SILVER HALIDE COLOR PHOTO-SENSITIVE MATERIAL

Abstract: A silver halide color photographic material is disclosed which has at least one silver halide emulsion layer on a support. Said silver halide emulsion layer contains at least one 1H-pyrazolo[3,2-c]-S-triazole type magenta coupler substituted at 6-position by a secondary alkyl group and at 7-position by a leaving group other than a hydrogen atom.

Description: SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a silver halide color photographic material that contains a magent coupler capable of effective color formation and which forms a magenta dye image having improved keeping quality, particularly in terms of light fastness. More specifically, the invention relates to a silver halide color photographic material containing a novel 1H-pyrazolo[3,2-c]-S-triazole derived magenta coupler. Description of the Prior Art The formation of dye images in most silver halide color photographic materials depends on the reduction of exposed silver halide grains with an aromatic primary amine color developing agent and the subsequent coupling of the resultant oxidation product of the color developing agent with couplers that respectively form yellow, magenta and cyan dyes. Pyrazolone type couplers are commercially used as couplers for providing magenta dyes, but they have an unwanted secondary absorption and their keeping quality, particularly their resistance to formalin gas, is relatively low. A variety of lH-pyrazolo[3,2-cj-S-triazole derived magenta couplers have been proposed to overcome these problems of the conventional pyrazolone type couplers. Reference should be had to U.S. Patent No. 3,725,067, as well as British Patent Nos. 1,252,418 and 1,334,515. The compounds disclosed in these patents avoid the problem of secondary absorption but the improvement is inadequate in terms of resistance to formalin gas and is insignificant in respect of the production of a light-fast magenta dye image. The compound disclosed in Research Disclosure No. 12443 has no commercial value because of its low color formation. The 1H-pyrazolo[3;2-c]-S-triazole type magenta coupler disclosed in Unexamined Published Japanese Patent Application No. 42045/1983 features significant improvements in formalin resistance and color formation but little improvement has been achieved in terms of the production of a light-fast image. Improved color development has also been achieved by the couplers described in Unexamined Published Japanese Patent Application Nos. 99437/1984 and 125732/1984 but the dye images produced by these couplers are still low in light fastness. The coupler disclosed in Unexamined Published Japanese Patent Application No. 99437/1984 depends on the concomitant use of additives for providing a light-fast image. The coupler disclosed as Compound No. 19 in Unexamined Published Japanese Patent Application No. 125732/1984 produces a dye image having slightly improved light fastness but the improvement is far from being satisfactory. In short, the lH-pyrazolo[3,2-c3-S-ttiazole derived magenta couplers that have been considered useful because of the absence of secondary absorption and their high resistance to formalin gas fall far short of satisfying the requirement for providing dye images with improved light fastness. SUMMARY OF THE INVENTION The primary object, therefore, of the present invention is to provide a silver halide color photographic material that contains a magenta coupler capable of effective color formation and which forms a magenta dye image having improved light fastness and resistance to formalin gas. This object of the invention is achieved by a silver halide color photographic material that has at least one silver halide emulsion layer on a support, said silver halide emulsion layer containing at least one lH-pyrazoro [3,2-c)-S-triazole type magenta coupler substituted at 6-position by a secondary alkyl group and at 7-position by a leaving group other than a hydrogen atom. As a result of various studies made to achieve the stated object, the inventors have found a 1H-pyrazolo [3,2-c)-s-triazole derived magenta coupler that exhibits effective color formation and which provides a magenta dye image having improved formalin resistance and light fastness. DETAILED DESCRIPTION OF THE INVENtION A typical example is a lH-pyrazolo[3,2-c)-S-triazole type coupler substituted at 6-position by a secondary alkyl group and at 7-position by a leaving group other than a hydrogen atom. That is to say, by the use of such coupler, it was possible to improve light-fastness greatly and also to achieve effective color development. Here, to explain the leaving group, the 7-position of a lH-pyrazolo[3,2-c]-S-triazole type compound is a position at which to couple with the oxidation product of a color developing agent to form a magenta dye, at which time the leaving group at 7-position leaves upon reaction with said oxidation product of a color developing agent. A more preferable lH-pyrazolo[3,2-c]-S-triazole type compound substituted at 6-position by a secondary alkyl group and at 7-position by a leaving group other than a hydrogen atom is represented by the following formula (I): EMI4.1 wherein R1 is a secondary alkyl group; R2 is an alkyl group, an aryl group, a heterocyclic group or a group bonded to the carbon atom of the nucleus through a bonding group selected from among an oxygen atom, a nitrogen atom, a sulfur atom, acylamino, carbamoyl, sulfonamido, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamido, sulfone and sulfonyloxy groups; and X is a leaving group other than a hydrogen atom that leaves upon reaction with the oxidation product of a color developing agent. The compound of formula (1) is preferably represented by the following formula (II): EMI5.1 wherein R'1 and R"1 each represents a halogen atom, a cyano group, a nitro group or a group which is the same as one represented by R2 in formula (1); R2 represents a group which is the same as one represented by R2 in formula (1); and X is the same in meaning as X in formula (I). R'1 and R"1 may be bonded to each other to form a carbon ring or a heterocyclic ring. The group represented by R'1 and R"1 is a halogen atom (e.g. chlorine, bromine or fluorine), or a straightor branched-chain alkyl group having 1 to 20 carbon atoms (e.g. methyl, ethyl, propyl, i-propyl, sec-butyl, n-butyl, t-butyl, n-octyl, t-octyl, dodecyl or octadecyl). These groups may have a substituent(s) such as halogen atom, nitro, cyano, alkoxy, aryloxy, amino, acylamino, carbamoyl, sulfonamido, sulfamoyl, imido, alkylthio, arylthio, aryl, alkoxycarbonyl or acyl. Examples of such substituent include chloromethyl, bromomethyl, trichloromethyl, 8-nitroethyl, 6-cyanobutyl, methoxymethyl, ethoxyethyl, phenoxyethyl, N-methylaminoethyl, dimethylaminobutyl, acetoaminoethyl, benzoylamino, propyl, ethylcarbamoylethyl, methanesulfonamidoethyl, ethylthioethyl, p-methoxyphenylthiomethyl, phenylmethyl, p-chlorophenylmethyl, naphthylethyl, ethoxycarbonylethyl and acetylethyl. The aryl group includes phenyl and naphthyl groups and may have such a substituent(s) as shown with respect to the alkyl group. The heterocyclic ring represents a 5- or 6-membered ring having at least one of the nitrogen, oxygen and sulfur atoms, and may be one having or not having aromaticity. Examples of such ring include pyridyl, quinolyl, pyrrolyl, morpholyl, furanyl, tetrahydrofuranyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl and thiadiazolyl. These may also have such a substituent(s) as shown with respect to the alkyl group. R'1 and R"1 may also be bonded to each other to form a carbon ring (e.g. cyclopropyl, cyclopentyl, cyclohexyl or cyclohexenyl) or a teterocyclic ring (e.g. piperidyl, pyrrolidyl, dioxanyl or morphorinyl). Examples of R1 in formulas (I) and (II) are as shown below: EMI7.1 EMI8.1 EMI9.1 Examples of the alkyl, aryl or heterocyclic group represented by R2 bonded through said bonding group or a nitrogen, oxygen or sulfur atom are shown below: EMI10.1 wherein R2' represents an alkyl1 aryl or heterocyclic group; and R2" and R2"' each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic ring. If the heterocyclic group is a lH-pyrazolo[3,2-c]- S-triazole-3-yl compound, a bis type lH-pyrazol[3,2ci- S-triazole compound is formed and this is of course a magenta coupler included within the scope of the present invention. The leaving group represented by X is a halogen atom or an organic group bonded to the coupling site through an oxygen atom, a nitrogen atom or a sulfur atom. Illustrative leaving groups that are bonded to the coupling site through an oxygen atom include alkoxy, aryloxy, acyloxy and heterocyclicoxyt exemplary leaving groups that are bonded to the coupling site through a nitrogen atom include acylamino, diacylamino, sulfonamido, and 5- or 6membered heterocyclic groups containing that nitrogen atom; and illustrative leaving groups that are bonded to the coupling site through a sulfur atom include thiocyano, alkylthio, arylthio, heterocyclicthio, arylsulfonyl and alkylsulfonyl. Examples of R2 in formulas (I) and (II) are as shown below: - C1 7ll3S - CH2CN2CN20Cs2H25 - CH2CH2CONHC,4H29 -)C12H2. EMI11.1 EMI12.1 EMI13.1 EMI14.1 Of R1) and R1", preferable are alkyl and aryl groups, and more preferable are unsubstituted alkyl groups. Further, R1' and R1 " may be bonded to each other to form a carbon ring. Most preferable R1 groups are shown below: EMI14.2 R2 is preferably an alkyl or aryl group. R2 is more preferably a group represented by any of the following formulas (III), (IV) and (V): EMI14.3 EMI15.1 wherein n is an integer of O to 4; m is an integer of 1 to 3; R3 is an alkyl, aryl or heterocyclic group; R4 is a hydrogen atom or an alkyl group; and R5 is an alkyl, alkoxy, sulfamoyl, sulfonamido or sulfonyl group. The lH-pyrazolo[3,2-c]-S-triazole derived magenta couplers in accordance with the present invention are illustrated by, but by no means limited to, the following compounds. EMI15.2 EMI16.1 EMI17.1 EMI18.1 EMI19.1 EMI20.1 EMI21.1 EMI22.1 EMI23.1 EMI24.1 EMI25.1 (46) -OC15H@@ (47) -SC15H37 (48) -SO2C18H37 (49) -NHCONHC11H23 EMI25.2 EMI26.1 EMI27.1 EMI28.1 EMI29.1 EMI30.1 EMI31.1 EMI32.1 EMI33.1 The methods for synthesizing several of the compounds listed are described below. The general reference was to Journal of the Chemical Society, Perkin I 1977, pages 2047 to 2052, U.S. Patent No. 3,725,067 and Unexamined Published Japanese Patent Application Nos 99437/1984 and 42045/1983. Synthesis of compound (1): The reaction scheme is shown below: EMI34.1 (1) Synthesis of Compound (I): Thiocarbohydrazide (53 g) was suspended in alcohol, followed by the addition of benzaldehyde (53 g) under boiling and agitation. After 10 minutes, a-chloroisobutyrylmethylacetate (89.5 g) was added dropwise, and after another 10 minutes, hydrazinehydrate was added dropwise for 1 hour, followed then by boiling and agitation for another one hour. Thereafter, insoluble substances were removed and the alcohol was distilled off. The residue was crystallized by addition of 250 ml of toluene and recovered by filtration. The recovered crystal was washed well with water, then dried and thereafter recrystallized from the toluene to obtain the end product. (2) Synthesis of Compound (II): Compound (I), 27 g, was added to a mixed solution of 250 ml of acetonitrile and 17 g of triethylamine, followed by the dropwise addition of 37 g of parmitoyl chloride for 30 minutes under agitation and refluxing. The mixture was thereafter further refluxed for 2 hours. The reaction mixture was cooled and the resulting crystal was recovered by filtration. The recovered crystal was washed well with water and dried to obtain the end product almost quantitatively. (3) Synthesis of Compound (III): Compound (II), 52 g, and 20 g of phosphorus oxychloride were added in to 500 ml of toluene, followed by refluxing for 2 hours. Thereafter, the toluene was distilled off under reduced pressure. To the residue were added 300 ml of acetonitrile and 25.6 g of pyridine, and the mixture was boiled for 2 hours. The acetonitrile was distilled off from the reaction mixture, to which water was added to form a crystal. The resulting crystal was recovered by filtration, washed with water, dried and thereafter recrystallized from the acetonitrile to obtain the end product (III). (4) Synthesis of Compound (IV): Compound (III), 20 g, was added to a mixture of 100 ml of glacial acetic acid and 10 ml of concentrated sulfuric acid. The resulting mixture was refluxed for 15 hours and left to cool. Into the reaction mixture was then poured an aqueous caustic soda solution comprising 100 ml of water and 18 g of caustic soda under agitation. After cooling, the deposited crystal was recovered by filtration and washed fully with water. After drying, the recovered crystal was purified by column chromatography on silica gel using benzene-acetone as a solvent. (5) Synthesis of Compound (1): Twenty grams of compound (IV) was dissolved in chloroform and, to the solution, an equivalent amount of N-chlorosuccinimide was added. The mixture was held at 200C for one hour to perform reaction. The reaction mixture was then washed with dilute alkali to remove the resulting succinimide. The chloroform was distilled off and the residue was purified by column chromatography on silica gel using benzene-acetone as a solvent. The purified residue was identified as the end compound or compound (1) by NMR spectrum. As for other compounds, the lH-pyrazolo[3,2-c]-S- triazole nucleus free of the leaving group X was synthesized by the method used in the production of compound (1). Compounds (3), (12) and (18) were synthesized by referring to the general method described in U.S. Patent No. 3,725,067. Compounds (4) and (19) were brominated by, for example, the method described in Example 31 of said U.S. Patent and the resulting bromine-substituted product was reacted with a silver salt of methanesulfonic acid. Compounds (9), (20) and (22) were also synthesized in accordance with the method of synthesis described in said U.S. Patent. Compounds (6), (13), (15) and (17) were synthesized by referring to the general method of synthesis described in Unexamined Published Japanese Patent Application No. 99437/1984. The silver halide color photographic material of the present invention may contain conventional dye-forming couplers. Known open-chain ketomethylene couplers may be us:d as yellow-forming couplers. Benzoylacetanilide and pivaloylacetanilide compounds are particularly useful. Specific examples of the usable yellow forming coupler:; are described in U.S. Patent Nos. 2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 3,725,072, and 3,891to45; German Patent No. 1,547,868, German Patent Applicatio (OLS) Nos. 2,219,917, 2,261,361 and 2,414,006; Britis} Patent No. 1,425,020; Japanese Patent Publication No. 10783/1976, Unexamined Published Japanese Patent Appl:a- tion Nos. 26133/1972, 73147/1983, 102036/1976, 6341/1 5, 123342/1975, 130442/1975, 21827/1976, 87650/1975, 82424/1977 and 115219/1977. Usable cyan forming couplers are phenolic and na,.tholic compounds. Specific examples are found in U.S. Pater: Nos. 2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,8(826, 3,034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,97 3,591,383, 3,767,411 and 4,004,929; German Patent AFica- tion (OLS) Nos. 2,414,830 and 2,454,329; and UnexamW d Published Japanese Patent Application Nos. 59838/19 :, 26034/1976, 5055/1973, 146828/1976, 69624/1977 and r 932/ 1977. As magenta forming couplers, one or more of t: couplers prepared in accordance with the present i notion may be used. They may also be used in combination with known magenta couplers such as pyrazolone compounds, indazolone compounds, cyanoacetyl compounds, pyrazolinobenzimidazole compounds and pyrazolotriazole compounds. It should however be emphasized that at least one of the magenta couplers incorporated in the silver halide color photographic material of the present invention must be the coupler defined in accordance with the invention The coupler of the present invention may also be used in combination with colored couplers capable of color correction, or development inhibitor releasing couplers (DIR couplers) that are effective for producing improved image quality. The magenta coupler of the present invention and the respective couplers associated thereto may be introduced into silver halide emulsion layers by any known method such as one described in U.S. Patent No. 2,322, 027. For example, the couplers are dispersed in hydrophilic colloids after being dissolved in high-boiling organic solvents or low-boiling organic solvents. Examples of the former type include alkyl esters of phthalic acid (e.g. dibutyl phthalate and dioctyl phthalate), phosphate esters (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and dioctylbutyl phosphate), citrate esters (e.g. tributyl acetylcitrate), benzoate esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), aliphatic acid esters (e.g. dibutoxyethyl succinate and dioctyl azelate) and trimesic acid esters (e.g. tributyl trimesate). The low-boiling organic solvents are those which boil at between about 300C and 1500C, and examples are lower alkyl acetates (e.g. ethyl acetate and butyl acetate), ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, 8-ethoxyethyl acetate and methyl cellosolve acetate. The high-boiling organic solvents may be used in combination with the low-boiling organic solvents. Dispersion methods using polymers may also be used and such methods are described in Japanese Patent Publication No. 39853/1976 and Unexamined Published Japanese Patent Application No. 59943/1976. - The magenta coupler of the present invention is incorporated in a silver halide emulsion layer usually in the amount of from 0.005 to 2 moles, preferably from 0.03 to 0.5 mole, per mole of silver halide. The magenta coupler of the present invention forms a satisfactorily light-fast dye image, but even higher light fastness may be obtained by using an anti-fading agent or hy overlaying the emulsion layer of interest with a layer containing an ultraviolet absorber. Illustrative anti fading agents include hydroquinone derivatives of the type described in U.S. Patent Nos. 2,3673,290, 2,418,613, 2,673,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, 2,710,801 and 2,816,028, as well as British Patent No. 1,363,921; gallic acid derivatives as describded in U.S. Patent Nos. 3,457,079 and 3,069,262; p-alkoxyphenols of the type described in U.S. Patent Nos. 2,735,765 and 3,698,909, as well as Japanese Patent Publication No. 20977/1974 and 6623/ 1977; p-oxyphenol derivatives of the type described in U.S. Patent Nos. 3,432,300, 3,573,050, 3,574,627 and 3,764,337, as well as Unexamined Published Japanese Patent Application Nos. 35633/1977, 147434/1977 and 152225/1977; and bisphenols as described in U.S. Patent No. 3,700,455. Exemplary ultraviolet absorbers includes arylsubstituted benzotriazole compounds (as described in U.S. Patent No. 3,533,794), 4-thiazolidone compounds (as described in U.S. Patent Nos. 3,314,794 and 3,352,681), benzophenone compounds (as described in Unexamined Published Japanese Patent Application No. 2784/1971), cinnamic acid ester compounds (as described in U.S. Patent Nos. 3,705,805 and 3,707,375), butadiene compounds (as described in U.S. Patent No. 4,045,229), and benzoxidole compounds (as described in U.S. Patent No. 3,700,455). Other compounds usable as UV absorbers are found in U.S. Patent No. 3,499,762 and Unexamined Published Japanese Patent Application No. 48535/1979. Any of the silver halides that are incorporated in conventional silver halide emulsions may be used in the present invention and they include silver bromide, silver chloride, silver iodobromide, silver chlorobromide and silver chloroiodobromide. - In order to provide sensitivity for the desired spectral wavelength region, the silver halides used in the present invention may be spectrally sensitized by suitable selected sensitizing dyes. Usable dyes include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl and hemioxonole dyes. Useful sensitizing dyes are described in, for example, 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 Publication Nos. 14030/1969 and 24844/1977. These sensitizing dyes may be used either individually or in combination. Combined sensitizing dyes are often used for the purpose- of supersensitization, as typically described in U.S. Patent Nos. 2,688,545, 2,977,229, 3,397,060, 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, 3,81,609, 3,837,862 and 4,026,707; British Patent Nos. 1,34C,281 and 1,507,803; Japanese Patent Publication Nos. 4936/1968 and 12375/1978; and Unexamined Published Japanese Patent Application Nos. 110618/1977 and 109925/1977. The silver halide emulsion used in the present in Invention may incorporate a variety of known photographic additives such as those described in Research Disclosure No. 17643. The silver halide color photographic material of the present invention may use any support material that is properly selected from among known materials depending on the specific object, such as plastic films, plastic laminated paper, baryta paper and synthetic paper. The silver halide color photographic material of the invention may adopt any of the layer arrangements commonly used in the photographic industry. The so arranged silver halide color photographic material of the invention is exposed and thereafter subejected to color development by a variety of photographic processing techniques. The color developer used to process this photographic material may contain any of the known aromatic primary amine color developing agents that are extensively used in various color photographic processes. Such developing agents include aminophenolic and p-phenylenediamine derivatives. These compounds are generally used in salt forms, such as hydrochlorides or sulfates, which are stabler than the free state. These compounds are used in concentrations that generally range from about 0.1 to about 30 g, preferably from about l g to about 1.5 g, per liter of the color developer. Illustrative aminophenolic developing agents include o-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2amino-3-oxytoluene, and 2-oxy-3-amino-1,4-dimethylbenzene. Particularly useful primary aromatic amino color developing agents are N,N'-dialkyl-p-phenylenediamine compounds wherein the alkyl or phenyl group may have a suitable substituent. Among these compounds, the following are particularly advantageous: N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N ,N ' -dimethyl-p-phenylenediamine hydrochloride, 2-amino-S- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N-ss-methanesulfonamidoethyl-3-methyl-4-aminOaniline sulfate, N-ethyl-N-B-hydroxyethylaminoaniline, 4-amino 3-methyl-N,N'-diethylaniline, and 4-amino-N-(2-methoxyethyl) N-ethyl-3-methylaniline-p-toluene sulfonate. In addition to these primary aromatic amino color developing agents, the color developer used in the processing of the photographic material of the present invention may contain a veriety of additives that are commonly incorporated in color developers and such additives in dude alkali agents (e.g. sodium hydroxide, sodium carbonate and potassium carbonate) , alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners. The pH of the color developer is usually at least 7 and most generally ranges from about 10 to about 13. After color development, the photographic material of the present invention is processed by a solution having the fixing ability. If this solution is a fixing bath, its use is preceded by a bleaching step. The bleaching bath used in the bleaching step or the bleaching agent used in a bleach-fixing bath is made of a metal complex salt of an organic acid. This metal complex salt has the ability not only to oxidize metallic silver (i.e., formed as a result of development) into silver halide but also to ensure complete color formation by a color former. The structure of this metal complex salt is such that an organic acid such as an aminopolycarboxylic acid, oxalic acid or citric acid is coordinated to a metal ion such as iron, cobalt or copper. The organic acids most preferred for use in forming metal complex salts are polycarboxylic acids or aminopolycarboxylic acids. The polycarboxylic acids or aminopolycarboxylic acids may be in the form of alkali metal salts, ammonium salts or water-soluble salts. Typical examples of polycarboxylic acids or aminopolycarboxylic acids are listed below: (1) ethylenediaminetetraacetic acid; (2) diethylenetriaminepentaacetic acid; (3) ethylenediamine-N- (8-oxyethyl)-N,N' ,N'-triacetic acid; (4) propylenediaminetetraacetic acid; (5) nitrilotriacetic acid; (6) cyclohexanediaminetetraacetic acid; (7) iminodiacetic acid; (8) dihydroxyethylglycincitric acid (or tartaric acid); (9) ethyletherdiaminetetraacetic acid; (10) glycoletherdiaminetetraacetic acid; (11) ethylenediaminetetrapropionic acid; (12) phenylenediaminetetraacetic acid; (13) ethylenediaminetetraacetic acid disodium salt; (14) ethylenediaminetetraacetic acid tetra(trimethyl ammonium) salt; (15) ethylenediaminetetraacetic acid tetrasodium salt; (16). diethylenetriaminepentaacetic acid pentasodium salt; ; (17) ethylenediamine-N (ss-oxyethyl)-N,N',N'-triacetic acid sodium salt; (18) propylenediaminetetraacetic acid sodium salt; (19) nitrilotriacetic acid sodium salt; and (20) cyclohexanediaminetetraacetic acid sodium salt. In addition to metal complex salts of these organic acids which are used as bleaching agents, the bleaching bath used in processing the color photographic material of the present invention may contain a variety of additives, and preferred additives are rehalogenating agents such as alkali or ammonium halides (e.g. potassium bromide, sodium bromide, sodium chloride and ammonium bromide), metal salts and chelating agents. Any other additives that are conventionally incorporated in bleaching baths may also be used and they include pH buffers (e.g. borate, oxalate, acetate, carbonate and phosphate salts), alkylamines and polyethylene oxides. The fixing bath and bleach-fixing bath may also contain one or more pH buffers that are selected from among sulfites (e.g. ammnium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite), and a variety of acids or salts (e.g. boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide). If the photographic material of the present invention is processed in a bleach-fixing bath as it is supplied with a blix replenisher, thiosulfates, thiocyanates, sulfites or other salts may be incorporated either in the bleach-fixing bath or in the replenisher that is fed to said blix bath. In order to increase the activity of the bleachfixing bath used in processing the photographic material of the present invention, air or oxygen may be blown into a tank containing the bleach-fixing bath or its replenisher. Alternatively, a suitable oxidant such as hydrogen peroxide, bromate or persulfate may be added into the tank. The following examples are provided for further illustration of the claimed photographic material but are not to be construed as limiting the invention. Example 1 One tenth of a mole, per mole of silver, of one of the magenta couplers listed in Table 1 (which follow) was mixed with an equal weight of tricresyl phosphate and three times the coupler's weight of ethyl acetate, and the mixture was heated to 600C to form a complete solution. The solution was then mixed with 1,200 ml of 5 % aqueous gelatin solution containing 120 ml of a 5 % aqueous solution of Alkanol B (trade name of du Pont for alkylnaphthalene sulfonate). The mixture was emulsified with an ultrasonic disperser and the dispersion obtained was added to 4 kg of a green-sensitive silver iodobromide emulsion (containing 6 mol% AgI). To the mixture, 120 ml of a 2 % solution (water:methanol = 1:1) of 1,2-bis(vinylsulfonyl)-ethane was added as a hardener, and the so prepared coating solution was applied to a subbed transparent polyester base, and the web was dried to provide a sample of color photographic material (with silver deposit of 20 mg/100 cm2). The other samples were prepared by the same procedure. Each of the samples thus prepared was subjected to exposure through an optical wedge as in the conventional process and subsequently processed by the following scheme. The results of such photographic processing are shown in Table 1 below. Processing scheme Steps Temperature, 0C Time Color development 38 3 min, 15 sec Bleaching 38 4 min, 20 sec Washing 38 3 min, 15 sec Fixing 38 4 min, 20 sec Washing 38 3 min, 15 sec Stabilizing 38 1 min, 30 sec Drying 47 to 55 16 min, 30 sec. The foumulation of each of the processing solutions used is indicated below. Color developer Potassium carbonate 30 g sodium hydrogencarbonate 2.5 g potassium sulfite 5g sodium bromide 1.3 g potassium iodide 2 mg hydroxylamine sulfate 2.5 g sodium chloride 0.6 g diethylenetriaminepentaacetic 2.5 g acid sodium salt 4-amino-3-methyl-N-ethyl-N- (- 4.8 g hydroxyethyl)aniline sulfate potassium hydroxide 1.2 g water to make 1,000 ml pF adjusted to 10.06 by addition of potassium hydroxide or 20 % H2SO4. Bleaching bath Ethylenediaminetetraacetic acid iron 100 g ammonium salt Ethylenediaminetetraacetic acid 10 g Ammonium bromide 150 g Glacial acetic acid 40 ml Sodium bromate 10 g water to make 1,000 ml pH adjusted to 3.5 by addition of ammonia water or glacial acetic acid. Fixing bath: Ammonium thiosulfate 180 g Anhydrous sodium sulfite 12 g Sodium metabisulfite 2.5 g Ethylenediaminetetraacetic acid disodium salt 0.5 g Sodium carbonate 10 g Water to make 1,000 ml Stabilizing bath Formalin (37E aq. sol.) 2 ml Konidax (product of Konishiroku Photo Industry Co., Ltd.) 5 ml Water to make 1,000 ml Table 1 EMI51.1 <tb> Sample <SEP> Coupler <SEP> Specific <SEP> Maximum <SEP> Formalin <SEP> Light <tb> No. <SEP> used <SEP> sensitivity1) <SEP> density <SEP> resistance2) <SEP> fastness3) <tb> <SEP> Comparative <tb> 1-11 <SEP> 100 <SEP> 2.65 <SEP> 92 <SEP> 27 <tb> <SEP> Coupler <SEP> 1 <tb> <SEP> Comparative <tb> 1-12 <SEP> 42 <SEP> 1.25 <SEP> 53 <SEP> 65 <tb> <SEP> Coupler <SEP> 2 <tb> <SEP> Couper <SEP> (1) <tb> 1-13 <SEP> of <SEP> the <SEP> 99 <SEP> 2.73 <SEP> 91 <SEP> 65 <tb> <SEP> invention <tb> <SEP> Coupler <SEP> (3) <tb> 1-14 <SEP> of <SEP> the <SEP> 105 <SEP> 2.82 <SEP> 89 <SEP> 65 <tb> <SEP> invention <tb> <SEP> Coupler <SEP> (4) <tb> 1-15 <SEP> of <SEP> the <SEP> 97 <SEP> 2.60 <SEP> 92 <SEP> 66 <tb> <SEP> invention <tb> EMI52.1 <tb> <SEP> Coupler <SEP> (6) <tb> 1-16 <SEP> 1 <SEP> of <SEP> the <SEP> 92 <SEP> 2.51 <SEP> 92 <SEP> 64 <tb> <SEP> invention <tb> <SEP> Coupler <SEP> (9) <tb> 1-17 <SEP> of <SEP> the <SEP> 98 <SEP> 2.65 <SEP> 93 <SEP> 64 <tb> <SEP> invention <tb> <SEP> Coupler <SEP> (22) <tb> 1-18 <SEP> of <SEP> the <SEP> 96 <SEP> 2.59 <SEP> 92 <SEP> 66 <tb> <SEP> invention <tb> <SEP> Coupler <SEP> (23) <tb> 1-19 <SEP> of <SEP> the <SEP> 102 <SEP> 2.83 <SEP> 93 <SEP> 64 <tb> <SEP> - <SEP> invention <SEP> <tb> Note: 1) The specific sensitivity is expressed as the reciprocal of the exposure that provides a fog plus 0.19 density, with the value for sample No. 11 (using comparative coupler 1) being taken as 100. 2) A sample was subjected to color development after it was held for 3 days in a sealed container of 0.9% aqueous formalin (6 ml) conditioned at 300C and 62% R.H. An untreated sample was also color developed. The formalin resistance of the first sample was calculated by the following formula: EMI52.2 3) A color-developed sample was illuminated in a xenon fadeometer for 5 days and the percentage residual dye for the initial density (D) of 1.0 was calculated to determine the lightfastness of the image: EMI53.1 Comparative coupler 1 EMI53.2 Comparative coupler 2 EMI53.3 The data in Table 1 show that the couplers prepared in accordance with the present invention satisfied all the requirements for high color density and the production of formalin-resistant and light-fast dye images. Example 2 Sample Nos. 1-11 to 1-49 prepared in Example 1 were exposed through an optical wedge and subsequently processed by the following scheme. The results are shown in Table 2. The specific sensitivity and light fastness were measured by the same methods as used in Example 1. Processing scheme: Color development 380C 3 min, 30 sec bleach-fixing 330C 1 min, 30 sec stabilizing or 25 - 300C 3 min washing drying 75 - 800C ca. 2 min. The solutions used in this scheme had the following formulations Color developer Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Tripolyphosphoric acid (TPPS) 2,5 g 3-Methyl-4-amino-N-ethyl-N-(B-methane- sulfonamidoethyl)aniline sulfate 5.5 g Brightener (4,4'-diaminostilbenzo sulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Water to make 1,000 ml pH adjusted to 10.20 Bleach-fixing bath Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate salt 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aq. sol.) 100 ml Ammonium sulfite (40% aq. sol.) 27.5 ml pH adjusted to 7.1 by addition of potassium carbonate or glacial acetic acid Water to make 1,000 ml Stabilizing bath 5-Chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10 g Table 2 EMI56.1 <tb> <SEP> Sample <SEP> Coupler <SEP> used <SEP> Specific <SEP> Maximum <SEP> Light <tb> <SEP> No. <SEP> sensitivity <SEP> density <SEP> fastness <tb> <SEP> 2-11 <SEP> Comparative <SEP> 100 <SEP> 2.40 <SEP> 22 <tb> <SEP> coupler <SEP> 1 <tb> <SEP> 2-12 <SEP> Comparative <SEP> 54 <SEP> 1.35 <SEP> 65 <tb> <SEP> coupler <SEP> 2 <tb> <SEP> 2-13 <SEP> Coupler <SEP> (1) <SEP> of <SEP> 98 <SEP> 2.32 <SEP> 64 <tb> <SEP> the <SEP> invention <tb> <SEP> 2-14 <SEP> Coupler <SEP> (3) <SEP> of <SEP> 105 <SEP> 2.40 <SEP> 66 <tb> <SEP> the <SEP> invention <tb> 2-15 <SEP> Coupler <SEP> (4) <SEP> of <SEP> 102 <SEP> 2.36 <SEP> 65 <tb> <SEP> the <SEP> invention <tb> <SEP> 2-16 <SEP> Coupler <SEP> (6) <SEP> of <SEP> 95 <SEP> 2.20 <SEP> 65 <tb> <SEP> the <SEP> invention <tb> <SEP> 2-17 <SEP> Coupler <SEP> (9) <SEP> of <SEP> 99 <SEP> 2.45 <SEP> 67 <tb> <SEP> the <SEP> invention <tb> <SEP> 2-18 <SEP> Coupler <SEP> (22) <SEP> of <SEP> 108 <SEP> 2.51 <SEP> 64 <tb> <SEP> the <SEP> invention <tb> <SEP> 2-19 <SEP> Coupler <SEP> (23) <SEP> of <SEP> 102 <SEP> 2.48 <SEP> 63 <tb> <SEP> the <SEP> invention <tb> As the data in Table 2 show, the samples containing the magenta couplers prepared in accordance with the present invention were superior to those containing the comparative couplers in respect to sensitivity, color density and the production of light-fast dye images. Example 3 A sample of silver halide color photographic material was prepared by coating the following layers in sequence on a support made of polyethylene coated paper containing anatase type TiO2. The amounts of the additives incorporated in each of the layers described below are based on an area of 100 cm2 (1) Layer containing 20 mg of gelatin, 5 mg in terms of silver of a blue-sensitive silver chlorobromide emul sion, and 3 mg of dioctyl phthalate coupler solvent having dissolved therein 8 mg of Y-coupler* and 0.1 mg of 2,5-di-t-octylhydroquinone: (2) Interlayer containing 12 mg of gelatin, and 2 mg of dibutyl phthalate W absorber solvent having 0.5 mg of 2,5-di-t-octylhydroquinone and 4 mg of W absorber dissolved therein: : (3) Layer containing 18 mg of gelatin, 4 mg in terms of silver of a green-sensitive silver chlorobromide emulsion, and 2.5 mg of dioctyl phthalate coupler solvent having dissolved therein 5 mg of M-coupler * 2 mg of antioxidant and 0.2 mg of 2,5-di-t octylhydroguinone: (4) Interlay having the same composition as (2): (5) Layer containing 16 mg of gelatin, 4 mg in terms of silver of a red-sensitive silver chlorobromide emul sion, and 2.0 mg of tricresyl phosphate coupler solvent having dissolved therein 3.5 mg of C-coupler and 0.1 mg of 2,5-di-t-octylhydroquinone: (6) Gelatin protective layer containing 9 mg of gelatin. Each of the layers (1) to (6) also contained a coating aid, while layers (4)and (6) further contained a gelatin crosslinking agent. The ultraviolet absorber used in each of the layers (2) and (4) was a mixture of W-l and W-2 having the structures shown below. The antioxidant incorporated in layer (3) was di-t-pentylhydroquinone-di-octyl ether. Thirteen samples of multi-layered photographic material were prepared as above and each was processed as in Example 2. The specific types of the Y-coupler, M-coupler and C-coupler used, and the results of the photographic processing are shown in Table 3 below. Each of the samples was checked for its magenta density after exposure to white light. The specific sensitivity and light fastness were measured by the same methods as used in Example 1. The data in Table 3 show the improved light fastness of the dye images produced by using the magenta couplers prepared in accordance with the present invention. It was also clear that the light fastness of the images could be further improved by using UV absorbers in combination with the magenta couplers. *Ultraviolet absorber EMI59.1 *Y-couplers EMI59.2 EMI60.1 EMI61.1 Table 3 EMI62.1 Sample <SEP> Layer <SEP> (1) <SEP> Layer <SEP> (3) <SEP> Layer <SEP> (5) <SEP> Specific <SEP> Maximum <SEP> Light <SEP> Remarks <tb> <SEP> No. <SEP> Y-coupler <SEP> M-coupler <SEP> C-coupler <SEP> UV <SEP> absorber <SEP> sensitivity <SEP> density <SEP> fastness <tb> 31 <SEP> Y <SEP> - <SEP> 1 <SEP> Comparative <SEP> c-1 <SEP> -- <SEP> 100 <SEP> .30 <SEP> 25 <SEP> - <SEP> coupler <SEP> (1) <tb> 32 <SEP> do. <SEP> Comparative <SEP> do. <SEP> UV-1 <SEP> 102 <SEP> 2.29 <SEP> 37 <SEP> 2 <SEP> mg <SEP> of <SEP> UV <SEP> absorber <SEP> in <tb> <SEP> coupler <SEP> (1) <SEP> UV-2 <SEP> layer(5) <tb> <SEP> Coupler <SEP> (5) <tb> 33 <SEP> do. <SEP> of <SEP> the <SEP> do. <SEP> -- <SEP> 102 <SEP> 2.35 <SEP> 78 <SEP> - <SEP> invention <tb> <SEP> UV-1 <tb> 34 <SEP> do. <SEP> do. <SEP> do. <SEP> UV-2 <SEP> 100 <SEP> 2.30 <SEP> 88 <SEP> 2 <SEP> mg <SEP> of <SEP> UV <SEP> absorber <SEP> in <tb> <SEP> layer <SEP> (5) <tb> 35 <SEP> Y <SEP> - <SEP> 2 <SEP> do. <SEP> C <SEP> - <SEP> 2 <SEP> -- <SEP> 99 <SEP> 2.31 <SEP> 86 <SEP> - <SEP> Another <SEP> layer <SEP> (2) <SEP> inserted <tb> 36 <SEP> do. <SEP> do. <SEP> do. <SEP> UV-1 <SEP> 97 <SEP> 2.28 <SEP> 94 <SEP> between <SEP> layers <SEP> 95) <SEP> and <SEP> (6) <tb> <SEP> UV-2 <SEP> in <SEP> eample <SEP> No. <SEP> 35 <tb> 37 <SEP> Y <SEP> - <SEP> 1 <SEP> do. <SEP> C <SEP> - <SEP> 3 <SEP> UV-1 <SEP> 96 <SEP> 2.33 <SEP> 84 <SEP> - <SEP> UV-2 <tb> <SEP> Same <SEP> layer <SEP> arrangenent <SEP> as <tb> 38 <SEP> do. <SEP> do. <SEP> do. <SEP> UV-1 <SEP> 98 <SEP> 2.30 <SEP> 93 <SEP> in <SEP> sample <SEP> No. <SEP> 36 <tb> <SEP> UV-2 <tb> 39 <SEP> Y <SEP> - <SEP> 2 <SEP> do. <SEP> C <SEP> - <SEP> 4 <SEP> UV-1 <SEP> 99 <SEP> 2.28 <SEP> 85 <tb> <SEP> UV-2 <tb> 40 <SEP> do. <SEP> do. <SEP> C <SEP> - <SEP> 1 <SEP> UV-1 <SEP> 101 <SEP> 2.35 <SEP> 85 <tb> <SEP> UV-2 <tb> <SEP> Coupler <SEP> (19) <SEP> UV-1 <tb> 41 <SEP> Y <SEP> - <SEP> 1 <SEP> of <SEP> the <SEP> do. <SEP> UV-2 <SEP> 105 <SEP> 2.36 <SEP> 83 <tb> <SEP> invention <tb> Table 3 (Continued) EMI63.1 Sample <SEP> Layer <SEP> (1) <SEP> Layer <SEP> (3) <SEP> Layer <SEP> (5) <SEP> Specific <SEP> Maximum <SEP> Light <SEP> Remarks <tb> <SEP> No. <SEP> Y-coupler <SEP> M-coupler <SEP> C-coupler <SEP> UV <SEP> absorber <SEP> sensitivity <SEP> density <SEP> fastness <tb> 42 <SEP> Y <SEP> - <SEP> 1 <SEP> Coupler <SEP> (24) <SEP> UV-1 <SEP> 102 <SEP> 2.38 <SEP> 96 <SEP> Same <SEP> layer <SEP> arrangement <tb> <SEP> of <SEP> the <SEP> C <SEP> - <SEP> 3 <SEP> UV-2 <SEP> as <SEP> in <SEP> sample <SEP> No. <SEP> 36 <tb> <SEP> Coupler <SEP> (25) <SEP> UV-1 <SEP> 105 <SEP> 2.40 <SEP> 95 <SEP> Same <SEP> layer <SEP> arrangement <tb> 43 <SEP> do. <SEP> of <SEP> the <SEP> do. <SEP> UV-2 <SEP> as <SEP> in <SEP> sample <SEP> No. <SEP> 36 <tb> <SEP> invention <tb> <SEP> invention <tb>

Claims: CLAIMS 1. A silver halide color photographic material comprising a support and at least one silver halide emulsion layer containing at least one lH-pyrazolo[3,2-c]- S-triazole type magenta coupler substituted at 6-position by a secondary alkyl group and at 7-position by a leaving group other than a hydrogen atom. 2. A silver halide color photographic material according to claim 1, wherein the magenta coupler is a compound of formula (I): EMI64.1 wherein Rl is a secondary alkyl group; R2 is an alkyl group, an aryl group, a heterocyclic group or a group bonded to the carbon atom of the nucleus through a bonding group selected from among an oxygen atom, a nitrogen atom, a sulfur atom, acylamino, carbamoyl, sulfonamido, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamido, sulfone and sulfonyloxy groups; and X is a leaving group other than a hydrogen atom susceptible to displacement during reaction of the compound of formula (I) with the oxidation product of a color developing agent. 3. A silver halide color photographic material according to claim 1 or claim 2, wherein the magenta coupler is a compound of formula (II): EMI65.1 wherein R1' and R1" are the same or different and each is a halogen atom, a cyano group, a nitro group or a group R2; and R2 and X are groups as defined in claim 2 with respect to formula (I). 4. A silver halide color photographic material according to claim 2, wherein Rl is a group EMI65.2 5. A silver halide color photographic material according to any one of claims 2 to 4, wherein R2 is a group of formula (III), (IV) or (V): EMI66.1 wherein R3 is an alkyl, aryl or heterocyclic group; R4 is a hydrogen atom or an alkyl group; R5 is an alkyl, alkoxy, sulfamoyl, sulfonamido or sulfonyl group; m is an integer of 1 to 3; and n is O or an integer of 1 to 4.

Inventors: KATOH, KATSUNORI, KAWAKATSU, SATOSHI, NAKAYAMA, NORITAKA, SHINOZAKI, KAORU
Applicants: KONICA CORPORATION
Application year: 1985
Main classification: G03C7
IPC codes: G03C7, C07D487