Silver halide color photographic light-sensitive material

Abstract: A silver halide color photographic light sensitive material is disclosed, comprising a support having thereon a silver halide emulsion layer containing silver halide grains, wherein said silver halide emulsion layer contains a cyan dye forming coupler represented by the following formula (1) or (2),

Description: FIELD OF THE INVENTION This invention relates to a comprising a cyan coupler silver halide color photographic light-sensitive material and, particularly to a silver halide color photographic light-sensitive material excellent in color developability and color reproducibility. BACKGROUND OF THE INVENTION As for the cyan color image forming couplers, phenols or naphthols have mostly been used so far. However, the cyan images obtained from the phenols and naphthols used so far have had serious problems on color reproduction. The problems have included that absorption has not been well-defined on the short-wavelength side and that unnecessary absorption, i.e., an asymmetric absorption, has also been produced in the green spectral region. Due to the problems, the asymmetric absorption has to be corrected by means of masking in the case of a color negative film and there has not been any asymmetric absorption correcting means in the case of a color negative paper. Therefore, the color reproduction was considerably deteriorated. Some problems of preservability have remained unsolved in dye images obtained from phenols and naphthols used so far. For example, heat fastness is generally inferior in a dye image obtained from the 2-acylaminophenol cyan coupler described in U.S. Patent Nos. 2,367,531 and 2,423,730; light fastness is generally inferior in a dye image obtained from the 2,5-diacylaminophenol cyan coupler described in U.S. Patent Nos. 2,369,929 and 2,772,162, and both light and heat fastness are generally unsatisfactory in a dye image obtained from the 1-hydroxy-2-naphthamido cyan coupler. Even using a 2,5-diacylaminophenol cyan coupler as described in U.S. Patent No. 4,122,368, Japanese Patent Application Open to Public Inspection (hereinafter referred to as JP OPI Publication) Nos. 57-155538/1982 and 57-157246/1982 and so forth, and a 2,5-diacylaminophenol cyan coupler having a hydroxyl group in the ballast portion as described in U.S. Patent No. 3,880, 661, a satisfactory level has not yet been achieved for preserving the respective dye images for a long time, from the view points of fastness against light and heat and yellow-stain production. For the purpose of solving the above-mentioned problems, JP OPI Publication Nos. 64-554/1989, 63-250649/1988 and EP-A-0 287 265 (63-250650/1988) and so forth have proposed cyan couplers of the pyrazoloazole type. However, these couplers have introduced an electron-withdrawing group and a hydrogen-bonding group thereinto for satisfying the absorption wavelength of the color dyes to be formed. Therefore, these couplers have not only been unsatisfactory in fully satisfying coupling activity, although a good color reproducibility has been displayed, but also they have not satisfied both color developability and color reproducibility at the same time. In view of the above mentioned problems, the present inventors have now developed a pyrazoloazole type cyan coupler excellent in color reproduction and color formation. SUMMARY OF THE INVENTION It is an object of the invention to provide a silver halide color photographic light-sensitive material from which an excellent color formation and a sufficient color density can be obtained and a cyan image can also be obtained so as to be excellent in spectral absorption characteristics including sharp absorption and no unwanted absorption in the blue and green regions. Another object of the invention is to provide a silver halide color light-sensitive material capable of forming a cyan image without producing any change of hue against heat and moisture. The above-mentioned objects of the invention can be achieved with a cyan coupler for a silver halide color photographic light-sensitive material, represented by the following formula (1) or (2). wherein R 1 and R 3 each represent a heterocyclic group, alkoxy group, aryloxy group, heterocyclic-oxy group or in which R 5 represents a substituent and n 1 is from 1 to 5; R 2 and R 4 each independently represent an aryl group or a heterocyclic group; and X 1 and X 2 each represent a hydrogen atom or a coupling-off group, which is capable of being released upon reaction with an oxidation product of a color developing agent. DETAILED DESCRIPTION OF THE INVENTION In the above-given formulae (1) and (2), the heterocyclic groups represented by R 1 and R 3 include, for example, 2-thienyl group, 2-furyl group, 1-pyrrolyl group, 2-imidazolyl group, 2-thiazolyl group, 3-isoxazolyl group, 2-pyridyl group, 3-pyridyl group, 2-pyrimidyl group and 3-pyrazolyl group. The alkoxy groups include, for example, methoxy group, ethoxy group, i-propyloxy group, t-butyloxy group, dodecyloxy group, i-hexadecyloxy group and so forth. The aryloxy groups include, for example, phenoxy group, naphthyloxy group and so forth. The heterocyclic-oxy groups include preferably those having a 5- to 7-membered heterocyclic ring including, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group and so forth. Among the above-given groups represented by R 1 and R 3 , a heterocyclic group is preferred from the viewpoint of color reproducibility. Next, there is no special limitation to the substituents represented by R 5 . However, they include, for example alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl groups and so forth. Besides the above, the substituents also include, for example, a halogen atom, each group of cycloalkenyl, alkinyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic-oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic-thio, thioureido, carboxy, hydroxyl, mercapto, nitro, sulfo and so forth, or also include spiro compound residual group, bridged hydrocarbon residue. In the group represented by R 5 , the alkyl group is preferably those having from 1 to 32 carbon atoms and they may be straight-chained or branched. As for the aryl group, a phenyl group is preferred. The acylamino group includes, for example, alkylcarbonylamino group, arylcarbonylamino group and so forth. The sulfonamido group includes, for example, alkylsulfonylamino group, arylsulfonylamino group and so forth. The alkyl and aryl components in the alkylthio and arylthio groups include, for example, the alkyl and aryl groups represented by R 5 . The alkenyl group includes preferably those having from 2 to 32 carbon atoms. The cycloalkyl group includes preferably those having from 3 to 12 carbon atoms and particularly those having from 5 to 7 carbon atoms. The alkenyl group may be straight-chained or branched. The cycloalkenyl group includes preferably those having from 3 to 12 carbon atoms and particularly those from 5 to 7 carbon atoms. The sulfonyl group includes, for example, alkylsulfonyl group, arylsulfonyl group and so forth; the sulfinyl group includes, for example, alkylsulfinyl group, arylsulfinyl group and so forth; the phosphonyl group includes, for example, alkylphosphonyl group, alkoxyphosphonyl group, aryloxyphosphonyl group, arylphosphonyl group and so forth; the acyl group includes, for example, alkylcarbonyl group, arylcarbonyl group and so forth; the carbamoyl group includes, for example, alkylcarbamoyl group, arylcarbamoyl group and so forth; the sulfamoyl group includes, for example, alkylsulfamoyl group, arylsulfamoyl group and so forth; the acyloxy group includes, for example, alkylcarbonyloxy group, arylcarbonyloxy group and so forth; the sulfonyloxy group includes, for example, alkylsulfonyloxy group, arylsulfonyloxy group and so forth; the carbamoyloxy group includes, for example, alkylcarbamoyloxy group, arylcarbamoyloxy group and so forth; the ureido group includes, for example, alkylureido group, arylureido group and so forth; the sulfamoylamino group includes, for example, alkylsulfamoylamino group, arylsulfamoylamino group and so forth; the heterocyclic group includes preferably, those having 5 to 7 membered rings, for example 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group and so forth; the heterocyclic-oxy group includes, preferably, those having 5 to 7 membered rings, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, l-phenyltetrazole-5-oxy group and so forth; the heterocyclic-thio group includes preferably, those having 5 to 7 membered rings, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group and so forth; the siloxy group includes, for example, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and so forth; the imido group includes, for example, succinimido group, 3-heptadecyl succinimido group, phthalimido group, glutarimido group and so forth; the spiro compound residual group includes, for example, spiro[3,3]heptane-l-il group and so forth; and the bridged hydrocarbon residue includes for example, bicyclo[2,2,1] heptane-1-yl, tricyclo[3,3,1,1 37 ]decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]heptane-1-yl and so forth. The substituents represented by R 2 and R 4 are aryl groups or heterocyclic groups, and, inter alia, aryl groups are particularly preferred, from the viewpoint of color reproducibility. Examples of suitable aryl and heterocyclic groups are given above for R 5 . The above-given groups are also allowed to have such a further substituent as a ballast group including, for example, a long-chained hydrocarbon group, a polymer residual group and so forth. X 1 and X 2 each represent a hydrogen atom or a coupling-off group capable of being released upon reaction with the oxidation product of a color developing agent. The coupling-off groups capable of being released upon reaction with an oxidation product of the color developing agent include, for example, a halogen atom (such as a chlorine atom, a bromine atom, a fluorine atom and so forth) and each of the groups of alkoxy, aryloxy, heterocyclic-oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic-thio, alkyloxythiocarbonylthio, acylamino, sulfonamido, nitrogen-containing heterocyclic ring coupled with an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl and so forth. Among them, a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic-oxy group, an alkylthio group, an arylthio group, a heterocyclic-thio group, a nitrogen-containing heterocyclic group coupled with an N atom and so forth. Among the cyan couplers for silver halide color photographic light-sensitive material represented by Formula (1) or (2), those represented by Formula (1) are preferable from the viewpoint of color reproducibility. A cyan coupler represented by the following formula (3) is more preferable: In the formula, R 6 represents a substituent; R 7 and R 8 each represent a hydrogen atom or a substituent; n 2 is from 1 to 4, and n 3 is from 1 to 5; and X 1 is the same as defined in formula (1). Now typical examples of cyan couplers for silver halide color photographic light-sensitive material represented by Formula (1) or (2) will be given below. However, the invention shall not be limited thereto. Examples of synthesizing the cyan couplers will be shown below: <Synthesis of Exemplified Compound I-7> (i) Synthesis of Intermediate 2 While stirring 175 g (0.59 mol) of intermediate 1, 1.2 liters of pyridine and 66 g (0.65 mol) of acetic acid anhydride, were reacted together at room temperature for 5 hours. After completing the reaction, the resulting crystals were filtrated and were then dispersed in 1.6 liters of 5% hydrochloric acid. After about 30 minutes, the resulting crystals were filtrated and were then washed, so that 190 g of intermediate 2 were obtained (yield of 95%). (ii) Synthesis of Intermediate 3 Intermediate 2 of 150 g (0.44 mol) was dispersed in 900 ml of chloroform and thereto 163 g (1.37 mol) of thionyl chloride and 30 ml of pyridine were added in this order. The resulting solution was reacted for 6 hours while heating and refluxing. After completing the reaction, the remaining solvent was distilled away under reduced pressure, so that 166 g of intermediate 3 was obtained (yield of 106%). Intermediate 3 was not further refined, but it was used as it was in the next reaction. (iii) Synthesis of Exemplified Compound I-7 Intermediate 3 of 3.58 g (0.01 mol) was dissolved in 30 ml of pyridine and 4.02 g (0.01 mol) of intermediate 4 was then added thereto. The resulting solution was reacted at room temperature for 8 hours. After completing the reaction, 20 ml of aqueous solution of 4.15 g (0.03 mol) of potassium carbonate was added thereto and the resulting solution was reacted for 2 hours while heating and refluxing. After completing the reaction, ethyl acetate was added thereto and extraction, washing, drying and condensation were carried out. Thereafter, the resulting residue was refined by column chromatography, so that 3.89 g of the objective exemplified compound I-7 was obtained (yield = 57%). The structure thereof was confirmed by 1 H-NMR, IR and MASS spectrography. Synthesis of Exemplified Compound (I-41) (i) Synthesis of Intermediate (41c) Intermediate (41a) in an amount of 80g (0.75 mol) was dispersed in 750 ml of ethanol, and 147g (0.75 mol) of intermediate (41b) was added thereto under ice-cooling. The reaction mixture was further stirred at room temperature and after being ice-cooled, the resulting crystals were filtered to obtain 157 g of intermediate (41c) (yield, 74%) with a melting point of 142 to 143° C. (ii) Synthesis of Intermediate (41d) The intermediate (41c) in an amount of 150 g (0.53 mol) was dispersed in 750 ml of acetonitrile and 99.9 g of 3-nitrobenzoyl chloride (0.53 mol) was added thereto and the mixture was reacted for 3 hours while being heated under reflux. The resulting crystals were extracted with ethyl acetate and sodium carbonate aqueous solution. After drying, the solvent was removed by distillation. The residue was recrystallized in ethanol to obtain 134g of intermediate (41d) (yield of 76%). (iii) Synthesis of Intermediate ((41e) The intermediate (41d) in an amount of 66.7 g (0.2 mol) was reacted in anhydrous acetic acid for 3.5 hours while being heated and refluxed. Anhydrous acetic acid was distilled away under reduced pressure and 480 ml of acetic acid, 105 ml of concentrated hydrochloric acid and 25 ml of 32-36% hypophosphorous acid were added thereto. The mixture was reacted for 4 hours while being heating under reflux and, after allowed to stand for cooling, the resulting crystals were filtered. The crystals were heated under reflux for 4 hours in 400ml of acetic acid, 30ml of water and 20ml of concentrated sulfuric acid. The reaction solution was poured into 500ml of water and the resulting crystals was filtered and washed with water and ethyl acetate to obtain 52.5g of intermediate (41e) (yield of 96%). (iv) Synthesis of Intermediate (41f) The intermediate (41e) in an amount of 52.4 g (0.192 mol) was dispersed in 250 ml of pyridine and 23.5g (0.23mol) of anhydrous acetic acid was added thereto while being ice-cooled. The mixture was allowed to react overnight at room temperature. Thereafter, the reaction mixture was poured into diluted hydrochloric acid and the resulting crystals were filtered, washed and dried to obtain 57.5g of intermediate (41f) (yield of 95%). (v) Synthesis of Intermediate (41g) The intermediate (41f) in an amount of 6.3 g (20 mmol was dispersed in 30 ml of chloroform and 1.58g (20mmol) of pyridine and 1.9g (0.1mol of) thionyl chloride was added thereto at 0°C under ice-cooling. The mixture was reacted at room temperature for 1.5 hours and then, the solvent was distilled away under reduced pressure. To the resulting residue was added 50 ml of pyridine containing 2.97 g (22 mmol) of mesitylamine at 0° C under ice-cooling and the mixture was allowed to react at room temperature. Thereafter, 35 ml of a 20% potassium carbonate aqueous solution was added thereto and the mixture was allowed to react for 1 hour while heating under reflux. After cooling, ice-cooled dilute hydrochloric acid was poured into the reaction mixture and the resulting crystals were filtered, washed and dried to obtain 7.8g of intermediate (41g) (yield of 100%). (vi) Synthesis of Intermediate (41h) The intermediate (19g) in an amount of 1.17 g (3 mmol) was reacted in 2.84g (15mmol) of anhydrous tin (II) chloride and 20 ml of ethanol while heating under reflux for 0.5 hour. After completing the reaction, the reaction mixture was poured into water and the resulting crystals were filtered, washed with an aqueous solution of sodium carbonate and extracted with tetrahydrofuran. After drying, the solvent was removed by distillation under reduced pressure to obtain 0.64g of intermediate (41h) (yield of 62%). (vii) Synthesis of Exemplified Compound (I-41) The intermediate (41h) in an amount of 0.67 g (1.86 mmol) was dissolved in 10 ml of pyridine and 0.77g (1.86 mol) of intermediate (41i) was added at room temperature. Thereafter, the mixture was allowed to react overnight. The reaction solution was poured into a diluted hydrochloric acid solution and the resulting crystals were filtered. The crystal were recrystallized in ethyl acetate to obtain 0.60g of exemplified compound (I-41) (yield of 44%) with a melting point of 141-143° C. The structure thereof was confirmed by 1 H-NMR, IR and MASS spectrography. The couplers used in the invention may be used ordinarily in an amount within the range of from 1x10 -3 mols to 1 mol and preferably from 1x10 -2 mols to 8x10 -1 mols per mol of silver halide used. The couplers may also be used together with other kinds of cyan couplers. Any means and techniques applicable to any ordinary dye-forming couplers may similarly be applied to the couplers used in the invention. In any color development processes, the couplers described herein may be used therein as a raw material for forming a color photograph. The color development processes include typically a coupler-in-developer type color development process and a coupler-in-emulsion type color development process. When making use of a coupler-in-developer type process, a coupler as defined herein may be used by dissolving it in an aqueous alkaline solution or an organic solvent (such as alcohol) and then by adding the resulting solution to a developing solution. When making use of a coupler as described herein as a raw material for forming a color photograph in a coupler-in-emulsion type color development process, the coupler may be used by containing it in a photographic light-sensitive material. Typically, it is preferable to use a process for forming a color light-sensitive material, in which a coupler as described herein is compounded in a silver halide emulsion and the resulting emulsion is coated on a support. The coupler is used in a color photographic light-sensitive material such as a color negative or positive film and a color printing paper. A light-sensitive material applied with a coupler as described herein, including the above-mentioned color printing paper, may be of the monochromatic type or the multi-colored type. In a multi-color type light-sensitive material, the coupler may be contained in any layer. It is, however, ordinarily contained in a green-sensitive silver halide emulsion layer or/and a red-sensitive silver halide. A multi-colored light-sensitive material has a dye image-forming component unit having light-sensitivity in each of the three primary color regions. Each of the component units can be comprised of a single or multilayered emulsion layer each light-sensitive to a certain region having a spectrum. The constitutional layers of a light-sensitive material, including an image-forming component unit layer, may be arranged in various orders known in the art. A typical multi-color type light-sensitive material is comprised of a support having thereon a cyan dye image forming component unit comprising at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler (in which at least one cyan coupler is that described herein), a magenta dye image forming component unit comprising at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, and a yellow dye image forming component unit comprising at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler. The above-mentioned light-sensitive material may have such an additional layer as a filter layer, an intermediate layer, a protective layer or a subcoated layer. The coupler described herein may be contained in an emulsion in the manner known so far. For example, the couplers may be dissolved independently or in combination in a high-boiling organic solvent having a boiling point of not lower than 175°C such as tricresyl phosphate and dibutyl phthalate or a low-boiling solvent such as butyl propionate independently, respectively or, if required, in the mixed solution of the above-mentioned solvents. After that, the resulting solution is mixed with an aqueous gelatin solution containing a surfactant and the mixture is then emulsified by a high-speed rotary mixer or a colloid mill. The resulting emulsion is added to silver halide, so that a silver halide emulsion can be prepared. The silver halide may be for example, silver chloride, silver chlorobromide and silver chloroiodobromide. Further, a compounded mixture of silver chloride and silver bromide may also be used. To be more concrete, in the case where a silver halide emulsion is used in a color printing paper, a particularly speedy developability is required. Therefore, it is preferable to contain therein a chlorine atom as a halogen component of the silver halide and it is particularly preferable that the silver halide is silver chloride, silver chlorobromide or silver chloroiodobromide each containing at least 1% of silver chloride. The silver halide emulsion may be chemically sensitized in an ordinary process, and it may also be optically sensitized to any desired wavelength region. For the purpose of preventing a fog from being produced in the course of manufacturing, preserving or processing a light-sensitive material and/or stabilizing the photographic characteristics of the light-sensitive material, it is allowed to add a compound having been known in the photographic industry as an antifoggant or a stabilizer. The color light-sensitive material may be applied with an anti-color-foggant, a dye-image stabilizer, a UV absorbent, an antistatic agent, a matting agent, a surfactant and so forth which may commonly be used. The above-given additives may be those referred to in the description of Research Disclosure Vol. 176, pp. 22-31, Dec., 1978. An image can be formed when the color photographic light-sensitive material is treated in a color-development process well-known in the art. The color photographic light-sensitive material may contain a color developing agent in the form of itself or a precursor thereof in the hydrophilic colloidal layer of the light-sensitive material, and the light-sensitive material can be treated in an alkaline activation bath. The color photographic light-sensitive material may be color-developed and then subjected to bleaching and fixing treatments. The bleaching and fixing treatments may also be carried out at the same time. After completing the fixing treatment, a washing treatment is usually carried out. A stabilizing treatment may be carried out in place of the washing treatment, and the two treatments may be carried out in combination. EXAMPLES Now, the invention will concretely be detailed with reference to the following examples. However, the invention shall not be limited thereto. Example 1 On a paper-made support laminated with polyethylene on both sides thereof, each of the following layers was coated in order from the support side, so that red-light sensitive color light-sensitive material sample 1 could be prepared. Hereinafter, the amounts of the compounds added will be shown in terms of an amount per sq. meter, unless otherwise expressly stated, (provided that silver halide will be shown in terms of the silver content thereof.) Layer 1: an emulsion layer A red-sensitive emulsion layer comprising 9.1x10 -4 mols of comparative cyan coupler was prepared by dissolving in 0.45 g of dioctyl phthalate, 1.3 g of gelatin and 0.2 liters of an red-sensitive silver chlorobromide emulsion (containing 99.5 mol% of silver chloride). Layer 2: a protective layer A protective layer containing 0.50 g of gelatin. Thereto, sodium 4-dichloro-6-hydroxy-s-triazine was added in an amount of 0.017 g per g of gelatin. Next, samples 2 to 14 were prepared in the same manner as for Sample 1, except that comparative coupler a was replaced respectively by the couplers shown in Table 1. The resulting Samples 1 to 14 were exposed to light through a wedge in an ordinary method and were then developed in the following development process. (Development process) Processing step Temperature Time Color developing 35.0±0.3°C 45 sec. Bleach-fixing 35.0±0.5°C 45 sec. Stabilizing 30°C to 34°C 90 sec. Drying 60°C to 80°C 60 sec. The compositions of the processing solutions used in each of the processing steps were as follows: (Color developer) Water 800 ml Triethanolamine 10 g N,N-diethyl hydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediamine tetraacetic acid 1.0 g Disodium catechol-3,5-disulfonate 1.0 g Diethylene glycol 10 g 3-Methyl-4-amino-N-ethyl-N-(β-methane sulfonamido ethyl)aniline 4.5 g Fluorescent whitening agent (4,4'-diamino stilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Add water to make a total of 1 liter Adjust pH to be pH10.10 (Bleach-fixer) Ferric ammonium ethylenediamine tetraacetate, dihydrate 60.0 g Ethylenediamine tetraacetic acid 3.0 g Ammonium thiosulfate (in an aqueous 70% solution) 100.0 ml Ammonium sulfite (in an aqueous 40% solution) 27.5 ml Add water to make a total of 1 liter Adjust pH with potassium carbonate or glacial acetic acid to pH 5.7 (Stabilizer) 5-Chloro-2-methyl-4-isothiazoline-3-one 0.2 g 1,2-Benzisothiazoline-3-one 0.3 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium o-phenylphenol 1.0 g Ethylenediamine tetraacetic acid 1.0 g Ammonium hydroxide (in an aqueous 20% solution) 3.0 g Fluorescent whitening agent (4,4'-diamino stilbene sulfonic acid derivative) 1.5 g Add water to make a total of 1 liter Adjust pH with sulfuric acid or potassium hydroxide to pH 7.0 For the processed Samples 1 to 5 and 7 to 14, the maximum density (D max ) thereof was measured by a densitometer (Model KD-7 manufactured by Konica Corp.). Further, the processed samples were allowed to stand under high temperature and high humidity conditions (at 85°C and 60%RH) for 21 days, and the heat resistance and moisture resistance of the resulting dye images were checked. The heat stability and humidity stability of each dye image were indicated in terms of a dye residual percentage obtained after completing the heat and humidity stability tests. The results thereof will be shown in Table 1. Sample No. Coupler used Color developability, Dmax Dye residual ratio (%) Heat·& humidity stability 1 Comparative a 2.30 81 2 Comparative b 1.79 94 3 Inventive I-1 2.48 97 4 Inventive I-5 2.51 98 5 Inventive I-12 2.46 97 7 Inventive I-16 2.44 97 8 Inventive I-23 2.50 98 9 Inventive I-27 2.48 99 10 Inventive I-32 2.46 99 11 Inventive I-41 2.51 98 12 Inventive I-43 2.50 99 13 Inventive II-1 2.40 95 14 Inventive II-13 2.47 95 As is obvious from the results shown in Table 1, it can be seen that every inventive sample is high in Dmax and dye residual ratio and excellent in color developability and heat·moisture resistance, as compared to the comparative samples. Example 2 On a paper-made support laminated with polyethylene on one side and with polyethylene containing titanium oxide on the other side, each of the layers having the following compositions was coated on the titanium oxide-containing polyethylene layer-side, so that Sample 15 of a multilayered silver halide photographic light-sensitive material was prepared. The coating solutions were prepared in the following manner: Coating solution for Layer 1 Sixty (60) ml of ethyl acetate was added to 26.7 g of yellow coupler (Y-1), 10.0 g of dye-image stabilizer (ST-1), 6.67 g of dye-image stabilizer (ST-2), 0.67 g of additive (HQ-1), anti-irradiation dye (AI-3) and 6.67 g of high-boiling organic solvent (DNP), and the mixture thereof was dissolved. The resulting solution was emulsified and dispersed in 220 ml of an aqueous 10% gelatin solution containing 7.0 ml of 20% surfactant (SU-1) by making use of an ultrasonic homogenizer, so that a yellow coupler dispersed solution could be prepared. The resulting dispersed solution was mixed with a blue light-sensitive silver halide emulsion (containing 8.68 g of silver) that was prepared under the following conditions, so that a coating solution for Layer 1 could be prepared. Coating solutions for Layers 2 to 7 were each prepared in a manner similar to the above-mentioned coating solution for Layer 1. As a hardener, (H-1) was added to each of Layers 2 and 4 and (H-2) to Layer 7. As a coating aid, surfactants (SU-2) and (SU-3) were added thereto, so that the surface tension of the layers was controlled. The amounts thereof added to a silver halide photographic light-sensitive material will be hereinafter indicated in terms of grams per sq.meter, unless otherwise expressly stated. The layer arrangements were as shown in the following table: Layer Composition Amount (g/m 2 ) Layer 7 (Protective layer) Gelatin 1.00 DIDP 0.05 Antistaining agent (HQ-2) 0.002 Antistaining agent (HQ-3) 0.002 Antistaining agent (HQ-4) 0.004 Antistaining agent (HQ-5) 0.002 Antimold (F-1) 0.002 Layer 6 (UV-absorption layer) Gelatin 0.40 UV-absorbent (UV-1) 0.10 UV-absorbent (UV-2) 0.04 UV-absorbent (UV-3) 0.16 Antistaining agent (HQ-5) 0.04 DNP 0.20 PVP 0.03 Anti-irradiation dye (AI-2) 0.02 Anti-irradiation dye (AI-4) 0.01 Layer 5 (Red-sensitive layer) Gelatin 1.30 - Red-sensitive silver chlorobromide emulsion (Em-R) 0.21 Cyan coupler (C-1) 0.17 Cyan coupler (C-2) 0.25 Dye-image stabilizer (ST-1) 0.20 Antistaining agent (HQ-1) 0.01 HBS-1 0.20 DOP 0.20 Layer 4 (UV-absorption layer) Gelatin 0.94 UV-absorbent (UV-1) 0.28 UV-absorbent (UV-2) 0.09 UV-absorbent (UV-3) 0.38 Antistaining agent (HQ-5) 0.10 DNP 0.40 Layer 3 (Green-sensitive layer) Gelatin 1.40 Green-sensitive silver 0.17 chlorobromide emulsion (Em-G) Magenta coupler (M-1) 0.23 Dye-image stabilizer (ST-3) 0.20 Dye-image stabilizer (ST-4) 0.17 DIDP 0.13 DBP 0.13 Anti-irradiation dye (AI-1) 0.01 Layer 2 (Intermediate layer) Gelatin 1.20 Antistaining agent (HQ-2) 0.03 Antistaining agent (HQ-3) 0.03 Antistaining agent (HQ-4) 0.05 Antistaining agent (HQ-5) 0.23 DIDP 0.06 Antimold (F-1) 0.002 Layer 1 (Blue-sensitive layer) Gelatin 1.20 Blue-sensitive silver chlorobromide emulsion (Em-B) 0.26 Yellow coupler (Y-1) 0.80 Dye-image stabilizer (ST-1) 0.30 Dye-image stabilizer (ST-2) 0.20 Antistaining agent (HQ-1) 0.02 Anti-irradiation dye (AI-3) Q.01 DNP 0.20 Support Polyethylene-laminated paper The coated amounts of silver halide emulsions were indicated as calculated in terms of silver. DBP= dibutyl phthalate DOP= dioctyl phthalate DNP= dinonyl phthalate DIDP= diisodecyl phthalate PVP= polyvinyl pyrrolidone Preparation of Blue-sensitive silver halide emulsion To 1000 ml of an aqueous 2% gelatin solution having been kept at 40°C, the following Solution A and Solution B were each added at the same time over 30 minutes while controlling the pHs thereof to 6.5 and 3.0, respectively. Further, (Solution C) and (Solution D) were each added at the same time over 180 minutes while controlling the pHs thereof to 7.3 and 5.5, respectively. Control of the pH was carried out by making use of an aqueous solution of sulfuric acid or sodium hydroxide. Control of the pAg control was carried out by making use of a controller having the following composition. The controller is comprised of an aqueous solution of the mixture of silver halides composed of sodium chloride and potassium bromide. The proportion of the chloride ions to bromide ions was 99.8 : 0.2 and the concentration of the controller was 0.1 mols per liter when Solutions A and B was mixed up and 1 mol per liter when mixing Solutions C and D. Solution A Sodium chloride 3.42 g Potassium bromide 0.03 g Add water to make 200 ml Solution B Silver nitrate 10 g Add water to make 200 ml Solution C Sodium chloride 102.7 g Potassium bromide 1.0 g Add water to make 600 ml Solution D Silver nitrate 300 g Add water to make 600 ml After completing the addition, a desalting treatment was carried out with an aqueous 5% solution of Demol N manufactured by Kao-Atlas Co. and an aqueous 20% magnesium sulfate solution and the desalted solution was then mixed with an aqueous gelatin solution, so that monodispersed cubic-shaped emulsion EMP-1 having an average grain-size of 0.85µm, a variation coefficient (S/R) of 0.07 and a silver chloride content of 99.5 mol% was obtained. The resulting emulsion EMP-1 was chemically ripened at 50°C for 90 minutes by making use of the following compounds, so that blue-sensitive silver halide emulsion (Em-B) could be obtained. Sodium thiosulfate 0.8 mg/mol of AgX Chloroauric acid 0.5 mg/mol of AgX Stabilizer STAB-1 6x10 -4 mols/mol of AgX Sensitizing dye BS-1 4x10 -4 mols/mol of AgX Sensitizing dye BS-2 1x10 -4 mols/mol of AgX Preparation of Green-sensitive Silver Halide Emulsion Monodisperse type cubic-shaped emulsion EMP-2 having an average grain-size of 0.43µm, a variation coefficient (S/R) of 0.08 and a silver chloride content of 99.5% could be obtained in the same manner as in the case of EMP-1, except that the time of adding Solution A and Solution B and the time of adding Solution C and Solution D were changed. The resulting EMP-2 was chemically ripened at 55°C for 120 minutes by making use of the following compounds, so that green-sensitive silver halide emulsion (Em-G) was obtained. Sodium thiosulfate 1.5 mg/mol of AgX Chloroauric acid 1.0 mg/mol of AgX Stabilizer STAB-1 6x10 -4 mols/mol of AgX Sensitizing dye GS-1 4x10 -4 mols/mol of AgX Preparation of Red-sensitive Silver Halide Emulsion Monodisperse type cubic-shaped emulsion EMP-3 having an average grain-size of 0.50µm, a variation coefficient (S/R) of 0.08 and a silver chloride content of 99.5% was obtained in the same manner as in the case of EMP-1, except that the time of adding Solution A and Solution B and the time of adding Solution C and Solution D were changed. The resulting EMP-3 was chemically ripened at 60°C for 90 minutes by making use of the following compounds, so that red-sensitive silver halide emulsion (Em-R) was obtained. Sodium thiosulfate 1.8 mg/mol of AgX Chloroauric acid 2.0 mg/mol of AgX Stabilizer STAB-1 6x10 -4 mols/mol of AgX Sensitizing dye RS-1 1x10 -4 mols/mol of AgX The variation coefficient was calculated from the following standard deviation (S) and an average grain-size (R), S = [Σ(R i -R) 2 /Σn i ] 1/2 wherein R i represents a grain size and ni represents the number of grains having a grain-size of R i . Samples 16 to 19, 21 to 24 and 26 to 39 were each prepared in the same manner as for Sample 15, except that cyan couplers (C-1) and (C-2) of Layer 5 of Sample 15 were replaced by the couplers shown in Table 3, (in which the amounts thereof added were the same mols as the total mols of the comparative couplers C-1 and C-2). The resulting samples were each exposed to light through an optical wedge as in Example 1 and were developed. The maximum density (Dmax) of each of the red light-sensitive layers was determined. With each of the above-mentioned samples 15 to 19, 21 to 24 and 26 to 39, the color reproducibility was evaluated in the following manner. By making use of a color negative film (a Konica Color Film LV-400 manufactured by Konica Corp.) and a camera (a Konica camera FT-1 MOTOR manufactured by Konica Corp.), a color checker (manufactured by MacBeth Co.) was photographed. Successively, the photographed color-negative film was developed (with a developer CNK-4 manufactured by Konica Corp.) and the resulting negative image was printed on each of the above-mentioned samples Nos. 15 to 39 to a size of 82mm x 117mm by making use of a Konica Color Printer CL-P2000 (manufactured by Konica Corp.), so that the practical prints were obtained in the same manner as mentioned above. When making every print, the printing conditions were so set as to reproduce the same gray on every print as on the color checker. Regarding the resulting practical prints, the color reproducibility and black background property thereof were visually evaluated, based on five grades ranging from 1 (poor) to 5 (excellent). The results thereof will be shown collectively in Table 3. Sample No. Cyan coupler Maximum density Color reproducibility Black background Remarks Cyan Blue Green 15 C-1/C-2 2.49 3 3 3 Excellent Comparison 16 Coupler C 2.10 3 5 3 Insufficient Comparison 17 Coupler d 2.27 3 5 3 Insufficient Comparison 17 Coupler e 2.27 3 5 3 Insufficient Comparison 18 I-3 2.51 5 5 5 Excellent Invention 19 I-7 2.54 5 5 5 Excellent Invention 21 I-10 2.47 5 5 5 Excellent Invention 22 I-13 2.52 5 5 5 Excellent Invention 23 I-18 2.54 4 5 5 Excellent Invention 24 I-20 2.42 4 5 5 Excellent Invention 26 I-25 2.56 5 5 5 Excellent Invention 27 I-31 2.50 5 5 5 Excellent Invention 28 I-35 2.53 4 5 4 Excellent Invention 29 I-36 2.49 4 5 4 Excellent Invention 30 I-38 2.49 5 5 5 Excellent Invention 31 I-41 2.59 5 5 5 Excellent Invention 32 I-42 2.57 5 5 5 Excellent Invention 33 I-43 2.54 5 5 5 Excellent Invention 34 I-47 2.50 5 5 5 Excellent Invention 35 II-2 2.46 4 5 4 Excellent Invention 36 II-4 2.46 4 5 4 Excellent Invention 37 II-10 2.47 3 5 4 Excellent Invention 38 II-16 2.42 4 5 4 Excellent Invention 39 II-19 2.40 4 5 4 Excellent Invention As can be seen from the Table 3, Sample No. 15 containing Comparative Couplers C-1 and C-2 was seriously unsatisfactory in color reproduction. Samples Nos. 16 and 17 each containing Comparative Couplers c and d were scarcely improved in cyan and green color reproducibility and were also insufficient in black background property because of the low maximum density, though the blue color reproducibility was apparently improved. In contrast to the above, the samples of the invention, were not only excellent in reproducibility of every color, cyan, blue and green, in color developability and in black background property, but also high in maximum density.

Claims: A silver halide color photographic light sensitive material comprising a support having thereon a silver halide emulsion layer comprising silver halide grains, wherein the silver halide emulsion layer comprises a cyan dye forming coupler represented by the following formula (1) or (2), wherein R 1 and R 3 each independently represent a heterocyclic group, alkoxy group, aryloxy group, heterocyclic-oxy group or in which R 5 represents a substituent and n 1 is from 1 to 5; R 2 and R 4 each independently represent an aryl group or a heterocyclic group; X 1 and X 2 each represent a hydrogen atom or a coupling-off group. The silver halide photographic material of claim 1, wherein the cyan coupler is represented by formula (3), wherein X 1 is as defined in formula (1); R 6 represents a substituent; R 7 and R 8 each represent a hydrogen atom or a substituent; n 2 is from 1 to 4; and n 3 is from 1 to 5. The silver halide photographic material of claim 1 or 2, wherein the cyan coupler is present in an amount of from 1 x 10 -3 to 1 mol per mol of the silver halide grains in the silver halide emulsion layer. The silver halide photographic material of any preceding claim, wherein the silver halide grains are chosen from silver chloride, silver chlorobromide and silver iodochlorobromide.

Inventors: FUKUDA MITSUHIRO, IKESU SATORU, KANEKO YUTAKA, RUDCHENKO VLADIMIR F, FUKUDA, MITSUHIRO, IKESU, SATORU, KANEKO, YUTAKA, RUDCHENKO, VLADIMIR F.
Applicants: KONISHIROKU PHOTO IND, KONICA CORPORATION
Application year: 1996
Main classification: G03C7
IPC codes: C07D487, G03C7