Definitions

• the present invention relates to a method for processing a silver halide color photographic light-sensitive material, particularly to a method for processing a silver halide color photographic light-sensitive material which exhibits an excellent processing stability even in low-replenishment processing or rapid processing.
• the processing of a light-sensitive material comprises the two processes of color development and desilverization, and the desilverization comprises a bleaching process and a fixing process, or a bleach-fixing process.
• a rinsing process and a stabilizing process are added thereto as additional processes.
• an exposed silver halide is reduced to silver and, at the same time, an oxidized aromatic primary amine developing agent reacts with a coupler to form a dye.
• halogen ions formed by the reduction of a silver halide are dissolved and accumulated in the color developer.
• components contained in a silver halide photographic light-sensitive material, such as inhibitors are also dissolved and accumulated in the developer.
• the silver formed in the developing process is bleached by an oxidizing agent and, then, all the silver salts are removed in the form of soluble salts from the photographic light-sensitive material with the aid of a fixing agent.
• development-inhibiting materials are accumulated in the color developer during the development of a photographic light-sensitive material; on the other hand, the color developing agent is consumed or taken out of the color developer by accumulating in the photographic light-sensitive material and, as a result, its component concentration continues to decrease.
• the bleach-fixer In the bleach-fixer, silver salts and halogen ions dissolved out of a light-sensitive material accumulate, and the bleach-fixer itself is diluted to a lower component concentration by a solution brought in from the preceding bath.
• any developing method which processes a large amount of silver halide photographic light-sensitive materials by use of an automatic processor cannot dispense with a means to keep the concentration of each color developer component within a prescribed range.
• the regeneration of a developer can be carried out by removing bromides, unnecessary accumulated components, and replenishing lacking components.
• this method (comprising ion exchange or electrodialysis) has a disadvantage that the characteristics of a developed light-sensitive material is degradated unless the concentrations of developer components are kept constant by means of chemical analyses which need complicated procedures; therefore, it can hardly be carried out in small processing laboratories including the so-called mini-laboratories which have no special skill. In addition, it has another disadvantage of high initial cost.
• the method of replenishing with a small amount of concentrated solution is suitable for small laboratories, because it needs no new installations and is easy to carry out.
• this method has some problems, too.
• matters dissolved out of light-sensitive materials are accumulated in large amounts and, in addition, decomposition products produced by air oxidation of developer components are also accumulated in large amounts.
• decomposition products produced by air oxidation of developer components are also accumulated in large amounts.
• the concentration of contaminants increases in a front tank and, as a result, decomposition and accumulation of the contaminants amount to an undesirable level.
• Primary undesirable effects caused by such phenomena are fluctuations in pH during processing, which deteriorate the processing results, and undesirable influences of the decomposed products on light-sensitive materials.
• recoloring property means an ability of recoloring of dye image in a bleaching solution by converting leuco-dye contained in a developed dye image to colored dye by oxidation.
• the object of the present invention is to provide a method for processing silver halide color photographic light-sensitive materials which causes neither stains nor recoloring failure in the photographic material even when applied to rapid processing or small volume replenishing.
• the object of the invention is achieved by a method for processing a silver halide color photographic light-sensitive material.
• the method comprises the steps of developing a silver halide color photographic light-sensitive with a color developer, and bleach-fixing the light-sensitive material with a bleach-fixer.
• a silver halide emulsion layer of the light-sensitive material comprises silver halide grains having a silver chloride content of not less than 80 mol %;
• the color developer contains a compound represented by the following Formula I or a monosuccharide;
• the bleach-fixer contains a ferric complex salt of aminopolycarboxylic acid selected from the following Group 1 and a aliphatic dibasic acid selected from the following Group 2; wherein L is a substituted or unsubstituted alkylene group;
• A is a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, hydroxyl group, an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group, in which the amino group, ammonio group, carbamoyl group and sulfamoyl group each may have an alkyl group as a substituent;
• R is a hydrogen
• L represents a linear or branched alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, which may have a substituent.
• substituent include a carboxyl group, sulfo group, phosphono group, phosphinic acid group, hydroxyl group, ammonio group which may have an alkyl substituent; among them, a carboxyl group, sulfo group, phosphono group and hydroxyl group are preferred.
• A represents a carboxyl group, sulfo group, phosphono group, phosphinic acid group, hydroxyl group, amino group which may have an alkyl substituent, ammonio group which may have an alkyl substituent, carbamoyl group which may have an alkyl substituent, sulfamoyl group which may have an alkyl substituent; preferred among them are a carboxyl group, sulfo group, hydroxyl group, phosphono group and carbamoyl group which may have an alkyl substituent.
• Preferred examples of -L-A- include a carboxymethyl, carboxyethyl, carboxypropyl, sulfoethyl, sulfopropyl, sulfobutyl, phosphonomethyl, phosphonoethyl and hydroxyethyl group; particularly preferred are a carboxymethyl, carboxyethyl, sulfoethyl, sulfopropyl, phosphonomethyl and phosphonoethyl group.
• R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, which may have a substituent.
• substituents examples include a carboxyl group, sulfo group, phosphono group, phosphinic acid group, hydroxyl group, amino group which may have an alkyl substituent, ammonio group which may have an alkyl substituent, carbamoyl group which may have an alkyl substituent and sulfamoyl group which may have an alkyl substituent. Two or more substituents may be present.
• R include a hydrogen atom and a carboxymethyl, carboxyethyl, carboxypropyl, sulfoethyl, sulfopropyl, sulfobutyl, phosphonomethyl, phosphonoethyl and hydroxyethyl group; among them, a hydrogen atom and a carboxymethyl, carboxyethyl, sulfoethyl, sulfopropyl, phosphonomethyl and phosphonoethyl group are particularly preferred.
• L and R may link with each other to form a ring.
• Typical examples of the compound represented by formula I are shown below. (19) HO-NH-CH2CO2H (20) HO-NH-CH2CH2CO2H (26) HO-NH-CH2CH2SO3H (28) HO-NH-(CH2)3SO3H (29) HO-NH-(CH2)4SO3H (30) HO-NH-CH2PO3H2 (32) HO-NH-CH2CH2PO3H2 (33) HO-NH-CH2CH2OH (34) HO-NH-(CH2)3OH (35) HO-NH-CH2-PO3H2 (46) HONHCH2CH(PO3H2)2
• These compounds are contained in a color developer in an amount of 1.5 ⁇ 10 ⁇ 3 to 1.5 ⁇ 10 ⁇ 1 mol, preferably 3.0 ⁇ 10 ⁇ 3 to 9.0 ⁇ 10 ⁇ 2 mol, per liter of color developer.
• These compounds may be further contained in a light-sensitive material. Further, when contained in a processing solution other than color developer, such as a bleach, bleach-fixer, rinsing solution or stabilizer as substitute for rinsing solution, these compounds act upon color developing agents or oxidation products thereof brought into these solutions from a color developer and provide a light-sensitive material with preferable photographic properties.
• a processing solution other than color developer such as a bleach, bleach-fixer, rinsing solution or stabilizer as substitute for rinsing solution
• these compounds act upon color developing agents or oxidation products thereof brought into these solutions from a color developer and provide a light-sensitive material with preferable photographic properties.
• the compounds represented by formula I can be synthesized by alkylation (nucleophilic displacement reactions, addition reactions or Mannich reactions) of hydroxylamines available on the market.
• alkylation nucleophilic displacement reactions, addition reactions or Mannich reactions
• Useful synthesis methods can be seen in German Pat. No. 1,159,634 and Inorganica Chimica Acta, Vol. 93 (1984), pp. 101-107.
• the term "monosaccharide” used in the invention is a general name for polyhydroxyaldehydes, polyhydroxyketones and a broad range of their derivatives including their reduction derivatives, oxidation derivatives, deoxy-derivatives, amino-derivatives and thio-derivatives.
• saccharides represented by formula C n H 2n O n as well as compounds derived from the saccharide skeleton represented by this formula are defined as monosaccharides.
• the addition amount of the monosaccharides is 1.5 ⁇ 10 ⁇ 3 to 1.5 ⁇ 10 ⁇ 1 mol, preferably 3.0 ⁇ 10 ⁇ 3 to 9.0 ⁇ 10 ⁇ 2 mol and especially 4.5 ⁇ 10 ⁇ 3 to 6.0 ⁇ 10 ⁇ 2 mol per liter of color developer.
• the color developer contains an aromatic compound having a sulfonic acid group or an aromatic compound having a sulfate group represented by the following formula II or III.
• a to F are each independently -SO3M, -OSO3M, a hydrogen atom, a halogen atom or a saturated or unsaturated hydrocarbon group provided that at least one of the groups represented by A to F is -SO3M group, M is a hydrogen atom, an alkali metal atom or an ammonium group.
• G to N are each independently -SO3M, -OSO3M, a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group or an alkynyl group, M is a hydrogen atom, an alkali metal atom or an ammonium group.
• the alkyl, ankenyl or alkynyl group represented by A to F or G to N is preferably one having 1 to 10 carbon atoms. Its carbon chain may be either linear or branched.
• the addition amount of the compounds represented by formula II or III is preferably not less than 5 g/l, more preferably in the range of 10 to 200 g/l.
• color developing agents In the invention, conventional P-phenylenediamine color developing agents can be used.
• Preferred color developing agents are those exemplified as follows. Concerning color developing agents Japanese Pat. O.P.I. Publication No. 86741/1992 may be referred. In the following, color developing agent (C-1) can bring out the effect of the invention most pronouncedly.
• these color developing agents are used in the form of hydrochlorides, sulfates, nitrates or p-toluenesulfonates.
• the color developing agents are used within the range of 2.5 ⁇ 10 ⁇ 3 to 5.5 ⁇ 10 ⁇ 2 mol, preferably 5.0 ⁇ 10 ⁇ 3 to 4.5 ⁇ 10 ⁇ 2 mol per liter of color developer.
• the color developer used in the invention may contain the following components usually used in color developer.
• alkali agents there may be used, singly or in combination, sodium hydroxide, potassium hydroxide, silicates, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate and borax within a range necessary to maintain the pH stabilizing effect without forming precipitates.
• sodium hydroxide, potassium hydroxide, silicates, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate and borax within a range necessary to maintain the pH stabilizing effect without forming precipitates.
• salts including disodium hydrogenphosphate, dipotassium hydrogenphosphate, sodium bicarbonate, potassium bicarbonate and borates.
• the color developing replenisher used in the invention contains an optical whitening agent.
• an optical whitening agent not only improves the whiteness of light-sensitive materials' nonexposed portions, but also prevents crystals from depositing.
• Triazinylstilbene optical whitening agents are preferred in the invention, particularly preferred are those represented by the following formula F.
• X1, X2, Y1 and Y2 are each a hydroxyl group, halogen atom such as chlorine and bromine, an alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group and a methoxyphenyl group, a group, a group or a -OR25 group
• R21 and R22 are each a hydrogen atom, an alkyl group which may have a substituent, or a aryl group which may have a substituent
• R23 and R24 are each an alkylene group which may have a substituent
• R25 is a hydrogen atom, an alkyl group or an aryl group, they may have a substituent
• M is a cation such as sodium, potassium, lithium or ammonium.
• An alkyl group represented by R21, R22 or R25 are preferably one having 1 to 6 carbon atoms, and an alkylene group represented R23 or R24 are a
• a group which may be a substituent of an alkyl group or an aryl group represented by R21, R22 or R25, or an alkylene group represented by R23 or R24 is preferably a hydroxyl group, a sulfo group, or a carboxylamino group.
• am amino group an alkylamino group such as a methylamino group, ethylamino group, propylamino group, dimethylamino group, cyclohexylamino group, ⁇ -hydroxyethylamino group, di( ⁇ -hydroxyethyl)amino group, ⁇ -sulfoethylamino group, N-( ⁇ -sulfoethyl)-N-methylamino group and N-( ⁇ -hydroxyethyl)-N-methylamino group; and an arylamino group such as an anilino group, o-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, o-chloroanilino group, m-chloroanilino group, p-chloroanilino group, o-toluidino group
• groups represented by a morpholino group As an example of groups represented by a morpholino group is cited.
• groups represented by -OR25 an alkoxy group such as a methoxy group, ethoxy group and methoxyethoxy group, and an aryloxy group such as a phenoxy group and p-sulfophenoxy group, are exemplified.
• preferable compounds are ones in which all groups represented by X1, X2, Y1 and Y2 are a group represented by or -OR25, and most preferable compounds are ones in which one of X1 and Y1 is -OR25 and the other is a group represented by and one of X2 and Y2 is -OR25 and the other is a group represented by or
• Typical examples of the compounds represented by formula F include compounds the following F-1 to F-7.
• Concerning the optical whitening agents Japanese Pat. Appl. No. 178833/1990 can be referred.
• These triazinylstilbene optical whitening agents can be synthesized by the usual method described, for example, in "Optical Whitening Agents", edited by Kaseihin Kogyo Kyokai (Aug., 1976), p. 8.
• the triazinylstilbene optical whitening agents are used in amounts of preferably 0.2 to 10 g, especially 0.4 to 5 g, per liter of color developing replenisher. Further, in order to enhance the effect of the invention much more, it is preferred that the chelating agent of the following formula K be added to the color developing replenisher.
• E is a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene group, a -R5OR5- group, a -R5OR5OR5- group or a -R5ZR5- group;
• Z is a >N-R5-A5 group or a >N-A5 group;
• R1 to R5 are each a substituted or unsubstituted alkylene group;
• A1 to A5 are each a hydrogen atom, a -OH group, a -COOM group or a -PO3(M)2 group; and
• M is a hydrogen atom or an alkali metal atom.
• Typical example of the compounds represented by Formula K include the following compounds K-1 to K-22.
• the pH of the color developer is preferably in the range of 9.5 to 13.0, more preferably in the range of 9.8 to 12.5.
• the replenishing rate of the color developer is not more than 120 ml/m2, preferably 20 to 100 ml/m2.
• the replenishing rate is in the range of 50 to 200 ml/m2.
• the aliphatic dibasic acid used in the invention undergoes a chelate exchange reaction more effectively than other acids in the coating layer of a light-sensitive material; therefore, it retards the chelate exchange reaction of aminopolycarboxylic acids and effectively prevents desilverizing failure and recoloring failure.
• the aliphatic dibasic acid used in the invention includes oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, glutaric acid and adipic acid.
• Preferred are oxalic acid, succinic acid, maleic acid, fumaric acid and adipic acid.
• aliphatic dibasic acids are added to the bleach-fixer in amounts of 1.5 ⁇ 10 ⁇ 2 to 8.5 ⁇ 10 ⁇ 1 mol, preferably 8.0 ⁇ 10 ⁇ 2 to 4.3 ⁇ 10 ⁇ 1 mol per liter of bleach-fixer.
• Aminopolycarboxylic acid complex salts used in the invention include ethylenediaminetetraacetic acid ferric complex salts, diethylenetriaminepentaacetic acid ferric complex salts, trans-1,2-cyclohexanediaminetetraacetic acid ferric complex salts, ⁇ -alaninediacetic acid ferric complex salts, ethylenediaminedisuccinic acid ferric complex salts, nitrilotriacetic acid ferric complex salts, N-hydroxyethylethylenediaminetriacetic acid ferric complex salts and glycol ether-diaminetetraacetic acid ferric complex salts.
• the aminopolycarboxylic acid ferric complex salts are used in an amount of not less than 0.01 mol per liter of bleach-fixer, preferably within the range of 0.03 to 0.3 mol/l and especially within the range of 0.05 to 0.25 mol/l.
• fixing agents contained in the bleach-fixer of the invention conventional ones can be used. Preferred are thiocyanates and thiosulfates.
• the addition amount of the fixing agents is preferably not less than 0.1 mol /l, more preferably 0.3 to 4 mol/l, even more preferably 0.5 to 3 mol/l, and most preferably 0.6 to 2.0 mol/l.
• the bleach-fixer contain the compound of formula FA or compound included in Group FB.
• sulfurous acid adducts represented by formula A-I or A-II.
• R' and R'' are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a nitrogen-containing heterocyclic group; and n' is an integer of 2 or 3.
• Typical example of the compounds represented by Formula FA are as follows.
• A2, A3, A4 and A5 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group.
• the alkyl groups having 1 to 6 carbon atoms including ones having straight chain and ones having a branched chain, include, for example, a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, n-pentyl group, iso-pentyl group, n-hexyl group or iso-hexyl group.
• the alkyl group may have a substituent.
• the substituted alkyl groups include ones having formyl group such as formyl methyl group and 2-formylethyl group, ones having amino group such as aminomethyl group and aminoethyl group, ones having hydroxyl group such as hydroxymethyl group, 2-hydroxyethyl group and 2-hydroxypropyl group, alkoxy group such as methoxy group and ethoxy group, ones having halogen atom such as chloromethyl group, trichlorometyl group and dibromomethyl group.
• the alkenyl group may have a substituent.
• Unsubstituted alkenyl groups include, for example, vinyl group and 2-propenyl group, and substituted alkenyl groups include, for example, 1.2-dichlorocarboxyvinyl group and 2-phenylvinyl group.
• Silver may be recovered by a conventional method from the bleach-fixer according to the invention.
• the bleach-fixer may contain, singly or in combination, sulfites and pH buffers selected from a variety of salts.
• rehalogenating agents including alkali halides and ammonium halides, such as potassium bromide, sodium bromide, sodium chloride and ammonium bromide, are preferably added thereto in large quantities.
• compounds such as alkylamines and polyethylene oxides which are known to be added to a bleach-fixer, may also be added.
• the bleach-fixer is used in the pH range of preferably 1.0 to 8.5, more preferably 1.5 to 8.0.
• the replenishing rate is 30 ml/m2 to 120 ml/m2 of light-sensitive material process, preferably 40 ml/m2 to 100 ml/m2.
• the replenishing rate is 50 to 250 ml/m2.
• the process using a fixing-capable processing solution is followed by a stabilizing process without performing a substantial washing process.
• the stabilizer used in the stabilizing process contains the chelating agent of formula CH-I, CH-II or CH-III.
• E is an alkylene group, a cycloalkylene group, a phenylene group, a -R5'-O-R5'- group, a -R5'-O-R5'-O-R5'- group, or -R5'-Z-R5'- group.
• Z is a >N-R5'-A5 group, a group, a >N-A5 group or a group.
• R1' to R6' are each an alkylene group
• A1 to A3 are each a -COOM group or a -PO3M2 group
• A4 and A5 are each a hydrogen atom, a hydroxyl group, a -COOM group or a -PO3M2 group.
• M is a hydrogen atom or an alkali metal atom.
• R7' is an alkyl group, an aryl group or a nitrogen-containing six-member ring
• M is a hydrogen atom or an alkali metal atom.
• R8', R9' and R10' are each a hydrogen atom, a hydroxyl group, a -COOM group, a -PO3M2 group or a group, in which J is a hydrogen atom, an alkyl group, a -C2H4OH group or a -PO3M2 group; M is a hydrogen atom or an alkali metal atom; and n and m are each 0 or 1.
• the addition amount of the chelating agent is preferably 0.01 to 100 g, more preferably 0.05 to 50 g, and most preferably 0.1 to 20 g per liter of stabilizer. It is also preferred that metal salts be contained in the stabilizer together with the chelating agent. Examples of such metal salts include salts of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al and Sr. These can be fed as inorganic salts including halides, hydroxides, sulfates, carbonates, and phosphates or as water-soluble chelated compounds.
• the stabilizer may contain organic acids such as citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid and pH adjustors such as phosphates, borates, hydrochlorides, sulfates.
• organic acids such as citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid and pH adjustors such as phosphates, borates, hydrochlorides, sulfates.
• conventional fungicides can be contained singly or in combination in the stabilizer within the range not harmful to the effect of the invention.
• Silver may be recovered from the stabilizer according to the usual method. Further, the stabilizer may be subjected to ion exchange treatment, electrodialysis (see Japanese Pat. O.P.I. Pub. No. 28949/1986) or reverse osmosis (see Japanese Pat. O.P.I. Pub. Nos. 240153/1985 and 254151/1987), or the water used in the stabilizer may be deionized in advance, in order to enhance the fungus resistance and stability of the stabilizer as well as image preservability.
• Any deionizing method can be used as long as it can reduce the content of calcium and magnesium ions in the water after treatment to 5 ppm or less; but, treatments with ion exchange resins or reverse osmosis membranes, or combinations thereof, are preferred. Details of ion exchange resins and reverse osmosis membranes can be seen in Journal of Technical Disclosure Nos. 1984/1987 and 20511/1989.
• the stabilizer pH is preferably in the range of 5.5 to 10.0. Any of the conventional alkali agents and acid agents can be used as a pH adjustor for the stabilizer.
• the stabilizing process is carried out at temperatures of preferably 15 to 70°C, more preferably 20 to 55°C.
• the stabilizing time is usually not longer than 120 seconds, preferably 3 to 90 seconds and most preferably 6 to 50 seconds.
• the replenishing volume of the stabilizer per unit area of light-sensitive material is preferably 0.1 to 80 times, more preferably 0.5 to 30 times the volume of the preceding solution, fixer or bleach-fixer, brought into the stabilizing bath, in view of rapid processability and dye image preservability.
• the stabilizing tank be made up of plural tanks, preferably 2 to 6 tanks. In a particularly preferred mode, two or three tanks are arranged countercurrently and the stabilizer is fed to the rear tank and overflowed from the front tank.
• silver chloride rich silver halide grains having a silver chloride content of 80 mol% or more are employed.
• the silver chloride content of these grains is preferably not less than 90 mol%, more preferably not less than 95 mol%, and most preferably not less than 98 mol%.
• Silver halide emulsions comprising the above silver chloride rich silver halide grains may contain, as silver halide components, silver bromide and/or silver iodide besides silver chloride.
• the content of silver bromide is preferably not more than 10 mol%, more preferably not more than 5 mol%, and most preferably not more than 2 mol%.
• silver iodide When silver iodide is contained, its content is preferably not more than 1 mol%, more preferably not more than 0.5 mol%, and most preferably zero.
• Such silver chloride rich silver halide grains containing 90 mol% or more silver chloride will work when used at least in one silver halide emulsion layer; but, preferably, these are used in all light-sensitive silver halide emulsion layers.
• the above silver halide grains may be regular crystals, twin crystals or other crystal forms, and these may have any [1.0.0] face to [1.1.1] face ratio.
• the crystal structure of these grains may be uniform from the inner portion to the outer portion or may be the core/shell structure that comprises inner and outer layers having phases different in composition. Further, these grains may be those which form latent images mainly on the surface or those which form latent images mainly inside of the grains.
• tabular silver halide grains disclosed, for example, in Japanese Pat. O.P.I. Pub. No. 113934/1983 and No. 47959/1986 as well as the silver halides disclosed in Japanese Pat. O.P.I. Pub. Nos. 26837/1989, 26838/1989, 77047/1989.
• silver halide grains may be prepared by any of the acid method, the neutral method and the ammoniacal method.
• seed grains are formed by the acid and, then, grown to a prescribed size by the ammoniacal method which can give a faster growth rate.
• silver ions and halide ions be simultaneously introduced in amounts corresponding to the growth rate of silver halide grains as described, for example, in Japanese Pat. O.P.I. Pub. No. 48521/1979 with the pH and pAg of the reaction system being controlled.
• Silver halide emulsion layers of the light-sensitive material to be processed according to the invention contain color couplers.
• the red-sensitive emulsion layer may contain, for example, nondiffusible color couplers to form cyan portion color images, namely, phenol-type or ⁇ -naphthol-type couplers in general.
• the green-sensitive emulsion layer may contain, for example, at least one nondiffusible color coupler to form magenta portion color images, namely, 5-pyrazolone-type or pyrazolotriazole-type color couplers in general.
• the blue-sensitive emulsion layer may contain, for example, at least one nondiffusible color coupler to form yellow portion color images, namely, color couplers having an open-chain ketomethylene group in general. These color couplers may be 6-, 4- or 2-equivalent couplers.
• Suitable couplers can be seen, for example, in W. Pelz, Farbkuppler (Color Couplers) contained in Mit gutteren aus den Anlagenslaboratorien der Agfa (Research Papers of Agfa), Leverkusen/Munchen, Vol. III, p. 111 (1961); K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. 4, pp. 341-387, Academic Press; The Theory of the Photographic Process, 4th edition, pp. 353-362; and Research Disclosure No. 17643, Sec. VII.
• magenta couplers represented by formula M-1 on page 26 of Japanese Pat. O.P.I. Pub. No. 106655/1988 typical examples thereof are magenta coupler Nos 1 to 77 shown on pages 29-34 of the same patent specification
• the cyan couplers represented by formula C-1 or C-II on page 34 of the same specification typical examples thereof are cyan couplers C'-1 to C'-82 and C''-1 to C''-36 shown on pages 37-42 of the same specification
• the rapid reactive yellow couplers described on page 20 of the same specification typical examples thereof are yellow couplers Y'-1 to Y'-39 shown on pages 21-26 of the same specification.
• nitrogen-containing heterocyclic mercapto compounds are used in a light-sensitive material comprising a silver chloride rich emulsion, not only is the effect of the invention well enhanced, but undesired influences on photographic properties caused by the contamination of a color developer with a bleach-fixer can be effectively diminished. Accordingly, use of these compounds is preferred in the embodiment of the invention.
• nitrogen-containing heterocyclic mercapto compounds include compounds I'-1 to I'-87 exemplified on pages 42-45 of Japanese Pat. O.P.I. Pub. No. 106655/1988.
• the silver halide emulsion can be prepared by the usual method, for example, constant rate or accelerated rate single-jet or double-jet pouring of the materials. Particularly preferred is the double-jet under a controlled pAg (see Research Disclosure No. 17643, Secs. I and II).
• the silver halide emulsion can be chemically sensitized.
• Sulfur-containing compounds such as allyl isothiocyanate, allyl thiourea and thiosulfates are particularly preferred chemical sensitizers.
• Reducing agents can also be employed as chemical sensitizers; examples thereof include silver compounds as disclosed in Belgian Pat. Nos. 493,464, 568,687 as well as polyamines such as diethylenetriamine and aminodimethylsulfinic acid derivatives as disclosed in Belgian Pat. No. 547,323.
• Other suitable sensitizers are noble metals, such as gold, platinum, palladium, iridium, ruthenium, rhodium, and compounds thereof.
• Such chemical sensitization is described in detail in R. Kosiovsky's monograph contained in Z. Wiss. Photo., Vol. 46, pp. 65-72 (1951) (see also Research Disclosure No. 17643, Sec. III).
• the silver chloride rich emulsion can be optically sensitized by conventional methods including those which employ ordinary polymethine dyes such as neutro-cyanine, basic or acid carbocyanine, rhodacyanine, hemicyanine; styryl dyes, oxonol and its analogues. Details of optical sensitization can be seen in F.M. Hamer, The Cyanine Dyes and Related Compounds (1964), Ullmanns Enzyklpadieder Technischen Chimi, 4th Edition, Vol. 18, p. 431 and Research Disclosure No. 17643, Sec. IV.
• the silver chloride rich emulsion can use conventional antifoggants and stabilizers.
• Azaindenes are useful stabilizers, preferred are tetra- and penta-azaindene, and particularly preferred are those substituted with a hydroxyl group or amino group. These compounds are described, for example, in Birr's monograph contained in Z. Wiss. Photo., Vol. 47 (1952), pp. 2-58 and Research Disclosure No. 17643, Sec. IV.
• the component of the light-sensitive material can be incorporated by conventional methods as described, for example, in U.S. Pat. Nos. 2,322,027, 2,533,514, 3,689,271, 3,764,336, 365,897.
• the components such as couplers and UV absorbents can be incorporated in the form of charged latex as described, for example, in German Offenlegungshrift No. 2,541,274 and European Pat. Appl. No. 14,921.
• the component can be set in the form of polymer in a light-sensitive material as described, for example, in German Offenlegungshrift No. 2,044,992 and U.S. Pat. Nos. 3,370,952, 4,080,211.
• supports for the color photographic light-sensitive material to be processed according to the invention there can be used baryta paper; polyethylene-coated paper; polypropylene synthetic paper; transparent supports having a reflective layer or functioning as a reflective body, such as glass plates, films of polyesters including cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films; and other conventional transparent supports.
• These supports are properly selected according to the end use of light-sensitive materials.
• reflective supports such as baryta paper, polyethylene-coated paper and polypropylene synthetic paper are preferred.
• the invention can be applied to color light-sensitive materials such as color paper, color negative films, color reversal films, color reversal paper and direct positive color paper for popular uses or for movies as well as color films for movies and color films for television.
• color light-sensitive materials such as color paper, color negative films, color reversal films, color reversal paper and direct positive color paper for popular uses or for movies as well as color films for movies and color films for television.
• the processing method of the invention is applicable to any automatic processor, but the effect of the invention can be most enhanced by use of an automatic processor whose opening area, per liter surface area of a processing solution, is not larger than 12 cm2/l, preferably not larger than 10 cm2/l.
• a multilayered silver halide color photographic light-sensitive material was prepared by forming the layers shown in Tables 1 and 2 on a paper support laminated with polyethylene on one side and with titanium-oxide-containing polyethylene on the other side to be coated with the above component layers.
• the coating solutions were prepared as follows:
• Coating solutions for the 2nd to 7th layers were prepared likewise.
• hardeners hardener H-1 was added to the 2nd layer and the 4th layer and hardener H-2 to the 7th layer.
• surfactants SU-2 and SU-3 were added to adjust the surface tension.
• the control of the pAg was carried out by use of a controlling solution, which was an aqueous solution of a halide salt mixture comprising sodium chloride and potassium bromide with a chloride ion-to-bromide ion ratio of 99.8:0.2. It was used at a concentration of 0.1 mol/l while solutions A and B were added, and at a concentration of 1 mol/l while solutions C and D were added.
• a controlling solution which was an aqueous solution of a halide salt mixture comprising sodium chloride and potassium bromide with a chloride ion-to-bromide ion ratio of 99.8:0.2. It was used at a concentration of 0.1 mol/l while solutions A and B were added, and at a concentration of 1 mol/l while solutions C and D were added.
• Emulsion EMP-1 so-prepared comprised monodispersed cubic grains having an average grain size of 0.85 ⁇ m, a coefficient of variation of grain size distribution of 7% and a silver chloride content of 99.5 mol%.
• Emulsion EMP-1 was chemically ripened for 90 minutes at 50°C, using the following compounds, to obtain a blue-sensitive silver halide emulsion (Em-A).
• Em-A blue-sensitive silver halide emulsion
• Sodium thiosulfate 0.8 mg/mol AgX Chloroauric acid 0.5 mg/mol AgX Stabilizer STAB-1 6 ⁇ 10 ⁇ 4 mol/mol AgX Sensitizing dye BS-1 4 ⁇ 10 ⁇ 4 mol/mol AgX Sensitizing dye BS-2 1 ⁇ 10 ⁇ 4 mol/mol AgX
• Emulsion EMP-2 so-prepared comprised monodispersed cubic grains having an average grain size of 0.43 ⁇ m, a coefficient of variation of grain size distribution of 8%, and a silver chloride content of 99.5 mol%.
• Emulsion EMP-2 was chemically ripened for 120 minutes at 55°C, using the following compounds, to obtain a green-sensitive silver halide emulsion (Em-B).
• Sodium thiosulfate 1.5 mg/mol AgX
• Chloroauric acid 1.0 mg/mol AgX Stabilizer STAB-1 6 ⁇ 10 ⁇ 4 mol/mol AgX Sensitizing dye GS-1 4 ⁇ 10 ⁇ 4 mol/mol AgX
• Emulsion EMP-3 so-prepared comprised monodispersed cubic grains having an average grain size of 0.50 ⁇ m, a coefficient of variation of grain size distribution of 8%, and a silver chloride content of 99.5 mol%.
• Emulsion EMP-3 was chemically ripened for 90 minutes at 60°C, using the following compounds, to obtain a red-sensitive silver halide emulsion (Em-C).
• Sodium thiosulfate 1.8 mg/mol Agx Chloroauric acid 2.0 mg/mol Agx Stabilizer STAB-1 6 ⁇ 10 ⁇ 4 mol/mol Agx Sensitizing dye RS-1 4 ⁇ 10 ⁇ 4 mol/mol Agx
• the silver chloride content of the color paper sample prepared as above was 99.5 mol%.
• Color paper samples 1 to 23 were prepared by varying the silver chloride content as shown in Table 3.
• the continuous processing was carried on, at a processing speed of 0.1 round per day, till the volume of the replenished stabilizer amounted to three times the volume of the developing tank solution.
• 1 round means that the color developer replenisher is replenished up to a volume equal to the capacity of color developing tank.
• the minimum reflection density (measured by blue-light) and the maximum reflection density (measured by red-light) were measured with color paper samples exposed wedgewise and processed at the beginning of the continuous run, and with samples exposed wedgewise and processed at the end of the continuous run.
• the amount of residual silver was determined by the fluorescence X-ray method with samples exposed and processed at the end of the continuous run.
• Table 3 shows measured values of the residual silver amount, the following difference in minimum density ( ⁇ B) and the difference in maximum density ( ⁇ R).
• Example 1 The procedure of Example 1 was repeated, except that the following process (2) was used and that an NPS-808SQA automatic processor made by Konica Corp. was employed in the continuous run. As a result, the same effect as that in Example 1 was observed.
• Example 1 The procedure of experiment No. 7 in Example 1 was repeated, except that the combination of ammonium ferric ethylenediaminetetracetate with the aliphatic dibasic acid in the bleach-fixer was changed to equal moles of the following combinations.
• the evaluation results were the same as those in Example 1, except that the difference in minimum reflection density ( ⁇ B) became slightly larger. No.
• Aminopolycarboxylic Acid Aliphatic Dibasic Acid 1 Ammonium ferric ⁇ -alaninediacetate Maleic acid 2 Ammonium ferric ⁇ -alaninediacetate Oxalic acid 3 Ammonium ferric ⁇ -alaninediacetate Succinic acid 4 Ammonium ferric ⁇ -alaninediacetate Adipic acid 5 Ammonium ferric ethylenediaminedisuccinate Maleic acid 6 Ammonium ferric ethylenediaminedisuccinate Oxalic acid 7 Ammonium ferric ethylenediaminedisuccinate Succinic acid 8 Ammonium ferric ethylenediaminedisuccinate Adipic acid 9 Ammonium ferric diethylenetriaminepentacetate Maleic acid 10 Ammonium ferric diethylenetriaminepentacetate Oxalic acid 11 Ammonium ferric diethylenetriaminepentacetate Succinic acid 12 Ammonium ferric diethylenetriaminepentacetate Adipic acid
• Example 1 The procedure of Example 1 was repeated, except that the replenishing rate of the bleach-fixer was changed to the following processing conditions, and that the processing speed was changed to 0.03 round per day. Processing Condition No. Replenishing Rate (ml/m2) 1 200 2 120 3 100 4 50
• Example 2 The procedure of Example 2 was repeated, except that the bleach-fixing time was changed to the following processing conditions, and that the processing speed was changed to 0.03 round per day.
• the effect of the invention becomes more conspicuous as the bleach-fixing time becomes shorter, and the effect can be best brought out when the bleach-fixing time is less than 30 seconds.

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• 1992
  • 1992-06-19 JP JP04161336A patent/JP3106221B2/ja not_active Expired - Fee Related
• 1993
  • 1993-06-10 DE DE1993609612 patent/DE69309612T2/de not_active Expired - Fee Related
  • 1993-06-10 EP EP19930109326 patent/EP0597179B1/de not_active Expired - Lifetime

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