersion method. Usually, a high-boiling point organic solvent with a boiling point of about 150°C or higher is used, and if necessary, a low-boiling point and/or water-soluble additive is used. emulsify and disperse using a dispersion means such as a stirrer, homogenizer, colloid mill, flow lift mixer, ultrasonic device, etc. using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After that, it may be added to the desired hydrophilic colloid layer. A step of removing the low-boiling organic solvent may be included simultaneously with the dispersion or dispersion.

High boiling point oils include phenol derivatives, phthalate esters, phosphate esters, which do not react with the oxidized form of the developing agent,
Boiling point 15 of citric acid ester, benzo 8M ester, alkyl amide, fatty acid ester, trimesic acid ester, etc.
An organic solvent having a temperature of 0° C. or higher is used.

Anionic surfactants, nonionic surfactants, cations are used as dispersion aids when hydrophobic compounds are dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using mechanical or ultrasonic waves. A surfactant can be used.

In the color photographic light-sensitive material of the present invention, color turbidity may occur due to the movement of the oxidized form of the developing agent or the electron transfer agent between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers).
Color antifogging agents are used to prevent deterioration of sharpness and noticeable graininess.

The antifoggant agent may be used in the emulsion layer itself, or may be used in an intermediate layer provided between adjacent emulsion layers.

In the color light-sensitive material using the silver halide emulsion according to the present invention, an image stabilizer that prevents deterioration of the dye image can be used.

Hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention are coated with ultraviolet rays to prevent fogging due to discharge caused by charging of the photosensitive material due to Fj rubbing, etc., and to prevent deterioration of images due to UV exposure. It may also contain an absorbent.

A color light-sensitive material using the silver halide emulsion according to the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other wood-loving colloid layer of the silver halide photosensitive material using the silver halide emulsion according to the present invention can be used to reduce the gloss of the photosensitive material, improve the addability, and to improve the interaction between the photosensitive materials. A matting agent can be added to prevent sticking.

A lubricant can be added to reduce the sliding friction of the photosensitive material using the silver halide emulsion according to the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion according to the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion according to the present invention may be used to improve coating properties, prevent static electricity, improve slipperiness, emulsification dispersion, prevent adhesion, (promote development, Various surfactants are used for the purpose of improving photographic properties (such as increasing contrast and sensitization).

The light-sensitive material using the silver halide emulsion according to the present invention includes a photographic emulsion layer, and other layers include a baryta layer or a flexible reflective support such as paper laminated with an α-olefin polymer, synthetic paper, etc., and an acetic acid layer. It can be applied to films made of semi-synthetic or synthetic polymers such as cellulose, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide photographic light-sensitive material of the present invention can be used directly after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, to improve the adhesion and antistatic properties of the support surface.
It may also be coated through one or more subbing layers to improve dimensional stability, abrasion resistance, hardness, antihalation, frictional properties and/or other properties.

When coating a photographic material using the silver halide emulsion according to the present invention, a thickener may be used to improve coating properties.As a coating method, two or more layers may be coated at the same time. Particularly useful are ex-dulsion coatings and curtain coatings.

The photosensitive material of the present invention can be exposed using 1i magnetic waves in the spectral region to which the emulsion layer constituting the photosensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, lightning rays, X-rays,
Any/all light sources can be used, such as light emitted from a phosphor excited by gamma rays, alpha rays, etc.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

An image can be formed using the silver halide photographic material of the present invention by color development, which is carried out in the art.

The aromatic primary amine color developing agents used in color developing the light-sensitive material of the present invention include various ones that are widely used in various color photographic processes. These developers are aminophenolic and p-
Contains phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds are generally used in amounts of about 0.1 g to 30 g for color developer IIl.
It is best to use the color developer at a concentration of 1 g, preferably 1 g.
Used at a concentration of about 1 g to about 1.5 g per 1 g.

Examples of aminophenol-based developers include O-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, in which the alkyl group and phenyl group may be substituted with any substituent.Among them, a particularly useful example of the compound is N,N'-diethyl-p-phenylene. Diamine hydrochloride, N-methyl-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-amino Aniline 6Atl salt, N-
Ethyl-N-β-hydroxyethylaminoaniline, 4
-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
) luenesulfonate and the like.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the processing of the silver halide photographic light-sensitive material of the present invention further contains various components normally added to color developers, For example, alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali gold yA sulfites, alkali metal bisulfites, alkali metal thiocyanates, Fluka lJ gold 11 halides, benzyl alcohol, water softeners and thickening agents. etc. may be optionally included. The pl+ value of this color developing solution is usually preferably 7 or more, and more preferably about 10 to about 13.

The silver halide photographic light-sensitive material of the present invention is processed with a processing solution having a fixing ability after color development processing, but if the processing solution having a fixing ability is a fixing solution, a bleaching treatment is performed before that. The bleaching agent used in the bleaching process is a metal complex salt of an organic acid, and the metal complex salt has the effect of oxidizing the metallic silver generated during development and converting it into a halogenated wire, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include 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] Disodium ethylenediaminetetraacetic acid [5]
Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid sodium salt The bleaching agent used contains the above-mentioned metal complex salts of organic acids as a bleaching agent, as well as various bleaching agents. Additives may be included. As additives, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide, metal salts, chelating agents, and the like.

Also, 9H such as borates, oxalates, acetates, carbonates, phosphates, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid A pH buffering agent consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination.

When processing the photosensitive material of the present invention while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. Alternatively, the bleach-fix replenisher may contain these salts and be replenished into the processing bath.

To increase the activity of the bleach-fix solution, air or oxygen may optionally be bubbled into the bleach-fix bath and in the bleach-fix replenisher storage tank, or a suitable oxidizing agent, such as peroxide, may be added. Hydrogen, bromate, persulfate, etc. may be added as appropriate.

〔Example〕

Next, the present invention will be specifically explained using examples. However, as a matter of course, the present invention is not limited to these.

First, the -catalytic CI used in the examples described below
A specific method for synthesizing the magenta coupler represented by +) will be explained.

Synthesis Example 1 (Synthesis of the above exemplified compound +11) (i)
50 g of methyl 2.2-bismethylmercapto-1-cyanoacrylate and 32.5 g of sodium thiophenolate were added to 300 ml of toluene and heated under reflux for 8 hours.

The precipitated solid was filtered off, and the filtrate was concentrated.

500mj+ of ethanol and 12.3 g of 100% hydrazine hydrate were added to the residue, and the mixture was heated and refluxed for 2 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the residue was recrystallized from methanol to give 25 g of methyl-5- Amino-3-phenylthio-4-virazolecarboxylate was obtained.

(ii) 24.0 g of methyl-5-amino-3
-Phenylthio-4-virazolecarpoxylate 4
The mixture was added to 300 ml of N sodium hydroxide and heated under reflux for 2 hours. After cooling, the pH was adjusted to around 5 with hydrochloric acid. 18.2 g of 5-amino-3-phenylthio-4-pyrazolecarboxylic acid were obtained.

(iii) 18.0 g of 5-amino-3-phenylthio-4-pyrazolecarboxylic acid at 140-150
Heated at ℃ for 20 minutes. After vigorous foaming was completed, the mixture was cooled to obtain 9.5 g of 5-amino-3-phenylthiopyrazole.

(iv) Dissolve 9.3 g of 5-amino-3-phenylthiopyrazole in 100 mj+ chloroform,
6.5 g of N-chlorosuccinimide was added. After stirring at room temperature for 30 minutes, the solvent was distilled off under reduced pressure. The residue was dissolved in ethyl acetate, washed with water, dried and the solvent was distilled off under reduced pressure. Methanol-chloro-3-phenylthiopyrazole was obtained from the precipitated crystals.

(v) 5.6 g of 5-amino-4-chloro-phenylthiopyrazole in 100 mj of 6N hydrochloric acid! In addition to
Cooled to 0°C. An aqueous solution prepared by dissolving 1.9 g of sodium nitrite in 5 ml of water was added dropwise little by little to this hydrochloric acid solution.

After stirring for 30 minutes at 0°C, 12g of stannous chloride dihydrate was added to 35mj! of solution dissolved in concentrated hydrochloric acid.
It was added dropwise at ~0°C.

Stirred at 0°C for 30 minutes and further stirred at room temperature for 1 hour.
Next, 250 ml of water was added and hydrogen sulfide gas was passed through. The precipitated inorganic salts were filtered off, and the filtrate was concentrated under reduced pressure. The precipitated crystals were washed with ethanol to obtain 2.9 g of 5-hydrazino-4-chloro-3-phenylthiopyrazole hydrochloride.

(vi) 2.8 g of 5-hydrazino-4-lytetra-3-phenylthiopyrazur hydrochloride and 2.8 g of palmitic acid chloride were added to 100 mj+ ethyl acetate, and 2 g of triethylamine was added dropwise. After stirring at room temperature for 1.5 hours, the precipitated crystals were filtered off, washed with water, and then recrystallized from acetonitrile. 3.8 g of 4-chloro-
3-phenylthio-5-(2-balmitoylhydrazino)pyrazole was obtained.

hi) 3.7 g of 4-chloro-3-phenylthio-
5-(2-valmitoylhydrazino)pyrazole and 1.
Add 2g of phosphorus oxychloride to 80ml of toluene and add 1
．． After heating under reflux for 5 hours, the solvent was distilled off under reduced pressure, and 2
0 g of pyridine and 80 ml of acetonitrile were added, and the mixture was further heated under reflux for 1.5 hours. The mixture was filtered while hot and cooled to obtain 2.2 g of the target product, 7-chloro-3-pentadecyl-6-phenylthio-1H-pyrazolo (3,2-C)-3-triazole.

Elemental analysis value (as CzsHsJ*CIS) C(χ)
H(χ) N(χ) S(χ) Calculated value: 65.
12 8.09 12.15 6.95 Actual value: 6
4.90 8.23 12.25 7.38 The FD-mass spectrum has M”460 as the parent peak, and the above (
The compound obtained in vi) is the target exemplary compound (1)
It was confirmed that the structure was

Synthesis Example 2 (Synthesis of the Exemplified Compound (4)) (i) 5
0 g of methyl 2,2-bismethylmercapto-1-cyanoacrylate and 79 g of sodium-2-butoxy-5
-t-Octylthiophenolate was added to 500ml of dimethylformamide and reacted at 120°C for 12 hours.The reaction solution was poured into 31ml of water, and the precipitated solid was filtered off. Add ethanol 11 and 100% to this filtered solid.
12.3 g of hydrazine hydrate was added and heated under reflux for 5 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethanol to give 54 g of methyl-5-amino-3-(
2-Butoxy-5-t-octylphenylthio)-4-
Virazole carboxylate was obtained.

(ii) 21 g of methyl-5-amino-3-(2
-ptoxy5-t-octylphenylthio)-4-virazolecarboxylate was added to 200 ml of 6N hydrochloric acid and cooled to 0°C. Add 3.8 g of sodium nitrite to this hydrochloric acid solution and add 10 mj of water! An aqueous solution dissolved in was added dropwise little by little. Stir for 30 minutes, then add a solution of 24 g of stannous chloride dihydrate to 70 ml of concentrated hydrochloric acid.
It was added dropwise at ~0°C. Stir at 0°C for 30 minutes, then at room temperature for 1 hour.
After stirring for an hour, 12 hours of water was added and hydrogen sulfide gas was passed through. The precipitated inorganic salts were filtered off, and the filtrate was concentrated under reduced pressure. The precipitated crystals were washed with ethanol. The crystals were dissolved in 100 ml of water, neutralized with sodium hydrogen carbonate,
8.4 g of methyl-5-hydrazino-3-(2-butoxy-5-t-octylphenylthio)-4-virazolecarboxylate was obtained.

(iii) 4.5 g of methyl-5-hydrazino-3
-(2-butoxy-5-t-octylphenylthio)-
4-virazolecarpoxylate and 3.4 g of 4-dodecylsulfonylbutanoic acid chloride were added to 200 ml of acetonitrile, and 1.5 g of triethylamine was added dropwise. After stirring at room temperature for 2 hours, the precipitated crystals were filtered off and recrystallized from acetonitrile. 6.1 g of methyl-3-(2-butoxy-5-t-octylphenylthio)-5-[2-(4-dodecylsulfonylbutanoyl)
hydrazino)-4-virazolecarpoxylate was obtained.

(iv) 6.0 g of methyl-3-(2-butoxy-
5-t-octylphenylthio)5-(2-(4-dodecylsulfonylbutanoyl)hydrazino)-4-pyrazolecarboxylic acid and 1.3 g of phosphorus oxychloride at 200 g
The mixture was added to mJ of toluene and heated under reflux for 2 hours. Next, the solvent was distilled off under reduced pressure, 1.5 g of pyridine and 150 mA of acetonitrile were added, and the mixture was further heated under reflux for 2 hours. Filter while hot, cool, and remove 4.3 g of 6-(2-butoxy-5
-L-octylphenylthio)-7-medoxycarponyl-3-(3-dodecylsulfonylpropyl)-1H-
Pyrazolo[3°2-C)-3-1 riazole was obtained.

(v) 4.2 g of pyrazolotriazole obtained in (iv) was added to 100 mff1. 25 m sulfuric acid
It.

The mixture was added to a mixed solvent of 5 ml of water and heated under reflux for 1 hour. Neutralize with aqueous sodium hydroxide solution, extract with ethyl acetate, concentrate, add water, and add 3.2 g of 6-(2-butoxy-
5-t-octylphenylthio")-3-(3-dodecylsulfonylpropyl) -LH-pyrazolo(3,2-
C)-3-triazole was obtained.

(vi) 3.0 g of pyrazolotriazole obtained in (v) was dissolved in 90 ml of chloroform, and 0.0 g of pyrazolotriazole obtained in (v) was dissolved in 90 ml of chloroform.
60g of N-chlorosuccinimide was added. 3 at room temperature
After stirring for 0 minutes, the mixture was concentrated, ethyl acetate and water were added, and the organic layer was separated. Concentrate under reduced pressure and recrystallize from acetonitrile to obtain 2.5 g of the target compound, 6-(2-butoxy-
5-t-octylphenylthio)-7-chloro-3-(
3-dodecylsulfonylpropyl)-1H-pyrazolo[
3°2-C)-5-) riazole was obtained.

As elemental analysis value CCxtHhINaOiStC1)C
(χ) H(χ)N(χ) S(χ) Calculated value:
62.64 8.67? , 90 9.04 Actual value:
62.32 8.81 7.88 9.39 The FD mass spectrum has M”709 as the parent peak, and the compound obtained in (vi) above is the target example compound (4
) structure was confirmed.

Next, an example will be described.

Example 1 A magenta coupler according to the present invention and a comparative coupler as shown in Table 1 were each taken in an amount of 0.1 mole per 111 moles, and tricresyl phosphate was added in an amount of 1 times the weight of the coupler and tricresyl phosphate was added in an amount of 3 times the weight of the coupler. Ethyl acetate was added and heated to 60°C to completely dissolve. This solution was mixed with 1200 mJ of a 5% aqueous gelatin solution containing 120 mA of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont). and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion.

After that, this dispersion was converted into a green-sensitive silver iodobromide emulsion (iodized!!
(containing 6 mol%) and added to 4 kg as a hardening agent.
Add 120 mj+ of bis(vinylsulfonyl (water: methanol = 1: 1)), coat on the subbed transparent polyester base and dry.
Samples 1-1 to 1-10 were prepared. (Coated silver amount 20■/
100aJ) The sample thus obtained was subjected to a conventional method and then subjected to the following development treatment.

(Development process) Color developer 38℃ 3 minutes 15 seconds Bleaching
Wash with water at 38°C for 4 minutes and 20 seconds.
Fixing solution at 38℃ for 3 minutes and 15 seconds
Wash with water at 38℃ for 4 minutes and 20 seconds
38℃ 3 minutes 15 seconds Stabilization solution 38℃ 1 minute 30
Drying for seconds: 47°C±55°C for 16 minutes and 30 seconds In each treatment step, the composition of the treatment liquid used was as follows.

(Color developer composition) Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 5 g Sodium bromide
1.3g potassium iodide
2 ■Hydroxyamine sulfate
2.5g sodium chloride
0.6g sodium diethylenetriaminepentaacetate2.
5g 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to 1
j! and using potassium hydroxide or 20% sulfuric acid,
Adjust to pH 10.06.

(Bleach solution composition) Ethylenediaminetetraacetic acid iron ammonium salt 100g Ethylenediaminetetraacetic acid 10g Ammonium bromide 150g Glacial acetic acid
40ml sodium bromate
The pH is adjusted to 11 by adding Loga water and adjusted to pH 3.5 using ammonia water or glacial acetic acid.

(Fixer composition) Ammonium thiosulfate 180g Anhydrous sodium sulfite 12g Sodium metabisulfite 2.5g Disodium ethylenediaminetetraacetate 0.5g Sodium carbonate 10g Add water to make 11.

(Stabilizing liquid composition) Formalin (37% aqueous solution) 2ml Conidax (manufactured by Konishiroku Photo Industry ■) 5m! Add water to make 11.

Then, the specific sensitivity, formalin resistance, and light resistance of the sample were determined as described in 1) to 3) below. In addition, the maximum concentration was also determined. The measurement results are shown in Table 1. In addition, in Table 1, couplers having the following structures were used for Comparative Couplers 1 to 3.

1) Specific sensitivity is the reciprocal of the exposure amount that gives a density of fog density + 0.1, and sample Na1-1 using comparative coupler 1)
was set as 100.

2) 0.9% temperature and humidity controlled to 30℃, 62%RH
After placing the sample in a sealed container containing 6 cc of formalin aqueous solution for 3 days, color development is performed.

For comparison, a sample not treated with formalin is also developed. In addition, formalin resistance was calculated|required according to the following formula.

Formalin Resistance - Color Density of Formalin-Untreated Sample 3) The sample after color development treatment was irradiated with a xenon fade meter for 5 days, and the percentage of dye remaining at the initial density of -1.0 was shown.

Light resistance - 1,0 Comparative coupler 1 (Compound described in Japanese Patent Publication No. 46-43947) Comparative coupler 2 (Compound described in Japanese Patent Publication No. 46-43941) Comparative coupler 3 N (Compound described in U.S. Patent No. 3,725,067) No. Table 1 reveals that the coupler according to the present invention is excellent in color development, formalin resistance, and light resistance.

Example-2 Samples 1-1 to 1-10 in Example-1 were used in Example-1
Wedge exposure was performed in the same manner as above, and the following development processing was performed. In addition, the measurement of non-devil, light resistance and maximum density was carried out by the same method as in Example-1.

(Development processing process) Color development 38°C 3 minutes 30 seconds Bleach fixing 33°C 1 minute 30 seconds Stabilization treatment/or washing process 25-30°C drying for 3 minutes
75-80℃ for 2 minutes In each treatment step,
The composition of the treatment liquid used is as follows.

(Color developer) Benzyl alcohol 15mj! Ethylene glycol 15mA! Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TP
PS) 2.5g3-methyl-4
-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate
5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative') 1.0
g Potassium hydroxide 2.0g Add water to bring the total amount to 11, and adjust the pH to 10.20.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) loomj! Ammonium sulfite (40% volume) Adjust the pH to 7.1 with 27.5 mJ potassium carbonate or glacial acetic acid, and add water to bring the total volume to 11.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 10 g Sample 2-
Table 2 shows the characteristic measurement results of Nos. 1 to 2-10. In addition,
In Table 2, comparative couplers 1 to 3 are the same as in Example-1.

As is clear from the results in Table 2, Samples 2-4 to 2-10 containing couplers according to the present invention have excellent color development properties (high specific sensitivity, and no color loss compared to conventional samples) containing couplers according to the present invention. )
It was found that it has excellent light resistance.

Example 3 By sequentially coating the following layers on polyethylene resin coated paper containing anatase-type titanium oxide,
A silver halide color photographic material was prepared.

The amounts added below are per 100.

+1120 ■ gelatin, 5 ■ blue-sensitive silver chlorobromide emulsion, and 8 ■ yellow coupler and 0.1 ■
A layer containing 3 parts of di-octyl phthalate coupler solvent in which 2,5-di-t-octylhydroquinone was dissolved.

(2112 ■ gelatin, 0.5 ■ 2,5-di-t-
Intermediate layer containing 21 Ilr dibutyl phthalate UV absorber solvent in which octylhydroquinone and 4 μ UV absorber were dissolved.

Gelatin of +3118 ■, green malignant silver chlorobromide emulsion of 4 curvature as silver amount, magenta coupler of 5 ■ and 0.2 ■
A layer containing 2.5 dioctyl phthalate coupler solvent in which 2,5-di-t-octylhydroquinone was dissolved.

+41 (middle layer containing the same composition as 21).

+5116 ■ gelatin, 4 ■ red-sensitive silver chlorobromide emulsion as SIN, and 3.5 ■ cyan coupler and 0.
A layer containing 2,0 μ of tricresyl phosphate coupler solvent in which 1 Qr of 2,5-di-t-octylhydroquinone was dissolved.

Gelatin protective layer containing t619w gelatin.

Coating aids are added to each layer (1) to (6), and (
A gelatin crosslinking agent was added to layers 4) and (6).

As the ultraviolet absorber (2) and (4), U with the following structure is used.
A mixture of V-1 and UV-2 was used.

The above multilayer photosensitive material was treated in the same manner as in Example-2. Each layer contains a yellow coupler (Y-1,
Y-2), cyan couplers (C-1 to C-4), a magenta coupler according to the present invention, and a comparative magenta coupler used in Example-1. The composition and test results of each sample are shown in Table 3.

Ultraviolet absorber UV-1 CJq (t) UV-2 CiH (1) Y coupler Y-2 C-coupler Each sample was measured for magenta density after white exposure.

Further, the ratio, maximum density, and light resistance were measured by the same method as in Example-1.

From Table 3, it is clear that the light fastness of the dye image of the coupler according to the present invention is excellent, and it is also clear that it can be further improved by using an ultraviolet absorber.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to obtain a silver halide color photographic material that is free from undesirable side absorption, has good light resistance and formalin resistance, and has high color development.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains 1H-pyrazolo[3
,2-C]-s-triazole type magenta coupler 6
1. A silver halide photographic material comprising a magenta coupler substituted in position with a substituent represented by the following general formula [I]. General formula [I] Ar-S- However, in the general formula [I], Ar represents an aryl group or a heteroaromatic group.