EP0514906A1 - Verarbeitungslösung und Verarbeitungsverfahren für photographische lichtempfindliche Silberhalogenidmaterialien - Google Patents

Verarbeitungslösung und Verarbeitungsverfahren für photographische lichtempfindliche Silberhalogenidmaterialien Download PDF

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Publication number
EP0514906A1
EP0514906A1 EP92108623A EP92108623A EP0514906A1 EP 0514906 A1 EP0514906 A1 EP 0514906A1 EP 92108623 A EP92108623 A EP 92108623A EP 92108623 A EP92108623 A EP 92108623A EP 0514906 A1 EP0514906 A1 EP 0514906A1
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EP
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Prior art keywords
group
solution
water
soluble
mol
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EP92108623A
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English (en)
French (fr)
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Hiroshi Konica Corporation Yoshimoto
Shigeharu Konica Corporation Koboshi
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0514906A1 publication Critical patent/EP0514906A1/de
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/37—Antiseptic agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • G03C5/3056—Macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/40—Chemically transforming developed images
    • G03C5/44—Bleaching; Bleach-fixing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents

Definitions

  • the present invention relates to a processing solution (hereinafter referred to as a photographic processing solution or a processing solution) and a processing method for a silver halide photographic light-sensitive material (hereinafter also referred to as a light-sensitive material). More particularly, the present invention relates to a processing solution and a processing method for a silver halide photographic light-sensitive material, which are improved in preservability of a photographic processing solution and capable of processing a light-sensitive material in high quality.
  • a processing solution hereinafter referred to as a photographic processing solution or a processing solution
  • a processing method for a silver halide photographic light-sensitive material hereinafter also referred to as a light-sensitive material
  • a more important preventive measure against pollution is to have mini-laboratories and micro-laboratories minimize the amount of replenishment.
  • a first object of the present invention is to provide a processing solution and a processing method for light-sensitive materials reduced in pollution load and conformable to environmental requirement with a minimized replenishing amount.
  • a second object of the present invention is to provide a processing solution and a processing method for light-sensitive materials improved in antistain means for unexposed portions.
  • a third object of the present invention is to provide a processing solution and a processing method for light-sensitive materials improved in preservability of a processing solution, and a fourth object of the present invention is to provide a processing solution and a processing method for light-sensitive materials lessened in unevenness of processing.
  • a solution for processing a silver halide photographic light-sensitive material which contains a water-soluble polyvinyl alcohol or a water-soluble ⁇ -polysaccharide compound
  • a method for processing a silver halide photographic light-sensitive material comprising a step of using the processing solution.
  • the above objects of the invention are attained more effectively by the method for processing a silver halide photographic light-sensitive material containing a compound represented by the following Formula B-1, B-2 or B-3 is processed by the solution containing a water-soluble polyvinyl alcohol or a water-soluble ⁇ -polysaccharide compound.
  • R1 represents an alkyl, cycloalkyl, aryl, hydroxyl, alkoxycarbonyl, amino, carboxyl group including its salts or sulfo group including its salts
  • R2 and R3 each represent a hydrogen or halogen atom, or an amino, nitro, hydroxyl, alkoxycarbonyl, carboxyl group including its salts or sulfo group including its salts
  • M represents a hydrogen atom, an alkali metal atom or an ammonium group.
  • R4 represents a hydrogen or halogen atom, or an alkyl, aryl, halogenated alkyl or aralkyl group, or -R12-OR13 or -CONHR14, where, R12 represents an alkylene group, and R13 and R14 each represent a hydrogen atom, or an alkyl or aralkyl group; R5 and R6 each represent a hydrogen or halogen atom, or a halogenated alkyl or alkyl group; R7 represents a hydrogen or halogen atom, or an alkyl, aryl, halogenated alkyl or aralkyl group, or -R15-OR16 or -CONHR17, where, R15 represents an alkylene group, and R16 and R17 each represent a hydrogen atom, or an alkyl group; R8, R9, R10 and R11 each represent a hydrogen or halogen atom, or a hydroxyl, alkyl, amino or nitro group.
  • One preferable embodiment of the invention is that (a) the water-soluble polymer be a polyvinyl alcohol type, and that (b) the processing solution for silver halide photographic light-sensitive materials be at least one selected from a group of color developer, black-and-white developer, bleacher, fixer, bleach-fixer and stabilizer.
  • the processing solution for light-sensitive materials of the invention contains a polyvinyl alcohol type or a water-soluble ⁇ -polysacchalide type compound, preferably a polyvinyl alcohol type water-soluble polymer to achieve the objects of the invention effectively.
  • the water-soluble polyvinyl alcohol to be used in the invention is selected from the group of saponificated products of polyvinyl acetate having various saponification degrees and molecular weights.
  • the polyvinyl alcohol preferably has a saponification degree of 60 to 99, more preferably 90 to 98, and a molecular weight of 10,000 to 100,000.
  • the water-soluble ⁇ -polysaccharide type compound to be used in the invention is an ⁇ -polysaccharide produced by a mold-like yeast so Pullularia pullulans yeast cultured in a glucose-containing culture.
  • the water-soluble ⁇ -polysaccharides are composed of maltotriose repeatedly bonded by ⁇ -1,6 bonding.
  • a number of maltotriose composing the polysaccharide is several tens to several thousands, which correspond to a molecular weight of 10,000 to 2,000,000.
  • Ones having a molecular weight of 10,000 to 1,000,000 are preferably used in the invention from the viewpoint of solubility in a processing solution.
  • the polysaccharides preferably used in the invention are available under the trade name of Plullulan.
  • the polysaccharides can be produced by the method described on "Properties are use of Plullulan", Nihon Kagaku Kyokai Geppo, p.253, 25.
  • Such water-soluble polymers can be manufactured by general methods, for example, those described in Japanese Patent O.P.I. Publication Nos. 124945/1990, 75650/1990, 218741/1988, 97348/1986, 158245/1985, 117867/1982 and 13565/1979.
  • water-soluble polymers which are commercially available under the trade names of Solvlon (product of Aicello Kagaku Co.) Hicallon (product of Nichigo Film Co.), and Pullulan (Hayashibara Co., Ltd.).
  • these water-soluble polymers are used in an amount not less than 0.02 g, preferably 0.05 to 3.0 g and especially 0.1 to 1.5 g, per liter of a processing solution.
  • Suitable examples of the compounds represented by B-1 include the following exemplified compounds.
  • the compounds represented by one of Formulas B-1 to B-3 are used in amount of preferably 0.1 to 500 mg, especially 0.5 to 100 mg per m2 of light-sensitive material. These may be used either singly or in combination of two or more types.
  • p-phenylenediamine compounds having a water-solubilizing group are preferably employed because of their high capability of achieving the objects of the invention and less tendency to fog.
  • At least one water-solubilizing group is present in the amino group or in the benzene nucleus.
  • a water-solubilizing group are -(CH2) n '-CH2OH, -(CH2) m' -NHSO2-(CH2) n ,CH3, -(CH2) m '-O-(CH2) n '-CH3, -(CH2CH2O) n 'C m 'H 2m ' +1 (m' and n' each represent an integer larger than 0), -COOH and -SO3H.
  • color developing agent are those exemplified as (C-1) to (C-16) on the 26th to 31st pages of Japanese Patent Application 203169/1990.
  • color developing agents are employed in the form of salts such as hydrochlorides, sulfates and p-toluenesulfonates.
  • the color developing agents may be used singly or in combination. When desired, these may be employed jointly with a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or metol.
  • a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or metol.
  • the compound represented by the following Formula A or B is contained in the developer used in the invention, for bringing out the effect of the invention and minimizing fog in unexposed portions of a light-sensitive material.
  • R1 and R2 each represent an alkyl or aryl group, or a hydrogen atom, and both of which are not hydrogen atoms concurrently.
  • the alkyl groups represented by R1 and R2 may be the same or different and are preferably alkyl groups having 1 to 3 carbon atoms, respectively. These alkyl groups may have a carboxyl, phosphoric, sulfon or hydroxyl group.
  • R' represents an alkoxy, alkyl or aryl group.
  • the alkyl and aryl group each represented by R1, R2 or R' include ones having a substituent.
  • R1 and R2 may be bonded with each other to form a ring, which includes a heterocycle such as piperidine, pyridine, triazine or morpholine.
  • R11, R12 and R13 each represent a hydrogen atom, or a substituted or unsubstituted alkyl, aryl or heterocyclic group.
  • R14 represents a hydroxyl or hydroxyamino group, or a substituted or unsubstituted alkyl, aryl, heterocyclic, alkoxy, aryloxy, carbamoyl or amino group.
  • the heterocyclic group is a 5- or 6-membered ring, which may include C, H, O, N, and S atom and may be saturated or unsaturated.
  • R15 represents a divalent group selected from -CO-, -SO2- and and n is 0 or 1, provided that R14 is a group selected from an alkyl, aryl and heterocyclic group when n is 0. R13 and R14 may jointly form a heterocyclic group.
  • Typical examples of the hydroxylamine compound represented by Formula A include those described in U.S. Patent Nos. 3,287,125, 33,293,034 and 3,287,124. Particularly preferred ones are those denoted by (A-1) to (A-39) on the 36th to 38th pages of Japanese Patent Application No. 203169/1990, those denoted by (1) to (53) on the 3rd to 6th pages of Japanese Patent O.P.I. Publication No. 33845/1991 and those denoted by (1) to (52) on the 5th to 7th pages of Japanese Patent O.P.I. Publication No. 63646/1991.
  • Typical examples of the compound represented by Formula B include those denoted by (B-1) to (B-33) on the 40th to 43rd pages of Japanese Patent Application No. 203169/1990 and those denoted by (1) to (56) on the 4th to 6th pages of Japanese Patent O.P.I. Publication No. 33846/1991.
  • the compounds represented by Formula A or B are used in the form of salts such as hydrochlorides, sulfates, p-toluenesulfonates, oxalates, phosphates and acetates.
  • a color developer and a black and white developer used in the invention may contain a small amount of sulfite as a preservative.
  • Suitable sulfites include sodium sulfite, potassium sulfite, sodium bisulfite and potassium bisulfite.
  • Suitable buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
  • the color developer should not substantially contain benzyl alcohol.
  • “Substantially” means that the content of benzyl alcohol is not more than 2.0 ml per liter of a processing solution, and preferably it is not contained at all. Fluctuations in photographic properties during continuous processing, particularly increase in fog, can be prevented under conditions containing substantially no benzyl alcohol, and thereby better results can be obtained.
  • the chlorine ion concentration of the color developer is preferably 1.0 ⁇ 10 ⁇ 2 to 1.5 ⁇ 10 ⁇ 1 mol/l, especially 4 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 1 mol/l.
  • the bromine ion concentration of the color developer is 3.0 ⁇ 10 ⁇ 3 to 1.0 ⁇ 10 ⁇ 3 mol/l, preferably 5.0 ⁇ 10 ⁇ 3 to 5 ⁇ 10 ⁇ 4 mol/l and especially 1 ⁇ 10 ⁇ 4 to 3 ⁇ 10 ⁇ 4 mol/l.
  • chlorine ions are directly added to the color developer, there can be used, as materials to supply chlorine ions, sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride. Of them, sodium chloride and potassium chloride are preferred.
  • Chlorine ions may also be added as a counter ion of an optical whitening agent which is incorporated in the color developer and the black and white developer.
  • bromine ion supplying materials include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, ceriumbromide and thallium bromide. Of them, potassium bromide and sodium bromide are preferred.
  • the color developer and the black and white developer used in the invention may employ other antifoggants when necessary.
  • Usable antifoggants are alkali metal halides such as potassium iodide and organic antifoggants.
  • Typical examples of the organic antifoggants are nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.
  • the color developer and the black and white developer used in the invention contain a triazinylstilbene type optical whitening agent.
  • a triazinylstilbene type optical whitening agent the compound represented by the following formula E is preferred.
  • X2, X3, Y1 and Y2 each represent a hydroxyl group, a halogen atom such as chlorine or bromine, or an alkyl, aryl, or -OR25 group.
  • R21 and R22 each represent a hydrogen atom, or a substituted or unsubstituted alkyl or a substituted or unsubstituted aryl group
  • R23 and R24 each represent a substituted or unsubstituted alkylene group
  • R25 represents a hydrogen atom, or a substituted or unsubstituted alkyl or a substituted or unsubstituted aryl group
  • M represents a cation.
  • the above compounds can be synthesized by known methods.
  • E-4, E-24, E-34, E-35, E-36, E-37 and E-41 are particularly preferred. These compounds are used in an amount of preferably 0.2 to 10 g, especially 0.4 to 5 g per liter of the color developer.
  • the color developer and the black and white developer may employ, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, ⁇ -cyclodextrin or the compounds disclosed in Japanese Patent Examined Publication Nos. 33378/1972 and 9509/1969 as an organic solvent to increase the solubility of the developing agent.
  • an auxiliary developing agent such as N-methyl-p-aminophenol sulfate (Metol), phenidone, N,N-diethyl-p-aminophenol hydrocloride or N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride, in an addition amount of 0.01 to 1.0 g/l.
  • additives such as antifoggants, antisludge agents, multilayer effect accelerators and the likes may be employed.
  • the color developer and the black and white developer contain the chelating agent represented by the formula K or one of its exemplified compounds K-1 to K-22 shown from the 8th line from the bottom of the 63rd page to the 3rd line from the bottom of the 64th page of Japanese Patent Application No. 240400/1990.
  • K-2, K-9, K-12, K-13, K-17, and K-19 are preferred; K-2 and K-9 are particularly effective when added to the color developer.
  • These chelating agents are used in an amount of preferably 0.1 to 20 g, especially 0.2 to 8 g per liter of the color developer or the black and white developer.
  • color developer and the black and white developer may contain an anionic, cationic, amphoteric or nonionic surfactant.
  • various surface active materials such as alkyl sulfonic acids, aryl sulfonic acids, aliphatic carboxylic acids and aromatic carboxylic acids, may be added thereto according to a specific requirement.
  • the bleaching agent suitable for the bleaching solution or the bleach-fixer used in the invention is a ferric complex salt of the organic acid represented by the following formula IV.
  • A1 to A4 may be the same or different and each represent -CH2OH, -COOM or -PO3M1M2, where M, M1 and M2 each represent a hydrogen atom, alkali metal or ammonium; X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.
  • ferric complex salt of compounds (IV-1) to (IV-12) exemplified above there can be used any of sodium, potassium and ammonium ferric complex salts of these compounds. Of them, ammonium ferric complex salts thereof are preferred for their capability of achieving the objects of the invention and high solubility.
  • (IV-1), (IV-3), (IV-4), (IV-5) and (IV-9) are preferably used in the invention, and (IV-1) is particularly preferred.
  • the bleacher or the bleach-fixer used in the invention can employ, as a bleaching agent, the ferric salts of the following compounds other than the ferric salts of the compounds represented by Formula IV:
  • the bleacher, bleach-fixer and fixer contain imidazole and its derivative disclosed in Japanese Patent O.P.I. Publication No. 295258/1989 or at least one of the compounds represented by one of formulas I to IX shown in the above patent application and the exemplified compounds thereof.
  • the bleaing solution or bleach-fixer may contain halides, such as ammonium bromide, potassium bromide, sodium bromide, and various optical whitening agents, defoamers, surfactants as well.
  • Preferable fixing agents used in the fixer or bleach-fixer according to the invention are thiocyanates and thiosulfates.
  • Thiocyanates are used at a concentration usually not less than 0.1 mol/l. When these are used in processing color negative films, the concentration is preferably not less than 0.5 mol/l, especially not more than 1.0 mol/l.
  • Thiosulfates are used at a concentration usually not less than 0.2 mol/l. When used in processing color negative films, the concentration thereof is preferably not less than 0.5 mol/l. In achieving the objects of the invention, combination of thiocyanates and thiosulfates is effective.
  • the fixer or bleach-fixer may contain one or more kinds of pH buffers comprised of various salts in addition to the above fixing agents. Further, it is preferable that alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, be contained in large amounts as rehalogenating agents. Furthermore, those which are usually known as additives to a fixer or bleach-fixer, such as alkylamines or polyethylene oxides, may also be added thereto.
  • the compound represented by the following formula FA, or its exemplified compounds, shown on the 56th page of Japanese Patent O.P.I. Publication No. 295258/1989 are contained in the fixer or bleach-fixer, so that the effect of the invention is well brought out and the formation of sludges is noticeably lessened in a fixing-capable processing solution used to process light-sensitive materials little by little over a long period of time.
  • the compound represented by Formula FA can be synthesized by generally known methods described, for example, in U.S. Patent Nos. 3,335,161 and 3,260,718.
  • the compound represented by Formula FA may be used singly or in combination of two or more types.
  • the stabilizer contains a chelating agent whose chelate stability constant against ferric ions is larger than 8.
  • chelate stability constant means the constant made generally known by L.G. Sillen and A.E. Martell, "Stability Constants of Metal-ion Complexes", The Chemical Society, London (1964) and S. Chaberek and A.E. Martell, "Organic Sequestering Agents", Wiley (1959).
  • the addition amount of such a chelating agent is preferably 0.01 to 50 g per liter of the stabilizer; particularly, that of 0.05 to 20 g per liter produces much better results.
  • Ammonium compounds can be favorably used in the stabilizer. These are added to the stabilizer in the form of ammonium salts of inorganic compounds in an amount of 0.001 to 1.0 mol, preferably 0.002 to 2.0 mol per liter.
  • the stabilizer contain a metal salt in combination with the above chelating agent.
  • a metal salt includes salts of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al, Sr and can be fed as a halide, hydroxide, sulfate, carbonate, phosphate or acetate, or as a water-soluble chelating agent. These are used in a range preferably from 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 1 mol, and especially from 4 ⁇ 10 ⁇ 4 to 2 ⁇ 10 ⁇ 2 mol per liter of the stabilizer.
  • the stabilizer may contain an organic acid salt, such as a citrate, acetate, succinate, oxalate or benzoate, and a pH regulator, such as a phosphate, borate, hydrochloride or sulfate.
  • organic acid salt such as a citrate, acetate, succinate, oxalate or benzoate
  • a pH regulator such as a phosphate, borate, hydrochloride or sulfate.
  • a conventional antimold may also be used, singly or in combination, within the limit not harmful to the effect of the invention.
  • silver iodobromide or silver iodochloride having an average silver iodide content not less than 3 mol% is used in the form of silver halide grains, and the use of silver iodobromide having a silver iodide content of 4 to 15 mol% produces good results.
  • this average silver iodide content is preferably from 5 to 12 mol%, especially from 8 to 11 mol%.
  • silver halide grains contained in the light-sensitive material for printing silver halide grains comprised mainly of silver chloride having a silver chloride content not less than 80 mol% are favorably used.
  • the silver chloride content is desirably not less than 90 mol%, more desirably not less than 95 mol% and most desirably not less than 99 mol%.
  • the above silver chloride rich silver halide emulsion may contain silver bromide and/or silver iodide, as the silver halide composition other than silver chloride.
  • the content of silver bromide is desirably not more than 20 mol%, more desirably not more than 10 mol% and most desirably not more than 3 mol%.
  • silver iodide is present, the content is desirably not more than 1 mol%, more desirably not more than 0.5 mol% and most desirably 0 mol%.
  • Silver chloride rich silver halide grains having a silver chloride content not less than 50 mol% are required to be used at least in one silver halide emulsion layer, and it is preferable to be used in all light-sensitive silver halide emulsion layers of a light-sensitive material.
  • the above silver halide grains may be regular crystals, twin crystals or other types of crystals, and may have any [1.0.0] face to [1.1.1] ratio.
  • the crystal structure of these silver halide grains may be uniform from the inner part to the outer part of grains or of layered structure (core/shell type) in which the silver halide composition is different from the inner portion to the outer portion.
  • These silver halide grains may be ones which form latent images mainly on their surfaces or ones which form latent images mainly at their inner portions.
  • tabular silver halide grains see Japanese Patent O.P.I. Publication No. 113934/1983 and Japanese Patent Application No. 170070/1984.
  • silver halide grains may be prepared by any of the acid method, the neutral method and the ammoniacal method.
  • these silver halide grains may also be prepared by steps of obtaining first seed grains through the acid method and then growing them to a prescribed size through the ammoniacal method which can grow them much faster.
  • the silver halide emulsion may be any of those described in Research Disclosure No. 308119 (hereinafter abbreviated to RD308119).
  • Silver halide emulsions are subjected to physical ripening, chemical ripening and spectral sensitization before use.
  • Additives employed in these processes are described in Research Disclosure Nos. 17643, 18716 and 308119 (hereinafter abbreviated to RD17643, RD18716 and RD308119, respectively). Phtographic additives are also described in the above numbers of Research Disclosure.
  • the light-sensitive material to be processed with the processing solution of the invention can use various couplers, of which typical examples can be seen in the above numbers of Research Disclosure.
  • additives can be incorporated by the dispersion method and the like described in XIV of RD308119
  • auxiliary layers such as a filter layer and an intermediate layer can be provided.
  • the light-sensitive material may have any of the layer configurations, such as conventional layer order, inverted layer order, unit layer structure, described in VII-Sec. K of RD308119.
  • the light-sensitive material to be processed with the processing solution of the invention is a color photographic material
  • its silver halide emulsion layers contain color couplers.
  • the red-sensitive layer may contain, for example, nondiffusible color couplers to form cyan color images such as phenol type or ⁇ -naphthol type couplers.
  • the green-sensitive layer may contain, for example, at least one nondiffusible color coupler to form magenta color images, usually a 5-pyrazolone type color coupler and pyrazolotriazole.
  • the blue-sensitive layer may contain, for example, at least one nondiffusible color coupler to form yellow color images, generally a color coupler having an open-chain ketomethylene group. These color couplers may be two-, four- or six-equivalent ones.
  • two-equivalent color couplers are particularly preferred.
  • Suitable couplers are those described, for example, in W. Pelz, Mitanderlnausden Anlagenslaboratorien der Agfa (Research Papers of Agfa), Farbkuppler (Color Couper), Leverkusen/Munchen, Vol. III, p. 111 (1961); K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. 4, Academic Press, pp. 341-387; The Theory of the Protographic Process, 4th Edition, pp. 353-362; and Research Disclosure No. 17643, Sec. VII.
  • the color light-sensitive material to be processed with the processing solution of the invention contain the magenta coupler represented by formula M-1 shown in Japanese Patent O.P.I. Publication No. 106655/1988 (typical examples are Nos. 1 to 77 shown on pages 29-34 of the same patent application), the cyan coupler represented by formula C-I or C-II on page 34 of the same (typical examples are C'-1 to C'-82 and C''-1 to C''-36 shown on pages 37-42 of the same), and the rapid yellow coupler shown on page 20 of the same (typical examples are Y'-1 to Y'-39 shown on pages 21-26 of the same).
  • M-1 shown in Japanese Patent O.P.I. Publication No. 106655/1988
  • the cyan coupler represented by formula C-I or C-II on page 34 of the same typically examples are C'-1 to C'-82 and C''-1 to C''-36 shown on pages 37-42 of the same
  • the rapid yellow coupler shown on page 20 of the same
  • Triethanolamine 10 g Diethylene glycol 5 g N,N-diethylhydroxylamine 3.0 g Potassium bromide 20 mg Potassium chloride 0.2 g Sodium diethylenetriaminepentacetate 5 g Potassium sulfite 0.2 g Color developing agent (3-methyl-4-amino-N-ethyl-N-( ⁇ -hydroxyethyl)aniline sulfate) 4.5 g Potassium carbonate 25 g Potassium hydrogencarbonate 5 g Water-soluble polymer (shown in Table 1) Surfactant (shown in Table 1)
  • a color paper sample was prepared by forming the following layers in numerical order on the side of a paper support laminated with titanium-oxide-containing polyethylene. The other side of the support was laminated with a polyethylene layer.
  • the coating solutions used were prepared in the following procedure.
  • Coating solutions for the 2nd to the 7th layers were prepared in similar manners as above.
  • hardener (H-1) was added to the 2nd and 3rd layers, and hardener (H-2) to the 7th layer; surfactants (SU-2) and (SU-3) were used to adjust the surface tension.
  • the resulting silver halide grains were desalted with the addition of a 5% aqueous solution of Demol N made by Kao Atlas Co. and a 20% aqueous solution of magnesium sulfate and dispersed in an aqueous gelatin solution to obtain an emulsion, EMP-1, which was comprised of monodispersed cubical grains having an average grain size of 0.85 ⁇ , a grain size distribution variation coefficient ( ⁇ /r) of 0.07 and a silver chloride content of 99.5 mol%.
  • ⁇ is a standard deviation of grain size distribution and r is an average grain size.
  • EMP-1 was chemically ripened for 90 minutes at 50° C by use of the following compounds, a blue-sensitive silver halide emulsion, Em-B, was thus obtained.
  • 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
  • EMP-2 an emulsion comprised of monodispersed cubical grains having an average grain size of 0.43 ⁇ , a grain size distribution variation coefficient ( ⁇ /r) of 0.08 and a silver chloride content of 99.5 mol%, was prepared in the same procedure as with EMP-1, except that the addition time of solutions A and B and that of solutions C and D were changed.
  • EMP-2 was chemically ripened for 120 minutes at 55° C by use of the following compounds to obtain a green-sensitive silver halide emulsion, Em-G.
  • 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 (BS-1) 4 ⁇ 10 ⁇ 4 mol/mol AgX
  • EMP-3 an emulsion comprised of monodispersed cubical grains having an average grain size of 0.50 ⁇ , a grain size distribution variation coefficient ( ⁇ /r) of 0.08 and a silver chloride content of 99.5 mol%, was prepared in the same procedure as with EMP-1, except that the addition time of solutions A and B and that of solutions C and D were changed.
  • EMP-3 was chemically ripened for 90 minutes at 60° C by use of the following compounds to obtain a red-sensitive silver halide emulsion, Em-R.
  • 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
  • Process Temperature Processing time Color developing 38 ⁇ 0.3°C 30 sec Bleach-fixing 38 ⁇ 3°C 30 sec Stabilizing* 38 ⁇ 5°C 20 sec 3 Drying 60 ⁇ 5°C 45 sec * Stabilizing was carried out in a three-tank countercurrent mode, in which the replenisher was fed to the 3rd tank (the last tank) and the overflow of each tank was poured into the preceding tank.
  • the processing solutions used in the above processes were as follows: As the color developer, the color developer preserved for 15 days under the foregoing conditions was used.
  • the stabilizer used was the following one.
  • Water 800 g 1,2-Benzoisothiazoline-3-one 0.1 g 1-Hydroxyethylidene-1,1-diphosphonic acid 5.0 g Ethylenediaminetetracetic acid 1.0 g Tinopal SFP (product of Ciba-Geigy AG) 2.0 g Ammonium sulfate 2.5 g Zinc chloride 1.0 g
  • Magnesium chloride 0.5 g o-Phenylphenol 1.0 g Sodium sulfite 2.0 g
  • PVA-1 indicates a water-soluble polyvinyl alcohol film (Hicellon S made by Nichigo Film Co., 30 ⁇ m thick)
  • PVA-2 a water-soluble polyvinyl alcohol film (Solvlon PH made by Aicello Kagaku Co., 30 ⁇ m thick)
  • PVA-3 a water-soluble polyvinyl alcohol film (Solvlon PW made by Aicello Kagaku Co., 40 ⁇ m thick)
  • PVA-4 a water-soluble polyvinyl alcohol film (Hicellon S made by Nichigo Film Co., 30 ⁇ thick)
  • PL-1 a Pullulan film (a natural ⁇ -polysaccharide whose minimum unit is glucose, product of Hayashihara Co., 20 ⁇ thick).
  • the evaluation was made by means of a 3-round continuous processing with a roller transporting type automatic processor.
  • the "3-round” processing means that the processing was continued until the added volume of the developer replenisher reached to 3 times of the initial volume of the developer in the developing tank.
  • a bleach-fixer for color paper was prepared in the following composition.
  • Powder bleach-fixer composition to be made up to 1 liter
  • Ammonium ferric ethylenediaminetetracetate 65 g Sodium ethylenediaminetetracetate 2 g Ammonium thiosulfate 70 g Ammonium thiocyanate 30 g Potassium sulfite 10 g Ammonium bromide 20 g Sulfinic acid 5 g
  • kinks of bleach-fixers were prepared, in which the water-soluble polymer, PVP and surfactant were added to this composition in amounts shown in Table 1, respectively, then the mixture was made up to 1 liter with the addition of water, followed by adjusting the pH to 6.5 with acetic acid and sodium hydroxide.
  • Triethanolamine 10 g Diethylene glycol 5 g N,N-diethylhydroxylamine 3.0 g Potassium bromide 20 mg Potassium chloride 0.2 g Sodium diethylenetriaminepentacetate 5 g Potassium sulfite 0.2 g Color developing agent (3-methyl-4-amino-N-ethyl-N-( ⁇ -hydroxyethyl)aniline sulfate 4.5 g Potassium carbonate 25 g Potassiu hydrogencarbonate 5 g
  • Example 1 As the stabilizer, that used in Example 1 was employed.
  • Example 2 The procedure in Example 1 was repeated, except that the optical whitening agent (Tinopal SFP) used in Experiment Nos. 1 to 7 of Example 1 was replaced by those shown in Table 2. The results are summarized in Table 2.
  • Table 2 Experiment No Optical whitening agent Reflected green density at unexposed portion of color paper sample Days till crystals and tar occur Stains on color paper sample 2-1 comparison 1 0.03 29days A - B 2-2 comparison 2 0.03 28days A - B 2-3 comparison 3 0.03 29days A - B 2-4 not added 0.04 27days A - B 2-5 E-2 0.01 30 days and more A 2-6 E-4 0.01 30 days and more A 2-7 E-10 0.01 29 days A 2-8 E-40 0.02 30 days and more A 2-9 E-42 0.02 30 days and more A 2-10 E-44 0.02 30 days and more A 2-11 E-24 0.01 30 days and more A 2-12 E-34 0.01 30 days and more A 2-13 E-43 0.02 29 days A - B 2-14 E-
  • a 50- ⁇ thick triacetylcellulose film support was subbed on one side. Then, the following backside layers were formed in sequence on the unsubbed side of the support.
  • Backside 1st layer Alumina sol AS-100 aluminium oxide made by Nissan Chemical Co.
  • Backside 2nd layer Diacetylcellulose 100 mg Stearic acid 10 mg Silica fine powder (average particle size: 0.2 ⁇ ) 50 mg
  • a-1 antihalation layer
  • HC antihalation layer
  • HC Black colloidal silver 0.15 g UV absorbent (UV-1) 0.20 g Colored cyan coupler (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling solvent (Oil-2) 0.20 g Gelatin 1.6 g 2nd layer: intermediate layer (IL-1) Gelatin 1.3 g 3rd layer: low-speed red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (average grain size: 0.3 ⁇ ) 0.4 g Silver iodobromide emulsion (average grain size: 0.4 ⁇ ) 0.3 g Sensitizing dye (S-1) 3.2 ⁇ 10 ⁇ 4 (mol/mol Ag) Sensitizing dye (S-2) 3.2 ⁇ 10 ⁇ 4 (mol/mol Ag) Sensitizing dye
  • the color negative film contained compounds Su-1, Su-2, viscosity regulator, hardeners H-1, H-2, stabilizer ST-1, antifoggants AF-1, AF-2 (weight average molecular weights were 10,000 and 1,100,000, respectively), dyes AI-1, AI-2, and compound DI-1 (9.4 mg/m2).
  • the silver iodobromide emulsion used in the 10 th layer was prepared in the following procedure.
  • a silver iodobromide seed emulsion comprised of monodispersed grains having an average grain size of 0.33 ⁇ m and a silver iodide content of 2 mol% were prepared by the double jet method.
  • solutions ⁇ H-2 ⁇ and ⁇ S-2 ⁇ were added at a constant flow ratio of 1:1 and at an accelerated flow (the final flow was 5.2 times as large as the initial flow) over a period of 65 minutes, while keeping the mother liquor pAg 10.1 and pH 6.0.
  • the pAg and pH were controlled by use of an aqueous solution of potassium bromide and a 56% aqueous acetic acid. After grains were formed, these were desalted by the usual flocculation method, dispersed again with the addition of gelatin, and then the resulting emulsion was adjusted to pH 5.8 and pAg 8.06 at 40° C.
  • the emulsion was comprised of monodispersed octahedral silver iodobromide grains having an average grain size of 0.08 ⁇ m, a grain size distribution extent of 12.4%, and a silver iodide content of 8.5 mol%.
  • Solution G-1 Ossein gelatin 100.0 g 10 wt% Methanol solution of compound-1 25.0 ml 28% Aqueous ammonia 440.0 ml 56% Aqueous acetic acid 660.0 ml Water is added to make up to 5000.0 ml Solution H-1 Ossein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Water is added to make up to 1030.5 ml Solution S-1 Silver nitrate 309.2 g 28% Aqueous ammonia equivalent Water is added to make up to 1030.5 ml Solution H-2 Ossein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Water is added to make up to 3776.8 ml Solution S-2 Silver nitrate 1133.0 g 28% Aqueous ammonia equivalent Water is added to make up to 3776.8 ml
  • the other emulsions different in average grain size and silver iodide content were prepared likewise by varying the average size of seed grains, temperature, pAg, pH, flow, addition time, and halide composition.
  • Each of the emulsions was a monodispersed emulsion comprised of core/shell type grains having an grain size distribution extent not more than 20%.
  • Each emulsion was chemically ripened under optimum conditions using sodium thiosulfate, chloroauric acid and ammonium thiocyanate. Then, sensitizing dyes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added thereto.
  • Water is added to make 1 liter, and the pH is adjusted to 10.01 with potassium hydroxide or 20% sulfuric acid.
  • Water is added to make 1 liter, and the pH is adjusted to 10.12 with potassium hydroxide or 20% sulfuric acid.
  • Ammonium ferric 1,3-propylenediaminetetracetate 0.35 mol
  • Sodium ferric ethylenediaminetetracetate 2 g
  • Ammonium bromide 120 g
  • Ammonium nitrate 50 g
  • Glacial acetic acid 40 g
  • Water is added to make 1 liter, and the pH is adjusted to 3.4 with aqueous ammonia or glacial acetic acid.
  • Water is added to make 1 liter, and the pH is adjusted to 7.0 with potassium hydroxide or sulfuric acid.
  • Example 3 the color negative film was processed as in Example 1 and then examined for reflected blue density at its unexposed portion. The results are summarized in Table 3.
  • the reflected bule density at the unexposed portion was 0.46 in every color negative film sample, and the frequency and degree of slip jams as well as the degree of stains and scratches of each sample was much the same as those in Example 4.

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EP92108623A 1991-05-23 1992-05-21 Verarbeitungslösung und Verarbeitungsverfahren für photographische lichtempfindliche Silberhalogenidmaterialien Withdrawn EP0514906A1 (de)

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JP14786391A JPH04346337A (ja) 1991-05-23 1991-05-23 ハロゲン化銀写真感光材料用処理液及び処理方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1016917A2 (de) * 1998-12-31 2000-07-05 Eastman Kodak Company Farbentwicklungszusammensetzung und ihre Verwendung in der photographischen Verarbeitung

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0330093A2 (de) * 1988-02-19 1989-08-30 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung von farbphotographischem Silberhalogenidmaterial

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0330093A2 (de) * 1988-02-19 1989-08-30 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung von farbphotographischem Silberhalogenidmaterial

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 5, no. 48 (P-55)(720) 7 April 1981 & JP-A-56 004 146 ( OLYMPUS ) 17 January 1981 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1016917A2 (de) * 1998-12-31 2000-07-05 Eastman Kodak Company Farbentwicklungszusammensetzung und ihre Verwendung in der photographischen Verarbeitung
EP1016917A3 (de) * 1998-12-31 2002-01-02 Eastman Kodak Company Farbentwicklungszusammensetzung und ihre Verwendung in der photographischen Verarbeitung

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