JP2964007B2 - Color image forming method and silver halide photographic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material containing a novel pyrazolotriazole coupler and a color image forming method. The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method in which the variation in color density and the speed of color development are extremely small with respect to the variation in ion concentration.

(Prior Art) Using an exposed silver halide as an oxidizing agent, an oxidized aromatic primary amine color developing agent and a coupler react with each other to form a magenta color image. Magenta couplers are widely used in practice.
However, it is known that the dye formed from the 5-pyrazolone-based coupler has an unnecessary absorption having a yellow component at around 430 nm, which causes color smearing.

This yellow component is reduced, as a magenta color image-forming skeleton, a pyrazolobenzimidazole skeleton described in British Patent 1,047,612, an indazolone skeleton described in U.S. Pat. (5,1-c) -1,2,4-triazole skeletons have been proposed, and more recently, U.S. Pat.
No. 630, imidazopyrazole skeleton, U.S. Pat.
1H-pyrazolo [1,5-b] -1,2,4-
A triazole skeleton and a pyrazolotetrazole skeleton disclosed in JP-A-60-33552 are disclosed and known.

Of these, pyrazoloazole couplers, especially pyrazolotriazole couplers, are an excellent group of couplers that have overcome many problems. However, these couplers often suffer from a phenomenon that the color developing property fluctuates with the fluctuation of the liquid composition of the color developing solution. That is, the developing process usually includes color development, a stop solution, a bleaching solution, a fixing solution, a bleach-fixing solution (Blix), and the like. However, the developing solution is rarely newly prepared for each developing process. It is used as a replenisher for the developer according to the processing amount. However, the composition of the solution is not maintained only by replenishing the water lost by the development, and the developing agent deteriorates over a long period of time, or the eluate in the photosensitive material accumulates, and the composition of the processing solution changes, It becomes a so-called running liquid. A coupler that does not change the color developability even for a running solution accompanied by such a change in the composition of the processing solution is desired.

(Problems to be Solved by the Invention) As described above, a so-called running solution having a magenta coupler skeleton having excellent color reproducibility without unnecessary side absorption and further having a fluctuation in the composition of a processing solution. On the other hand, a color image forming method and a silver halide photographic light-sensitive material, which have little change in coloring property, have been desired.

Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material containing a coupler satisfying the above-mentioned demands, and to provide a color image forming method using such a coupler.

(Means for Solving the Problems) An object of the present invention is to develop a silver halide photographic material containing at least one kind of coupler represented by the general formula [I] with a developer containing an aromatic primary amine. A color image forming method (however, the coupler is not contained in the red-sensitive silver halide agent layer of the silver halide light-sensitive material) and at least one of the couplers. (However, the coupler is not contained in the red-sensitive silver halide emulsion layer of the silver halide color photographic light-sensitive material).

(However, R ₁ represents an alkyl group, an aralkyl group, a cycloalkyl group, or an alkenyl group, R ₂ represents a hydrogen atom,
Or a substituent as defined for R ₁ . R ₁ and R ₂ may be mutually bonded to form a 5- to 7-membered ring. X represents a hydrogen atom or a substituent which is eliminated in a coupling reaction with an oxidized form of an aromatic primary amine developing agent. Y represents a substituent, and n represents 0 or an integer of 1 to 4. R ₃ is
Represents an alkyl group or an aryl group. The general formula [I] will be described in more detail below.

R ₁ represents a substituted or unsubstituted alkyl group, aralkyl group, cycloalkyl group, or alkenyl group,
R ₂ represents a hydrogen atom or a substituent having the same meaning as R ₁ . Also R ₁
And R ₂ may combine with each other to form a 5- to 7-membered ring.

To describe R _{1 in} more detail, the unsubstituted alkyl group is a straight-chain or branched-chain alkyl group having 1 to 24 carbon atoms (eg, methyl, ethyl, butyl, isopropyl, isobutyl,
t-butyl, pentyl, hexyl, 2-ethylhexyl, octyl, dodecyl, t-octyl, hexadecyl), and the unsubstituted alkenyl group is an alkenyl group having 3 to 24 carbon atoms (eg, allyl, 2,4-pentedienyl). Represents an unsubstituted cycloalkyl group having 5 to 5 carbon atoms.
Up to 7 cycloalkyl groups (eg, cyclopentyl, cyclohexyl); and unsubstituted aralkyl groups represent aralkyl groups having 7 to 24 carbon atoms (eg, benzyl, phenylethyl). Each substituted alkyl group,
As a substituent of the alkenyl group, the cycloalkyl group or the aralkyl group, a halogen atom (for example, fluorine, chlorine,
Bromine), hydroxy group, cyano group, carboxyl group, sulfonic acid group, alkoxy group (for example, methoxy, ethoxy, butoxy, cyclohexyl, hexyloxyethoxy, dodecyloxy), aryloxy group (for example, phenoxy, t-octylphenoxy, 2, 4-di-t-amylphenoxy, naphthoxy), an alkylthio group (for example, methylthio, ethylthio, butylthio, octylthio,
Hexadecylthio), an arylthio group (for example, phenylthio, 2-ethoxy-5-t-octylphenylthio,
2-pivaloylaminophenylthio), an acylamino group (eg, acetylamino, pivaloylamino, 2-ethylhexanoylamino, tetradecanoylamino),
Sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, p-toluenesulfonamide), carbamoyl group (eg, N-butylcarbamoyl, N, N-diethylcarbamoyl), sulfamoyl group (eg, N-ethylsulfamoyl) , N, N-diisopropylsulfamoyl), an alkoxycarbonyl group (eg, ethoxycarbonyl, 2-ethyl-hexyloxycarbonyl), an alkylamino group (eg, ethylamino, isopropylamino, hexylamino, cyclohexylamino, t-octylamino, Dodecylamino, hexadecylamino), carbamoylamino group, alkoxycarbonylamino group, acyloxy group, sulfonyl group and the like.

Examples of the 5- to 7-membered ring in which R ₁ and R ₂ are mutually bonded and closed include pyrrolidine, piperidine, pyrazolidine, imidazolidine, oxazolidine, morpholine, piperazine, and thiazolidine.

Y represents a substituent, and the substituent is a straight-chain or branched-chain substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (eg, methyl, ethyl, isopropyl, t-butyl, cyclohexyl, adamantyl), an aryl group ( For example, phenyl, p-tolyl, 2-methoxyphenyl, 2-pivaloylamidophenyl, 2-chlorophenyl, 2,4-dimethoxyphenyl, naphthyl), a heterocyclic group (for example, 4-
Pyridyl, 2-furyl), alkoxy group (for example, methoxy, ethoxy, isopropyloxy, 2-phenoxyethoxy, 2-methoxyethoxy), aryloxy group (phenoxy, 2-methoxyphenoxy, 2-chlorophenoxy, 2,4-) Dimethoxyphenoxy, 3-butanesulfonamidophenoxy, 2,5-di-t-amylphenoxy, 2-naphthoxy), a heterocyclic oxy group (for example,
2-furyloxy), an amino group (eg, N-methylamino, N, N-dibutylamino), an anilino group (eg, 2-
Methoxyanilino, 2-chloroanilino, 2,4-dichloroanilino, N-methylanilino), heterocyclic amino group (for example, 4-pyridylamino), amide group (for example, acetamido, benzamide), urethane group (for example, N-hexylurethane, N, N-dibutyl urethane), ureido group (eg, N, N-dimethylureide, N-phenylureide), sulfonamide group (eg, butanesulfonamide, p-toluenesulfonamide), alkylthio group (eg, ethylthio, octylthio), arylthio group (Eg phenylthio, 4-dodecylphenylthio),
A sulfinyl group (eg, benzenesulfinyl), a sulfonyl group (eg, methanesulfonyl, octanesulfonyl, p-toluenesulfonyl), a sulfo group, a cyano group,
Represents a nitro group or the like.

R ₃ represents a linear or branched substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (eg, methyl, ethyl, isopropyl, t-butyl, cyclohexyl, adamantyl), an aryl group (eg, phenyl, p-tolyl, 2-methoxyphenyl, 2-pivaloylamidophenyl, naphthyl)
Represents n represents 0 or an integer of 1 to 4, and when n is 2 or more, Y may be the same or different.

X represents a hydrogen atom or a substituent which leaves upon coupling with an oxidized form of an aromatic primary amine developing agent, and the substituent is an aryloxy group (for example, p-methylphenoxy, p-carboxyphenoxy, 2,4- J-ter
t-amylphenoxy), a heterocyclic oxy group (for example, furyloxy), an alkylthio group (for example, dodecylthio, 2-hydroxyethylthio, carboxymethylthio, 1-ethoxycarbonyltridecylthio), an arylthio group (for example, 2-pivalo) Ilamidophenylthio, 2-butoxy-5-tert-octylphenylthio), a heterocyclic thio group, a halogen atom (for example, fluorine,
Represents a nitrogen-containing heterocyclic group (eg, triazolyl, pyrazolyl, imidazolyl) bonded with a nitrogen atom.

The monomer containing the coupler represented by the general formula [I] may form a copolymer with a non-color-forming ethylene-like monomer which does not couple with the oxidation product of the aromatic primary amine developer.

Non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid,
α-chloroacrylic acid, α-alkylacrylic acid (eg, methacrylic acid) and esters or amides derived from these acrylic acids (eg, acrylamide, n-butylacrylamide, t-butylactylamide, diacetoneacrylamide, Acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate,
Ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibisacrylamide, vinyl esters (eg, vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, Styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester , N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. Two or more non-color-forming ethylenically unsaturated monomers used herein can be used together. For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the polymer color coupler art, the non-color-forming ethylenically unsaturated monomer for copolymerization with the solid water-insoluble monomer coupler depends on the physical and / or chemical properties of the copolymer formed. (Eg, solubility), compatibility of the photographic colloid composition with a binder (eg, gelatin),
It can be selected such that its flexibility, thermal stability, etc. are favorably affected.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, and among them, a polymer coupler latex is particularly preferable.

Further, the coupler of the general formula [I] may form a dimer via R ₃ .

Among the couplers of the general formula [I], preferred are R ₁
And R ₂ are both alkyl groups or condensed ring-closed groups, and R ₃ is a branched alkyl group. X is preferably a halogen atom or an aryloxy group, and Y is preferably an electron donating group (more preferably an alkyl group or an alkoxy group). More preferred couplers are those represented by the general formula [I] having the above substituents and leaving groups.

Hereinafter, specific examples of the coupler of the present invention will be shown, but the present invention is not limited thereto.

Next, a general synthesis method of the present invention will be described.

1H-pyrazolo [1,5-] represented by the general formula [I]
b] The 1,2,4-triazole skeleton can be synthesized, for example, by the method described in JP-A-60-197688.

 A general method for introducing a coupling-off group will be described.

(1) A method of introducing a halogen atom.

The halogenation at the coupling active position is performed by adding 1 equivalent of bromine, N-bromosuccinimide, sulfuryl chloride, or halogenating agent such as N-chlorosuccinimide to 4 equivalent coupler (A) in an inert solvent such as dichloromethane. It is easily obtained by acting.

(2) A method of communicating oxygen atoms.

It can be synthesized by the method described in JP-A-61-53644.
That is, (a) a method in which a halogen atom of a coupler having a halogen atom at a coupling active position is substituted with a phenoxy group.

The halogenated compound (B) is converted to dimethylformamide (DM
F), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), in an aprotic polar solvent such as N- methyl-2-pyrrolidone, suitable R ₅
—OM, (R ₅ —O) ₂ M ′ or (R ₅ —O) ₃ M ″ (R ₅ represents an aryl group, M, M ′ and M ″ are each monovalent,
Represents divalent and trivalent metal ions. ) To give (C) in which an aryloxy group has been introduced into the desired coupling active site. Preferably, the halide (B) is mixed with an equivalent to 20-fold (molar ratio) sodium or potassium salt of a suitable phenol in an equivalent to 50-fold (weight) of the above solvent at 50 to 150 ° C.
It is desirable to react at a temperature of In this reaction, the addition of a quaternary ammonium salt such as tetrabutylammonium bromide or an alkali metal halide such as cesium bromide may accelerate the reaction.

(B) After introducing an aryloxy group into active methylene of β-ketonitrile, 1H-pyrazolo [1,5-b] -1,
A method for forming a 2,4-triazole skeleton.

The halogenated form (E) obtained by treating 3-oxonitrile (D) with a halogenating agent such as bromine or sulfuryl chloride in an inert solvent such as dichloromethane is treated with an appropriate R _{5 in} the presence of a tertiary amine. Treatment with -OH or a metal salt such as R ₅ -OM described in (1) above gives an aryloxy compound (F). The desired coupler (I) of the present invention is synthesized from the aminopyrazole (G) obtained by reacting this with foamed water hydrazine in a solvent such as ethanol by the method described in JP-A-60-215687. it can.

3-Oxonitrile (D) is disclosed in U.S. Pat. No. 4,411,753.
DE 3,209,472 and Synthesi
s, 472 (1977) and the like.

(2) Method for linking a sulfur atom A coupler in which an aromatic mercapto or heterocyclic mercapto group is substituted at the 7-position is prepared by the method described in US Patent No. 3,227,554, that is, aryl mercaptan, heterocyclic mercaptan and its corresponding disulfide are halogenated and carbonized. It can be synthesized by dissolving in a hydrogen-based solvent and adding it to a 4-equivalent coupler dissolved in an aprotic solvent as sulfenyl chloride with chlorine or sulfuryl chloride. A method for introducing an alkyl mercapto group at the 7-position is described in US Pat.
No. 4,264,723, that is, a method in which a mercapto group is introduced into a coupling active position of a coupler and a halide is allowed to act on the mercapto group, and S- (alkylthio)
A method of synthesizing in one step using isothiourea and hydrochloride (or bromine hydrochloride) is effective.

3) Method of linking nitrogen atoms (1) Method of modifying an amino group by introducing an amino group into a coupling active site.

The introduction of an amino group into the coupling active site is disclosed in U.S. Pat.
No. 419,391, that is, it can be easily obtained by nitrosating the coupling active site, reducing it by an appropriate method, and modifying the resulting amino compound. Also, by coupling a diazonium salt derived from, for example, aniline anthranilic acid and sulfanilic acid to the coupling active site to obtain an azo dye, reducing the azo dye with a suitable reducing agent such as hydrosan phyt soda. It can be easily obtained by modifying the obtained amino compound.

(2) A halogen atom is introduced into the coupling active site, and the halogen atom is Substitution with a group.

R ₈ or R ₉ is an alkyl group, an aryl group, a heterocyclic group,
And R ₈ and R ₉ are mutually bonded to form a 5- or 6-membered nitrogen heterocyclic group together with a nitrogen atom, And the halogen-substituted product (B) are dissolved in an alcoholic solvent, an aprotic polar solvent or a halogenated hydrocarbon solvent in a temperature range of 0 ° C. to 180 ° C. and reacted in the presence of a suitable base. I can do it.

 Next, a typical synthesis example of the coupler of the present invention will be described.

(Synthesis Example-1) Synthesis of exemplified coupler M-4.

20.4 g (0.1 mol) of (5-methyl-2-nitrobenzoyl) acetonitrile is dissolved in 100 ml of isopropanol and stirred. Add 80% aqueous solution of hydrazine monohydrate 6.56
After the dropwise addition of g (0.105 mol), the mixture is heated and stirred. About 12
After heating and stirring for an hour, isopropanol is distilled off under reduced pressure to obtain 21.5 g (98.6%) of 3- (5-methyl-2-nitrophenyl) -5-aminopyrazole as a reddish brown oil. Acetonitrile 200m
Add l and stir at room temperature. To this was added 2-methyl-3-phthalimidopropylimidic acid methyl ester hydrochloride (28.3).
g (0.1 mol) is added and the mixture is stirred at room temperature for 5 hours to precipitate crystals. The crystals are collected by filtration and dispersed in 150 ml of methanol. A methanol solution of hydroxylamine (7.56 g of hydroxylamine hydrochloride was added to methanol 8
0 ml was dissolved and 22.1 ml of a 28% methanol solution of CH ₃ ONa was added for neutralization), and the mixture was stirred at room temperature for 4 hours. After the reaction,
300 ml of water was slowly added dropwise to sufficiently precipitate crystals, which was collected by filtration and dried to obtain 29.6 g (67.0%) of an amide oxime compound.

29.6 g (0.066 mol) of this amide oxime compound is dissolved in 100 ml of dimethylacetamide and stirred at room temperature. After 13.1 g (0.069 mol) of paratoluenesulfonic acid chloride is added to this solution, 5.7 ml (0.07 mol) of pyridine is slowly added dropwise. After stirring at room temperature for about 2 hours, the reaction mixture is poured into 1,000 pieces of water while stirring, and a harz-like substance precipitates. After removing the aqueous layer, the harz-like material is washed with water. Next, add 400 ml of methanol to this harz-like material,
After heating and stirring for about 2 hours, the mixture is cooled to room temperature. The precipitated crystals are collected by filtration and dried to give 6- (5-methyl-2).
13.7 g (48.2%) of -nitrophenyl) -2- (1-methyl-2-phthalimidoethyl) -1H-pyrazolo- [1,5-b] -1,2,4-triazole are obtained.

6- (5-methyl-2-nitrophenyl) -2- (1
-Methyl-2-phthalimidoethyl) -1H-pyrazolo-
100 ml of isopropanol is added to 13.7 g (0.0318 mol) of [1,5-b] -1,2,4-triazole, and the mixture is heated and stirred.
To this is added 2.19 g (0.035 mol) of an 80% aqueous solution of hydrazine monohydrate, and the mixture is heated and stirred for about 2 hours. After the completion of the reaction, the mixture is cooled to room temperature and the precipitated phthalhydrazide is removed by filtration. After the filtrate was concentrated to dryness under reduced pressure, the residue was dissolved in 30 ml of dimethylacetamide, cooled to 5 ° C and stirred. To this solution, 11.7 g (0.0318 mol) of 2- (2,4-di-tert-amylphenoxy) hexanoic acid chloride is slowly added dropwise. Then 4.6 ml (0.033 mol) of triethylamine are further added dropwise. After completion of the dropwise addition, stirring was continued at room temperature for about 2 hours, followed by extraction with 250 ml of ethyl acetate. This ethyl acetate solution is washed with water and dried over anhydrous magnesium sulfate, and then ethyl acetate is distilled off under reduced pressure. This residue is treated with isopropanol 50
Heat and dissolve in ml. This solution is added dropwise to a solution obtained by adding 200 ml of isopropanol to 25 g of reduced iron, 1.0 g of ammonium chloride and 20 ml of water and heating and stirring. After completion of the dropwise addition, the mixture is heated and stirred for about 2 hours, cooled to room temperature, and filtered to remove inorganic substances. The filtrate is concentrated under reduced pressure and the residue is dissolved in 100 ml of dimethylacetamide. 12.4 g (0.09 mol) of anhydrous potassium carbonate is added to this solution, and the mixture is heated and stirred at 100 ° C. 8.2 g (0.06 mol) of butyl bromide are added dropwise thereto. After completion of the dropwise addition, stirring was continued at 100 ° C. for about 2 hours, then cooled to room temperature and filtered to remove inorganic substances. The filtrate is extracted with 300 ml of ethyl acetate, and the ethyl acetate solution is washed with water. After drying the ethyl acetate solution over anhydrous magnesium sulfate, the ethyl acetate is distilled off under reduced pressure. The residue was purified by column chromatography (silica gel-n-hexane / ethyl acetate) to obtain 8.64 g (38.1%) of a 4-equivalent coupler.

8.64 g (0.0121 mol) of this 4-equivalent coupler was dissolved in 86 ml of dichloromethane and stirred at room temperature. N
2.20 g (0.012 mol) of chlorosuccinimide are added in several portions. After stirring at room temperature for about 1 hour after completion of the addition,
The dichloromethane solution is washed with water and dried over anhydrous magnesium sulfate. The dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel-n-hexane / ethyl acetate) to give a glass-like exemplified coupler 4.
5.69 g (62.9%) was obtained.

When the coupler represented by the general formula (I) or (II) of the present invention is contained in a photographic material, it is preferably used in an amount of 0.1 to 1.0 per mol of silver halide in a photosensitive layer used in combination with the coupler. Mol, more preferably 0.1 to 0.5 mol.

When the coupler is used by being added to a color developing solution, the amount of the coupler is preferably 0.001 to 0.1 mol, more preferably 0.002 to 0.01 mol, per developer.

In addition, the coupler can be added to the light-sensitive material by a conventional coupler addition method described later.

Hereinafter, the color light-sensitive material and the color image forming method of the present invention will be described in detail.

The color light-sensitive material of the present invention can be widely used as various photosensitive materials for photography and various photosensitive materials for printing.

The silver halide emulsion may be a negative emulsion or a direct positive emulsion. Silver halide that can be used is silver bromide, silver iodobromide,
Silver chloride, silver chlorobromide, silver chloroiodobromide and the like.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, the color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

As the silver halide emulsion used in the present invention, an emulsion composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (Shell) [Layer or multiple layers] and a grain having a so-called laminated structure having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface (when the particles are on the grain surface, the edge of the grain,
A structure in which different composition parts are joined on corners or surfaces)
And the like can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver halide / silver chloride ratio can be used. Although this ratio can take a wide range according to the purpose, a silver chloride ratio of 2% or more can be preferably used.

Further, a so-called high silver chloride emulsion having a high silver chloride content is preferably used as a photosensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%,
It is more preferably at least 95 mol%.

Such high silver chloride emulsions preferably have a structure in which a silver bromide localized layer is formed in a layered or non-layered form as described above on the inside and / or on the surface of silver halide grains.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized layers can be on the inside of the grain, on the edge, corner, or plane of the grain surface. One preferred example is a layer grown epitaxially on the corner of the grain.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in a high silver chloride emulsion having a silver chloride content of 90 mol% or more, grains having a uniform distribution of the halogen composition in the grains are used. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 88 mol% to 10 mol%.
Emulsions of substantially pure silver chloride, such as 0 mol%, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μm to 2 μm. preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture of those having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is Chmie by P. Glafkides.
et Phisique Photographique (published by Paul Montel, 1967
Photographic Emulsion Chemistry by GFDuffin
(Focal Press, 1966), M by VLZelikman et al
aking and coating Photographic Emuldion (Focal Pre
ss, published in 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used.
According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. Examples of spectral sensitizing dyes used at this time include, for example, Heterocyclic compo by FM Harmer.
unds-Cyanine dyes and related compounds (John Wil
ey & sons [New York, London], 1964). As specific examples of the compounds, those described in the above-mentioned JP-A-62-215272, page 22, upper right column to page 38, are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

The emulsion used in the present invention is any of a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface and a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good.

As the color light-sensitive material, yellow couplers, magenta couplers and cyan couplers which are coupled with an oxidized form of an aromatic amine color developing agent to form yellow, magenta and cyan, respectively, are usually used.

Cyan coupler preferably used in the present invention,
The magenta coupler and the yellow coupler are represented by the following formulas (C-I), (C-II), (M-I), (M-II) and (Y).

In the general formulas (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

In the general formula (CI), preferred R ₁ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, they are aryl groups substituted by a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

When R ₃ and R ₂ do not form a ring in formula (CI), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-II), preferred R ₅ has 2 to 15 carbon atoms.
And a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (C-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

Preferred R ₆ in formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred Y ₁ and Y ₂ in the general formulas (CI) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (MI), R ₇ and R ₉ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The substituents permitted for the aryl group (preferably phenyl group) of R ₇ and R ₉ are the same as the substituents permitted for the substituent R ₁ , and when there are two or more substituents, they are the same. But they may be different. R ₈
Is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Desirable Y ₃ is of a type capable of releasing at any of a sulfur, oxygen or nitrogen atom, and particularly preferred is a type of releasing at a sulfur atom as described in, for example, US Pat. No. 4,351,897 and International Publication WO88 / 04795.

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R ₁₀ or Y ₄ forms a dimer or more multimer, Za,
When Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is included.

Among the pyrazoloazole couplers represented by the general formula (M-II), the imidazo [1,2-b] pyrazole described in U.S. Pat. No. 4,500,630 is advantageous in terms of low yellow side absorption and light fastness of a coloring dye. Are preferred, US Pat.
The pyrazolo [1,5-b] [1,2,4] triazole described in 4,540,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 226,849 and pyrazoloazole couplers having an alkoxy group or aryloxy group at the 6-position as described in EP-A-226,849 and EP 294,785. The use of zorotriazole couplers is preferred.

In the general formula (Y), R ₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is _{-NHCOR 13, -NHSO 2 -R 13,} -SO 2 NHR 13,
−COOR ₁₃ , Represents Here, R ₁₃ and R ₁₄ each represent an alkyl group, an aryl group or an acyl group. Y ₅ represents a leaving group. R ₁₂
And the substituents of R ₁₃ and R ₁₄ are the same as the substituents permitted for R ₁ and the leaving group Y ₅ is preferably of a type capable of leaving at either an oxygen atom or a nitrogen atom. And a nitrogen atom-elimination type is particularly preferable.

Formulas (C-I), (C-II), (M-I), and (M-
Specific examples of the couplers represented by II) and (Y) are listed below.

The couplers represented by the above general formulas (C-I) to (Y) are usually added in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
0.50.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method. After dissolution in a solvent, the emulsion is dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used.

General formula (B) W ₁ -COO-W ₂ Formula (E) W ₁ —O—W ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group; W ₄ is W ₁ , OW ₁ or SW
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different. In the general formula (E), W ₁ and W ₂ represent a condensed ring. May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, which is described in the lower right column of page 137 to the upper right column of page 144.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. No. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP 52-152225, etc. UK Patent 2,0
No. 66,975, JP-A-59-10539, JP-B-57-19765, and the like, hindered phenols are disclosed in U.S. Pat.
JP-A-52-72224, U.S. Pat.No. 4,228,235, JP-B-52-6623, and the like, gallic acid derivatives, methylenedioxybenzenes, aminophenols are U.S. Pat.Nos. 3,457,079 and 4,332,886, respectively. In Japanese Patent Publication No. 56-21144, hindered amines are disclosed in U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,
Nos. 354,313, 1,410,846, JP-B-51-1420, JP-A-58-114036, JP-A-59-53846, and JP-A-59-78344, the metal complexes are U.S. Pat. 4,241,1
55 and British Patent 2,027,731 (A). These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
3,406,070 and 3,677,672 and 4,271,307) can be used. UV-absorbing couplers (eg, α-naphthol-based cyan dye-forming couplers)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

It is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable from the viewpoint of preventing the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or oxidant remaining in the film and the coupler.

Preferred as the compound (F) is a compound having a secondary reaction rate constant k ₂ (in trioctyl phosphate at 80 ° C.) of 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with the second reaction rate constant with p-anisidine. Compound. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

General formula (FI) R _1- (A) _n -X In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by formulas (FI) and (F II) are described in JP-A-63-158545, JP-A-62-283338,
Those described in specifications such as European Patent Publication Nos. 298321 and 277589 are preferable.

On the other hand, the compound (G) which forms a chemically inactive and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development processing is more preferably represented by the following general formula (GI) ).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearso
n, et al., J. Am. Chem. Soc., 90 , 319 (1968)) or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
-229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 277589 are preferred.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material prepared according to the present invention contains a water-soluble dye or a dye which becomes water-soluble by photographic processing as a filter dye in the hydrophilic colloid layer, or for various purposes such as prevention of irradiation or halation. You may. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Wuice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate which is usually used for a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

The color developer used in the development of the photosensitive material of the present invention is
Preferably, it is an aqueous alkaline solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof.
These compounds can be used in combination of two or more depending on the purpose.

The color developing solution includes a pH buffer such as an alkali metal carbonate or phosphate, a development inhibitor such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. It is common to include. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N-
Hydrazines such as biscarboxymethylhydrazine,
Various preservatives such as phenylsemicarbazides, triethanolamine, catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, and dye formation Couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids ,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, Ethylenediamine-N, N, N ',
N'-tetramethylenephosphonic acid, ethylenediamine-
Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal processing is performed, color development is usually performed after black-and-white development and reversal processing are performed. In this black developer,
Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. .

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 or less per square meter of the light-sensitive material. By reducing the bromide ion concentration in the replenishing solution, 500 m
It can be less than l. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = contact area with treatment liquid (cm ² ) / capacity of treatment liquid (cm ³ ) The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05.

As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in Japanese Patent Application No. 62-241342, Examples of the method include a slit developing method described in JP-A-63-216050.

The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization.

Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further reduced by using a high temperature, a high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (III) is used. A typical bleach is iron (II
Organic complex salts of I), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid, or citric acid and tartaric acid And complex salts such as malic acid. Of these, aminopolycarboxylate iron (III) complex salts such as ethylenediaminetetraacetate iron (III) complex salt are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually
4.0 to 8.0, but lower for faster processing
It can be treated at pH.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-812.
No. 95630, Research Disclosure No. 17,129 (July, 1978), etc .; compounds having a mercapto group or disulfide bond; thiazolidine derivatives described in JP-A-50-140129; US Pat. No. 3,706,561 Thiourea derivatives; iodide salts described in JP-A-58-16235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B-45-8836; it can. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858,
Compounds described in West German Patent No. 1,290,812 and JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. Preservatives for the bleach-fix solution include sulfites and bisulfites, p
-Sulfinic acids such as toluenesulfinic acid or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevisin Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Also, isothiazolone compounds, thiabendazoles, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A-57-8542, Hiroshi Horiguchi, "Bactericidal and antifungal chemistry," 1986
Year) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japanese Society of Antimicrobial and Antifungal Studies, "Encyclopedia of Antifungal Agents" (1986) A bactericide can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Patent Application Laid-Open
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, 3,342,599, Schiff base-type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, and metals described in U.S. Pat. Complex, JP 5
Examples thereof include urethane compounds described in 3-135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547, and
No. 15438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to this.

Example 1 A multilayer color photographic paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 27.2 cc of ethyl acetate in 4.4 g and (Cpd-7) 1.8 g
Then, 4.1 g of each of the solvents (Solv-3) and (Solv-6) were added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a silver chlorobromide emulsion (silver bromide 80.0 mol%, cubic; one having an average grain size of 0.85 μm and a variation coefficient of 0.08;
A mixture of 80.0% silver bromide, cubic; one having an average grain size of 0.62 μm and a variation coefficient of 0.07, mixed at a ratio of 1: 3 (Ag molar ratio) with sulfur was sensitized with a blue-sensitive sensitizing dye shown below. To silver 1
A solution prepared by adding 5.0 × 10 ⁻⁴ mol per mol was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
4.0 × 10 ⁻⁶ mol, 3.0 × 10 ⁻⁵ mol, 1.0 × 10 ⁻⁵ mol or 2-methyl-5-t-octylhydroquinone was added to each of 8 × 10 ⁻³ mol and 2 × 10 ⁻ mol per mol of silver halide. ² mol and 2 × 10 ^-2 mol were added.

Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol, 1.1 ×
10 ^-2 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultramarine)] First layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion (AgBr: 80 mol%) 0.26 gelatin 1.83 yellow coupler (ExY) 0.83 color image stabilizer (Cpd-1) 0.19 color image stabilizer (Cpd-7) 0.08 solvent (Solv-3) 0.18 solvent (Solv-6) 0.18 second layer (mixing prevention) Layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (AgBr 90 mol%, cube, average particle size) 0.47 μm, coefficient of variation 0.12, 90 mol% AgBr, cubic, average particle size 0.36 μm, coefficient of variation 0.09 mixed in a 1: 1 ratio (Ag mole ratio) 0.16 Gelatin 1.79 Magenta coupler (ExM) 0.32 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-3) 0.20 Color image stabilizer (Cpd-4) 0.0 1 Color image stabilizer (Cpd-8) 0.03 Color image stabilizer (Cpd-9) 0.04 Solvent (Solv-2) 0.65 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (AgBr 70 mol%, cubic, average grain size 0.49 μm, variation coefficient 0.08, AgBr 70 mol%, A mixture of cubic particles with an average particle size of 0.34 µm and a coefficient of variation of 0.10 is mixed in a ratio of 1: 2 (Ag molar ratio). 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.30 Color image stabilizer (Cpd-6) 0.17 Color image stability Agent (Cpd-7) 0.40 Solvent (Solv-6) 0.20 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seven layers (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation 17%) 0.17 Liquid paraffin 0 .03 It was produced in this manner. This is designated as Sample A.

Next, exemplary couplers M-4, M-6, M-9, M-11,
M-12, M-19, and M-20 were weighed in equimolar amounts instead of the (ExM) magenta coupler, and the tris (2-ethylhexyl) phosphate and the tris (2-ethylhexyl) phosphate having a volume (ml) twice the weight of each were measured. A mixture of cresyl phosphate was added, emulsified and coated in the same manner as in Sample A, and the samples (B), (C), (D), (E), (F), (G),
(H) was prepared.

Further, comparative couplers (1) to (4) shown below were also emulsified and coated in the same manner to prepare Samples (I), (J), (K), and (L).

First, using a sensitometer (Fuji Photo Film Co., Ltd., FWH type, light source color temperature of 3200 ° K), each sample was given light such as gradation of a three-color separation filter for sensitometry. The exposure at this time was performed so that the exposure amount could be 250 CMS with an exposure time of 0.1 second.

The exposed samples were processed using an automatic processor (Fuji Color Paper Processor FP)
RP115).

The composition of each processing solution is as follows.

The photographic properties were evaluated by comparing the three items of gradation (γ), maximum density (Dmax) and fog density (Dmin) when each sample was processed with a fresh developing solution and when processed with a running solution. did. The results are shown in Table 1.

The fresh liquid referred to here is an unused processing liquid adjusted based on the processing liquid prescription, and the running liquid is a continuous processing until the processing step replenishes twice the color developing tank capacity. Refers to the processing liquid at the point of time.

The gradation (γ) indicates the slope of the characteristic curve from a value obtained by adding the magenta density 0.5 to the fog density (Dmin) to a value obtained by further adding the magenta density 0.5.

As shown in Table 1, the coupler of the present invention has a smaller difference in Dmin, gradation and Dmax between the case treated with the fresh solution and the case treated with the running solution than the comparative coupler. From these results, it can be said that the coupler of the present invention is a specific excellent coupler which is less susceptible to a change in coloring property due to a change in the composition of the processing solution.

Example 2 A multilayer color photographic paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 27.2 cc of ethyl acetate and 8.2 g of a solvent (Solv-1) were added to 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7) and dissolved, and the resulting solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (average grain ratio) of 0.88 μm and 0.70 μm) (silver molar ratio) The coefficient of variation of the particle size distribution is 0.08 and 0.10, and each emulsion is silver bromide
The following blue-sensitive sensitizing dyes are added to the large-sized emulsion in an amount of 2.0 × 10 ⁻⁴ mol per mol of silver, and the small-sized emulsion is added to the small-sized emulsion. , Each of which was subjected to sulfur sensitization after addition of 2.5 × 10 ^-4 mol. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, and each for small-size emulsion
2.5 × 10 ^-4 mol) (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) and (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mole) (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY ) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (mixing prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-5) 0.08 Solvent ( Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 0.55 μm average particle size and 0.39 μm emulsion are mixed 1: 3 (Ag mole) The coefficient of variation of the grain size distribution is 0.10 and 0.08, and each emulsion is AgBr
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv) -5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 µm and 0.45 µm in average grain size, Ag molar ratio) Coefficient of variation in grain size distribution Are 0.09 and 0.11, AgBr0 for each emulsion.
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (17% denaturation degree) 0.17 Liquid paraffin 0.03 Created in this way. This was designated as Sample A ', and Samples B' to L 'were prepared by using the coupler of the present invention and the comparative coupler used in Example 1 in the same manner in place of the magenta coupler of this sample.

The photosensitive material was subjected to imagewise exposure in the same manner as in Example 1, and then subjected to color development in the following processing steps using a paper processor.

The composition of each processing solution is as follows.

Rinse solution (the tank solution and the replenisher are the same) Deionized water (calcium and magnesium are each 3 ppm or less) The definitions of the fresh solution and the running solution are the same as in Example 1.

Evaluation of the photographic properties was performed in the same manner as in Example 1 by treating each sample with a fresh solution and a running solution, and comparing the gradation (γ), the maximum density (Dmax), and the fog density (Dmin). In each case, the difference between the fresh solution and the running solution shown in Example 1 was reduced in all cases, but the tendency between the couplers was the same as in Example 1. Table 2 shows the results of comparison based on relative sensitivity.

The relative sensitivity is a relative value when the sensitivity of the sample A 'is taken as 100, and the sensitivity is represented by a reciprocal of an exposure amount required to give a density obtained by adding 0.5 to the minimum density.

As shown in Table 2, the coupler of the present invention is less susceptible to fluctuations in the composition of the processing solution even in rapid processing than the comparative coupler, and can be said to be an excellent coupler.

(Effect of the Invention) When the coupler of the present invention is used, even if the processing solution composition fluctuates due to continuous processing, the obtained photographic performance (maximum color density, gradation, fog density, sensitivity, etc.) is little changed. Is obtained.

Claims (2)

(57) [Claims] 1. A color image forming method comprising developing a silver halide light-sensitive material containing at least one kind of coupler represented by the following general formula [I] with a developer containing an aromatic primary amine. However, the coupler is not contained in the red-sensitive silver halide emulsion layer of the silver halide light-sensitive material. (Wherein, R ₁ represents an alkyl group, an aralkyl group, a cycloalkyl group or an alkenyl group,, R ₂ represents a hydrogen atom or R ₁ as defined substituents. Moreover, R ₁ and R ₂ are bonded to each other X represents a hydrogen atom or a substituent that is eliminated in a coupling reaction with an oxidized form of an aromatic primary amine developer, Y represents a substituent, and n represents 0. Or an integer of 1 to 4. R ₃ represents an alkyl group or an aryl group.) 2. A silver halide color photographic light-sensitive material comprising at least one kind of coupler represented by the following general formula [I]. However, the coupler is not contained in the red-sensitive silver halide emulsion layer of the silver halide color photographic light-sensitive material. (Wherein, R ₁ represents an alkyl group, an aralkyl group, a cycloalkyl group or an alkenyl group,, R ₂ represents a hydrogen atom or R ₁ as defined substituents. Moreover, R ₁ and R ₂ are bonded to each other X represents a hydrogen atom or a substituent that is eliminated in a coupling reaction with an oxidized form of an aromatic primary amine developer, Y represents a substituent, and n represents 0. Or an integer of 1 to 4. R ₃ represents an alkyl group or an aryl group.)