SILVER HALIDE COLOR PHOTO-SENSITIVE MATERIAL

Abstract: A silver halide color photographic light-sensitive mate­ rial comprising a reflective support bearing thereon a green light-sensitive silver halide emulsion layer containing a magenta forming coupler of formula (I) wherein R₁ is a tertiary alkyl group; R₂ is an alkyl group or an aryl group and X is a releasable group other than hydrogen which is susceptible to displacement by reaction of the compound of formula (I) with the oxidation products of a color developing agent; a blue light-sensitive silver halide emulsion layer containing a yellow-forming coupler of formula (II) wherein X₁ is a halogen, an alkoxy group or an alkyl group; Y₁ is a group capable of displacement by formation of a dye during a coupling reaction of the compound of formula (II) with the oxidation products of an aromatic primary amine color developing agent; R₄ is a substituent for a benzene ring and n is an integer of 1 or 2 and a red light-sensitive silver halide emulsion layer containing a cyan-forming coupler of formula (III) or (IV) wherein R₅ is an alkyl group having 1 to 4 carbon atoms; R₆ is hydrogen or an alkyl group having 1 to 15 carbon atoms and R₇ is a halogen, an alkyl group, a hydroxy group or an acyloxy group wherein R₈ is an alkyl group, a halogen, a sulfonamido group, a sulfamoyl group, an arylsulfonyl group, or a hydroxy group; R₉ is hydrogen or an alkyl group and R₁₀ is hydrogen, a halogen, an alkyl group, a sulfamoyl group or a sulfonamido group.

Description: BACKGROUND OF THE INVENTION This invention relates to a silver halide color photo-sensitive material capable of displaying a high color-developability and producing an image having a high preservability and in particular an excellent color-fastness to light. Generally, in a silver halide color photosensitive material, a dye-image may be obtained in that exposed silver halide grains are reduced by making use of an aromatic primary amine color developing agent and the resulting oxidation products of the above-mentioned color developing agent are coupled to the couplers for producing yellow, magenta or cyan dyes, respectively. There are generally known an open-chained ketomethylene yellow coupler for forming the above-mentioned yellow dyes; a pyrazolone magenta coupler and an 1H-pyrazolo[3,2-c]-s-triazole magenta coupler for forming the magenta dyes; and a phenol cyan coupler, a naphthol cyan coupler or the like for forming the cyan dyes. Such couplers as mentioned above and the dyes obtained therefrom should satisfy various requirements when they are to be put into practical use. The couplers are, for example, required to possess as high as possible a coupling rate, i.e., the color developability, when they couple to the oxidation products of a color developing agent; and the couplers and the dyes obtained therefrom are required to be stable for long preservation, in particular against light, i.e., a color-fastness to light; and the couplers are also required to possess as low as possible unnecessary side or collateral absorption. If the above-mentioned requirements should be satisfied by only some part of the yellow, magenta and cyan coulers, unbalanced colors will appear. It is, therefore, necessary for all these requirements to be satisfied where all the three kinds of couplers are in combination. The conventional dyes produced from yellow, magenta or cyan couplers have so far been disadvantageous in that the color fastness to light thereof is unsatisfactory and an unbalance of colors is caused by the irradiation of light for a long time because the three kinds of dyes are different from each other in their color fastness to light. SUMMARY OF THE INVENTION It is an object of the invention to provide a silver halide color photo-sensitive material not only capable of keeping stable over a long preservation time and in particular the color-balance even when it is irradiated by light for a long time, but also capable of displaying an excellent color developability. The above-mentioned objects of the invention have, to a large extent, been attained by a silver halide color photo-sensitive material, which forms the subject of the present invention, comprising a reflective support bearing thereon a green-sensitive silver halide emulsion layer containing a magenta coupler having the following Formula (I), a blue-sensitive silver halide emulsion layer containing a yellow coupler having the following Formula (II), and a red-sensitive silver halide emulsion layer containing a cyan coupler having the following Formula (III) or (IV). Formula (I) wherein R₁ represents a substituent connected via tertiary carbon atom; R₂ represents an alkyl group or an aryl group; and X represents a split-off group other than hydrogen, which is capable of splitting off through a reaction with the oxidation products of a color developing agent. Formula (II) wherein X₁ represents a halogen, an alkoxy group or an alkyl group; Y₁ represents a group capable of splitting off when a dye is formed by coupling the group with the oxidation products of an aromatic primary amine color developing agent; R₄ represents a substituent for a benzene ring; and n is an integer of 1 or 2. Formula (III) wherein R₅ represents an alkyl group having 1 to 4 carbon atoms; R₆ represents hydrogen or an alkyl group having 1 to 15 carbon atoms; and R₇ represents a halogen, an alkyl group, a hydroxy group or an acyloxy group. Formula (IV) wherein R₈ represents an alkyl group, a halogen, a sulfonamido group, a sulfamoyl group, an arylsulfonyl group, or a hydroxy group; R₉ represents hydrogen or an alkyl group; and R₁₀ represents hydrogen, a halogen, an alkyl group, a sulfamoyl group or a sulfonamido group. EP-A-0095722 discloses a similar material except that the magenta coupler is a pyrazole-type coupler. DE-A-3339201 and FR-A-2075583 discloses IH-pyrazole (3,2-c) S-triazole magenta couplers. EP-A-0178788, which may form part of the state of the art by virtue of Article 54(3) EPC discloses silver halide color photographic materials which have at least one silver halide emulsion layer on a support, the layer containing at least one magenta coupler of formula (I) in which R₁ is a tertiary alkyl group, R₂ is a secondary or tertiary alkyl group and X is as defined above. DETAILED DESCRIPTION OF THE INVENTION Now, the invention will be described in more detail. The magenta couplers used in the invention can be represented by the following Formula (I); Formula (I) wherein R₁ represents a substituent connected via a tertiary carbon atom, typically a tertiary alkyl group; R₂ represents an alkyl group or an aryl group; and X represents a split-off group other than hydrogen, which is capable of splitting off through a reaction with the oxidation products of a color developing agent. The tertiary carbon atom of the group R₁ can be substituted by an alkyl group, an aryl group such as a phenyl group, or an alkoxy group, for example. In addition, the tertiary carbon atom can form part of another cyclic group. Furthermore, an alkyl group attached to the tertiary carbon atom can be substituted by a halogen atom or an alkoxy group, for example. Such groups include tert-butyl, 1,1-dimethyl-2-methoxyethyl, 1,1-dimethyl-2-chloroethyl, 1-methyl-1-methoxyethyl, 1-methyl-1-phenylethyl, 1,1-di-n-amylhexyl, 7,7-dimethylnorbornan-1-yl, 1,1-dimethylbutyl, 1-ethyl-1-methylpropyl, and adamantyl groups. The alkyl group represented by R₂ can be a methyl, primary alkyl, or branched secondary or tertiary alkyl group. The primary alkyl group represents an alkyl group in which two hydrogen atoms are attached to the linking carbon; the secondary alkyl group represents an alkyl group in which one hydrogen atom is attached to the linking carbon; and the tertiary alkyl group represents an alkyl group in which no hydrogen atom is attached to the linking carbon. An alkyl group represented by R₂ can be substituted by, for example, an aryl group, heterocyclic group, a halogen atom, cyano group; substituents linked through a carbonyl group such as alkoxycarbonyl, acyl or carbamoyl groups; and substituents linked through a hetero atom such as nitro, alkoxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl and dialkylamino groups. However, such a substituent group is preferably selected from among alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, and arylsulfinyl groups. An aryl group represented by R₂ is preferably a phenyl group. Further, needless to say, magenta-forming couplers in the invention include also bis-type 1H-pyrazolo[3,2-c]-s-triazole compounds, which are formed when the heterocyclic residue is a 1H-pyrazolo[3,2-c]-s-triazole-3-yl residue. The split-off group represented by X can be, for example, a halogen atom, or an organic group linked in a coupling position, through an oxygen, nitrogen, or sulfur atom. Among such split-off groups those linked through an oxygen atom include alkoxy, aryloxy, acyloxy, and heteroclycloxy groups. Those linked, in the coupling position, via a nitrogen atom include acylamino, diacylamino, and sulfonamido groups, and the nitrogen-containing 5- or 6-membered heterocyclic groups. Those linked, in the coupling position, through an sulfur atom include thiocyano, alkylthio, arylthio, heterocyclothio, arylsulfonyl, and alkylsulfonyl groups. Exemplary compounds represented by Formula (I) are listed below. Exemplary compounds (1) to (24): Description of typical synthetic processes of the above couplers of the invention is given below. The experimental synthesis was carried out on referring to the descriptions in Research Disclosure, No. 12443; Journal of the Chemical Society, Perkin I, 1977, P. 2047-2052; U.S. Patent No. 3,725, 067; and Japanese Patent O.P.I. Publication No. 99437/1984. Synthesis of Exemplary Compound (1): The reaction scheme of the synthesis of Exemplary Compound (1) is represented as follows: Synthesis of (I) Seventy grams (70g) of 1-methyl-2-octadecylsulfonylpropionic acid, and 10g of thiocarbohydrazide are refluxed for about 30 minutes in methyl cellosolve solution. After cooling, the precipitated crystals are filtered off, and recrystallized from an ethanol/water mixed solvent to obtain (I). Synthesis of (II) A solution of 8.8g of (I), and 3.6g of tert-butyl bromomethyl ketone in 200 ml of ethanol is boiled for 6 hours under stirring. After cooling, the precipitated crystals are filtered off, and dissolved into methanol. After adjusting pH of the solution to 8 by adding 10% sodium carbonate solution, the precipitated crystals are filtered off, and washed well. The crystals obtained are recrystallized from ethanol containing a small amount of water to obtain (II) . Synthesis of (III) Six grams (6g) of (II) is dispersed into 500 ml of n-dodecane, and boiled for 3 hours in a stream of nitrogen under stirring. After cooling, the precipitated solid matter is filtered off and recrystallized from acetonitrile. Synthesis of (IV) Three grams (3g) of (III) is dissolved into chloroform, mixed with the equivalent quantity of N-chlorosuccinimide, and made to react together at 20°C for 30 minutes. Then, the resulting mixture is washed with dilute alkali solution to remove by-produced succinimide. After distilling off the chloroform, the residue is purified by column chromatography using silica gel carrier, and benzene/acetone developing solvent. The product is identified as exemplary compound (1) with nuclear magnetic resonance spectrometry. Other 1H-pyrazolo[3,2-c]-s-triazole residues without X as a split-off group were synthesized according to similar manners to those in the above synthesis of (I). Exemplary Compounds (4), (6), (12), (14) and (21) were synthesized according to the description in U.S. Patent No. 3,725,067. Exemplary Compounds (8), (11), (15), (16), (18) and (22) were synthesized on referring to the general synthetic method described in Japanese Patent O.P.I. Publication No. 99437/1984. The yellow-developing couplers used in the invention can be represented by the following Formula (II); Formula (II) where X₁ is a halogen atom such as a chlorine atom: an alkoxy group such as a methoxy group and a ethoxy group; or an alkyl group such as a methyl group, and a ethyl group. Y₁ is a group (a split-off component) which is split-off, when the coupler couples to the oxidation product of a color developing agent of aromatic primary amine type to form a dye. Y₁ is preferably an aryloxy group, a heterocycloxy group, or the following group: where Z₁ represents a group of atoms which is selected from carbon, oxygen, nitrogen and sulfur atoms, so as to form a 5- or 6-membered ring with the nitrogen atom in this formula; R₄ represents a substituent for the benzene ring; and n is 1 or 2, provided that R₄ can be either the same or different when n is 2. R₄ is a halogen atom (for example, F, Cl or Br), or one of the following groups; where R ' / 4, R '' / 4 and can be the same or different from each other, and each of them represents a hydrogen atom or an alkyl group, aryl group, or heterocyclic group (each group can be substituted). They are preferably R ' / 4 CONH-, R ' / 4SO₂NH-, or R ' / 4OCONH- (where R ' / 4 is an alkyl group, and can be substituted). They are most preferably R ' / 4 CONH-, where R ' / 4 is an alkyl group having a substituent. When Y₁ is an aryloxy group, the aryl portion thereof is preferably the phenyloxy group which can be substituted. Thus, the aryloxy group is preferably a phenoxy, 4-carboxyphenyloxy or 4-(4-benzyloxybenzenesulfonyl)-phenyloxy group. When Y₁ is a heterocycloxy group, it is a 1-phenyl-5-tetrazolyloxy group, isoxazolyloxy group, or 4-pyridinyloxy group, for example. When Y₁ is a group represented by it is one of the following groups, for example: Typical compounds used as the yellow-developing couplers represented by Formula (II) are listed as follows; The splitting-off component of the yellow-developing coupler which is used in combination with a magenta-developing coupler is preferably a group represented by: where B represents a group of atoms necessary for forming a 5-membered ring with the combination of carbon-nitrogen or carbon-oxygen interposed between the two carbonyl groups. Then the split-off component of the group is preferably the above Y-5, Y-6, Y-7 or Y-21, for example. The split-off components of Y-1, Y-8, and Y-13 also are preferable for displaying the same effects, but less significantly. The yellow developing couplers are preferably the above compounds Y-1, Y-5, Y-6, Y-7, Y-8, or Y-9. The cyan-developing couplers are represented by the following Formula (III) or (IV); Formula (III) where R₅ is a C₁ to C₄ alkyl group; R₆ is a hydrogen atom, or C₁ to C₁₅ alkyl group. R₇ is a halogen atom, alkyl group, hydroxy group, or acyloxy group, or, in addition a combination of two or more of them in case of polysubstitution. The position of R₇ on the benzene ring is not specified. The C₁ to C₄ alkyl group represented by R₅ is preferably a methyl, ethyl, propyl, isopropyl, or butyl group. The C₁ to C₁₅ alkyl group represented by R₆ is a straight or branched alkyl chain, and is preferably a methyl, ethyl, propyl, isopropyl, butyl, octyl, decyl or dodecyl group. When R₇ is a halogen atom, it is preferably chlorine. When R₇ is an alkyl group, it can be either aliphatic or alicyclic, and preferably a pentadecyl, tert-amyl, or cyclopentyl group. When R₇ is an acyloxy group, it is preferably an aliphatic acyloxy group. When R₇ represents a combination of two or more groups, preferred combinations include 2,4-di-tert-butyl; 2,4-di-tert-acyl; 4-chloro-2-(1-methyl-tridecyl); 2-pentyl-4-tert-butyl; or 4-hydroxy-3-tert-butyl. Formula (IV) where R₈ is a halogen atom, or an alkyl, sulfonamido, sulfamoyl, arylsulfonyl, or hydroxy group; R₉ is a hydrogen atom, or an alkyl group; R₁₀ is a hydrogen or halogen atom, or an alkyl, sulfamoyl, or sulfonamido group. R₈ and R₁₀ can be present more than once in which case the substituents can be the same or different. The position of R₈ on the benzene ring is not specified. Such is also the case for R₁₀. The alkyl group represented by R₈ can be either aliphatic or alicyclic, and is preferably a tert-butyl, tert-amyl, pentadecyl, or cyclopentyl group. The halogen atom represented by R₈ can be chlorine, bromine, or fluorine, but is preferably chlorine. When R₈ represents a sulfonamido group, it is an alkylsulfonamido group, or an arylsulfonamido (preferably substituted or unsubstituted phenylsulfonamido) group. The alkylsulfonamido group is preferably an aliphatic alkylsulfonamido group. When R₈ represents a sulfamoyl group, it is generally an alkylsulfamoyl, dialkylaminosulfamoyl, or arylsulfamoyl (preferably substituted or unsubstituted phenylsulfamoyl) group. Said alkylsulfamoyl group is preferably an aliphatic alkylsulfamoyl group. The dialkylaminosulfamoyl group is typically a dimethylaminosulfamoyl group. In the arylsulfonyl group represented by R₈, the aryl group is preferably a phenyl group. Then the arylsulfonyl group is preferably a p-hydroxyphenylsulfonyl group. The alkyl group represented by R₉ is a straight or branched alkyl chain, and is preferably a methyl, ethyl, propyl, isopropyl, butyl, octyl, decyl or dodecyl group. When R₁₀ is a halogen atom, it can be chlorine, bromine, or fluorine, but is preferably chlorine or fluorine. The alkyl group represented by R₁₀ is a straight or branched alkyl chain. When R₁₀ represents a sulfonamido group, it is an alkylsulfonamido group, or an arylsulfonamido (preferably substituted or unsubstituted phenylsulfonamido) group. The alkylsulfonamido group is preferably an alphatic alkylsulfonamido group. When R₁₀ represents a sulfamoyl group, it is an alkylsulfamoyl group, or an arylsulfamoyl (preferably substituted or unsubstituted phenylsulfamoyl) group. The alkylsulfamoyl group is preferably an aliphatic alkylsulfamoyl group. Exemplary compounds represented by the Formula (III) are listed as follows. Exemplary compounds represented by the Formula (IV) is listed as follows: The cyan-developing couplers represented by Formula (III) or (IV) can be used either singly or in combination with each other. As for the magenta-developing couplers, each of these couplers can be used either singly or in combination. In addition, it can be used in combination with well-known conventional couplers including pyrazolone, indazolone, cyanoacetyl, pyrazolinobenzimidazole, and pyrazolotriazole compounds. Further, a colored coupler having a color correcting effect, or a coupler (DIR coupler) releasing a development inhibitor, can be used in combination with the specified coupler if necessary. The specified magenta-forming coupler, and other couplers used in combination with said magenta-forming coupler can be incorporated into a silver halide emulsion layer according to well-known methods including the method described in U.S. Patent No. 2,322,027. The couplers are, for example, dissolved in a a solvent such as an alkyl phthalate such as dibutyl phthalate, and dioctyl phthalate; phosphoric acid ester such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctyl butyl phosphate; citric acid ester such as tributyl acetylcitrate; benzoic acid ester such as octyl benzoate; alkylamide such as diethyllauramide; aliphatic acid ester such as dibutoxyethyl succinate, and dioctyl azelate; trimesic acid ester such as tributyl trimesate; and an organic solvent boiling at about 30 to 150°C such as ethyl acetate, butyl acetate, ethyl propionate, sec-butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, and methyl cellosolve acetate, and then dispersed into a hydrophilic colloid. As a solvent, a mixture of a higher-boiling solvent, and a lower-boiling solvent among the above can be used. In addition, the dispersing process with polymer, described in Japanese Patent Examined Publication No. 39853/1976, and Japanese Patent O.P.I. Publication No. 59943/1976, also can be used. The magenta-forming coupler is typically added to a silver halide emulsion in the range of 0.005 to 2 moles per mole of silver halide and preferably 0.03 to 0.5 moles per mole of silver halide. While the dye image formed by the magenta-forming coupler generally exhibits a strong light-resistance by itself, the light resistance can be further improved by means of the combined use of an antifading agent, or by the addition of a UV absorber-containing layer on the upper side. As such an antifading agent, there are cited, for example, hydroquinone derivatives described in U.S. Patent Nos. 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659 2,732,300, 2,735,765, 2,710,801 and 2,816,028, and British Patent No. 1,363,921; gallic acid derivatives described in U.S. Patent Nos. 3,457,079 and 3,069,262; p-alkoxyphenol compounds described in U.S. Patent Nos. 2,735,765, and 3,698,909, and Japanese Patent Examined Publication Nos. 20977/1974 and 6623/1977; p-hydroxyphenol derivatives described in U.S. Patent Nos. 3,432,300, 3,573,050, 3,574,627 and 3,764,337, and Japanese Patent O.P.I. Publication Nos. 35633/1977, 147434/1977 and 152225/1977, and bisphenol compounds described in U.S. Patent No. 3,700,455. As the above UV absorber, there can be cited, for example aryl-substituted benzotriazole compounds described, for example, in U.S. Patent No. 3,533,794; 4-thiozolidone compounds described, for example, in U.S. Patent Nos. 3,314,794 and 3,352,681; benzophenone compounds described, for example, in Japanese Patent O.P.I. Publication No. 2784/1971; cinnamic acid ester compounds described, for example, in U.S. Patent Nos. 3,705,805 and 3,707,375; butadiene compounds described, for example, in U.S. Patent No. 4,045,229; benzoxidole compounds; and compounds described in U.S. Patent No. 3,499,762, and Japanese Patent O.P.I. Publication No. 48535/1979. As silver halide used in the silver halide emulsion in the invention, there can be cited those used commonly in silver halide emulsions in the art such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Silver halide used in the invention can be spectrosensitized by an appropiately selected sensitizing dye so as to be provided with the color sensitivity to the light of the required range of wavelength. Suitable sensitizing dyes include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonole dyes. Especially useful sensitizing dyes are those described, for example, in West German Patent No. 929,080; U.S. Patent Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656.959, 3,672,897, 3,694,217, 4,025,349 and 4,046,572; British Patent No. 1,242,588; and Japanese Patent Examined Publication Nos. 14030/1969 and 24544/1977. While these sensitising dyes can be present either singly or in combination, they are often used in combination for the purpose of intensive sensitization, as typically shown, for example, in U.S. Patent Nos. 2,688,545, 2,977,229, 3,897,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862 and 4,026,707; British Patent Nos. 1,344,281 and 1,507,803; Japanese Patent Examined Publication Nos. 4936/1968 and 12375/1978; and Japanese Patent O.P.I. Publication Nos. 110618/1977 and 109925/1977. Silver halide emulsions used in the invention can contain various well-known photographic additives described, for example, in Research Disclosure, No. 17643. The support of the silver halide color photo-sensitive material of the invention can be selected from among well-known materials including plastic film, plastic-laminated paper, baryta paper, and synthetic paper, according to the intended purpose. The silver halide color photo-sensitive material of the invention can have arbitrarily any layer structure used in the present art. The silver halide color photo-sensitive material of the invention can be submitted to various color developing processes after exposure. Color developing agents of the aromatic primary amine type which can be used include well-known compounds widely used in various color photographic processings. These developing agents include both aminophenol derivatives, and p-phenylenediamine derivatives. In general, these compounds are used in the form of a salt such as the hydrochloride, and sulfate rather than in the form of free amine, because of more stable nature of the salt. They are usually used at concentrations from 0.1 to 30 grams, and preferably from 1 to 1.5 grams, per liter of developer. The developing agents of aminophenol type include o-aminophenol, p-aminophenol, 5-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene, and 2-hydroxy-3-amino-1,4-dimethylbenzenyl, for example. Especially useful color developing agents of aromatic primary amine type are N,N'-dialkyl-p-phenylenediamine compounds, whose alkyl groups and/or phenylene group can have various substituent groups. Thus, especially useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino) toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethlaminoaniline, 4-amino-3-methyl-N,N'-diethylaniline, and 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline p-toluenesulfonate, for example. A color developer used in processing the material of the invention can contain, besides the above color developing agent of aromatic primary amine type, various additives, which are commonly added to color developers, such as sodium hydroxide, sodium carbonate, potassium carbonate, and other alkaline agents; alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water-softening agents, and thickening agents. The pH of the color developer is usually more than 7.0, and very often 10 to 13. After color development, the silver halide photo-sensitive material of the invention can be treated by a processing solution capable of fixing the color. When the processing solution is a fixer, the material is preliminarily submitted to a bleaching treatment. A metal complex of an organic acid is typically used as a bleaching agent in the bleaching solution or bleach-fix solution used in the bleaching process. Such a metal complex is capable of oxidizing metallic silver, formed through the developing process, to silver halide, and of color-developing undeveloped part of the color developing agent at the same time. The metal complex is formed by coordinating a metal such as iron, cobalt, or copper to an organic acid such as an aminopolycarboxylic acid, oxalic acid, and citric acid. The organic acid is preferably a polycarboxylic acid, or aminopolycarboxylic acid. The polycarboxylic acid or aminopolycarboxylic acid is useful also in the form of its alkali metal or ammonium salt, or water-soluble amine salt. Thus organic acids, and their salts useful to form metal complexes include the following typical compounds: (1) Ethylenediaminetetraacetic acid (2) Diethylenetriaminepentaacetic acid (3) Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid (4) Propylendiaminetetraacetic acid (5) Nitrilotriacetic acid (6) Cyclohexanediaminetetraacetic acid (7) Iminodiacetic acid (8) Dihydroxyethylglycinecitric acid (or - succinic acid) (9) Ethyletherdiaminetetraacetic acid (10) Glycoletherdiaminetetraacetic acid (11) Ethylenediaminetetrapropionic acid (12) Phenylenediaminetetraacetic acid (13) Disodium ethylenediaminetetraacetate (14) Tetratrimethylammoium ethylenediaminetetraacetate (15) Tetrasodium ethylenediaminetetraacetate (16) Pentasodium diethylenetriaminepentaacetate (17) Sodium ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetate (18) Sodium propylenediaminetetraacetate (19) Sodium nitrilotriacetate (20) Sodium Cyclohexanediaminetetraacetate The beaching solution used in said processing can contain various additives besides the above organic acid salts. Such additives especially include an alkali metal or ammonium halide as a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide; metal salts; and sequestering agents. The bleaching solution can contain also various other additives well-known as common bleaching solution additives, such as borates, oxalates, acetates, carbonates and phosphates as pH buffer agent; alkylamines; and polyethylene oxide compounds. Further, the fixer or bleach-fix solution can contain, either singly or in combination, a pH buffer composed of sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite; boric acid, borax, sodium hydroxide, potassium hydroxide, ammonium hydroxide; salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and sodium acetate; acetic acid, and ammonium hydroxide. When the bleach-fix processing is conducted while more bleach-fix solution is added to the bleach-fix bath, such salts as thiosulfates, thiocyanates, and bisulfites can be present either in said bleach-fix bath, or the supplementary bleach-fix solution. In the invention, it is allowed, for the purpose of improving the activity of the bleach-fix solution, that air or oxygen is blown into either bath or storage vessel of the solution, or that an oxidizing agent such as hydrogen peroxide, bromate, and persulfate is added. EXAMPLE Each of the Samples of silver halide color photo-sensitivity material listed in Table 1 was prepared by applying the following layers on polyethylene resin-coated paper containing anatase titanium dioxide, in the described order. Each quantity is represented as mg per 100 cm² of the paper. Layer 1 ... A layer which contains (1) 20 mg of gelatin, (2) blue-sensitive silver chlorobromide emulsion (5mg as Ag), and (3) 8mg of Y-coupler, and 0.1 mg of 2.5-di-tert-octylhydroquinone dissolved in 3 mg of dioctyl phthalate. Layer 2 ..... An intermediate layer which contains (1) 12 mg of gelatin, and (2) 0.5 mg of 2,5-di-tert-octylhydroquinone, and 4 mg of UV absorber dissolved in 2 mg of dibutyl phthalate. Layer 3 ..... A layer which contains (1) 18 mg of gelatin, (2) green-sensitive silver chlorobromide emulsion (4 mg as Ag), and (3) 5 mg of M-coupler, 2 mg of antioxidant, and 0.2 mg of 2,5-di-tert-octylhydroquinone dissolved in 5 mg of dioctylphthalate. Layer 4 ..... An intermediate layer with the same composition as Layer 2. Layer 5 ... A layer which contains (1) 16 mg of gelatin, (2) red-sensitive silver chlorobromide emulsion (4 mg as Ag), and (3) 3.5 mg of C-coupler, and 0.1 mg of 2,5-di-tert-octylhydroquinone dissolved in 2.0 mg of tricresyl phosphate. Layer 6 ... A gelatin protective layer containing 9 mg of gelatin. Each of Layers 1 to 6 was included a coating aid, and each of Layers 4 and 6 included a gelatin cross-linking agent. As a UV absorber for Layers 2 and 4, a mixture of the following UV-1 and UV-2 was used: As an antioxidant for Layer 2,5-tert-pentylhydroquinone dioctyl ether was used. Each of the above multilayered photo-sensitive materials was exposed to light through an optical wedge and was then developed according the following steps. The test results are shown in Table 1. (Developing process) In each of the processing steps, the following processing solution was used. (Composition of Processing Solution) The light resistance was determined in the following way: The color-developed sample is irradiated for 5 days by a xenon fade meter. The percent residual dye is determined based on 1.0 for the initial density. In the table, Y, M, C represent the light resistance of the dye images produced by yellow, magenta and cyan couplers, respectively. As is obvious from Table 1, any combination of the yellow, magenta and cyan couplers used in the invention can display an excellent light-resistance and can stabilize the color-balance of a color-image formed in a color photographic light-sensitive material even when irradiated by light for a long period of time.

Claims: A silver halide color photographic light-sensitive material comprising a reflective support bearing thereon a green light-sensitive silver halide emulsion layer containing a magenta forming coupler of formula (I) wherein R₁ is a substituent connected via a tertiary carbon atom; R₂ is an alkyl group or an aryl group and X is a releasable group other than hydrogen, which is susceptible to displacement by reaction of the compound of formula (I) with the oxidation products of a color developing agent; a blue light-sensitive silver halide emulsion layer containing a yellow-forming coupler of formula (II) wherein X₁ is a halogen, an alkoxy group or an alkyl group; Y₁ is a group capable of displacement by formation of a dye during a coupling reaction of the compound of formula (II) with the oxidation products of an aromatic primary amine color developing agent; R₄ is a substituent for a benzene ring and n is an integer of 1 or 2 and a red light-sensitive silver halide emulsion layer containing a cyan-forming coupler of formula (III) or (IV) wherein R₅ is an alkyl group having 1 to 4 carbon atoms; R₆ is hydrogen or an alkyl group having 1 to 15 carbon atoms and R₇, which can be present more than once in which case each R₇ can be the same or different, is a halogen, an alkyl group, a hydroxy group or an acyloxy group wherein R₈, which can be present more than once in which case each R₈ can be the same or different, is an alkyl group, a halogen, a sulfonamido group, a sulfamoyl group, an arylsulfonyl group, or a hydroxy group; R₉ is hydrogen or an alkyl group and R₁₀, which can be present more than once in which case each R₁₀ can be the same or different is hydrogen, a halogen, an alkyl group, a sulfamoyl group or a sulfonamido group. The silver halide color photographic light-sensitive material as claimed in claim 1, wherein in the compound of formula (I) X is a halogen atom. The silver halide color photographic light-sensitive material as claimed in claim 1 or claim 2, wherein in the compound of formula (I) R₂ is an alkyl group of 1 to 32 carbon atoms. The silver halide color photographic light-sensitive material as claimed in any one of claims 1 to 3, wherein in the compound of formula (II) Y₁ is a 5- or 6-membered heterocyclic group of formula wherein the moiety Z₁ comprises 4 or 5 ring atoms each selected from carbon, oxygen, nitrogen and sulfur. The silver halide color photographic light-sensitive material as claimed in any one of claims 1 to 4, wherein the cyan coupler in the red-sensitive layer is a compound of formula (III). The silver halide color photo-sensitive material as claimed in any one of claims 1 to 5, wherein in the compound of formula (I) R₁ is a tertiary alkyl group having a carbon atom directly bonded to the 1H-pyrazolo[3,2-c]-S-triazole nucleus, said carbon atom having no hydrogen atom.

Inventors: KATOH, KATSUNORI, KAWAKATSU, SATOSHI, NAKAYAMA, NORITAKA, SHINOZAKI, KAORU
Applicants: KONICA CORPORATION
Application year: 1985
Main classification: G03C7
IPC codes: G03C7