JPH0820713B2 - Silver halide photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more specifically, stability during development processing (hereinafter referred to as processing stability) and stability over time of raw film. At the same time relates to a silver halide photographic light-sensitive material (hereinafter simply referred to as light-sensitive material).

[Background of the Invention]

In recent years, there has been a demand for the development of a light-sensitive material having high image quality and excellent stability over time, and at the same time, development processing has become more automated and faster. That is, even if a light-sensitive material having high image quality performance is not sufficiently stable at the time of development processing, not only the original performance of the light-sensitive material cannot be brought out but also a slight development It becomes a photosensitive material with a large variation in performance due to changes in processing conditions, and cannot meet the needs of users.

As a method for improving the processing stability, for example, a method of controlling the developability of silver halide, a method of using a coupler having a good developability, a method of improving with various additives, etc. are known. Not a sufficient level.

[Purpose of the present invention]

An object of the present invention is to provide a light-sensitive material in which processing stability and raw film stability with time are simultaneously improved.

[Structure of Invention]

As a result of studying various materials based on the above technical background, the present inventor has found that a silver halide having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support. In the photographic light-sensitive material, at least one of the light-sensitive silver halide emulsion layers contains a pyrazolotriazole-based magenta coupler, and the total amount of couplers in all emulsion layers containing the pyrazolotriazole-based magenta coupler is 15 A colored magenta coupler of less than mol% is contained in the emulsion layer containing the pyrazolotriazole type magenta coupler, and at least one of the photosensitive silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer is substantially contained. A silver halide photographic light-sensitive material characterized by containing a non-photosensitive fine grain silver halide,
It has been found that the object of the present application is achieved.

[Specific Description of the Invention]

The pyrazolotriazole-based magenta coupler according to the present invention is represented by the general formulas [I] and [II], and is represented by the general formula [I] General formula (II) In the above general formula [I], R ₁ and R ₂ represent alkyl, aryl or heterocycle, and the alkyl, aryl or heterocycle may be bonded via an oxygen atom, a nitrogen atom or a sulfur atom. Further, the above-mentioned alkyl, aryl and hetero ring may be bonded via the following bonding groups. That is, acylamino, carbamoyl, sulfonamide, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl,
Ureido, thioureido, thioamide, sulfone, sulfonyloxy.

The groups represented by R ₁ and R ₂ are linear or branched alkyl groups having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl,
i-propyl, sec-butyl, n-butyl, t-butyl, n-octyl, t-octyl, dodecyl, octadecyl and the like). These groups may further have a substituent (for example, a halogen atom, nitro, cyano, alkoxy, aryl, oxy, amino, acylamino, carbamoyl, sulfonamide, sulfamoyl, imide, alkylthio, arylthio, aryl, alkoxycarbonyl, acyl). Specifically, chloromethyl, brommethyl, trichloromethyl, β-nitroethyl, δ-cyanobutyl, methoxymethyl, ethoxyethyl, phenoxyethyl, N-methylaminoethyl, dimethylaminobutyl, acetaminoethyl, benzoylamino, propyl, ethyl. Carbamoylethyl, methanesulfonamidoethyl, ethylthioethyl, p-methoxyphenylthiomethyl, phenylmethyl, p-chlorophenylmethyl,
Naphthylethyl, ethoxycarbonylethyl, acetylethyl, etc.).

Further, the aryl group represents a phenyl group or a naphthyl group and may have the substituent shown in the section of the alkyl group.

The heterocycle represents a 5-membered or 6-membered ring having at least one of a nitrogen atom, an oxygen atom and a sulfur atom, and may or may not have aromaticity. For example pyridyl, quinolyl, pyrrolyl,
Examples thereof include morpholyl, furanyl, tetrahydrofuranyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl, thiadiazolli and the like. Moreover, these may have the substituent shown in the item of the alkyl group.

Further, R ₁ ′ and R ₁ ″ may be bonded to each other to form a carbocycle (eg, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, etc.) and a heterocycle (eg, piperidyl, pyrrolidyl, dioxanyl, morpholinyl, etc.).

Examples of the alkyl, aryl or hetero ring represented by R ₁ R ₂ which is bonded via the above-mentioned bonding group or nitrogen atom, oxygen atom or sulfur atom include Etc. Here, R ₂ ′ represents an alkyl, aryl or hetero ring, and R ₂ ″ and R ₂ represent a hydrogen atom, alkyl, aryl or hetero ring.

When the heterocyclic group is a pyrazolotriazolyl-based compound, it forms a bis-type pyrazolotriazole-based compound, but it is of course a magenta coupler included in the present invention.

Next, specific examples of R ₁ and R ₂ represented by the above general formula are shown.

_{CH 3 - C 2 H 5 -} (n) C 3 H 7 - (n) C 8 H 17 - (n) C 15 H 31 - _{(T) C 4 H 9 -} (t) C 5 H 11 - (t) C 8 H 17 - -C 17 H 35 -CH 2 CH 2 CH 2 OC 12 H 25 -CH 2 CH 2 CONHC 14 H 29 - OC ₁₂ H ₂₅ -S-C ₁₆ H ₃₃ -CONHC ₁₄ H ₂₉ -NHSO ₂ C ₁₆ H ₃₃ -SO ₂ NHC ₁₆ H ₃₃ -COC ₁₁ H ₂₃ -OCOC ₁₅ H ₃₁ −COOC ₁₂ H ₂₅ −SO ₂ C ₁₆ H ₃₃ Z represents a hydrogen atom or a group which is released when a dye is formed by coupling with an oxidized form of an aromatic primary amine color developing agent.

Specifically, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, (Z ₂ is a carbon atom, an oxygen atom, a nitrogen atom,
It represents a group of atoms required to form a 5- or 6-membered ring with an atom selected from sulfur atoms. ) Specific examples are given below.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: ethoxy group, benzyloxy group, methoxyethylcarbamoylmethoxy group, etc. Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group, etc. Acyloxy group: acetoxy group, myristoyl Oxy group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-butoxy-5
-Octylphenylthio group, 2,5-dihexyloxyphenylthio group, etc.Alkylthio group: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2- (diethylamino) ethylthio group, ethoxycarbonylmethylthio group, ethoxyethylthio group, phenoxy Ethylthio group, etc. Imidazolyl group, triazolyl group, tetrazolyl group, etc. For example, The pyrazolotriazole-based magenta coupler of the present invention can be used in any of the above silver halide emulsion layers, but is generally used in a green-sensitive silver halide emulsion layer. When the green-sensitive silver halide emulsion layer is composed of two or more emulsion layers, it must be used in at least one emulsion layer, preferably in two or more emulsion layers.

The coupler of the present invention usually contains 1 × per mol of silver halide.
10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻² mol to 8 ×
It can be used in the range of 10 ^-1 mol.

In the present invention, the amount of all couplers in the emulsion layer containing the pyrazolotriazole-based magenta coupler of the present invention is
Less than 15 mol% of colored magenta couplers are used in the pyrazolotriazole-based magenta coupler-containing emulsion layer.

In the present invention, examples of the colored magenta coupler that can be used include those described in US Pat. Nos. 2,801,171, 3,519,429 and JP-B-48-27930.

In the present invention, a magenta coupler of a type other than the pyrazolotriazole-based magenta coupler of the present invention can be used in combination. That is, the green-sensitive silver halide emulsion containing the magenta coupler of the present invention may contain a magenta coupler other than the present invention.

As the magenta coupler that can be used in combination with the green-sensitive silver halide emulsion of the present invention, a pyrazolone compound, an indazolone compound, a cyanoacetyl compound, a pyrazoloazole compound other than the present invention can be used, and particularly a pyrazolone compound. Is advantageous.

Specific examples of magenta couplers that can be used are disclosed in JP-A-49-111.
No. 631, No. 56-29236, No. 57-94752, No. 48-27930
U.S. Pat.Nos. 2,600,788, 3,062,653, and 3,408,
Nos. 194, 3,519,429 and Research Disclosure 12443.

When the magenta coupler and other couplers of the present invention are added, they can be incorporated in the green-sensitive silver halide emulsion layer by the above oil-protect dispersion or latex dispersion method, and when the coupler is alkali-soluble, it is alkaline. It may be added as a solution.

As the non-photosensitive fine grain silver halide according to the present invention, any non-photosensitive one can be used as long as it is substantially non-photosensitive, that is, one which is not substantially developed in the developing solution. It is preferable that it is not substantially developed and dissolved. In general, it is necessary that the sensitivity in the log unit is 0.5 or more lower than the sensitivity of the relatively low-sensitivity layer of the photosensitive silver halide, and 1.0 or lower is more preferable. The average particle size is preferably 0.3 μm or less, more preferably 0.02 to 0.2 μm. Also,
The distribution of particles may be wide or narrow, but a narrow distribution is preferable.

The silver halide grains used as the substantially light-insensitive silver halide fine grains are silver chloride, silver bromide, silver iodide,
Any silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. may be used. These silver halides may be used alone or in combination of two or more kinds. Further, the silver halide grains are preferably silver halide containing silver bromide from the viewpoint of solubility, and particularly 15 mol%
Silver iodobromide containing less silver iodide is preferred. The silver halide grains may be physically aged with a rhodanate ion, a cyano ion, a thiocyanate ion or the like, or may be etched with a silver halide solvent. These silver halide grains are neutral, half-ammonia,
It is manufactured by various manufacturing methods such as the ammonia method, and also manufactured by various manufacturing molds such as the simultaneous mixing method and the conversion method.

The non-light-sensitive fine grain silver halide of the present invention can be used in any light-sensitive silver halide emulsion layer and / or any non-light-sensitive hydrophilic colloid layer, but preferably any non-light-sensitive hydrophilic layer. It is preferably used for the colloid layer, and more preferably for the non-photosensitive hydrophilic colloid layer located farther from the support than the emulsion layer containing the pyrazolotriazole type magenta coupler of the present invention.

The light-insensitive fine grain silver halide for use in the hydrophilic colloid layer is being coated at 0.01~3.0Ag / m ² is generally, preferably be coated by 0.1~1.0Ag / m ² Used. For the non-photosensitive layer, a colloidal silica, a matting agent such as polymethylmethacrylate, a high boiling point solvent (eg, tricresyl phosphate, dioctyl phthalate, etc.),
An antioxidant, a lipophilic component such as a hydroquinone derivative, a coating aid such as a surfactant, a gelatin hardened milk and the like may be used at the same time.

Gelatin is generally used as a binder for the non-photosensitive hydrophilic colloid layer, but colloidal albumin may be used in place of part or all of gelatin.
Cellulose derivatives such as agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose and methyl cellulose, and synthetic binders may be used.

When the light-sensitive material of the present invention is used together with tabular silver halide grains having an average aspect ratio of 5: 1 or more, the effect of the present invention becomes more remarkable.

That is, the tabular silver halide emulsion preferably used contains silver halide grains having an average aspect ratio of 5: 1 or more. Aspect ratio refers to the ratio of diameter to thickness of a particle. Here, the diameter of a silver halide grain refers to the diameter of a circle having an area equal to the projected area of the grain. Silver halide grains specified by the above aspect ratio (tabular silver halide grains)
Has an aspect ratio of 6 or more, preferably 100 or less, more preferably 7 or more and 50 or less, and particularly preferably 8 or more and 20 or less.

Preferred tabular silver halide grains have a diameter of 0.5 to 30 μm.
m, and more preferably 1.0 to 20 μm.

In the layer containing tabular silver halide grains of the present invention, the tabular grains are preferably present in an amount of 40% or more, particularly 60% or more by weight based on the total silver halide grains in the layer.

The halogen composition of the tabular silver halide grains may be silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, etc., but it should be silver bromide or silver iodobromide. Is preferred,
The silver iodobromide having a silver iodide content of 0 to 1.8 mol% is more preferable.

 Particularly preferable silver iodide content is 4 to 12 mol%.

The tabular silver halide emulsion is disclosed in JP-A-52-153428 and JP-A-54-15.
5827, 54-118823, 58-127921, 58-113928 and the like can be obtained by known methods.

Particularly preferred tabular silver halide emulsions are those in which silver iodide is localized in the central part in the silver iodobromide.

The content of the high iodine content phase at the center is preferably 80% or less of the total volume of the grains, particularly preferably 60% to 10%.

The silver iodide content in the central portion is preferably 5 to 40 mol%, particularly preferably 10 to 30 mol%.

The low iodide content phase surrounding the central high iodide content phase has a silver iodide content of 0 to 10 mol%, preferably 0.1 to 6.0 mol%.
Is preferably silver iodobromide.

A tabular silver halide emulsion in which silver iodide is localized in the center can be obtained by a known method disclosed in JP-A-59-99433.

As a method for confirming the halogen composition structure in the grains of the silver halide grains of the present invention, JI Goldstein (goldatei) is used.
n) and DB Williamtams “X-ray analysis in TEM / ATEM”, Scanning Electron Microscopy (1977), Volume 1, IIT Research Institute, March 1977, P.651. Has been done. The particles to be examined were placed on a grid and cooled to the temperature of liquid nitrogen. A focused beam of electrons is directed at a 0.2 micrometer spot on each particle to be examined. 7
Inspect the sample at a 5 kilovolt accelerating voltage. By measuring the intensity and energy of the X-rays generated by the electron beam, the ratio of iodide to bromide in the grain at the spot where the electron hits can be determined.

A pyrazolotriazole-based magenta coupler of the present invention,
The silver halide and additives described below can be used in the light-sensitive material containing non-photosensitive fine grain silver halide.

For silver halide emulsions, silver bromide as silver halide,
Any of silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride and the like which are commonly used in ordinary silver halide emulsions can be used. Silver halide and silver chloroiodobromide are preferred.

The silver halide grains used in the silver halide emulsion are
It may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. Alternatively, it may be produced by sequentially adding halide ions and silver ions simultaneously while controlling the pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. The halogen composition of the grains may be changed using a conversion method in any step of the formation of AgX.

A known silver halide solvent such as ammonia, thioether or thiourea can be present during the growth of silver halide grains.

The silver halide grains are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt (in the process of forming grains and / or growing grains). By adding a metal ion using at least one selected from the group consisting of complex salts), these metal elements can be contained inside the particles and / or on the surface of the particles, and by placing in a suitable reducing atmosphere,
A reduction sensitization nucleus can be provided inside the grains and / or on the grain surface.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. The removal of the salts can be carried out according to the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643, Item II.

The silver halide grain may be a grain having a uniform silver halide composition distribution within the grain, or a core / shell grain having a different silver halide composition between the inside and the surface phase of the grain.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grain may have a regular crystal form such as a cube, octahedron or tetradecahedron, or may have an irregular crystal form such as a sphere or a plate. In these grains, any ratio of {100} faces to [111} faces can be used. Further, those having a composite form of these crystal forms may be used, and particles of various crystal forms may be mixed.

The size of silver halide grains may be 0.05 to 30 μm, preferably 0.1 to 20 μm.

The silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. When divided by the average grain size, the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown). Further, a polydisperse emulsion and a monodisperse emulsion may be used in combination.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion can be chemically sensitized by a conventional method. That is, the sulfur sensitizing method, the selenium sensitizing method, the reduction sensitizing method, the noble metal sensitizing method using gold and other noble metal compounds can be used alone or in combination.

The silver halide emulsion can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Good.

As the sensitizing dye, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, hemicyanine dye, steryl dye and hemioxanol dye are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

The silver halide emulsion includes chemical ripening, chemical ripening at the end of chemical ripening, and / or chemical ripening for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage, or photographic processing, or maintaining stable photographic performance. After the completion of ripening, a compound known as an antifoggant or a stabilizer in the photographic art can be added by the time of coating the silver halide emulsion.

Silver halide emulsion binder (or protective colloid)
It is advantageous to use gelatin, but a gelatin derivative, a graft polymer of gelatin and another polymer,
Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers or copolymers can also be used.

The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention and other hydrophilic colloid layers are one or two hardeners that crosslink binder (Nunder (or protective colloid) molecules to enhance film strength. Hardening agent can be added by the above-mentioned amount. The hardening agent can be added in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution. It is also possible to add agents.

For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5 -Triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol and the like), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalogen acids (mucochloric acid, Mucophenoxycyclo acid, etc.) can be used alone or in combination.

A plasticizer can be added to the silver halide emulsion layer and / or another hydrophilic colloid layer of the light-sensitive material for the purpose of enhancing flexibility. Preferred plasticizers are the compounds described in A of RD17643, section XII.

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

For example, alkyl (meth) acrylate, alkoxyalkyl (meth) actate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

In the color developing process, the emulsion layer of the photosensitive material undergoes a coupling reaction with an oxidized aromatic primary amine developer (for example, a p-phenylenediamine derivative or an aminophenol derivative) to form a dye. Couplers are used. The dye-forming couplers are usually selected such that for each emulsion layer a dye is formed that absorbs the light in the sensitive spectrum of the emulsion layer, with the blue-sensitive emulsion layer containing a yellow dye-forming coupler and a green dye-forming coupler. A magenta dye-forming coupler is used in the light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Also, these dye-forming couplers need only reduce two molecules of silver ions, even if they are four-equivalent, in which four molecules of silver ions need to be reduced in order to form one molecule of dye. Either of two equivalents may be used. The dye-forming coupler has a color-correcting effect and is coupled with a colored coupler and an oxidation product of a developing agent to develop a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent. , Hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizing compounds that release photographically useful fragments. Among these, a coupler which releases a development inhibitor with development and improves the sharpness of images and the graininess of images is called a DIR coupler. Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as producing a colorless compound by coupling reaction with an oxidized product of a developing agent may be used.

The DIR coupler and the DIR compound used include those in which an inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, and within the group which is released by the coupling reaction. (A timing DIR coupler and a timing DIR compound) in which an inhibitor is released by an intramolecular nucleophilic reaction, an intramolecular electron transfer reaction, or the like. Further, as the inhibitor, those having a diffusibility after release and those having a low diffusivity can be used alone or in combination depending on the use. A colorless coupler that performs a coupling reaction with an oxidized form of an aromatic primary amine developer but does not form a dye (also referred to as a competitive coupler) can be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow color couplers that can be used include, for example, U.S. Pat.
No. 5,057, No. 3,265,506, No. 3,408,194, No. 3,5
No. 51,155, No. 3,582,322, No. 3,725,072, No. 3,
891,445, West German Patent No. 1,547,868, West German Published Application 2,2
19,917, 2,261,361, 2,414,006, UK patent
1,425,020, JP-B-51-10783, JP-A-47-26133,
48-73147, 50-6341, 50-87650, 50-1233
42, 50-130442, 51-21827, 51-102636,
52-82424, 52-115219, 58-95346, etc.

As the magenta dye-forming coupler, known 5-pyrazolone-based couplers, pyrazolone-benzimidazole-based couplers, open-chain acylacetonitrile-based couplers, indazolone-based couplers and the like can be used. Specific examples of magenta color couplers that can be used include, for example, U.S. Pat.
No. 788, No. 2,983,608, No. 3,062,653, No. 3,12
No. 7,269, No. 3,311,476, No. 3,419,391, No. 3,5
19,429, 3,558,319, 3,582,322, 3,
615,506, 3,834,908, 3,891,445, West German patent 1,810,464, West German patent application (OLS) 2,408,665,
2,417,945, 2,418,959, 2,424,467, JP-B-40-6031, JP-A-49-74027, 49-74028, 49-
129538, 50-60233, 50-159336, 51-20826
No. 51, No. 51-26541, No. 52-42121, No. 52-58922, No. 53
-55122, Japanese Patent Application No. 55-110943, and the like.

As the cyan dye-forming coupler, a phenol or naphthol coupler is generally used. Specific examples of cyan coloring couplers that can be used include, for example, U.S. Pat.
No. 730, No. 2,474,293, No. 2,801,171, No. 2,8
95,826, 3,476,563, 3,737,326, 3,
No. 758,308, No. 3,893,044, JP-A-47-37425
No. 50, No. 50-10135, No. 50-25228, No. 50-112038, No. 5
The couplers described in JP-A Nos. 0-117422 and 50-130441 and the couplers described in JP-A-58-98731 are preferable.

Among the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, antifoggants, UV absorbers, and fluorescent brighteners that do not need to be adsorbed on the surface of silver halide crystals, hydrophobic compounds are Various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water emulsion dispersion method can be used, which can be appropriately selected depending on the chemical structure of the hydrophobic compound such as a coupler. The oil-in-water emulsion dispersion method may be a conventionally known method of dispersing a hydrophobic additive such as a coupler, and usually has a low boiling point of about 150 ° C. or higher and a high boiling point organic solvent, and / or an aqueous solution. Using a dispersing means such as a stirrer, homogenizer, colloid mill, flowgit mixer, ultrasonic device, etc., using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After emulsifying and dispersing, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

Organic solvents having a boiling point of 150 ° C or higher such as phenol derivatives, alkyl phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters and trimesic acid esters which do not react with the oxidized form of the developing agent as high boiling solvents A solvent is used.

A bottom boiling or water soluble organic solvent can be used with or instead of the high boiling solvent. As the organic solvent having a low boiling point and substantially insoluble in water, there are ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane nitroethane, benzene and the like.

Dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, antifoggants, UV absorbers, fluorescent brighteners and the like have an acid group such as carboxylic acid or sulfonic acid, an alkaline aqueous solution. It can also be introduced as a hydrophilic colloid.

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant,
Nonionic surfactants, cationic surfactants and amphoteric surfactants can be used.

Between the emulsion layers of the light-sensitive material (same color-sensitive layer and / or different color-sensitive layer), the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity, deterioration of sharpness, and graininess. An antifoggant can be used to prevent the property from being conspicuous.

The color antifoggant may be contained in the emulsion layer itself, or an intermediate layer may be provided between adjacent emulsion layers to be contained in the intermediate layer.

An image stabilizer that prevents deterioration of a dye image can be used in the light-sensitive material. Compounds which can be preferably used are those described in Item VII J of RD17643.

The hydrophilic colloid layer such as the protective layer and the intermediate layer of the photosensitive material may contain an ultraviolet absorber to prevent fogging due to discharge caused by the photosensitive material being charged by friction or the like and to prevent deterioration of an image due to ultraviolet rays. Good.

A formalin scavenger can be used in the light-sensitive material in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material.

When the hydrophilic colloid layer of the light-sensitive material contains a dye, an ultraviolet absorber or the like, they may be mordanted with a solvent agent such as a cationic polymer.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, a compound such as a development accelerator or a development retarder which changes the developability and a bleaching accelerator can be added. A compound which can be preferably used as a development accelerator is RD17643.
And the development retarder is a compound described in 17643, Item XXI, Item E. A black-and-white developing agent and / or a precursor thereof may be used for development promotion and other purposes.

The emulsion layer of the photographic light-sensitive material comprises a polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine compound, a quaternary ammonium compound or a urethane derivative for the purpose of increasing sensitivity, increasing contrast or promoting development. It may include a urea derivative, an imidazole derivative and the like.

A fluorescent whitening agent can be used in the light-sensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background inconspicuous. The compound which can be preferably used as the fluorescent brightening agent is described in the item V of RD17643.

The photosensitive material includes a filter layer, an antihalation layer,
An auxiliary agent such as an irradiation prevention layer can be provided. In these layers and / or in the emulsion layers, dyes which may be bleached or bleached from the light-sensitive material during development processing may be incorporated. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.

A matting agent can be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving writing properties, and preventing sticking of the light-sensitive materials to each other.

Any matting agent may be used, for example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonate and styrene. And the copolymers thereof. The matting agent preferably has a particle size of 0.05 μ to 10 μ.
The amount to be added is preferably 1 to 300 mg / m ² .

A lubricant can be added to the light-sensitive material to reduce sliding friction.

An antistatic agent for the purpose of antistatic can be added to the light-sensitive material. The antistatic agent may be used in the antistatic layer on the side of the support where the emulsion is not laminated, and a protective colloid layer other than the emulsion layer and / or the emulsion layer on the side where the emulsion layer is laminated on the support. May be used. Antistatic agents preferably used are the compounds described in RD17643 XIII.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the photosensitive material, coating property improvement, antistatic property, slip property improvement, emulsification dispersion, adhesion prevention, photographic properties (development acceleration, hardening, sensitization, etc.)
Various surfactants can be used for the purpose of improvement and the like.

The support used in the light-sensitive material of the present invention includes paper laminated with α-olefin polymer (for example, polyethylene, polypropylene, ethylene / butene copolymer), a flexible reflective support such as synthetic paper, cellulose acetate, Films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and flexible supports provided with a reflective layer on these films, glass, metal, pottery, etc. included.

The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support as required, and then directly or on the surface of the support, antistatic property, dimensional stability, abrasion resistance, hardness, It may be applied via one or more subbing layers to improve antihalation properties, friction properties, and / or other properties.

When coating the photosensitive material, a thickener may be used to improve the coating property. In addition, for example, for a hardener such as a hardener, which causes gelation before coating when added to a coating solution in advance due to its high reactivity, it is recommended to mix it immediately before coating using a static mixer or the like. preferable.

As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful, but bucket coating is also used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The surfactant is not particularly limited, for example, natural surfactants such as savonin, alkylene oxides, glycerin, nonionic surfactants such as glycidol,
Including higher alkyl amines, quaternary ammonium salts, pyridine and other heterocycles, cationic surfactants such as phosphonium or sulfonium, and acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester, and phosphoric acid ester You may add an amphoteric surfactant, such as an anionic surfactant, amino acids, aminosulfonic acid, and sulfuric acid or phosphoric acid ester of amino alcohol. Further, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the light-sensitive material of the present invention, color photographic processing is performed after exposure. The color processing includes a color development processing step, a bleaching step, a fixing step, a washing step, and a stabilizing step as required. Instead of the bleaching step and the fixing step, In addition, a bleach-fixing process can be performed using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing bleach-fixing solution capable of performing color development, bleaching, and fixing in one bath. Can also be performed.

A pre-hardening treatment step, a neutralization step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed in combination with these treatment steps. In these processes, instead of the color development processing step, an activator processing step in which a color developing agent or its precursor is contained in the material and the development processing is performed with an activator solution may be performed, or the monobath processing thereof may be performed. An activator treatment can be applied. Among these processes, representative processes are shown below. (These processes are any of a water-washing process, a water-washing process, and a stabilization process as a final process.)-Color developing process-Bleaching process-Fixing process-Color developing process-Bleaching-fixing process Process-Pre-hardening process-Color developing process-Stop fixing process-Rinsing process-Bleaching process-Fixing process-Rinsing process-Post-hardening process-Color developing process-Rinsing process-Supplement Color development processing step-Stop processing step-Bleaching processing step-Fixing processing step-Activator processing step-Bleaching fixing processing step-Activator processing step-Bleaching processing step-Fixing processing step-Mono bath processing step The processing temperature is usually 10 ° C. ~ 65 ° C, but 65 ° C
The temperature may exceed ℃. The treatment is preferably performed at 25 ° C to 45 ° C.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenylesinamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. it can.

These compounds are generally about 0.
It is used at a concentration of 1 to 30 g, more preferably at a concentration of about 1 to 15 g per color developing solution 1. If the amount is less than 0.1 g, a sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include o-
Aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4, -dimethyl-
Benzene etc. are included.

Particularly useful primary aromatic amino color developing agents are N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl and phenyl groups may be substituted or unsubstituted. Among them, examples of particularly useful compounds include NN-dimethyl-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-aminoaniline sulfate, N
-Ethyl-N-β-hydroxyethylaminoaniline,
4-amino-3-methyl-N, N-diethylaniline, 4
-Amino-N- (2-methoxyethyl) -N-ethyl-
Examples thereof include 3-methylaniline-p-toluenesulfonate.

The color developing agents may be used alone or in combination of two or more kinds. Further, the color developing agent may be incorporated in a color photographic material. In this case, the silver halide color photographic light-sensitive material can be processed with an alkali solution (activator solution) instead of the color developing solution, and bleach-fix processing is performed immediately after the alkali solution processing.

The color developing solution used in the present invention may contain an alkaline agent usually used in a developing solution, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development regulators such as citrazinic acid, and preservatives such as hydroxyamine or sulfite. You may. Further, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide, diethyl sulfoxide and the like can be appropriately contained.

The pH of the color developer used in the present invention is usually 7 or higher,
It is preferably about 9 to 13.

In the color developer used in the present invention, diethyloxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid, bentose or Hexose, pyrogallol-1,
3-dimethyl ether and the like may be contained.

In the color developing solution used in the present invention, various chelating agents can be used together as a sequestering agent for sequestering metal ions. For example, as the chelating agent, ethylenediaminetetraacetic acid, amine polycarboxylic acid such as diethylenetriaminepentaacetic acid,
Organic phosphonic acid such as 1-hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acid such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phosphonobutane 1 Examples thereof include phosphonocarboxylic acid such as 2,2,4-atricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compound.

The bleaching step may be performed simultaneously with the fixing step as described above, or may be performed individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid or citric acid, which is coordinated with a metal ion such as iron, cobalt, or copper is used. . The most preferred organic acids among the above organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′, N ′.
-Triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediamine Tetraacetic acid and the like can be mentioned.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

These bleaching agents are 5-450 g / l, more preferably 20-25
Use at 0g / l.

As the bleaching liquid, a liquid having a composition containing a sulfite as a preservative, if necessary, is applied in addition to the bleaching agent as described above.
Further, it may be a bleaching solution having a composition containing an ethylenediaminetetraacetic acid iron (III) acetate bleaching agent and adding a large amount of a halide such as ammonium bromide. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The bleaching solution used in the present invention includes JP-B-46-280, JP-B-45-8506, JP-B-46-556, and Belgian Patent No. 770,910.
Various bleaching accelerators described in JP-B Nos. 45-8836, 53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0-
It is used at 9.5, preferably at 4.5-8.0, most preferably at 5.0-7.0.

A fixing solution having a commonly used composition can be used. As the fixing agent, a compound which reacts with silver halide to form a water-soluble complex salt as used in a usual fixing process, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixing agents are 5g
It should be used in an amount that can dissolve at least 1 / l, but generally 70
Use at ~ 250g / l. A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank.

The bleaching solution and / or the fixing solution are various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. The agents can be contained alone or in combination of two or more. Further, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. Further, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, hardening agents such as water-soluble aluminum salts, methanol,
An organic solvent such as dimethylsulfonamide and dimethylsulfoxide can be appropriately contained.

The fixer is used at a pH of 3.0 or higher, but generally 4.5-
It is used at 10, preferably 5 to 9.5, most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above-mentioned bleaching step, and preferred compounds and the concentrations in the processing solution are the same as those in the above-mentioned bleaching step.

As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of a halogenide such as ammonium bromide other than the above-mentioned silver halide fixing agent and an ethylenediaminetetraacetic acid iron (III) complex bleaching agent is added, or conversely, a halide such as ammonium bromide Use a bleach-fixing solution containing a large amount of added, and a special bleach-fixing solution containing a combination of ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. You can Examples of the halide include hydrochloric acid, hydrobromic acid, in addition to ammonium bromide,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the fixing agents described in the above fixing processing step. The concentration of the fixing agent and the pH buffer and other additives that can be contained in the bleach-fixing solution are the same as those in the above-mentioned fixing process.

The bleach-fix solution is used at a pH of 4.0 or higher, but generally
Used in 5.0-9.5, preferably used in 6.0-8.5,
Most preferably, it is 6.5 to 8.5.

Example 1 Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

Sample-1 (comparative) First layer: Antihalation layer (HC-1) A gelatin layer containing black colloidal silver.

Second layer: intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer; low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Monodisperse emulsion (Emulsion I) consisting of AgBrI containing 0.30 μm average grain size () and 6 mol% AgI ... Silver coating amount 1.8 g / m ² Sensitizing dye I: 6 × 10 ^-5 mol per mol of silver Sensitizing dye II: 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-1): per mol of silver In contrast, 0.06 mol Colored cyan coupler (CC-1) ... 0.003 mol per mol of silver DIR compound (D-1) ... 0.0015 mol per mol of silver DIR compound (D-2) ... silver 1 0.002 mol per mol Fourth layer: high-sensitivity red-sensitive silver halide emulsion layer (RH-1) Emulsion composed of AgBrI containing 80.0 mol% AgI with an average grain size () 0.8 μm and aspect ratio 3: 1 ( However, the AgI content in the central portion is 15 mol%) (Emulsion A): Silver coating amount 1.3 g / m ² Sensitizing dye I: 3 × 10 ^-5 mol per 1 mol of silver Sensitizing dye II: Silver To 1 mole Te 1.0 × 10 ^-5 mol cyan coupler (C-1) 0.02 mol colored cyan coupler relative ...... silver mole (CC-1) 0.0015 mol DIR compound against ...... silver mole (D-2) ... ... 0.001 mol per mol of silver Fifth layer; intermediate layer (IL) The same gelatin layer as the second layer.

Sixth layer: low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-I ... Coating silver amount 1.5 g / m ² Sensitizing dye III: 2.5 × 10 ^-5 mol increase per 1 mol silver Dye IV: 1.2 × 10 ^-5 mol / mol silver Magenta coupler (M-1): 0.050 mol / mol silver Colored magenta coupler (CM-1): 1 mol silver 0.009 mol DIR compound (D-1) ... 0.0010 mol per 1 mol of silver DIR compound (D-3) ... 0.0030 mol per 1 mol of silver 7th layer; high-sensitivity green-sensitive silver halide emulsion layer ( GH-1) Emulsion-A: coating amount of silver 1.4 g / m ² Sensitizing dye III: 1.5 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 1.0 × 10 per mol of silver ^-5 mol magenta coupler (M-1) ...... silver mole with respect to 0.020 mol colored magenta coupler (CM-1) 0.002 mol of DIR compound against ...... silver mole (D-3) ...... silver Yellow filter layer (YC-1) Gelatin layer containing an emulsified dispersion of yellow colloidal silver and 2,5-di -t- octyl Jairo Doki Non; 0.0010 mol eighth layer moles.

Ninth layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion consisting of AgBrI with average grain size 0.48 μm and AgI 6 mol% (Emulsion III) ...... Silver coating amount increased 0.9 g / m ² Sensitizing dye V: 1.3 × 10 ^-5 mol per mol of silver Yellow coupler (Y-1): 0.29 mol per mol of silver Tenth layer: High-sensitivity blue-sensitive emulsion layer (BH-1) average Monodisperse emulsion consisting of AgBrI with grain size 0.8 μm and AgI 15 mol% (Emulsion IV) …… Silver coating amount 0.5 g / m ² Sensitizing dye V …… 1.0 × 10 ^-5 mol yellow silver coupler to 1 mol silver (Y-1) ... 0.08 mol per mol of silver DIR compound (D-2) ... 0.0015 mol per mol of silver 11th layer; first protective layer (Pro-1) silver iodobromide ( AgI 1 mol% average particle diameter 0.07 μm) Silver coating amount 0.5 g / m ² Gelatin layer containing UV absorber UV-1.UV-2.

Twelfth layer; Second protective layer (Pro-2) Gelatin layer containing polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1) Each layer contains a gelatin hardener (H −
1) and a surfactant were added.

 The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; anhydro 5,5'-dichloro-9-ethyl 3,
3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide sensitizing dye II; anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) Oxacarbocyanine hydroxide sensitizing dye IV; anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -5,6,5 ', 6'-dibenzoxacarbocyanine hydroxide Sensitizing dye V; anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxy Thiacyanine Sample-1 was prepared in this manner. Sample-2 to sample-18 were prepared by substituting the couplers and silver halide emulsions of the sixth and seventh layers or by adding non-photosensitive fine grain silver halide. Created. The content of the colored magenta coupler in the sample with respect to the magenta coupler according to the present invention is the amount of the colored magenta coupler contained in the sixth or seventh layer (both If it is included in the sum) is determined by.

(See Tables 1 to 3) Fine grain silver halides and silver halide emulsions shown in Tables 1 and 2 were prepared by a known method.

(1) Non-photosensitive fine grain silver halide (2) Silver halide emulsion used for the seventh layer Each sample obtained in this way was kept at 65 ° C and 20% relative humidity.
After leaving it in the place of 3 days, white exposure is given through the wedge by the usual method, and then the following development processing is performed,
The results in the table were obtained.

In Table 3, the difference in fog value is a value obtained by subtracting the green fog value of the high temperature untreated sample from the green fog value of the sample after the high temperature treatment. The larger this value is, the poorer the thermal stability is.

Also, for samples that were not treated at high temperature, the gamma value (γo) of the green density under the following development conditions and
Gamma value (γ at short development time (2 minutes 55 seconds)
The ratio γa / γo × 100 (%) of a) was measured. Ratio is 100
The closer to (%), the better the development stability.

 The results are shown in Table 4.

Treatment process (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the treatment solution used in each processing step is as follows. Is the street.

[Color developer]

4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1.

[Bleaching solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100.g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1 and pH = 6.
Adjust to 0.

[Fixer]

Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust to pH = 6.0 with acetic acid.

[Stabilizer]

 Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konishi Roku Photo Industry Co., Ltd.) 7.5 ml Add water to make 1

As is clear from Table 4, the samples according to the present invention have improved heat resistance and processing stability. Especially when the tabular silver halide grains having an average aspect ratio of 5: 1 or more are used together with the silver halide color light-sensitive material of the present invention, the effect of the present invention becomes more remarkable.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer on a support, wherein at least one light-sensitive silver halide emulsion layer is provided. One layer contains a pyrazolotriazole-based magenta coupler, and further,
In the emulsion layer containing the pyrazolotriazole-based magenta coupler, less than 15 mol% of the total amount of couplers in the total emulsion layer containing the pyrazolotriazole-based magenta coupler is contained, and a photosensitive halogen A silver halide photographic light-sensitive material characterized in that at least one layer of a silver halide emulsion layer and / or a non-light-sensitive hydrophilic colloid layer contains substantially light-insensitive fine grain silver halide.