JPS62269141A - Silver halide photographic sensitive material containing novel magenta coupler - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material free from subordinate unfavorable absorption, good in resistances to light and formaline and high in color formation performance by incorporating a specified magenta coupler in a silver halide emulsion layer. CONSTITUTION:At least one of the silver halide emulsion layers formed on the support of the silver halide photographic sensitive material contains the magenta coupler substituted by an optionally substituted cycloalkyl group at the 6-position of a 1H-pyrazolo[3,2-C]-s-triazole type magenta coupler, preferably, in an amount of 1.5X10<-3>-7.5X10<-1>, especially, 1X10<-2>-5X10<-1>mol per mol of silver halide. One of these magenta couplers is embodied by the formula shown on the right.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention forms magenta dye images that are free from undesirable side absorption, have high color development, and have improved storage stability, particularly light fastness and formalin fastness. This invention relates to a silver halide photographic material containing a magenta coupler. More specifically, it relates to a silver halide color photographic window optical 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.

The coupler that has been used in practice to form the magenta dye is a pyrazolone type coupler, but this has unfavorable side absorption and is said to have poor storage stability, especially resistance to formalin gas (formalin resistance). There are problems.

In order to improve the above problems, various 1H-pyrazolo(3,2-C)-s-triazole based magenta couplers have been commercially available. For example, U.S. Patent No. 3,725
,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 the improvement in formalin resistance is insufficient, and little improvement has been made in terms of color development and image light resistance. ,research·
Research Disclosure
(Sure) The compound described in No. 12443 cannot be put to practical use at all in terms of color development. The 1H-pyrazolo(3,2-C)-3-triazole type magenta coupler described in JP-A No. 58-42045 has been significantly improved in terms of formalin resistance and color development, but it still has improved light resistance. has hardly been done.

Although the couplers described in JP-A No. 59-99437 and JP-A No. 59-125732 have been improved in color forming properties, there is still no improvement in the light resistance of dye images based on the described couplers.

In the technique described in JP-A-59-125732, the light resistance of images is simply improved by the additives used in combination. However, although the coupler of Compound Example 19 described in the specification of JP-A-59-99437 has slightly improved light resistance, it is still not sufficient.

In other words, 1H-pyrazolo(
3,2-C) -s-Triazole based magenta couplers also have little improvement in the light resistance of dye images.

[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 described above is to reduce the number of silver halide emulsion layers having at least one silver halide emulsion layer on a support (in each layer, 1H-pyrazolo(3,2-C)-5
-) This is achieved by a silver halide photographic light-sensitive material containing a magenta coupler in which the 6-position of the lyazole-type magenta coupler is substituted with a substituted or unsubstituted cycloalkyl group.

The 1H-pyrazolo(3,2-C)-s-triazole type magenta coupler mentioned here is represented by the following general formula [■].

General formula (1) However, in the above general formula [.■], R1 represents a substituted or unsubstituted cycloalkyl group.

R2 represents a hydrogen atom or a substituent.

X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized color developing agent.

The cycloalkyl group represented by R1 in the general formula (1) is preferably a 3- to 7-membered cycloalkyl group from the viewpoint of ease of synthesis.

Examples of substituents that can be substituted on the cycloalkyl group represented by R1 include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), alkyl groups, aryl groups, heterocyclic groups, nitro groups, cyano groups, Alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonamide group, irisulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, acylamino group, alkyl Carbamoyl group, arylcarbamoyl group, alkylsulfonyl group, irisulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkylcarbonyloxy group, arylcarbonyloxy group,
Alkoxycarbonyl group, aryloxycarbonyl group, hydroxy group, carboxy group, amino group, or -,
Examples include secondary amino groups.

Specifically, the substituent represented by R2 in the general formula (1) includes 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, and a sulfonyl group. group, sulfinyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, organic hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group , sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, iri-ruthio group, or heterocyclic thio group It is the basis.

Next, the magenta coupler represented by the general formula CI) will be explained in more detail.

In general formula (I), examples of the halogen atom represented by R2 include a chlorine atom, a bromine atom, and a fluorine atom.

The alkyl group represented by R2 in the general formula (1) preferably has 1 to 32 carbon atoms, and the alkenyl group and alkynyl group preferably have 2 to 32 carbon atoms. As a group, carbon number is 3 to 12
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 substituents (e.g., aryl, cyano, halogen atom, petero ring, cycloalkyl, cycloalkenyl, spiro compound residue, organic hydrocarbon compound residue). In addition to groups, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a hetero atom such as '', specifically hydroxy, alkoxy, aryloxy, Substituents via an oxygen atom such as heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfona, etc. Those substituted through a nitrogen atom such as mido, imide, and ureido, those substituted through a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl, and those substituted through a phosphorus atom such as phosphonyl. Examples include methyl group, ethyl group, isopropyl group, L-butyl group, pentadecyl group, heptadecyl group, 1-hexylnonyl group, 1, 1'-dipentylnonyl group, 2-chloro-t
-butyl group, trifluoromethyl group, -ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl 5.3 −
m-butanesulfonaminophenoxypropyl group, 3-
4'-(α-[4" (p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino)phenylpropyl group, 3-(4'-(α-(2",4"-di[-amylphenoxy)butanamide] phenyl)-propyl group, 4-[α-(0-chlorophenoxy)tetradecanamidophenoxy]propyl group, allyl group, cyclopentyl group, cyclohexyl group, and the like.

The aryl group represented by R2 is preferably a phenyl group, and this aryl group has a substituent group (for example, an alkyl group,
(alkoxy group, acylamino group, etc.).

Specifically, phenyl group, 4-t-butylphenyl u,
2.4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4
Examples include '-(α-(4'-t-butylphenoxy)tetradecanamidophenyl group).

The heterocyclic group represented by R2 is preferably a 5- to 7-membered one, which may be substituted or fused. Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-hendithiazolyl group.

Examples of the acyl group represented by R2 include acetyl group,
Alkylcarbonyl groups such as phenylacetyl group, dodecanoyl group, α-2,4-di-t-amylphenoxybutanoyl group, benzoyl group, 3-pentadecyloxyhendiyl'J,I)-chlorobenzoyl group, etc. Examples include a carbonyl group and the like.

Examples of the sulfonyl group represented by R2 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 R2 include alkylsulfinyl groups such as ethylsulfinyl group, octylsulfinyl group, and 3-phenoxybutylsulfinyl group, phenylsulfinyl group, and alkylsulfinyl group such as m-pentadecylphenylsulfinyl group. etc.

The carbamoyl group represented by R2 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-pentylcarbamoyl group), Examples thereof include decyl octylethyl) carbamoyl group, N-ethyl-N-dodecyl carbamoyl group, and N-(3-(2,4-di-t-amylphenoxy)propyl) carbamoyl group.

The sulfamoyl group represented by R2 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, N, N-
MtAf includes a diethylsulfamoyl group, an N-(2-pentadecyloxyethyl)sulfamoyl group, an N-ethyl-N-dodecylsulfamoyl group, an N-phenylsulfamoyl group, and the like.

Examples of the spiro compound residue represented by R2 include spiro(3,3)hebutan-1-yl and the like.

The organic carbonized compound residue represented by R2 includes, for example, bicyclo(2,2,1)hebutan-1-yl, tricyclo(3,3,1,1)decane-1-yl, 7,7-cymethyl, Examples include thirubicyclo(2,2°1)hebutan-1-yl and the like.

The alkoxy group represented by R2 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-dodecyl group. Examples include oxyethoxy group and phenethyloxyethoxy group.

The aryloxy group represented by R2 is preferably phenyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, such as phenoxy, p- Examples include t-butylphenoxy group and m-pentadecylphenoxy group.

The heterocyclic oxy group represented by R2 preferably has a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, for example, 3, 4. 5.
Examples include 6-tetrahydropyranyl-2-oxy group and l-phenyltetrazol-5-oxy group.

Examples of the acyloxy group represented by R2 include an alkylcarbonyloxy group and an arylcarbonyloxy group, which may further have a substituent, specifically an acetyloxy group, an α-chloro group, etc. Examples include acetyloxy group and benzoyloxy group.

The carbamoyloxy group represented by R2 is an alkyl group,
It may be substituted with an aryl group, and examples thereof include an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, and an N-phenylcarbamoyloxy group.

The amine group represented by R2 may be substituted with an alkyl group, a teryl group (preferably a phenyl group), etc., such as ethylamino group, anilino group, m-chloroanilino group, 3-pentadecyloxycarbonyl group. Anilino group, 2-
Examples include chloro-5-hexadecaneamide anilide group.

Examples of the acylamino group represented by R2 include an alkylcarbonylamino group, a 7-arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent. For example, specifically, an acetamide group, an α-ethylpropanamide group, an N-phenylacetamide group, a dodecanamide group, a 2゜4-di-t-amylphenoxyacetamide group,
Examples include α-3-t-butyl-4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group represented by R2 include an alkylsulfonylamine group and an arylsulfonylamino group, and may further have a substituent. Examples of the substituent include specifically methylsulfonylamino group, pentadecylsulfonylamino group, benzenesulfonamide group, p
-1-luenesulfonamide group, 2-methoxy-5-t
-amylbenzenesulfonamide group and the like.

The imide group represented by R2 may be open-chain or cyclic, and may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group. , glutarimide group, and the like.

The ureido group represented by R2 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc. (eg, N-ethylureido group, N-methyl-N-decylureido group, N-phenylureido group). group, N-p-tolylureido group, and the like.

The sulfamoylamino group represented by -R2 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino%, N-methylsulfamoylamino Examples include moylamino group and N-phenylsulfamoylamino group.

The alkoxycarbonylamino group represented by R2 may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like.

The roxycarponylamino group represented by R2 is
It may have a substituent, such as a phenoxycarbonylamino group or a 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R2 may further have a substituent, such as methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, The 1,000-ton sword Ruhoniruji Temple is killed.

The aryloxycarbonyl group represented by R2 may further have a substituent, such as a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, a m-pentadecyloxyphenoxycarbonyl group, and the like.

The alkylthio group represented by R2 may further have a substituent, for example, an ethylthio group, a dodecylthio group,
Examples include octadecylthio group, phenethylthio group, and 3-phenoxypropylthio group.

The ruthio group represented by R2 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,
Examples thereof include 2-carboxyphenylthio group and p-7doaminophenylthio group.

The heterocyclic thio group represented by R2 is preferably a 5- to 7-membered heterocyclic thio group, and may further contain 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.

Examples of the group that can be separated by the campling reaction with the oxidized color developing agent represented by X in the general formula (1) include halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.), amino groups, Substituted amino 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), alkoxy group (e.g. methoxy group, ethoxy group, 2
-methoxyethyloxy group, etc.), arylthio group (e.g. phenylthio group, p-carboxyphenylthio group, etc.)
, alkylthio groups (e.g. methylthio group, 2-hydroxyethylthio group, etc.), heterocyclic thio groups (e.g. l-ethyltetrazole-5-thioyl group, 2-pyridylthio group, etc.), heterocyclic groups (e.g. 1-pyrazolyl group, (1-imidazolyl group, 2.5-biraprindione-1-yl group, etc.), carboxy group, sulfo group, alkoxycarbonyl group, aralkoxycarbonyl group, aralkoxycarbonyl group, etc.

Next, specific examples of the magenta coupler represented by the above general formula (1) are shown below in (1) to (24), but the present invention is not limited thereto as a matter of course.

Exemplary compound ■ H3 CII1H! + CIolltl CH3 (lO) CH.

C&)Ill CH.

NIICCFs Cttl.

CH3 CHl Specific synthesis examples will be described later.

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 colloid layer is further formed on the silver halide emulsion as a protective layer. A colloid layer may also be applied. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, eg high and low sensitivity. In this case, between the silver halide emulsion layers having different sensitivities, an intermediate layer of a hydrophilic colloid layer may be provided,
Further, an intermediate layer may be provided between the silver halide emulsion layer and the protective layer.

The compound used in the present invention, such as the magenta coupler represented by the general formula (1), may be contained in a hydrophilic colloid layer coated on at least one side of the support, but it may be contained in at least one layer of the silver halide emulsion layer. It is preferable that it is contained.

The amount of the magenta coupler according to the present invention to be added to the photographic material of the present invention is 1.5×to-2 per mole per coupler.
Mol~? , 5X10-' mol, more preferably 1X10-' mol to 5X10-' mol.

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. In particular, when the silver halide photographic material is a color photographic paper used for direct viewing, the halogenated photographic material of the present invention The effects of silver photographic materials are effectively exhibited.

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 light-sensitive 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 photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver halide as silver halide in a silver halide emulsion,
Any of those used in conventional silver halide emulsions can be used, such as silver chlorobromide and silver chloride.

The silver halide grains used in the silver halide emulsion according to the present invention may be obtained by any one of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, a halide ion and an antiion may be mixed simultaneously, or one of them may be present while the other is mixed. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and ions to the
Growth may be performed by sequentially and simultaneously adding H, I)Ag while controlling it. After growth, a conversion method may be used to change the halogen composition of the particles.

When producing 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 by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion according to the present invention may be prepared from cadmium salt, zinc salt, lead salt, thallium salt, I'IJium salt or complex salt during the process of grain formation and/or grain growth. Rhodium salts or complex salts, iron salts or complex salts can be used to add metal ions and incorporate them inside the particles and/or on the particle surfaces. Can add reduction/multiplying nuclei to the surface.

In the silver halide emulsion according to the present invention, unnecessary soluble salts may be removed after the growth of /''% silver halide grains, or they may be left contained.

In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17634.

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 in 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. In these particles, the [1°0.0] plane and (1,1,1)
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 used in the present invention consists of two separately formed silver halide emulsions.
More than one type of silver halide emulsion may be mixed and used.

The silver halide emulsion used in the present invention may be chemically sensitized by conventional methods. Namely, the sulfur enhancement method uses a sulfur-containing compound that can react with negative ions or activated gelatin, the selenium enhancement method using a selenium compound, the reduction sensitization method using a reducing substance, and the noble metal sensitization method using gold or other noble metal compounds. These can be used alone or in combination.

The silver halide emulsion used in the present invention can be optically enhanced to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The exacerbating pigment may be used alone, or in combination with 21ff1 or more. Along with aggravating dyes, dyes that do not themselves have spectral sensitizing effects,
Or a compound that does not substantially absorb visible light,
A superenhancing agent that enhances the sensitizing effect of the enhancing dye may be included in the emulsion.

The silver halide emulsion used in the present invention contains chemically aged and/or Compounds known in the photographic industry as antifoggants or stabilizers can be added at the end of the process and/or after chemical ripening and before coating the silver halide emulsion.

As the binder (or protective colloid) for the silver halide emulsion used in the present invention, it is advantageous to use gelatin, but other materials include gelatin derivatives, graft polymers of gelatin and other polymers, proteins, IP derivatives, cellulose. Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as derivatives, monopolymers, or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. 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 the light-sensitive material of the present invention.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

When the present invention is applied to a silver halide multicolor photographic light-sensitive material, an aromatic primary amine developer (for example, a p-phenylenediamine derivative, an aminophenol derivative, etc.) is used in the emulsion layer in the color development process. A dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized form of.

The dye-forming couplers are typically selected to form a dye for each emulsion layer that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming dye forming for the blue light sensitive emulsion layer. A magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, 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 or the like in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Moreover, these dye-forming couplers are 1
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-ice emulsion dispersion can be used. It can be selected as appropriate depending on the chemical structure of the hydrophobic compound. The oil-in-water emulsion dispersion method can be applied to various methods for dispersing hydrophobic additives such as couplers. 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. A stirrer, a homogenizer, a surfactant in a hydrophilic binder such as an aqueous gelatin solution,
After emulsifying and dispersing it using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, 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, benzoic acid 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.

Between the emulsion layers of the color photographic light-sensitive material using the present invention (same-
(between color-sensitive layers and/or between different color-sensitive layers), to prevent color turbidity caused by migration of oxidized developing agents or electron transfer agents, deterioration of sharpness, and noticeable graininess. Anticapri agents may be used.

The color antifoggant may be used in the emulsion layer itself, or may be used in a film intermediate layer by providing an intermediate layer 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.

A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent capri due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

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.

A matting material is added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photosensitive material of the present invention with the aim of reducing the gloss of the photosensitive material, increasing the ease of writing, and preventing the photosensitive materials from sticking together. Can be added.

A lubricant can be added to reduce the sliding friction of the light-sensitive 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 may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they may be used to protect the emulsion layer and/or the side on which the emulsion layer is laminated to the support other than the emulsion layer. It may also be used in colloid layers.

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 can be used to improve coating properties, prevent static electricity, improve slipperiness, emulsification dispersion, prevent adhesion, and (promote phenomena, Various surfactants can be 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 has 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, cellulose acetate, nitric acid, etc. It can be applied to films made of semi-synthetic or synthetic polymers such as cellulose, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide photographic material of the present invention can be produced directly or (adhesiveness, antistatic property,
1 to improve dimensional stability, wear resistance, hardness, antihalation properties, frictional properties and/or other properties;
or two or more undercoat layers).

When coating a photographic light-sensitive material using the silver halide emulsion according to the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten 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, electron beams, X-rays,
Any of a variety of light sources can be used, such as light emitted from a phosphor excited by T-rays, alpha-rays, etc.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposures shorter than 1 microsecond, such as 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.

The silver halide photographic material of the present invention can form images by performing color phenomena that can be performed in the art.

The aromatic primary amine color developing agent used in the color developing solution used for developing the light-sensitive material of the present invention includes a variety of aromatic primary amine color developing agents that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, because they are more stable than the free state. Additionally, these compounds generally have a concentration of about 0.1% per liter of color developer.
It is best to use the color developer at a concentration of 1 g, preferably 1 g.
It is used at a concentration of about 1 g to about 1.5 g per 1 g.

Examples of aminophenol-based developers include 〇-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 amino color developers include N, N
It is a '-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be π-substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine 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-aminoanilide sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 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 metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol,
A water softener, a thickening agent, etc. can also be optionally included. The pH value of this coloring phenomenon liquid is usually 7 or more, preferably about 10 to about 13.

The light-sensitive material of the present invention is subjected to color development processing and then processed with a processing liquid having a fixing ability. If the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment can be performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. Its composition is that metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid, KM, and organic acids such as citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids and naminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching agent used as sodium acetate contains a metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents 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, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
111 buffer agents, alkyl amines, polyethylene oxides, and the like that are normally added to bleaching solutions can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite,
Potassium metabisulfite, sodium metabisulfite and other gnitrite salts, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate , p consisting of various salts such as ammonium hydroxide
The HPftfJi agent may be contained alone or in combination.

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

The magenta coupler according to the present invention can be synthesized by various methods, for example, according to the synthesis method described in Japanese Patent Publication No. 46-43947. Next, a specific synthesis example will be shown.

Synthesis example 1. (Synthesis of Exemplary Compound (1)) The reaction scheme is as follows.

(II) (m) (IV) Synthesis of intermediate (+).

53 g of thiocarbohydrazide was suspended in ethanol and 53 g'dl of benzaldehyde was obtained by stirring with boiling FA. After 10 minutes of pumping, 88.5 g of methyl chloro-α-cyclopropylcarbonylacetate was added dropwise, and after 10 minutes of pumping, 150 g of drazine hydra was added dropwise over 1 hour. After dropping, the mixture was further boiled and stirred for 1 hour. Thereafter, insoluble matter was removed, and ethanol was distilled off under reduced pressure.

300n+1 of toluene was added to the residue, cooled, and the crystals were collected by filtration. Further, the crystals were recrystallized from toluene to obtain 78 g of intermediate (1).

Synthesis of intermediate (II).

49 g of the above intermediate (I) and 26 g of triethylamine were added to 400 ml of acetonitrile, and 69 g of palmitic acid chloride was added dropwise. After continuing to heat under reflux for 2 hours, the reaction solution was cooled and the formed crystals were collected by filtration. After washing the crystals with water, they were further recrystallized from acetonitrile.
As a result, 85 g of intermediate (n) was obtained.

Synthesis of intermediate (III).

43 g of the above intermediate (II) and 16 g of phosphorus oxychloride were added to 40011 Ill of toluene, and the mixture was heated under reflux for 1 hour. Thereafter, toluene was distilled off under reduced pressure, and 280 ml of acetonitrile and 20 g of pyridine were added to the residue, followed by heating under reflux for 2 hours. After the reaction was completed, acetonitrile was distilled off under reduced pressure, 500 ml of water was added, and the precipitated crystals were collected by filtration. Further, the crystals were recrystallized from acetonitrile to obtain intermediate (DI).
31.2 g of was obtained.

Synthesis of intermediate (IV).

30 g of the above intermediate (III) was added to a mixed solution of 150 ml of glacial acetic acid and tetrasulfur fJjXL15Il11, and the mixture was heated for 8 hours.

After cooling, an aqueous solution consisting of 150 m 1 of water and 24 g of thorium hydroxide was added and cooled. The precipitated crystals were collected by filtration and further recrystallized from ethanol to obtain the intermediate (rV).
I got 11.

7.5 g of N-chlorosuccinimide (N CC),
It was added little by little at room temperature. After stirring at room temperature for 30 minutes,
The reaction solution was reduced to 0. It was washed with IN aqueous sodium hydroxide solution and further washed with water. After dehydrating the chloroform solution with anhydrous magnesium sulfate, chloroform was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using a toluene/acetone (1:1) mixture to obtain Exemplary Compound (1) as 16 g of a white amorphous solid.

Elemental analysis value (as CttHzJaCl) C (%) II
(%) N (%) C1 (%) Calculated value: 67.2
3 9.47 14.26 9.02 Actual value:
67.56 9.67 14.39 9.41F
The D-mass spectrum shows M''392 as a parent peak, indicating that this compound has the structure of the target exemplary compound (1).

Other 1H-pyrazolo(3,2-]-5- excluding leaving group X
) The lyazole nucleus itself was synthesized according to the method of Synthesis Example (1). X other than chlorine atoms can be introduced by various methods, for example, Japanese Patent Publication No. 46-43947, Japanese Patent Application Laid-open No. 59-99.
Reference was made to the synthesis examples described in No. 437, JP-A-60-140241, and the like.

〔Example〕

Next, the present invention will be specifically explained with reference to examples, but it goes without saying that the present invention is not limited to these examples.

Example-1 Magenta coupler (1) according to the present invention as shown in Table 1
), (2), (5), (8), (10), (
19), (21) and Comparative couplers 1 to 3 described later were each taken in an amount of 0.1 mol per 1 mol of silver, and tricresyl phosphate in an amount of 1 times the weight of the coupler and ethyl acetate in an amount of 3 times the weight of the couplers were added. It was heated to 60°C to completely dissolve it. this? The solution was mixed with 1200 ml of a 5% aqueous gelatin solution containing alkanolphonate, and emulsified and dispersed using an ultrasonic disperser to obtain an emulsion. After that,
Add the solution to this portion 11 to form a green-sensitive silver iodobromide emulsion (silver iodide 6 mol%).
2% solution of 1,2-bis(vinylsulfonyl)ethane (water:methanol=
l: 1) Add 120 ml, coat and dry on the undercoated transparent polyester base, and apply to samples 1-1 to 1.
-10 was produced. (Coated silver amount 20mg/100ca
l).

The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment.

Then, the specific sensitivity, formalin resistance, and light resistance of each sample were measured as described in 1) to 3) below, and the maximum density was also measured.

(Development process) Color developer: 38°C, 3 minutes 15 seconds Bleaching solution: 38°C, 4 minutes 20 seconds Washing with water
38℃ 3 minutes 15 seconds Fixer 38℃
Washing with water for 4 minutes 20 seconds 38℃ 3 minutes 15 seconds Stabilizing solution 38℃ 1 minute 30 seconds Drying 47℃±55℃ 16 minutes 30
The composition of the treatment liquid used in each treatment step is as follows.

(Color developer composition) Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 5 g Sodium bromide 1.3 g Potassium iodide
2 mg hydroxyamine sulfate 2.5 g sodium chloride
0.6 g sodium diethylenetriaminepentaacetate 2,5 g 4-amino-3-methyl-N-
Ethyl-N-(β-hydroxyethyl)aniline sulfate 4.8 g Potassium hydroxide 1.2 g Water was added to make 11, and potassium hydroxide or 20% sulfuric acid was used to adjust the pH to 11. Adjust to 06.

(Bleach solution composition) Ethylenediaminetetraacetic acid iron ammonium salt 100
g Ethylenediaminetetra vinegar M 10 g
Ammonium bromide 150 g Glacial acetic acid 40 tall Sodium bromate 10 g Add water to make 11, and use aqueous ammonia or glacial acetic acid to adjust the pH to 3.
,5.

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

(Stabilizing liquid composition) Formalin (37% aqueous solution) 2 t
alconida socks (manufactured by Konishiroku Photo Industry ■) 5mj! Add water to make IIl.

The measurement results are shown in Table 1. From Table 1, it can be seen that the samples using the coupler according to the present invention have high color development (that is, higher specific sensitivity, maximum density and no color loss compared to conventional ones), and have lower formalin resistance and light resistance. Ta.

Margin below.

Beta1 self! ,, -,7,t l) Specific sensitivity is the exposure m that gives a density of fog density + 0.1
The reciprocal of the sample size l-1 using the comparison coupler l) is 1
It was set as 00.

2) Temperature and humidity at 30°C and 62% RH' for two periods,
A sample is placed in a sealed container containing 6 cc of 9% formalin aqueous solution for 3 days, and then color development is performed. For comparison, samples not treated with formalin are also developed. In addition, formalin resistance was calculated|required according to the following formula.゛Formalin resistance = 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 = 1.0 was measured.
showed that.

1, O Comparative coupler 1 Comparative coupler 2 Comparative coupler 3 (Compound described in JP-A-60-65245) Example-2 Samples 1-1 to 1-10 in Example-1 were replaced with Example-1
Wedge exposure was performed in the same manner, and the following development processing was performed. These results are shown in Table 2. Insensitivity and light resistance were measured by the same method as in Example-1.

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

(Color developer) Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide
0.7g sodium chloride
0.2 g potassium carbonate
30.0 g Hydroxyamine sulfate 3.0 g Polyphosphoric acid (TPPS)
) 2.5 g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5 g Fluorescent brightener (4,4'-diaminostilhensulfonic acid derivative ) 1.0 g potassium hydroxide Add 2.0 g water to bring the total amount to 1
1 and adjust the pH to 10,20.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5mj! p with potassium carbonate or glacial acetic acid
Adjust to H7.1 and add water to bring the total volume to 11.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0g ethylene glycol
10 g As is clear from the results in Table 2, samples 2-4 to 2-IO containing couplers according to the present invention
It can be seen that compared to the comparative sample, the sample has excellent color development (that is, the specific anger is good, and the maximum density is as good as the conventional one, with no discoloration) and has excellent light resistance.

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

The amounts added below are per tooci.

(L) Di-octyl phthalate of 3B in which 20 n+g gelatin, 5 mg of silver-based chlorobromide emulsion, and 8 mg of yellow coupler and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved. Layer containing coupler solvent.

(2) 12 mg gelatin, 0.5 mg 2,5-
Interlayer comprising 2 mg of dibutyl phthalate UV absorber solvent in which di-t-octylhydroquinone and 4 mg of UV absorber were dissolved.

(3) 18 mg of gelatin, 4 mg of green-sensitive silver chlorobromide emulsion as Li amount, and 2.5 mg of dioctyl phthalate coupler solvent in which 5 mg of magenta coupler and 0.2 mg of 2,5-di-octylhydroquinone were dissolved. layer containing.

(4) An intermediate layer containing the same composition as (2).

(5) 16 mg of gelatin, 4 mg of silver as a red-sensitive silver chlorobromide emulsion, and 2.0 mg of trichloride in which 3.5 mg of cyan coupler and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved. Layer containing cresyl phosphate coupler solvent.

(6) Gelatin protective layer containing 9 mg 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 absorbers (2) and (4), a mixture of UV-1 and UV-2 having the structures described below was used.

The above multilayer photosensitive material was treated in the same manner as in Example-2. The couplers are yellow couplers (Y-1, Y-2),
Cyan couplers (C-1 to C-4) and magenta couplers (1) and (2) according to the present invention.

(10) and the comparative coupler used in Example 1 were used.

The composition of the sample and the test results are shown in Table 3.

Each sample was measured for magenta density after white exposure.

Further, the specific anger, maximum density, and light resistance were measured using the same method as in Example 1.

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

J゛-1 Ultraviolet absorber uv-i JV-2 Y coupler C coupler (J [Effects of the invention] As described above, the silver halide photographic material of the present invention has no undesirable side absorption, and has good light resistance and formalin resistance. It has good coloring and color development.

Patent applicant: Konishiroku Photo Industry Co., Ltd., agent patent attorney
Takatsuki Torite Zoku Neho Seisha (Voluntary) August 25, 1986 Commissioner of the Japan Patent Office Kuro 1) Akio Tono 1, Indication of the case 1986 Patent side No. 113371 Address 1 Nishi-Shinjuku, Shinjuku-ku, Tokyo Chome 26-2 Name (127)
Roku Konishi Photo Industry Co., Ltd. Representative Director Megumi Ide 4, Representative (1) In the specification, "dechromatic color reproduction" on line 33017 is corrected to "subtractive color reproduction".

(2) Same, page 36, line 7, amend "statement" to "surface."

(3) Correct "ballast etc." in the 4th opt line to "ballast group".

(4) Correct "film intermediate layer" in line 11 of 42 to "the intermediate layer".

(5) Same, p. 44, line 8, “can be used” is changed to “
amended to ``can be used.''

(6) Same, on page 45, line 8, "EXDOOR" is corrected to "EXTR-".

(7) Same, page 46, line 19, rO, 1gJ is “0.1g
Corrected to ~30g.

(8) Same, page 48, line 9, "alkali metal sulfite" is corrected to "alkali metal sulfite".

(9) Same, on page 51, line 4, "2 or more types" is corrected to "2 or more types."

1. Indication of the case 1988 Patent Application No. 113371 2. Name of the invention Silver halide photographic light-sensitive material containing a novel magenta coupler 3. Person making the amendment Relationship to the incident Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent address: 506 Dia Palace Niban-cho, 11-9 Niban-cho, Chiyoda-ku, Tokyo 102 FAX: 03 (221) 19245, Date of amendment order: Voluntary (1) Mei 1 III In the book, page 58, line 1, “47℃±5
5℃'' is corrected to ``47℃~55℃1.

(2) In the fourth line of page 60 of the same document, the word "poor color" is corrected to "poor color."

(3) "Ethylene glycol 10 gJ" on page 66, page 411 of the same is corrected as follows.

``Add 10 g of ethylene glycol water to make ζl/'' (4) Correct the structural formula of Y-1 on page 72 of the same as follows.

(5) The structural formula of Y-2 on page 73 is corrected as follows.

(6) The structural formula of C-1 on page 73 of the same is corrected as follows.

(7) The structural formula of C-2 on page 73 of the same is corrected as follows.

(, -2 (8) The structural formula of C-3 in No. 74R is corrected as follows.

(9) The structural formula of C-4 on page 74 of the same is corrected as follows.

that's all

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 with a substituted or unsubstituted cycloalkyl group at one position.