LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL

Abstract: A silver halide light-sensitive photographic material comprising a support bearing at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer, wherein the green-sensitive silver halide emulsion layer comprises a magenta coupler of formula [M-1]: wherein: Z is a group of non-metallic atoms which, together with the nitrogen and carbon to which it is attached, completes a nitrogen-containing optionally substituted heterocyclic ring; X is a group which is capable of being split off upon a reaction with an oxidation product of a color developing agent; and R is hydrogen or a substituent; and the blue-sensitive silver halide emulsion layer comprises a yellow coupler of formula [Y-I]; wherein: R₂₁ is an alkyl or cycloalkyl group; R₂₂ is an alkyl, cycloalkyl, acyl or aryl group; R₂₃ is a substituent; n is 0 or 1; R₂₄ is an organic group containing a carbonyl or sulfonyl group; J is a wherein R₂₅ is hydrogen or an alkyl, aryl or heterocyclic group; and X₁ is a group which is capable of being split off upon a reaction with an oxidation product of a color developing agent.

Description: The present invention relates to a light-sensitive silver halide color photographic material capable of forming a dye image. The dyes formed have a satisfactory spectral absorption characteristic, exhibit excellent color reproducibility and image preservability and have a maximum density. In light-sensitive silver halide photographic materials for use in making images for direct appreciation, particularly color photographic paper, generally, yellow couplers, magenta couplers and cyan couplers are used in combination as the dye forming couplers. Pyrazoloazole-type magenta couplers have been developed in recent years. The pyrazoloazole-type magenta coupler, unlike 5-pyrazolone-type magenta couplers, which have conventionally been used, has advantages for color reproducibility because the dye formed therefrom has no secondary absorption in the proximity of 430 nm. On the other hand, yellow couplers which are used generally with the above-mentioned magenta coupler have disadvantages that the absorption maximum wavelength of the dye formed therefrom is generally positioned on the longer wave side than the absorption wavelength desirable for color reproducibility, and the absorption of the dye in the longer wavelength region exceeding 500 nm does not sharply diminish to nil. Accordingly, in such a silver halide light-sensitive photographic material, there has been a problem that, even if a pyrazoloazole-type coupler is used as a magenta coupler, color reproducibility for colors such as yellow, green and yellowish green is inadequate due to the above-mentioned disadvantages of the yellow coupler. For this reason, there is demand for a yellow coupler wherein the maximum absorption wavelength of the dye formed therefrom is positioned on the shorter wavelength side and the absorption of the dye in the longer wavelength side exceeding 500 nm sharply diminishes. EP-A-0 267 491 describes a silver halide light-sensitive photographic material which uses a novel two-equivalent-type yellow coupler of formula [Y-I] shown below. The present invention provides a silver halide light-sensitive photographic material comprising a support and, provided thereon, at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer, in which said green-sensitive silver halide emulsion layer contains a magenta coupler having the following Formula [M-1], and said blue-sensitive silver halide emulsion layer contains a yellow coupler having the following Formula [Y-I]: wherein Z is a group of non-metal atoms necessary to form a nitrogen-containing heterocyclic ring, provided that the ring formed by the Z may have a substituent; X is hydrogen or halogen, or a group capable of being split off upon the reaction with the oxidation product of a color developing agent; and R is a hydrogen atom or a substituent; wherein R₂₁ is an alkyl group or a cycloalkyl group; R₂₂ is an alkyl group, a cycloalkyl group, an acyl group or an aryl group; R₂₃ is a group substitutable to the benzene ring; n is an integer of 0 or 1; R₂₄ is an organic group containing one linkage group having a carbonyl or sulfonyl unit; J is a group or a group (wherein R₂₅ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group); and X₁ is a group capable of being split off upon the reaction with the oxidation product of a color developing agent. DETAILED DESCRIPTION OF THE INVENTION In a magenta coupler represented by the foregoing Formula [M-I]: the Z represents a group of non-metal atoms necessary to form a nitrogen-containing heterocyclic ring, provided that the ring formed by the Z may have a substituent. The X is a hydrogen or halogen atom or a group capable of being split off upon the reaction with the oxidation product of a color developing agent. The R is a hydrogen atom or a substituent. The substituent represented by the R, although not particularly restricted, is typified by various groups including alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl and cycloalkyl, and also halogen atoms and cycloalkenyl, alkinyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and heterocyclic thio groups, and in addition, spirocompound residues and cross-linked hydrocarbon compound residues. The alkyl group represented by the R is preferred to be one having from 1 to 32 carbon atoms, which may be in either straight-chain or branched-chain form. The aryl group represented by the R is preferably a phenyl group. The acylamino group represented by the R is generally an alkylcarbonylamino groups or arylcarbonylamino group. The sulfonamido group represented by the R is generally an alkylsulfonylamino group or arylsulfonylamino group. The alkyl and aryl constituents of the alkylthio and arylthio groups represented by the R may be the same as the alkyl and aryl groups, respectively, as defined in the above R. The alkenyl group represented by R preferably has from 2 to 32 carbon atoms, and the cycloalkyl group preferably has from 3 to 12 carbon atoms, and particularly preferably from 5 to 7 carbon atoms. The alkenyl group may be in the either straight-chain or branched-chain form. The cycloalkenyl group represented by the R is one having from 3 to 12 carbon atoms, and particularly preferably from 5 to 7 carbon atoms. The sulfonyl group represented by the R is an alkylsulfonyl group or arylsulfonyl group. The sulfinyl group is generally an alkylsulfinyl group or arylsulfinyl group. The phosphonyl group is an alkylphosphonyl group, alkoxyphosphonyl group, aryloxyphosphonyl group or arylphosphonyl group. The acyl group is generally an alkylcarbonyl group or arylcarbonyl group. The carbamoyl group is generally an alkycarbamoyl group or arylcarbamoyl group. The sulfamoyl group is generally an alkylsulfamoyl group or arylsulfamoyl group. The acyloxy group is generally an alklcarbonyloxy group or arylcarbonyloxy group. The carbamoyloxy group is generally an alkylcarbamoyloxy group or arylcarbamoyloxy group. The ureido group is generally an alkylureido group or arylureido group. The sulfamoylamino group is generally an alkylsulfamoylamino group or arylsulfamoylamino group. The heterocyclic group is preferably a 5- to 7-member heterocyclic group, and is, for example, a 2-furyl group, 2-thienyl group, 2-pyrimidinyl group or 2-benzothiazolyl group. The heterocyclic oxy group is preferably one having a 5- to 7-member heterocyclic ring, such as, 3,4,5,6-tetrahydropyranyl-2-oxy group or 1-phenyltetrazolo-5-oxy group. The heterocyclic thio group is preferably a 5- to 7-member heterocyclic thio group, and is, for example, a 2-pyridylthio group, 2-benzothiazolylthio group or 2,4-diphenoxy-1,3,5-triazolo-6-thio group. The siloxy group is preferably a trimethylsiloxy group, triethylsiloxy group or dimethylbutylsiloxy group. The imido group is preferably a succinic acid imido group, 3-heptadecyl-succinic acid imido group, phthalimido group or glutarimido group. The spiro compound residue is preferably a spiro [3.3] heptan-1-yl. The cross-linked hydrocarbon compound residue is preferably a bicyclo-[2.2.1]heptan-1-yl, tricyclo[3.3.1.1 3,7 ]decan-1-yl or 7,7-dimethyl-bicyclo[2.2.1]heptan-1-yl. The group represented by the X, which is capable of being split off upon the reaction with the oxidation product of a color developing agent, is, for example, hydrogen, a halogen atom (such as chlorine, bromine, fluorine) or an alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, sulfonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyl group, alkyloxalyloxy group, alkoxyoxalyloxy group, alkylthio group, arylthio group, heterocyclic thio group, alkyloxythiocarbonylthio group, acylamino group, sulfonamido group, nitrogen-containing heterocyclic group whose ring is formed by the bonding of an N atom, alkyloxycarbonylamino group, aryloxycarbonylamino group, carboxyl group or a group having the formula: (wherein R₁' is as defined in the foregoing R; Z' is as defined in the foregoing Z; R₂' and R₃' each is a hydrogen atom, an aryl, alkyl or heterocyclic group, for example, but is preferably a halogen atom, and more preferably a chlorine atom. The nitrogen-containing heterocyclic ring formed by the Z or Z' is preferably a pyrazole ring, imidazole ring, triazole ring or tetrazole ring, and the substituent which any of these rings may have includes those as defined in the foregoing R. The magenta couplers having Formula [M-I] include those having the following Formulas [M-II] through [M-VII]: In the above Formulas [M-II] through [M-VII], R₁ through R₈ and X are the same as the foregoing R and X, respectively. Preferred among those having Formula [M-I] are ones having the following Formula [M-VIII]: wherein R₁, X and Z₁ are as defined in the R, X and Z, respectively, of the foregoing Formula [M-I]. Particularly preferred among the magenta couplers having the foregoing Formulas [M-II] through [M-VII] are those magenta couplers having the Formula [M-II]. Most preferred as the substituents R and R₁ to the foregoing heterocyclic ring are those having the following Formula [M-IX]: wherein R₉, R₁₀ and R₁₁ are as defined in the foregoing R. Two out of the R₉, R₁₀ and R₁₁, e.g., R₉ and R₁₀, may combine with each other to form a saturated or unsaturated ring (such as a cycloalkane. cycloalkene or heterocyclic ring), and further R₁₁ may additionally combine with them to form a cross-linked hydrocarbon residue. The preferred compounds of Formula [M-IX] are those (i) where at least two out of R₉ through R₁₁ are alkyl groups and (ii) where one out of R₉ through R₁₁, e.g., R₁₁, is a hydrogen atom and the others, R₉ and R₁₀, combine with each other to form a cycloalkyl group together with the carbon atom at the base. More preferred in the case (i) are those where two out of R₉ through R₁₁ are alkyl groups and the other one is a hydrogen atom or an alkyl group. As the substituent which may be on a ring formed with the Z of Formula [M-I] or on a ring formed with the Z₁ of Formula [M-VIII] and as the R₂ through R₈ of Formulas [M-II] through [M-VI], those having the following Formula [M-X] are preferred: Formula [M-X] -R¹-SO₂-R² wherein R¹ is an alkylene group; and R² is an alkyl group, a cycloalkyl group or an aryl group. The alkylene group represented by the R¹ is a straight-chain or branched-chain alkylene group, the straight-chain portion of which has preferably 2 or more carbon atoms, and more preferably 3 to 6 carbon atoms. The cycloalkyl group represented by the R² is preferred to be a 5- or 6-member cycloalkyl group. The following are typical examples of the compound used in the material of this invention: Aside from these exemplified typical examples of the compound described herein, other additional examples of the compound described herein include the exemplified compounds Nos. 1 through 4, 8 through 17, 19 through 24, 26 through 43, 45 through 59, 61 through 104, 106 through 121, 123 through 162 and 164 through 223 out of those compounds described in pages 66 through 122 of Japanese Patent Application No. 9791/1986. Any of these magenta couplers having the foregoing Formula [M-I] may be easily synthesized by those skilled in the art by making reference to Journal of the Chemical Society, Perkin I (1977), 2047-2052; U.S. Patent No. 3,725,067; Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 99437/1984, 42045/1983, 162458/1984, 171956/1984, 33552/1985, 43659/1985, 172982/1985 and 190779/1985. The magenta coupler described herein may generally be used in the amount range of from 1x10⁻³ mole to 1 mole per mole of silver halide, and preferably from 1x10⁻² mole to 8x10⁻¹ mole. The magenta coupler described herein may be used alone or in combination of two or more kinds thereof, and may also be used in combination with any different other magenta couplers. Subsequently, those yellow couplers having the foregoing Formula [Y-I] will be explained below: In Formula [Y-I], the alkyl group represented by the R₂₁ is, for example, a methyl group, ethyl group, isopropyl group or t-butyl group. Alkyl groups represented by R₂₁ also include those each having a substituent. The substituent is, for example. a halogen atom or an aryl group, alkoxy group, aryloxy group, alkylsulfonyl group, acylamino group, alkoxy group or hydroxy group. The cycloalkyl group represented by the R₂₁ , is, e.g., a cyclopropyl group, cyclohexyl group or adamantyl group. The preferred one as the R₂₁ is a branched-chain alkyl group. In Formula (Y-I], the alkyl and cycloalkyl groups represented by R₂₂ include the same groups as those defined in R₂₁, and the aryl group is, for example, a phenyl group. These alkyl, cycloalkyl and aryl groups represented by R₂₂ also include those each having a substituent the same as those defined for R₂₁. The acyl group is, e.g., an acetyl group, propionyl group, butyryl group, hexanoyl group or benzoyl group. R₂₂ is preferably an alkyl or aryl group, and more preferably an alkyl group. In Formula [Y-I], the benzene ring-substitutable group represented by the R₂₃ is, e.g., a halogen atom (such as chlorine atom) or an alkyl group (such as ethyl, i-propyl, t-butyl), alkoxy group (such as methoxy), aryloxy group (such as phenyloxy), acyloxy group (such as methylcarbonyloxy, benzoyloxy), acylanlino group (such as acetamido, phenylcarbonylamino), carbamoyl group (such as N-methylcarbamoyl, N-phenylcarbamoyl), alkylsulfonamido (such as ethylsulfonylamino), arylsulfonamido group (such as phenylsulfonamino), sulfamoyl group (such as N-propylsulfamoyl, N-phenylsulfamoyl) or imido group (such as succinic acid imido, glutarimido). And the n is 0 or 1. In Formula [Y-I], R₂₄ represents an organic group containing one linkage group having a carbonyl or sulfonyl unit. The group having a carbonyl unit is, e.g., an ester group, amido group, carbamoyl group, ureido group or urethano group, and the sulfonyl unit-having group is, e.g., a sulfo group, sulfonamido group, sulfamoyl group or aminosulfonamido group. The J is a group or group, wherein R₂₅ is a hydrogen atom or an alkyl, aryl or heterocyclic group. The alkyl group represented by R₂₅ is, e.g., a methyl group, ethyl group, isopropyl group, t-butyl group or dodecyl group and the aryl group represented by R²⁵ is a phenyl or naphthyl group. These alkyl, aryl and heterocyclic groups represented by R₂₅ include those each having a substituent. In Formula [Y-I], X₁ is a group capable of being split off upon the reaction with the oxidation product of a color developing agent, and includes those groups having the following Formula [Y-II] or Formula [Y-III]: -OR₂₆ [Y-II] wherein R₂₆ is an aryl group or heterocyclic group, both being allowed to have a substituent. wherein Z₁ is a group of non-metal atoms necessary to form in cooperation with a nitrogen atom a 5- or 6-member ring. Examples of the atom or atomic group necessary to form such the group of nonmetallic atoms include methylene, methine, substituted methine, >C=O, -NH-, -N=, -O-, -S-, and -SO₂. Those two-equivalent yellow couplers represented by Formula [Y-I] may be in the form of a bis-type compound by combining with each other through R₂₁, R₂₃ or R₂₄. The preferred ones as the two-equivalent yellow coupler described herein are those having the following Formula [Y-IV]: wherein R₂₁, R₂₂, R₂₃ and J are as defined in the R₂₁, R₂₂, R₂₃ and J, respectively, of Formula [Y-I]; n is an integer of 0 or 1; R₂₇ is an alkylene group, arylene group. alkylene-arylene group, arylene-alkylene group or -A-V₁-B- group (wherein A and B each is an alkylene, arylene, alkylene-arylene or arylene-alkylene group, and V₁ is a bivalent linkage group such as -O-, -S-, etc. ); R₂₈ is an alkyl group, cycloalkyl group, aryl group or heterocyclic group; P is a linkage group having a carbonyl or sulfonyl unit; and X₂ is the same as the foregoing X₁. In the above Formula [Y-IV], the P is a linkage group having a carbonyl or sulfonyl unit, and more preferably represents the following groups [Y-V]: wherein R' and R'' each is a hydrogen atom or an alkyl group. aryl group or heterocyclic group, provided that R' and R'' may be either the same or different. Those groups represented by the R' or R'' include the same groups as those defined in the foregoing R₂₅, and also include those each having a substituent the same as those defined in the R₂₅. The R' and R'' each is preferably a hydrogen atom. In Formula [Y-IV], the X₂ is a group capable of being split off upon the coupling reaction, and more preferably represents those groups having the following Formulae [Y-VI] through [Y-XII]: wherein R₂₉ is a carboxyl group, ester group, acyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy group or a substituent the same as any of those groups represented by the R₂₃; and 1 is an integer of from 1 to 5, provided that when 1 is 2 or more, the R₂₉s may be the same or different. wherein R₃₀ and R₃₁ each is a hydrogen atom, a halogen atom or an alkyl group, alkoxy group, aryl group. heterocylic group, carboxylic ester group, amino group, acylamino group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonamido group, arylsulfonamido group or carboxylic acid group, and these groups represented by both R₃₀ and R₃₁ may be either the same or different. Also, the R₃₀ and R₃₁ may form together a ring. wherein Z₂ and Z₃ each is a hetero atom; and R₃₂, R₃₃ and R₃₄ each represents groups the same as those defined in the above R₃₀ and R₃₁; R₃₅ is an alkyl group, aryl group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group or arylsulfonyl group. wherein Y is a hetero atom or or a group of hetero atoms (such as -NH-, -N=, -O-, -S-, etc.) or a sulfonyl group, carbonyl group or carbon atom represented by and Z⁴ is a group of non-metal atoms necessary to form in cooperation with the -Y-N-CO- a 5- or 6-member ring. The R₃₆, R₃₇ and R₃₈ each represents groups the same as those respresented by the foregoing R₃₀ or R₃₁. Also, the R₃₆, R₃₇ and R₃₈ may form a ring in cooperation with part of the Z₄. The two-equivalent yellow coupler having the foregoing Formula [Y-IV] may be a bis-type compound formed by combining with each other through the R₂₁, R₂₃ or a ballasting group. The following are typical examples of the yellow coupler having Formula [Y-I] described herein. The yellow coupler described herein may be synthesized in accordance with conventionally known methods, and particularly can be synthesized according to those methods as described in pages 27 through 33 of the publication of Japanese Patent Application No.269216/1986. The yellow coupler described herein may be used alone or in combination, and may also be used in combination with different yellow couplers. In the light-sensitive silver halide photographic material of this invention, the yellow coupler is added in an amount of preferably from 10 to 300 g per mole of silver halide, but the amount may, if necessary, be changed arbitrarily. The incorporation of the magenta coupler and yellow coupler into the light-sensitive silver halide photographic material of this invention may be performed according to any of various methods such as the solid dispersing method, latex dispersing method or oil-in-water-type emulsifiedly dispersing method. For example, in the case of the oil-in-water-type emulsion dispersing method, a hydrophobic additive such as a magenta coupler or yellow coupler is dissolved in a high-boiling solvent having a boiling point of more than about 150°C such as tricresyl phosphate or dibutyl phthalate, if necessary, along with a low-boiling solvent such as ethyl acetate or butyl propionate and/or an water-soluble organic solvent, and the solution is dispersed as an emulsion, using a surface active agent, into a hydrophilic binder such as an aqueous gelatin solution, and the dispersed product is then added to an objective hydrophilic colloid layer. The light-sensitive silver halide photographic material of this invention is applicable to, e.g., color negative and positive films and color photographic paper,; above all, this invention can exhibit its effect significantly when applied to color photographic paper for direct use. The light-sensitive silver halide photographic material of this invention, including color photographic paper, in order to effect the color reproduction according to the subtractive color process, generally has a multilayer construction of green-sensitive, blue-sensitive and red-sensitive silver halide emulsion layers containing the magenta and yellow couplers described herein and a known cyan coupler, respecttively, as photographic couplers, and non-light-sensitive layers, coated in an arbitrary number of layers in arbitrary order on the support thereof, but the number of layers and the coating order may be altered according to the principal characteristics or purposes for which the light-sensitive material is used. Those yellow couplers usable in combination with the yellow coupler described herein include, for example, benzoyl-acetanilide-type and pivaloylacetanilide-type compounds, while those magenta couplers usable in combination with the magenta coupler described herein include pyrazolone-type, pyrazolo-benzimidazole-type and open-chain acylacetonitrile-type couplers. Those cyan couplers usable in the light-sensitive photographic material of this invention include phenol-type and naphthol-type compounds, and concrete examples thereof are described in U.S. Patent Nos. 2,369,929, 2,434,272, 2,474,493, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,971, 3,591,383, 3,767,411 and 4,004,929, West German OLS Patent Nos. 2,414,830 and 2,454,329, Japanese Patent O.P.I. Publication Nos. 59838/1973, 26034/1976, 5055/1973, 146828/1976, 69624/1977 and 90932/1977. In the silver halide emulsion to be used in the light-sensitive silver halide photographic material of this invention, as the silver halide thereof any arbitrary one for use in preparing ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide or silver chloride, The silver halide emulsion described herein may be chemically sensitized by any of the sulfur sensitization method, selenium sensitization method, reduction sensitization method or noble-metal sensitization method, for example. The silver halide emulsion may be optically sensitized to desired wavelength regions by using those dyes known as sensitizing dyes to those skilled in the art in the photographic field. The light-sensitive silver halide photographic material of this invention may use arbitrarily anti-color-stain agent, hardening agent, plasticizer, polymer latex, ultraviolet agent, formal in scavenger, mordant, development accelerator, development retarder, brightening agent, matting agent, lubricant, antistatic agent and surface active agent, for example. The durability of the yellow dye image formed from the light-sensitive silver halide photographic material containing the yellow coupler can be improved, by incorporating an ultraviolet absorbing agent therein. The light-sensitive silver halide photographic material may be processed in arbitrary procedure steps that are used commonly by those skilled in the art, such as the steps comprising color developing, bleaching and fixing or bleach-fix, stabilizing, washing and stopping As has been described, the light-sensitive silver halide photographic material of this invention, since it comprises both the magenta coupler and the yellow coupler is capable of forming magenta and yellow dyes having improved spectral absorption characteristics with the image preservability and color formability thereof retained enough for practical use and thus having a largely improved color reproducibility for all colors. EXAMPLES The present invention will be illustrated further in detail by the following examples. EXAMPLE-1 (Preparation of Silver Halide Emulsions) Three different silver halide emulsions were prepared as given in Table 1 by the neutral process and the simultaneously mixing method. Emulsion No. AgCl % AgBr % Average grain size µm Chemical sensitizer Spectral sensitizer Em-1 99.5 0.5 0.67 Sodium thiosulfate SD-1 Em-2 99.5 0.5 0.46 '' SD-2 Em-3 99.5 0.5 0.43 Chloro- auric acid SD-3 To each of the silver halide emulsions, after being chemically sensitized, was added 5x10⁻³ mole per mole of silver halide of the following emulsion sensitizer STB-1. (Preparation of Light-Sensitive Silver Halide Color Photographic Material Samples) Subsequently, the following layers 1 through 7 were simultaneously coated in the described order on a both-side-polyethylene-laminated paper support, whereby light-sensitive silver halide color photographic material samples Nos. 1 through 15 were prepared. (In the following examples, every adding amount is indicated in an amount per m² of the light-sensitive material.) Layer 1 A layer containing 1.2 g of gelatin, 0.29 g (silver equivalent) of the blue-sensitive silver halide emulsion (Em-1) and 0.3 g of dinonyl phthalate (DNP) into which are dissolved 1.0 millimole of the yellow coupler given in Table-2, 0.3 g of a stabilizer ST-1 and 0.015 g of 2,5-dioctylhydroquinone (HQ-1). Layer 2 A layer containing 0.9 g of gelatin and 0.2 g of DOP (dioctyl phthalate) into which is dissolved 0.04 g of HQ-1. Layer 3 A layer containing 1.4 g of gelatin, 0.2 g of the green-sensitive silver halide emulsion (Em-2), 0.3 g of DOP into which are dissolved 0.9 millimole of the magenta coupler given in Table-2, 0.25 g of a stabilizer ST-2, 0.3 g of ST-3 and 0.01 g of HQ-1, and 6 mg of the following filter dye AI-1. Layer 4 A layer containing 1.2 g of gelatin and 0.3 g of DNP into which are dissolved 0.6 g of the following ultraviolet absorbing agent UV-1 and 0.05 g of HQ-1. Layer 5 A layer containing 1.4 g of gelatin, 0.20 g of the red-sensitive silver halide emulsion (Em-3) and 0.3 g of DOP into which are dissolved 0.54 g of a cyan coupler (C-1) , 0.01 g of HQ-1 and 0.3 g of ST-1. Layer 6 A layer containing 1.1 g of gelatin, 0.2 g of DOP into which is dissolved 0.2g of UV-1, and 5mg of the following filter dye AI-2. Layer 7 A layer containing 1.0g of gelatin and 0.05 g of sodium 2,4-dichloro-6-hydroxytriazine. Each of the obtained samples was exposed through an optical wedge to separate monochromatic blue, green and red lights by using a sensitometer KS-7 (manufactured by Konishiroku Photo Industry Co., Ltd.), and then processed in accordance with the following color developing procedure, and after that, each of the processed samples was measured with respect to the maximum densities (Dmax) of the green-sensitive emulsion layer and blue-sensitive emulsion layer thereof by using an optical densitometer PDA-65 (manufactured by Konishiroku Photo Industry Co., Ltd.). Also, the obtained samples each was subjected to a 15-day discoloration test in a fade-o-meter®, and the residual rate (%) of the dye image at the initial density of 1.0 was found with respect to each of the blue-sensitive emulsion layer and green-sensitive emulsion layer to thereby evaluate the resistance to light thereof. In addition, a Color Checker (manufactured by Macbeth Co.) was photographed with use of Sakuracolor SRV-100 film (manufactured by Konishiroku Photo Industry Co.. Ltd.), and the film was processed, and the thus obtained negative, after adjusting the tone of its image portion corresponding to the grey area, was used to print its image on each of the above-obtained samples to thereby evaluate the color reproducibility for the respective colors. The obtained results are shown in Table-2. Processing Steps Temperature Time Color developing 34.7 ± 0.3°C 45 seconds Bleach-fix 34.7 ± 0.5°C 50 seconds Stabilizing 30 to 34°C 90 seconds Drying 60 to 80°C 60 seconds [Color Developer Solution] Pure water 800 ml Triethanolamine 8 g N,N-di-ethylhydroxyamine 5 g Potassium chloride 2 g N-ethyl-N-β-methansulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5 g Sodium tetrapolyphosphate 2 g Potassium carbonate 30 g Potassium sulfite 0.2g Brightening agent (4,4'-diaminostilbene-disulfonic acid derivative) 1 g Pure water to make 1 liter. Adjust the pH to 10.2. [Bleach-Fix Bath] Ferric-ammonium ethylenediaminetetraacetate dihydrated 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (aqueous 70 % solution) 100 ml Ammonium sulfite (aqueous 40 % solution) 27.5 ml Use potassium carbonate or glacial acetic acid to adjust the pH to 5.7, and add water to make 1 liter. [Stabilizer Bath] 5-Chloro-2-methyl-4-isothiazolin-3-one 1 g 1-Hydroxyethyliden-1,1-diphosphonic acid 2 g Water to make 1 liter. Use sulfuric acid or potassium hydroxide to adjust the pH to 7.0. As is apparent from the results shown in Table-2, in comparison with Sample No. 1, in which the non-invention yellow coupler and magenta coupler are used, Sample No. 2, in which the magenta coupler alone is replaced by the pyrazole-type coupler of this invention, is recognized to have been improved on the color reproducibility for the respective blue, green, red and magenta colors, while Sample No. 3, in which the yellow coupler alone is replaced by the yellow coupler of formula [Y-I], is recognized to have been improved on the color reproducibility for the respective green, yellow and yellow-green colors. However, any of the above samples are not considered to have adequate colors from the stand point of color reproducibility, so that they cannot be regarded as photographic light-sensitive materials collectively excellent in the color reproducibility. In contrast, Samples Nos. 4 through 15, in which the magenta coupler and yellow coupler described herein are used, are excellent in the color reproducibility for all colors, so that they prove the effect of this invention to be excellent. Further, as is apparent from Table 2, Samples Nos. 4 through 15, in which both the magenta coupler and the yellow coupler as described herein are combinedly used, have sufficiently high maximum densities as compared with those of Samples No. 1 through 3, in which the non-invention magenta coupler and/or the non-invention yellow coupler are used, and in addition, in the resistance to light, the former samples are equal to or better than the latter samples.

Claims: A silver halide light-sensitive photographic material comprising a support bearing at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer, wherein the green-sensitive silver halide emulsion layer comprises a magenta coupler of formula [M-1]: wherein: Z is a group of non-metallic atoms which, together with the nitrogen and carbon to which it is attached, completes a nitrogen-containing optionally substituted heterocyclic ring; X is hydrogen or halogen, or a group which is capable of being split off upon a reaction with an oxidation product of a color developing agent; and R is hydrogen or a substituent; and the blue-sensitive silver halide emulsion layer comprises a yellow coupler of formula [Y-I]; wherein: R₂₁ is an alkyl or cycloalkyl group; R₂₂ is an alkyl, cycloalkyl, acyl or aryl group; R₂₃ is a substituent; n is 0 or 1; R₂₄ is an organic group containing a carbonyl or sulfonyl group; J is a group wherein R₂₅ is hydrogen or an alkyl, aryl or heterocyclic group; and X₁ is a group which is capable of being split off upon a reaction with an oxidation product of a color developing agent. A silver halide light-sensitive photographic material according to claim 1 wherein the nitrogen-containing heterocyclic ring is a pyrazole, imidazole, triazole or tetrazole ring. A silver halide light-sensitive photographic material according to claim 1 or 2, wherein R is hydrogen, a halogen or an alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl or heterocyclicthio group, a spiro compound residue or a cross-linked hydrocarbon compound residue. A silver halide light-sensitive photographic material according to any one of claims 1 to 3 wherein X is hydrogen, a halogen or an alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclicthio, alkyloxythiocarbonylthio, acylamino, sulfonamido, nitrogen-containing heterocyclic bonded by a ring-nitrogen atom, alkyloxycarbonylamino, aryloxycarbonylamino or carboxyl group or a group of formula; wherein: R₁' is as defined for R in claim 1 or 3; Z' is as defined for Z in claim 1; and R₂' and R₃' are each independently hydrogen or an aryl, alkyl or heterocyclic group. A silver halide light-sensitive photographic material according to any one of claims 1 to 4 wherein the magenta coupler is of one of the following formulae: wherein: R₁ is as defined for R in claim 1 or 3; each of R₂ to R₈ is hydrogen or a substituent; and X is as defined in claim 1 or 4. A silver halide light-sensitive photographic material according to any one of claims 1 to 4 wherein the magenta coupler is of formula [M-VIII]: wherein: R₁ is as defined for R in claim 1 or 3; X is as defined in claim 1 or 4; and Z₁, together with the two nitrogens to which it is attached and the carbon to which the two nitrogens are attached, completes a nitrogen-containing optionally substituted heterocyclic ring.

Inventors: HIRABAYASHI, SHIGETO, MIZUKURA, NOBORU, TSURUTA, MAYUMI
Applicants: KONICA CORPORATION
Application year: 1988
Main classification: G03C7
IPC codes: G03C7