Silver halide photographic light sensitive material and its processing method

Abstract: A silver halide photographic light-sensitive material with excellent dye image storage stability and processing stability is provided, comprising a support having thereon a silver halide emulsion layer, wherein the silver halide emulsion layer contains a cyan coupler represented by the following formula, gelatin contained in said silver halide photographic light-sensitive material having an average iron content of less than 5 ppm by weight, based on total weight of gelatin. There is further provided a method of processing the ligh-sensitive material, in which color development is continuously coducted at an replenishing rate of 20 to 60 ml/m².

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, (hereinafter sometimes referred to as a light-sensitive material), and its processing method, and specifically to a light-sensitive material having excellent performance stability during continuous processing and its processing method. BACKGROUND OF THE INVENTION Discoloration of photographic dyes in color photographs preserved for a long time is desirably as little as possible, so that the photographs may be fully appreciated. Especially, the improvement of the heat and moisture resistance (dark storage stability) of the cyan dye is an important subject. The conventional cyan dye forming couplers which are disclosed, for instance, in Japanese Patent L.O.P. Nos. 47-37425, 50-10135, 50-25228, 50-112038, 50-117422 and 50-130441, and U.S. Patent Nos. 2,369,929, 2,423,730, 2,434,272, 2,474,293 and 2,698,794 are inferior with regard to the above-mentioned dark storage stability. Various cyan dye forming couplers have been investigated to improve this dark storage stability. For instance, the 2,5-diacylamino type cyan dye forming coupler disclosed in U.S. Patent No. 2,895,826 and Japanese Patent L.O.P. Nos. 50-112038, 53-109630, and 55-163537, and a phenol type cyan dye forming coupler which has an alkyl group having a number of carbon atoms not less than two at 5-position described in U.S. Patent Nos. 3,772,002 and 4,443,536 are excellent cyan dye forming couplers with regard to the dark storage stability. However, with regard to the 2,5-diacylamino type cyan dye forming coupler, not only is the color forming property insufficient to achieve sufficient dye density, but color reproduction is insufficient due to the large sub-absorption of the formed dye. On the other hand, the cyan dye forming coupler which has an alkyl group having a number of carbon atoms not less than two at 5-position has excellent color forming property, dark storage stability and color reproduction. Japanese Patent L.O.P. Nos. 63-44658, 63-250648, 64-537 and WO No. 88/00723 disclose the technique of enhancing the dark storage stability of the dye image formed by emulsifying a water-insoluble and organic solvent-soluble polymer with the coupler. However, the light-sensitive material which contains the above-mentioned cyan dye forming coupler which has an alkyl group having a number of carbon atoms not less than two at 5-position has a problem in that the variation of photographic performance increases as it is subjected to continuous running processing comprising processing steps including color development. This photographic variation furthermore increases when the above-mentioned water-insoluble and organic solvent-soluble polymer is used with this cyan dye forming coupler to obtain sufficient dark storage stability, and improvement is demanded. On the other hand, to prevent a change of the characteristics of finished prints caused by changes in the concentration of processing solutions, the light-sensitive material is generally subjected to continuous running processing while a replenishing solution of each processing solution is replenished. In this case, however, a large amount of solution overflows with the replenishment of the solution and causes a serious environmental problem. Therefore, in recent years, it has been strongly demanded to reduce the replenishing amount of the color developer (reduction of replenishment rate) to reduce the overflowing solution, and furthermore, to reduce replenishment so that no solution overflows. Recently, light-sensitive material containing silver halide grains with a high silver chloride content, with excellent rapid processing ability has been used for color paper. The reduction of replenishment rate of the color developer is advantageous when processing light-sensitive material containing silver halide grains with high silver chloride content, because bromide ions which strongly inhibit development do not flow out to the color developer. When the light-sensitive material which has excellent dark storage stability, containing the above-mentioned cyan dye forming coupler which has an alkyl group having not less than two carbon atoms at the 5-position, is continuously processed with reduced color developer replenishment, the variation of the photographic performance becomes remarkable. EP-A-0 315 833 describes silver halide photographic color materials which contain less than 5 ppm of iron in the layers. The materials exemplified show the use of a cyan dye forming coupler which has an alkyl group having not less than two carbon atoms at the 5-position. The problems arising from continuous processing with reduced color developer are not addressed. SUMMARY OF THE INVENTION The present invention has been achieved considering the above-mentioned circumstances. The object of the present invention is to provide a light-sensitive material with excellent fastness of the dye image, improved in the stability of photographic performance during continuous processing, and to provide a method of processing the above-mentioned light-sensitive material with a reduced amount of replenishment of color developer. The above-mentioned object of the present invention is achieved by a silver halide photographic light-sensitive material comprising a support having thereon a silver halide emulsion layer, in which said silver halide emulsion layer contains a cyan coupler represented by the following formula C-I; wherein R₁ represents an alkyl group having from 2 to 6 carbon atoms, R₂ represents a ballast group, Z represents a hydrogen atom or a group capable of being released upon reaction with an oxidation product of a color developing agent, the gelatin contained in said silver halide photographic light-sensitive material has an average iron content of less than 5 ppm by weight, based on the total weight of gelatin, characterised in that the total amount of gelatin contained in the silver halide photographic material is less than 6.5 g/m² of the silver halide photographic material. DETAILED DESCRIPTION OF THE INVENTION Especially, the effect of the present invention is enhanced effectively when the iron content of the gelatin contained in the above-mentioned silver halide photographic light-sensitive material is less than 3 ppm. The effect of the present invention is enhanced when a water-insoluble and organic solvent soluble polymer compound is contained in the silver halide emulsion layer containing the cyan dye froming coupler represented by formula C-I and/or when at least one silver halide emulsion layer contains silver halide grains having a silver chloride content of not less than 95 mol%. Further, the object of the present invention is achieved by a method of processing the above mentioned silver halide photographic light-sensitive material, of which at least one silver halide emulsion layer contains silver halide grains having a silver chloride content of not less than 95 mol%, wherein the silver halide photographic light-sensitive material is processed continuously using color developer which contains a color developing agent; and the replenishing amount of the color developer is 20 to 60 ml per 1m² of said silver halide photographic light-sensitive material. The present invention is explained in more detail as follows. In the cyan dye forming coupler represented by the above-mentioned formula C-I, the alkyl group having 2 to 6 carbon atoms represented by R₁ may be a straight chain or a branched chain and includes those having a substituent. R₁ is preferably an ethyl group. The ballast group represented by R₂ is an organic group having a size and shape which gives the coupler molecules sufficient bulkiness to substantially prevent diffusion to other layers from the layer containing the coupler. The preferable ballast group is represented by the following formula. C-II -CH(R₃)-O-Ar R₃ represents a hydrogen atom an alkyl group having 1 to 12 carbon atoms. Ar represents an aryl group such as a phenyl group, and this aryl group includes those having a substituent. In formula C-I, the group capable of releasing upon reaction with an oxidation product of the color developing agent represented by Z includes a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imido group, which includes those having a substituent, and preferably, a halogen atom, an aryloxy group, and an alkoxy group. Specific examples of the coupler represented by formula C-I are shown as follows, but they are not limited thereby. Exemplified compounds IV-1 to 19 described in pages 12 to 13 of Japanese Patent L.O.P. No. 1-196048 and exemplified compounds C-2 to C-5, C-7 and C-9 to C-12 described in page 19 of Japanese Patent L.O.P. No. 64-537 are given as specific examples of the cyan dye forming coupler used in the present invention including those described above. The cyan dye forming coupler represented by above-mentioned formula C-I of present invention is usually used in an amount of a range of 1×10⁻³ mol to 1 mol, and preferably 1×10⁻² mol to 8×10⁻¹ mol. The water-insoluble and organic solvent-soluble polymer compound preferably used with the cyan dye forming coupler represented by formula C-I of the present invention includes (1) vinyl polymer and copolymer, (2) condensation polymer of polyhydric alcohol and 1 polybasic acid, (3) polyester obtained by the ring-opening-polymerization method and (4) polycarbonate resin, polyurethane resin, and other polyamide resins. The average molecular weight of these polymers are not especially limited, but preferably, it is not more than 200,000, and more preferably between 5,000 to 100,000. Specific examples of the polymer preferably used is shown as follows. The weight ratio of the monomer is shown for the copolymer. (PO-1) Poly (N-t-butylacrylamide) (PO-2) N-t-butylacrylamide-methylmethacrylate copolymer (60:40) (PO-3) Polybutylmethacrylate (PO-4) Methylmethacrylate-styrene copolymer (90:10) (PO-5) N-t-butylacrylamide-2-methoxyethylacrylate copolymer (55:45) (PO-6) ω-methoxypolyethyleneglycolacrylate (addition molecular number n=9) -N-t-butylacrylamide copolymer (25:75) The exemplified compounds P-1 to P-200 described in pages 10 to 15 of Japanese Patent L.O.P. No. 64-537 may be furthermore included besides the above-mentioned compounds. Next, the gelatin used for the present invention is explained. The gelatin contains various heavy metals such as iron, copper, zinc and manganese as impurities, and, generally contains 5 to 20 ppm iron ion. The iron content of gelatin contained in the light-sensitive material of the present invention is less than 5 ppm, and preferably less than 3 ppm. In the present invention, the iron content of the gelatin is the content of iron and the iron ions contained in the gelatin, and it is measured based on the method (atomic absorption method) described in PAGI method, 6th edition, issued by the Conference of Methods for Testing Photographic Gelatin, in October 1987. When two or more different gelatins are contained in the light-sensitive material of the present invention, it is expressed as the average value of the iron content of all gelatins contained in the light-sensitive material, i.e., the weight ratio of iron contained in all the gelatins of the light-sensitive material to the gelatins. In general, ion exchange treatment using the ion exchange resin is applied as a method to decrease metallic ions in the gelatin. However, it is not always effective to remove a small amount of iron ions contained in the gelatin, and methods such as using chelate resin, solvent extraction and foaming separation are further used. In addition, it is also effective for reducing the iron content in the gelatin to manufacture the gelatin by using materials with a small iron content, to prevent contamination of iron from the manufacturing equipment during the gelatin manufacturing process, or to remove contaminated iron powder with a magnet. The jelly strength (according to PAGI method) of the gelatin used for the present invention is preferably not less than 250g, and especially not less than 270g. The calcium content (according to PAGI method) of the gelatin used for the present invention is preferably not more than 1000 ppm, and more preferably not more than 500 ppm. In general, the treatment by the ion exchange resin column is preferable to decrease the content of calcium in the gelatin. Though the average molecular weight of the gelatin of the present invention is not especially limited, it is preferably 10,000 to 200,000. The total amount of the gelatin contained in the light-sensitive material of the present invention is less than 6.5 g/m². Though the lower limit is not especially limited, generally not less than 3.0 g/m² is preferable with respect to the physical properties or photographic performance. The amount of the gelatin is converted into the weight of gelatin containing 11.0% moisture by the moisture measurement method described in the PAGI method. The gelatin contained in the light-sensitive material of the present invention is hardened by a hardener. The hardener is not especially limited and any hardener well-known in the photographic industry, including hardeners such as aldehyde type, active vinyl type, active halogen type, epoxy type, ethyleneimine type, methanesulfonic acid ester type, carboxyl-activating hardeners such as carbodiimide type, isooxazole type, and carbamoylpyridinium salt and polymer hardeners may be used. Preferable hardeners include vinylsulfon type hardeners such as compounds H-1 to H-24 described in pages 13 to 14 of Japanese Patent L.O.P. No. 2-188753, chlorotriazine type hardener such as compounds II-1 to II-13 and III-1 to III-10 described in pages 20 to 21 of Japanese Patent L.O.P. No. 1-216340, and carboxyl-activating type hardener described in Japanese Patent L.O.P. No. 2-82237 and 1-129245. Swelling ratio (layer thickness of the hydrophilic colloidal layer in the processing solution/layer thickness of the hydrophilic colloidal layer when dry) of the light-sensitive material of the present invention is preferably 1.5 to 4.0 and more preferably 2.0 to 3.0. The silver halide used for the silver halide emulsion layer of the present invention includes arbitrary silver halides such as silver chloride, silver bromide, silver iodide, silver bromochloride, silver iodobromide and silver iodochloride. The silver halide grain used preferably in the present invention has a silver chloride content of not less than 95 mol%, the silver bromide content of not more than 5 mol% and a silver iodide content of not more than 0.5 mol%. More preferable is silver bromochloride having a silver bromide content of 0.1 to 2 mol%. The silver halide grain may be either used alone or mixed with other silver halide grains of a different composition. It may also be mixed with silver halide grains having a silver chloride content of not less than 95 mol%. In the silver halide emulsion layer containing silver halide grains having a silver chloride content of not less than 95 mol%, the proportion of silver halide grains having a silver chloride content of not less than 95 mol% occupying all silver halide grains contained in the emulsion layer is not less than 60% by weight, preferably, not less than 80%. The composition of silver halide grains may be uniform from the inside to the outside, or the composition of the inside and the outside may be different. When the compositions of the inside and the outside are different, the composition may change either continuously or discontinuously. Though the grain size of silver halide grains is not especially limited, it is preferably from 0.2 to 1.6 µm, and more preferably from 0.25 to 1.2 µm, with respect to other photographic performance, such as rapidity and sensitivity. The distribution of the particle size of silver halide grains may be either polydispersed or monodispersed. The preferable one is monodispersed silver halide grains having a coefficient of variation of not more than 0.22, more preferably 0.15, in the particle size distribution thereof. The coefficient of variation here means a coefficient which shows the width of particle size distribution, defined by the following formula. Coefficient of variation = standard deviation of particle size distribution/average grain size Silver halide grains obtained in any one of an acid method, a neutral method and an ammonia method may be used for the present invention. The particle may be grown at one time or may be grown after making a seed particle. The method of making seed particles and the method of the growing thereof may be the same or different. Moreover, as a form of reacting a soluble silver salt with a soluble halide, any one of a normal precipitation method, reverse precipitation method, double jet method and a combination thereof may be used, and the double jet method is preferable. The pAg controlled double jet method described in Japanese Patent L.O.P. No. 54-48521 may further be used as one form of the double jet method. In addition, silver halide solvents such as thioether and imidazoles may be used if necessary. The mercapto group-containing compound, the nitrogen-containing heterocyclic compound or compounds such as sensitizing dye may also be added after the formation of silver halide grains or at the end of the grain formation. The shape of silver halide grains used for the present invention may be arbitrary. One of the preferable examples is a cube having {100} face as a crystal surface. It is possible to make and use grains having the shape of an octahedron, tetradecahedron or dodecahedron by the method described in, for example, U.S. Patent Nos. 4,183,756 and 4,225,666, Japanese Patent L.O.P. No. 55-26589, Japanese Patent Examined Publication No. 55-42737 and Journal of Photographic Science, 21 , 39 (1973). Grain having a twin crystal plane may also be used. The silver halide grain used in the present invention may be either a single shape or a mixture of various forms. In the process of forming and/or growing the silver halide grain in the present invention, metallic ion may be added and included inside and/or on the surface of the grain by using cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (containing complex salt), rhodium salt (containing complex salt) or iron salt (containing complex salt). Under a suitable reductive atmosphere, reduction sensitized speck may be given to the inside and/or the outer surface of the grain. After growth of the silver halide grain has finished, unnecessary soluble salts in the emulsion which contain silver halide grains, may either be removed or be contained as they are. In the present invention, silver halide grains used for the emulsion may be either those in which the latent image is substantially formed on the surface, or the particle substantially formed inside. The grain in which the latent image is substantially formed on the surface is preferable. In the present invention, the emulsion is chemically sensitized by conventional methods, such as the sulfur sensitization method which uses a sulfur-containing or active gelatin compound capable of reacting with silver ions, the selenium sensitization method which uses a selenium compound, the reduction sensitization method which uses reducing substances, the noble metal sensitization method which uses gold and other noble metal compounds. These methods may be used independently or in combination. The emulsion is spectrally sensitized using the sensitizing dye in a desired wavelength region. Cyanine dye, merocyanine dye, composite cyanin dye, composite merocyanine dye, holopolarcyanin dye, hemicyanine dye, styryl dye and hemioxanole dye may be used as the sensitizing dye. Specific examples of them include, for instance, exemplified compounds BS-1 to BS-9, GS-1 to GS-5, RS-1 to RS-8, and IRS-1 to IRS-10 described in pages 76 to 82 of Japanese Patent Application No. 2-76278. The supersensitizing agent, which may be used in combination therewith includes exemplified compounds SS-1 to SS-9 described in pages 84 to 85 of Japanese Patent Application No. 2-76278. Dye-forming couplers used for the light-sensitive material of the present invention are usually selected so as to form a dye which absorbs the spectrum to which the emulsion is sensitive, for each emulsion layer. A yellow dye-forming coupler is used for the blue-sensitive emulsion layer, a magenta dye-forming coupler is used for the green-sensitive emulsion layer, and a cyan dye-forming coupler is used for the red-sensitive emulsion layer. The color photographic light-sensitive material may also be made differently from the above-mentioned combination, depending on the object. In the present invention, acylacetoanilide type couplers may preferably be used as yellow dye-forming couplers, and benzoylacetoanilide type and pivaloylacetoanilide type compounds are advantageous among them. Specific examples of the yellow dye-forming coupler used preferably in the present invention are shown as follows. Besides the above compounds, exemplified compounds Y-1 to Y-146 described in pages 7 to 16 of Japanese Patent L.O.P. No. 63-85631, exemplified compounds Y-1 to Y-98 described in pages 6 to 10 of No. 63-97951, exemplified compounds Y-1 to Y-24 described in pages 18 to 20 of No. 1-156748, exemplified compounds I-1 to I-50 described in pages 4 to 7 of No. 2-298943 and exemplified compounds Y-1 to Y-48 described in pages 114 to 120 of No. 62-215272 may be used. In the present invention, well-known couplers such as the 5-pyrazolone type, the pyrazoloazole type, and the pyrazolobenzimidazole type coupler may be used as a magenta dye-forming coupler. Specific examples of the magenta coupler used preferably in the present invention are shown as follows. Besides the above compounds, exemplified compounds 1 to 223 described in pages 18 to 32 of Japanese Patent L.O.P. No. 62-166339, exemplified compounds M-1 to M-29 described in pages 5 to 6 of Japanese Patent L.O.P. No. 2-100048, exemplified compounds M-1 to M-30 described in pages 9 to 12 of Japanese Patent L.O.P. No. 3-214155, exemplified compounds M-1 to M-47 described in pages 104 to 114 of Japanese Patent L.O.P. No. 62-215272, may be used. In the present invention, the cyan dye forming coupler shown by above-mentioned formula C-I is used as a cyan dye-forming coupler, and other cyan dye forming couplers may also be used within the range not adversely affecting the present invention. The cyan dye forming coupler preferably used in combination includes 2,5-diacylaminophenol type cyan dye forming couplers disclosed in U.S. Patent No. 2,895,826, Japanese Patent L.O.P. No. 50-112038, 53-109630, 55-163537 and 63-96656. Hydrophobic compounds such as dye-forming couplers are usually dissolved in a high boiling organic solvent having a boiling point of about 150°C or more, or the above-mentioned water-insoluble and organic solvent-soluble polymer compound with, if necessary, the low boiling and/or water-soluble organic solvent. After being emulsified into a hydrophilic binder solution such as a gelatin solution with a surfactant using a stirrer, homogenizer, colloid mill, flow jet mixer or ultrasonic wave equipment, it is added to aimed hydrophilic colloidal layer. The high boiling organic solvent used for the present invention includes esters such as phthalic acid ester and phosphoric acid ester, organic acid amides, ketons and hydrocarbon compounds. These specific examples contain the exemplified compounds A-1 to A-120 described in pages 4 to 7, the exemplified compounds II-1 to II-29 described in pages 8 to 9, the exemplified compounds H-1 to H-22 described in pages 14 to 15 of Japanese Patent L.O.P. No. 1-196048, the exemplified compounds S-1 to S-69 described in pages 3 to 7 of Japanese Patent L.O.P. No. 1-209446, and the exemplified compounds I-1 to I-95 described in pages 10 to 12 of Japanese Patent L.O.P. No. 63-253943. Color antifoggant, image stabilizer, hardener, plasticizer, antirradiation dyestuff, polymer latex, ultraviolet ray absorbent, formalin scavenger, development accelerator, development retarder, fluorescent brightening agent, matting agent, lubricant, antistatic agent, and surfactant may be used arbitrarily for the light-sensitive material of the present invention. These compounds are described in Japanese Patent L.O.P. No. 62-215272 and 63-46436. The aminophenol or the p-phenylenediamine type compounds widely used for various color photographic processes are used as a color developing agent in the photographic processing of the light-sensitive material related to the present invention. Especially, an aromatic primary amine type color developing agent is preferably used. The aromatic primary amine type color developing agent includes, for instance, the following agents. (1) N,N-dimethyl-p-phenylenediamine hydrochloric acid salt (2) N-methyl-p-phenylenediamine hydrochloric acid salt (3) 2-amino-5-(N-ethyl-N-dodecylamino) toluene (4) N-ethyl-N-(β-methanesulfonamideethyl)-3-methyl-4-aminoaniline sulfate (5) N-ethyl-N-(β-hydroxyethyl)-3-methyl-4-aminoaniline sulfate (6) 4-amino-3-methyl-N,N,-diethylaniline (7) 4-amino-N-(β-methoxyethyl)-N-ethyl-3-methylaniline· p-toluene sulfonic acid salt (8) 4-amino-N-ethyl-N-(γ-hydroxypropyl)-3-methylaniline· p-toluene sulfonic acid salt It is preferable that these color developing agents are used within the range of 0.001 to 0.2 mol, more preferably the range of 0.005 to 0.2 mol, per one liter of developer. In addition to the above-mentioned color developing agent, already-known developer constituent compounds may be added to the color developer. Normally, an alkali agent having pH buffering action, a development retarder such as chloride ion and benztriazole, a preservative and a chelating agent are used. Potassium carbonate, potassium borate and trisodium phosphate may be used as an alkali agent for the above-mentioned color developer, and sodium hydroxide and potassium hydroxide may be mainly used for the purpose of pH adjustment. The pH of the color developer is generally from 9 to 12, and preferably from 9.5 to 11. Though halogenide ions are often used for the purpose of development control, chloride ions such as potassium chloride and sodium chloride are chiefly used to accelerate photographic processing. The amount of chloride ion is not less than 3.0×10⁻² mol, preferably 4.0×10⁻² to 5.0×10⁻¹ mol, per one liter of color developer. Since the bromide ion has a large retarding effect on development, the amount is not more than 1.0×10⁻³ mol, preferably not more than 5.0×10⁻⁴ mol, per a liter of color developer. As the preservative, hydroxylamine derivatives (except hydroxyl amine), hydroxamic acid hydrazines, hydrazideaminoketons, saccharoid, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxyradicals, alcohols, oximes, diamido compounds and condensed cyclic amines are especially effective organic preservatives. Dialkyl substituted hydroxylamines such as diethylhydroxylamine and alkanolamines such as triethanolamine are preferably used. Aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid or phosphonocarboxylic acid may be used as a chelating agent for the color developer related to the present invention. Especially, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, or 1-hydroxyethylidene-1,1-diphosphonic acid are preferably used. The temperature of color development is usually not less than 15°C, and generally it is in a range of from 20 to 50°C. Not less than 30°C is preferable for rapid processing. The color development processing time generally ranges from 10 seconds to 4 minutes, and from 10 seconds to 1 minute is preferable for rapid processing. The range of 10 to 30 seconds is more preferable. When the color developer is continuously replenished during running processing in the present invention, the preferable replenishing amount of the color developer is 20 to 60 ml per 1m² of light-sensitive material to eliminate overflowing of the color developer solution. Such reduction of replenishment enhances the effect of the present invention. The light-sensitive material of the present invention is subjected to bleaching processing and fixing processing after color development. The bleaching processing can be done with fixing processing simultaneously. Usually the fixing processing is followed by washing processing, or stabilization processing may substitute for the washing processing. The equipment used for the photographic processing of the light-sensitive material of the present invention may be a roller transport type, by which the light-sensitive material is conveyed by rollers arranged in the processing tanks, or an endless belt type by which the light-sensitive material is fixed to the belt and transported, or especially, the type in which the processing tank is formed with a slit through which the light-sensitive material is transported and the processing solution is supplied to this processing tank. EXAMPLES Example 1 (comparative) Polyethylene was laminated on one side, and titanium oxide containing-polyethylene was laminated on the other side (emulsion layer coating side) of the paper support, on which each layer of the constitution shown in Table 1 and Table 2 was coated with a slide hopper, and sample 101 of the multilayer color light-sensitive material was made. The coating solutions were prepared as follows. Coating solution for the first layer 26.7 g of yellow dye-forming coupler (YC-8), 10.0 g of dye image stabilizer (ST-1) and 6.67 g of (ST-2), 0.67 g of antistaining agent (HQ-1) and 6.67 g of high boiling point organic solvent (DNP) were dissolved with 60 ml of ethyl acetate. This solution was emulsified to 220 ml of 10% gelatin solution which contains 7 ml of 20% surfactant (SU-2) with a supersonic wave homogenizer, and a yellow dye-forming coupler dispersant was made. This dispersant was mixed with the blue-sensitive silver halide emulsion (containing silver 8.67 g) made by a following condition, and antirradiation dyestuff (AI-3) was added to prepare the coating solution for the first layer. Coating solutions for the second layer to the seventh layer were prepared in the same manner as the coating solution for the first layer. Moreover, (HH-1) was added to the second and fourth layers and (HH-2) was added to the seventh layer as a hardener. Surfactants (SU-1) and (SU-3) were added as a coating aid to adjust surface tension. The added amount of silver halide emulsion was converted to silver. Additives used for each layer are as follows. HH-1 : Tetrakis (vinylsulfonylmethyl) methane HH-2 : 2,4-dichloro-6-hydroxy-s-triazine·sodium SU-1 : Sodium tri-i-propylnaphthalenesulfonate SU-2 : Di(2-ethylhexyl) sodium sulfosuccinate SU-3 : Di(2,2,3,3,4,4,5,5-octafluoropentyl) sodium sulfosuccinate DOP : Dioctylphthalate DNP : Dinonylphthalate DIDP : Di-i-decylphthalate PVP : Polyvinylpyrrolidone HBS-1 : Di(cyclohexyl) phthalate HBS-2 : Mixture of tri(2-ethylhexyl) phosphate and tricresylphosphate with the capacity ratio 2:1 HQ-1 : 2,5-di-t-octylhydroquinone HQ-2 : 2-hexadecyl-5-methylhydroquinone HQ-3 : 2-hexadecylhydroquinone F-1 : 5-chloro-2-methylisothiazoline-3-on A mixture of the above compounds in a weight ratio of 2:4:4 Preparation for blue-sensitive silver halide emulsion (Em-B) The following solutions A and B were added simultaneously controlling pAg at 6.5 and pH at 3.0, spending 30 minutes in 1000 ml of a 2% gelatin solution at 40°C. Then, following solutions C and D were added simultaneously controlling pAg at 7.3 and pH at 5.5, spending 30 minutes. At this time, pAg was controlled according to the method of the description in Japanese Patent L.O.P. No. 59-45437 and pH was controlled using aqueous solution of sulfuric acid or sodium hydroxide. (solution A) (solution B) (solution C) (solution D) After addition, a 5% aqueous solution of Demol N, made by Kao Atlas company, and a 20% aqueous solution of magnesium sulfate were used for desalinization. Then, the gelatin solution was mixed and a mono-dispersed cubic grain emulsion EMP-1, with an average grain size of 0.85 µm, a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% was obtained. Above-mentioned emulsion EMP-1 was ripened chemically using the following compound for 90 minutes at 50°C, and blue-sensitive silver halide emulsion (Em-B) was obtained. Preparation for green-sensitive silver halide emulsion (Em-G) Mono-dispersed cubic grain emulsion EMP-2 with an average grain size of 0.43 µm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained in the same manner as EMP-1 except that the addition time of solution A and solution B and the addition time of solution C and solution D were changed. EMP-2 was ripened chemically by using the following compound for 120 minutes at 55°C, and green-sensitive silver halide emulsion (Em-G) was obtained. Preparation for red-sensitive silver halide emulsion (Em-R) Mono-dispersed cubic grain emulsion EMP-3 with an average grain size of 0.50 µm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained in the same manner as EMP-1 except that the addition time of solution A and solution B and the addition time of solution C and solution D were changed. EMP-3 was ripened chemically by using the following compound for 90 minutes at 60°C, and red-sensitive silver halide emulsion (Em-R) was obtained. STAB-1: 1-(3-acetamidephenyl)-5-mercaptotetrazole Next, samples 102 to 129 were made in the same manner as sample 101 except that gelatin A contained in sample 101 was substituted for an equal amount of gelatin, cyan dye forming coupler CC-1 contained in the fifth layer for the equal mol of cyan dye forming coupler as shown in Table 3, and the polymer compound of the present invention was added as shown in Table 3. The obtained samples were evaluated as follows. <Dark storage stability> After wedge exposure by a red light according to the conventional method, the samples were processed according to the following processing steps, and kept for 20 days under the conditions of 60%RH and 85°C, and persistence (%) of the dye image from the initial concentration 1.0 was calculated. <Running variation fastness> The samples which were subjected to wedge exposure by a red light were processed according to the following processing steps and the variation Δγ was calculated by calculating γ just after the beginning of running and after the end of running when the color developer had been replenished in an amount of twice the tank capacity. Δγ = | γ just after the beginning of running - γ of running | γ here is a value represented by a reciprocal of the difference of the logarithm of each exposure necessary to obtain 0.8 and 1.8 in density. The composition of each processing solution is shown as follows. Replenishing amount of each processing solution is 80 ml per 1m² of light-sensitive material. Color developer The whole quantity was adjusted to one liter adding water. The pH of the tank solution was adjusted to 10.10, and that of the replenished solution was adjusted to 10.60. Bleach fixer (Tank solution and replenishing solution are the same). The whole quantity was adjusted to one liter adding water. The pH was adjusted to 5.7 with potassium carbonate or glacial acetic acid. Stabilizer (Tank solution and replenishing solution are the same). The whole quantity was adjusted to one liter adding water and pH was adjusted to 7.0 with sulfuric acid or the potassium hydroxide. The results are shown in Table 3. Gelatin A: Alkali processed gelatin made from cattle bone (iron content 8.2 ppm) Gelatin B: Ion exchange processed gelatin of gelatin A (iron content 5.8 ppm) Gelatin C: Ion exchange processed gelatin of gelatin A (iron content 4.1 ppm) Gelatin D: Chelate resin processed gelatin of gelatin A (iron content 2.5 ppm) As is clear from Table 3, samples 105 to 112 and 117 to 129, which used the cyan dye forming couplers used in the invention, show improved dark storage stability compared with samples 101 to 104 and 113 to 116 which used other cyan dye forming couplers. Among them, gelatins A and B which are not of the present invention both show decreased running variation fastness. On the other hand, it was found that the samples using cyan dye forming couplers and gelatins C and D were excellent in dark storage stability and running variation fastness. Especially, the sample using gelatin D whose content of iron in the gelatin was less than 3 ppm was excellent in running variation fastness. It was also found that the cyan dye forming coupler used in the present invention combined with the polymer compound of the present invention especially had excellent dark storage stability, and the sample using the gelatin of the present invention showed improved running variation fastness. Example 2 (comparative) Samples 101 to 129 in Example 1 were evaluated in the same way as in Example 1 except that the processing steps were changed as follows. The results are shown in Table 4. The compositions of the processing solutions are shown as follows. The replenishing amount of each processing solution is an amount per 1m² of light-sensitive material. The stabilization processing was replenished by the countercurrent system from stabilization tank 3 to 1. Color developer Water was added to adjust to one liter. The pH of the tank solution was adjusted to 10.10 and that of replenishing solution to 11.50 with potassium hydroxide or sulfuric acid. Bleach fixation tank solution and replenishment solution The pH was adjusted to 5.4 with ammonia water or glacial acetic acid. Water was added to adjust to one liter. Stabilization tank solution and replenished solution The pH was adjusted to 7.8 with ammonia water or glacial acetic acid. The whole quantity was adjusted to one liter adding water. Example 3 Samples 301 to 312 shown in Table 5 were made in the same manner as Example 1 except that the gelatins of each layer of samples 102, 104, 106, 108, 118 and 120 made in Example 1 were reduced by 5% or 10%. They were evaluated in the same was as Example 2. The results are shown in Table 5. The effect of the present invention was achieved in this example. Among samples of the present invention, 308 and 312, in which the amount of gelatin in the light-sensitive material was less than 6.50 g/m², were especially excellent in running variation fastness.

Claims: A silver halide photographic light-sensitive material comprising a support having thereon a silver halide emulsion layer, in which said silver halide emulsion layer contains a cyan coupler represented by the following formula C-I; wherein R₁ represents an alkyl group having from 2 to 6 carbon atoms, R₂ represents a ballast group, Z represents a hydrogen atom or a group capable of being released upon reaction with an oxidation product of a color developing agent, the gelatin contained in said silver halide photographic light-sensitive material has an average iron content of less than 5 ppm by weight, based on the total weight of gelatin, characterised in that the total amount of gelatin contained in the silver halide photographic material is less than 6.5 g/m² of the silver halide photographic material. The silver halide photographic material of claim 1, characterised in that said iron content is less than 4 ppm. The silver halide photographic material of claim 1, characterised in that said silver halide emulsion further contains a water-insoluble and organic solvent soluble polymer compound. The silver halide photographic material of claim 3, characterised in that said polymer compound is selected from poly N-t-butylacrylamide, N-t-butylacrylamidemethylmethacrylate copolymer, polybutylmethacrylate, methylmethacrylate-styrene copolymer, N-t-butylacrylamide-2-methoxyethylacrylate copolymer, ω-methoxypolyethyleneglycolacrylate-N-t-butylacrylamide copolymer. The silver halide photographic material of claim 1, characterised in that said silver halide emulsion layer contains silver halide grains having a silver chloride content of not less than 95 mol%. A method of continuously processing a silver halide photographic material of claim 5 by a color developer, characterised in that the replenishing amount of said color developer is from 20 to 60 ml per square metre of said silver halide photographic material.

Inventors: NISHIMURA MOTOI C O KONICA COR, SATO HIROKAZU C O KONICA CORPO, NISHIMURA, MOTOI, C/O KONICA CORPORATION, SATO, HIROKAZU, C/O KONICA CORPORATION
Applicants: KONISHIROKU PHOTO IND, KONICA CORPORATION
Application year: 1993
Main classification: G03C1
IPC codes: G03C1, G03C7