EP0476434A2 - Procédé de traitement des matériaux photosensibles à l'halogénure d'argent pour la photographie en couleur - Google Patents

Procédé de traitement des matériaux photosensibles à l'halogénure d'argent pour la photographie en couleur Download PDF

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Publication number
EP0476434A2
EP0476434A2 EP91114954A EP91114954A EP0476434A2 EP 0476434 A2 EP0476434 A2 EP 0476434A2 EP 91114954 A EP91114954 A EP 91114954A EP 91114954 A EP91114954 A EP 91114954A EP 0476434 A2 EP0476434 A2 EP 0476434A2
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European Patent Office
Prior art keywords
group
processing
solution
acid
integer
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EP91114954A
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German (de)
English (en)
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EP0476434A3 (en
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Ichirou Konica Corporation Tsuchiya
Shigeharu Konica Corporation Koboshi
Hiroshi Konica Corporation Yoshimoto
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Konica Minolta Inc
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Konica Minolta Inc
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Priority claimed from JP30829690A external-priority patent/JPH04194855A/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0476434A2 publication Critical patent/EP0476434A2/fr
Publication of EP0476434A3 publication Critical patent/EP0476434A3/en
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    • 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
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
    • 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

Definitions

  • This invention relates to a method for processing a silver halide color photographic light sensitive material and, particularly, to a method for processing a silver halide color photographic light sensitive material, which is capable of providing a light sensitive material excellent in dye image stability and stain prevention and, at the same time, reducing a harmful compound contained in a processing solution or not using any one of the compound and, in addition, performing a rapid processing.
  • a silver halide color photographic light sensitive material is exposed imagewise to light and is then processed in the following order, a color developing step, a bleaching step, a fixing step or a processing step having a fixing function such as a bleach-fixing step, and the processing steps such as a stabilizing and washing steps.
  • the countermeasures thereto include, for example, the methods in which water is counter- flowed by providing a washing tank with a multistage structure, such as described in West German Patent No. 2,920,222 and S.R. Goldwasser, 'Water Flow in Immersion-Washing of Motion-picture Film', SMPTE, Vol.64, pp.248 - 23, May 1955.
  • the above-mentioned technique is not a processing method in which any washing water is not used at all. Therefore, under the recent situations where the water resources are so short that a washing cost is raised by increasing the costs of crude oil, the problems are getting more serious.
  • the formaldehyde applied to the above-mentioned stabilizing bath has the effects of protecting the physical properties of a color light sensitive material including, particularly, an effect of preventing the surface of a photographic light sensitive material from being scratched and an effect of preventing a gradation from being varied by the fact that a photographic light sensitive material is gradually hardened by allowing it to stand.
  • it has also a further known effect of preventing a dye-image stability from being deteriorated by a coupler remaining unreacted in the color photographic light sensitive material.
  • Japanese Patent Publication Open to Public Inspection - hereinafter referred to as Japanese Patent O.P.I. Publication-Nos. 62-196660/1987, 62-54261/1987 and 63-298344/1988 each disclose the techniques in which a color photographic light sensitive material containing a 2-equivalent coupler is processed with a stabilizer not substantially containing any formaldehyde.
  • Japanese Patent O.P.I. Publication-Nos. 62-196660/1987, 62-54261/1987 and 63-298344/1988 each disclose the techniques in which a color photographic light sensitive material containing a 2-equivalent coupler is processed with a stabilizer not substantially containing any formaldehyde.
  • the other problems were raised. Namely, a problem that stains are liable to produce due to a sensitizing dye eluted from a light sensitive material to be processed, and another problem that a reticulation is liable to produce.
  • an object of the invention to provide an improved method for processing a silver halide color photographic light sensitive material, wherein any stains and reticulations can be prevented from producing even in carrying out a rapid processing.
  • Another object of the invention is to provide an improved method for processing a silver halide color photographic light sensitive material, wherein a dye transfer can be improved in the stabilizing tank of an automatic processor.
  • a further object of the invention is to provide a method for processing a silver halide color photographic light sensitive material, wherein any formaldehyde is not used substantially and an excellent social environment can be maintained.
  • the method for processing a silver halide color photographic light sensitive material which relates to the invention, is comprised of processing the silver halide color photographic light sensitive material with a processing solution having a fixing ability and, in succession, processing the same directly with a stabilizer without carrying out a washing step, and the method is characterized in that the silver halide color photographic light sensitive material contains at least one kind of 2-equivalent couplers, that the above-mentioned processing solution having the fixing ability contains ammonium ions in a proportion of not more than 50 mol% to the whole cation, and that the above-mentioned stabilizer does not contain any formaldehyde substantially, but contains at least one kind of the compounds represented by the following formula I or II.
  • R 2 represents a univalent organic group
  • R 22 represents an ethylene, propylene or isopropylene group
  • m is an integer of 4 to 50
  • X represents a hydrogen atom, -S0 3 M or -P0 3 M in which M represents a hydrogen atom, an alkali metal or ammonium.
  • Rg represents a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group, or in which R 10 , R 11 and R 12 represent each a hydrogen atom or a lower alkyl group (including, preferably, an alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group and a propyl group), provided, Rio, R 11 and R 12 may be the same with or different from each other; l 1 to l 3 are each an integer of 0 or 1 to 30; p, q 1 and q 2 are each an integer of 0 or 1 to 30; and X and X 2 represent each -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -,
  • processing steps preferably carried out in the processing method in which the processing solution of the invention is to be used include the following processing steps;
  • the processing steps (1), (2) and (5) may preferably be carried out.
  • the bath or solution include, for example, a bleach-fixer or a fixer used in the above-given processing steps.
  • the fixer or bleach-fixer contains ammonium ions in a proportion of not more than 50 mol% of the whole cation, desirably not more than 20 mol% thereof and, preferably not more than 10 mol% thereof.
  • a thiocyanate or a thiosulfate may be used as the fixer.
  • the thiosulfates include, for example, sodium thiosulfate, ammonium thiosulfate and potassium thiosulfate.
  • the thiocyanates include, for example, ammonium thiocyanate, sodium thiocyanate and potassium thiocyanate.
  • the fixer and bleach-fixer are also allowed to contain a pH buffer comprising various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bycarbonate, acetic acid, sodium acetate and ammonium hydroxide, independently or in combination.
  • the fixer and bleach-fixer are further allowed to contain an alkali halide or ammonium halide such as potassium bromide, sodium bromide, sodium chloride and ammonium bromide.
  • the compounds such as alkyl amines and polyethylene oxides may also suitably be added thereto. When adding an ammonium salt thereto, the ammonium content thereof may be within the scope of the invention.
  • the fixer or bleach-fixer is also allowed to contain the compounds represented by formula [FA] given in Japanese Patent O.P.I. Publication No. 64-295258/1989, p.56 and the exemplified compounds thereof. If this is the case, another effect that sludge productions can remarkably be reduced when a small quantity of light sensitive materials are processed with the fixer or bleach-fixer for a long time.
  • the compounds having formula [FA] appeared in the above-given Japanese Patent Publication can be synthesized in the common processes such as those described in U.S. Patent Nos. 3,335,161 and 3,260,718.
  • the compounds having the formula [FA] may be used independently or in combination. When they are added in an amount within the range of 0.1 g to 200 g per liter of a processing solution to be used, a good effect can be obtained.
  • a sulfite and a sulfurous acid-releasing compound may also be used in the fixer or bleach-fixer.
  • the typically exemplified compounds include, for example, potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogensulfite, potassium hydrogensulfite, sodium hydrogensulfite, potassium metabisulfite, sodium metabisulfite and ammonium metabisulfite. It is further allowed to include therein the compounds given by formula [B-1] or [B-2] appeared in Japanese Patent O.P.I. Publication No. 64-295258/1989, p.60.
  • the above-given sulfites and sulfurous acid-releasing compounds are to contain sulfurous acid ions in an amount of at least 0.05 mols per liter of the fixer or bleach-fixer used, desirably within the range of 0.08 mols/liter to 0.65 mols/liter, preferably 0.10 mols/liter to 0.50 mols/liter and, particularly 0.12 mols/liter to 0.40 mols/liter.
  • Silver may be recovered from the fixer or bleach-fixer in any known methods.
  • the effectively applicable silver recovery methods include, for example, an electrolyzing method (such as detailed in French Patent No. 2,299,667), a precipitating method (such as detailed in Japanese Patent O.P.I. Publication No. 52-73037/1977 and German Patent No. 2,331,220), an ion-exchange method (such as detailed in Japanese Patent O.P.I. Publication No. 51-17114/1976 and German Patent No. 2,548,237), and a metal-substitution method (such as detailed in British Patent No. 1,353,805).
  • an electrolyzing method such as detailed in French Patent No. 2,299,667
  • a precipitating method such as detailed in Japanese Patent O.P.I. Publication No. 52-73037/1977 and German Patent No. 2,331,220
  • an ion-exchange method such as detailed in Japanese Patent O.P.I. Publication No. 51-17114/1976 and German Patent No. 2,548,
  • silver is particularly preferable to recover silver in an in-line system by making use of an electrolyzing method or an anionic-exchange resin from a tank solution, because a rapid processing aptitude can further be improved.
  • silver may be recovered from a waste over-flow solution and then reused.
  • a fixer or bleach-fixer relating to the invention can be replenished in an amount of not more than 900 ml per m 2 of a light sensitive material to be processed, preferably in an amount within the range of 20 ml to 750 ml per m 2 of the light sensitive material and particularly 50 ml to 620 ml.
  • the processing time is preferably not longer than 150 seconds and, particularly, within the range of 5 to 100 seconds.
  • the invention can display an excellent effect in such a rapid process as mentioned above.
  • the expression, 'a processing time when a light sensitive material is processed with a fixer or bleach-fixer' means a period of time from the point of time when starting to dip the leading edge of the light sensitive material into the fixer or bleach-fixer to the point of time when the leading edge thereof comes out of the fixer or bleach-fixer.
  • a stabilizing bath is preferably comprised of a plurality of tanks.
  • the flow of a solution connecting between the tanks is preferably a multistaged counter current flowing in the direction relative to the direction of transporting the light sensitive material.
  • the stabilizing bath is preferably comprised of 2 to 4 units of tanks.
  • a stabilizer not substantially containing any formaldehyde' means that containing formaldehyde in an amount of not more than 1.0x1 0-2 mols/liter.
  • a replenishment rate into a stabilizer is preferably not more than 800 ml per m 2 of a light sensitive material to be processed.
  • An excessive reduction of the replenishment causes the discoloration of a dye and the deposition of a salt on the surface of a light sensitive material after it is dried up. Therefore, the replenishment rate is preferably within the range of not less than 100 ml to not more than 620 ml per m 2 .
  • the determination of a further concrete amount replenished may be varied according to the tank constitution of a stabilizing bath. The more the number of tanks is increased, the more the amount replenished can be saved.
  • the pH value of the stabilizing bath relating to the invention is, desirably, within the range of 5.5 to 11.0 and, from the viewpoint of enhancing the effects of the invention, it is, preferably, within the range of 7 to 10.5 and, particularly, 7.5 to 10.
  • the temperature thereof is, desirably, within the range of 15°C to 70 ° C and, preferably, 20 ° C to 55 C.
  • the processing time for the stabilizing bath relating to the invention is, desirably, not longer than 120 seconds, preferably, within the range of 3 seconds to 90 seconds and, most preferably, 6 seconds to 60 seconds.
  • a squeegee between a processing bath having a fixing function and a stabilizing bath and between the stabilizing baths so that a satisfactorily squeeze a solution.
  • a replenishment rate can be saved and a light sensitive material can also be prevented from staining, more effectively.
  • the amount carried- over from a processing bath having a fixing function to a stabilizing bath is, desirably not more than 150 ml/m 2 , preferably, within the range of 10 ml/m 2 to 100 ml/m 2 and, particularly, 20 ml/m 2 to 70 ml/m 2 .
  • R 1 represents a univalent organic group including, for example, an alkyl group having 4 to 30 carbon atoms and preferably 6 to 20 carbon atoms, (such as each of the groups of hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl) or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, of which the substituents include, preferably, an alkyl group having 3 to 12 carbon atoms such as each of the groups of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and doceyl.
  • the aryl groups include, for example, a phenyl group, a tolyl group, a xynyl group, a diphenyl group and a naphthyl group and, among them, a phenyl group and a tolyl group are preferable.
  • the alkyl group may be coupled to an aryl group in any one of an ortho, meta and para positions.
  • R 2 represents a substituted or non-substituted ethylene or propylene group.
  • m is an integer of 4 to 50.
  • X represents a hydrogen atom, -S03M or -P0 3 M 2 in which M represents a hydrogen atom, an alkali metal atom (such as an Na, K or Li atom) or NH 4 + .
  • the compounds having the afore-given formula I can be used in an amount within the range of 0.1 to 40 g and, preferably, 0.3 to 20 g per liter of the stabilizer of the invention
  • the water-soluble organic siloxane type compound having a polyoxyalkylene group is added in an amount within the range of 0.01 to 20 g per liter of a stabilizer used, the excellent effects including, particularly, any precipitation and scratch prevention effects can be displayed.
  • the water-soluble organic siloxane type compounds of the invention means the common water-soluble organic siloxane type compounds such as those described in, for example, Japanese Patent O.P.I. Publication Nos. 47-18333/1972 and 49-62128/1974, Japanese Patent Examined Publication Nos. 55-51172/1980 and 51-37538/1976, and U.S. Patent No. 3,545,970.
  • water-soluble organic siloxane type compounds can usually be available from Union Carbide Co., Shinetsu Chemical Industry Co. and so forth.
  • a stabilizer contains a chelating agent having a chelate-stability constant of not less than 8 to iron ions.
  • the term, 'a chelate-stabilization constant' means herein a generally known constant described in L.G.Sillen * A.E. Martell, 'Stability Constants of Metal-ion Complexes', The Chemical Society, London, 1964, and S. Chaberek'A.E. Martell, 'Organic Sequestering Agents', Wiley, 1961.
  • the chelating agents having a chelate-stability constant of not less than 8 to iron ions include, for example, an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent and a polyhydroxy compound.
  • the above-mentioned iron ions mean ferric ions (Fe 3+ ).
  • the typical examples of the chelating agents each having a chelate-stability constant of not less than 8 to ferric ions include the following compounds. It is, however, to be understood that they shall not be limited thereto. They include, for example, ethylenediamine diorthohydroxyphenyl acetic acid, diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylenediamine triacetic acid, dihydroxyethyl glycine, ethylenediamine diacetic acid, ethylenediamine dipropionic acid, iminodiacetic acid, diethylenetriamine pentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanol tetraacetic acid, transcyclohex- anediamine tetraacetic acid, glycoletherdiamine tetraacetic acid, ethylenediaminetetrakismethylene phosphonic acid, nitrilotrimethylene phosphonic acid, 1-hydroxy
  • diethylenetriamine pentaacetic acid, dinitrilotriacetic acid, nitrilotrimethylene phosphonic acid and 1,hydroxyethy!idene-1,1-diphosphonic acid are preferable and, inter alia, 1-hydroxyethylidene-1,1- diphosphonic acid is most preferable.
  • the above-mentioned chelating agent is to be used in an amount within the range of 0.01 to 50 g per liter of a stabilizer and, preferably, 0.05 to 20 g.
  • a metal salt in a stabilizer used together with the above-mentioned chelating agent in combination.
  • a metal salt include, for example, the metal salts of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, AI or Sr, which may be supplied as an inorganic salt of a halide, a hydroxide, a sulfate, a carbonate, a phosphate or a acetate or a water-soluble chelating agent. They may be added in an amount within the range of 1x10- 4 to 1x10 ⁇ ⁇ mols per liter of a stabilizer used and, preferably, 1x10- 4 to 2x10- 2 mols
  • the stabilizers are each allowed to contain an organic acids (such as citric acid, acetic acid, succinic acid, oxalic acid and benzoic acid) and a pH controller (such as a phosphate, a borate, hydrochloric acid and a sulfate).
  • an organic acids such as citric acid, acetic acid, succinic acid, oxalic acid and benzoic acid
  • a pH controller such as a phosphate, a borate, hydrochloric acid and a sulfate.
  • any antimoulds can be used indenpendently or in combination, provided, the effects of the invention cannot be spoiled.
  • silver may also be recovered from a stabilizer used therein.
  • a stabilizer used therein.
  • an electrolytic method (refer to French Patent No. 2,299,667), a precipitation method (refer to Japanese Patent O.P.I. Publication No. 52-73037/1977 and German Patent No. 2,331,220), an ion-exchange method (refer to Japanese Patent O.P.I. Publication No. 51-17114/1976 and German Patent No. 2,548,237) and a metal substitution method (refer to British Patent No. 1,353,805) may effectively be utilized.
  • silver recovery it is particularly preferable that silver is to be recovered in an in-line system from a tank solution in an electrolytic method or by making use of an anion-exchange resin, because the rapid processing aptitude can further be improved. Besides the above, silver may also be recovered from the waste over-flow so as to be reused.
  • a stabilizer may be subjected to an ion-exchange treatment, an electrodialytic treatment (refer to Japanese Patent O.P.I. Publication No. 61-28949/1986) or a reverse osmotic treatment (refer to Japanese Patent O.P.I. Publication Nos. 60-240153/1985 and 62-254151/1987).
  • an electrodialytic treatment (refer to Japanese Patent O.P.I. Publication No. 61-28949/1986) or a reverse osmotic treatment (refer to Japanese Patent O.P.I. Publication Nos. 60-240153/1985 and 62-254151/1987).
  • a reverse osmotic treatment reference to Japanese Patent O.P.I. Publication Nos. 60-240153/1985 and 62-254151/1987.
  • any one of the means for deionizing treatments may be used, provided that Ca or Mg ions of washing water can be made not higher than 5 ppm after completing the treatment.
  • the above-mentioned ion-exchange resins and reverse dialytic films are detailed in Journal of Technical Disclosure Nos. 87-1984 and 89-20511.
  • the salt concentration of a stabilizer is preferably not more than 1000 ppm and particularly not more than 800 ppm.
  • the color developing agents applicable to a color developing step include, for example, an aminophenol type compound and a p-phenylenediamine type compound.
  • a p-phenylenediamine type compound having a water-soluble group may preferably be used.
  • At least one of the above-mentioned water-soluble groups is present on the amino group or benzene nucleus of a p-phenylenediamine type compound.
  • the typical water-soluble groups include, preferably, the following groups;
  • the compounds preferably applicable to the invention include, for example, the exemplified compounds A-1, A-2, A-3, A-4, A-6, A-7 and A-15.
  • the color developing agents may be added preferably in an amount not less than 0.5x10- 2 mols per liter of a color developer used, preferably, within the range of 1.0x10 -2 to 1.0x10 -1 mols and, most preferably, 1.5x10 -2 to 7.0x10 -2 mols.
  • the above-mentioned color developing agents are usually used in the form of the salts such as a chloride, a sulfate and a p-toluenesulfinate.
  • the color developers applicable to a color developing step are allowed to contain an alkalizing agent commonly used in developers, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate and borax. Further, they are also allowed to contain a variety of additives including, for example, bezyl alcohol, an alkali halide such as potassium bromide and potassium chloride; a development controller such as citradinic acid; and a preservative such as hydroxylamine, a hydroxylamine derivatives (e.g., diethyl hydroxylamine), a hydradine derivative (e.g., hydradinodiacetic acid) and a sulfite.
  • an alkalizing agent commonly used in developers, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate and borax.
  • additives including, for example, bezyl alcohol
  • defoaming agents such as methanol, dimethyl formamide and dimethyl sulfoxide.
  • surface active agents such as methanol, dimethyl formamide and dimethyl sulfoxide.
  • pH value of such a color developer as mentioned above is usually not lower than 7 and, preferably, within the range of about 9 to 13.
  • the color developers are each allowed, if required, to contain an antioxidant including, for example, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxy acetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose, and pyrogallol-1,3-dimethyl ether.
  • an antioxidant including, for example, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxy acetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose, and pyrogallol-1,3-dimethyl ether.
  • chelating agents can be used in combination so as to serve as a metal ion sequestering agent.
  • the above-mentioned chelating agents include, for example, aminopolycarboxylic acids such as ethylenediamine tetraacetic acid and diethylenetriamine pentaacetic acid; organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid; aminopolyphosphonic acids such as aminotri (methylene phosphonic acid) or ethylenediamine tetraphosphoric acid; oxycarboxylic acids such as citric acid and gluconic acid; phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid; and polyphosphoric acids such as tripolyphosphoric acid and hexametaphosphoric acid.
  • the amount of the developer to be replenished is, desirably, not more than 1.5 liters per 1.0 m 2 of the film subject to the processing, more desirably, within the range of 250 ml to 900 ml and, preferably, 300 ml to 700 ml.
  • the bleaching agents each applicable to a bleaching solution or a bleach-fixing solution include, for example, the ferric complex salts of the organic acids each represented by the following formula A or B and the ferric complex salts of the exemplified compounds each represented by the following formulas A'-1 through A'-16.
  • a through A4 represent each -CH 2 0H, -COOM or -PO 3 M 1 M 2 , provided that they may be the same with or the different from each other, in which M, M and M 2 represent each a hydrogen atom, an alkali metal or ammonium; and
  • X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.
  • a through A4 are each synonymous with those defined in the above-given formula A; n is an integer of 1 to 8; and B and B 2 represent each a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, provided that they are the same with or the different from each other.
  • a through A4 represent each -CH 2 0H, -COOM or -PO 3 M 1 M 2 , provided that they may be the same with or the different from each other, in which M, M and M 2 represent each a hydrogen atom, an alkali metal such as sodium or potassium or ammonium; and X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms, such as a propylene, butylene or pentamethylene group.
  • the substituents thereof include, for example, a hydroxyl group and an alkyl group having 1 to 3 carbon atoms.
  • the ferric complex salts of the compounds A-1 through A-12 the sodium, patassium or ammonium salts of the above-given ferric complex salts may freely be used.
  • the ammonium salts of the ferric complex salts can preferably be used.
  • those preferably applicable to the invention include, for example, the compounds A-1, A-3, A-5 and A-9 and, particularly, A-1.
  • a through A4 are each synonymous with those afore-given; n is an integer of 1 to 8; and B and B 2 represent each a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, such as an ethylene, propylene, butylene or pentamethylene group, provided that they are the same with or the different from each other.
  • the substituents thereof include, for example, a hydroxyl group and a lower alkyl group having 1 to 3 carbon atoms, such as a methyl, ethyl or propyl group.
  • the sodium, potassium or ammonium salts of the ferric complex salts of the compounds may freely be used for.
  • those applicable to the invention include, preferably, B-1, B-2 and B-7 and, particularly, B-1.
  • the ferric complex salts of organic acids may be added in an amount within the range of 0.1 mols to 2.0 mols per liter of a bleaching solution used and, preferably, 0.15 to 1.5 mols per liter.
  • ferric complex salts such as those of ammonium, sodium, potassium or triethanolamine of the following compounds may be exemplified below so as to serve as the preferable bleaching agents other than the compounds having formula A or B. It is, however, understood that the bleaching agents shall not be limited to those above-given.
  • a single kind or plural kinds of the ferric complex salts of the compounds A'-1 through A'-16 can be used independently or in combination with the ferric complex salts of the compounds represented by formula A or B.
  • the ferric complex salts of the compounds represented by formula A or B occupy, desirably not less than 70% of the whole ferric complex salts in terms of mols, more desirably not less than 80%, preferably not less than 90% and, most preferably not less than 95%, from the viewpoint of displaying the effects of the invention more excellently.
  • the iron (III) complex salts of an organic acid may be used in the form of a complex salt or may produce an iron (III) ion complex salt in a solution by making use of aminopolycarboxylic acids such as a ferric ammonium sulfate, ferric chloride, ferric acetate, ferric ammonium and ferric phosphate, or the salts thereof.
  • aminopolycarboxylic acids such as a ferric ammonium sulfate, ferric chloride, ferric acetate, ferric ammonium and ferric phosphate, or the salts thereof.
  • a bleach-fixing solution or a bleaching solution containing the above-mentioned iron (III) ion complexes is also allowed to contain metal ion complexes such as those of cibalt, copper, nickel and zinc, as well as those of iron.
  • a bleaching solution, a bleach-fixing solution or a fixing solution contains at least one kind of the imidazole and the derivatives thereof described in Japanese Patent O.P.I. Publication No. 64-295258/1989 or the compounds represented by the formulas I through IX and the exemplified compounds thereof each described in the same Patent O.P.I. Publication.
  • the above-mentioned accelerators may be used independently or in combination. They may be added generally in an amount within the range of, desirably, about 0.01 to 100 g per liter of a bleaching solution used, preferably, 0.05 to 50 g and, particularly, 0.05 to 15 g.
  • the accelerator When adding the accelerator, it may be added and dissolved as it is. It is, however, usual to add it after dissolving it in water, alkali or an organic acid in advance. Besides the above, it may be added after dissolving it in an organic solvent such as methanol, ethanol or acetone, if required.
  • the bleaching solution or bleach-fixing solution may be used at a temperature within the range of 20°C to 50 ° C and, desirably, 25 ° C to 45 ° C.
  • the bleaching solution is to have a pH of, desirably, not higher than 6.0 and, preferably, within the range of not lower than 1.0 to not higher than 5.5.
  • the bleach-fixing solution is to have a pH within the range of, desirably, 5.0 to 9.0 and, preferably, 6.0 to 8.5.
  • the pH values of the bleaching solution or the bleach-fixing solution are the same with the pH values of a processing tank solution when processing a silver halide light sensitive material.
  • the pH values thereof can clearly be distinguished from the pH values of the so-called replenishers.
  • the bleaching solution or the bleach-fixing solution are commonly used after adding a halide such as ammonium bromide, potassium bromide or sodium bromide thereinto.
  • the bleaching solution or the bleach-fixing solution are also allowed to contain a variety of fluorescent brightening agents, defoamers or surface active agents.
  • the bleaching solution or the bleach-fixing solution may be replenished in an amount of, desirably, not more than 500 ml per m 2 of a silver halide color photographic light sensitive material to be processed, preferably, within the range of 20 ml to 400 ml and, most preferably, 40 ml to 350 ml.
  • the air or oxygen may be blown into a processing bath or a processing replenisher reservoir tank, or a suitable oxidizer such as hydrogen peroxide, a bromate and a persulfate may be added thereinto, if required for enhancing the activity of a bleaching solution or a bleach-fixing solution.
  • a suitable oxidizer such as hydrogen peroxide, a bromate and a persulfate may be added thereinto, if required for enhancing the activity of a bleaching solution or a bleach-fixing solution.
  • a forcible agitation means that a forcible agitation is given by adding an agitating means, but not that a solution is diffusively stirred in an ordinary manner.
  • the forcibly agitating means the means described in Japanese Patent O.P.I. Publication Nos. 64-222259/1989 and 1-206343/1989 may be utilized.
  • a cross-over time required from a color developing tank to a bleach-fixing tank is preferably within 10 seconds and particularly within 7 seconds, the other effect than the effects of the invention can be displayed to a bleaching fog.
  • RD 308119 the silver halide emulsions described in Research Disclosure No. 308119 (hereinafter referred simply to as RD 308119) can be used for the silver halide emulsions thereof.
  • the following table indicates where the descriptions are.
  • the silver halide emulsions each physically and chemically ripened and spectrally sensitized are to be used.
  • the additives used in preparing the emulsions are described in Research Disclosure Nos. 17643, 18716 and 308119 (hereinafter referred simply to as RD 17643, RD 18716 and RD 308119).
  • the 2-equivalent couplers each applicable to the invention will now be detailed below.
  • the couplers represented by the following formula 2eq-1 may preferably be used.
  • Cp represents a coupler residual group
  • * represents the coupling position of a coupler
  • X represents a group released when a dye is produced upon coupling to the oxidized products of an aromatic primary amine color developing agent.
  • the typical yellow coupler residual groups are described in, for example, U.S. Patent Nos. 2,298,443, 2,407,210, 2,875,057, 3,048,194, 3,265,506 and 3,447,928; and (Farbkupplerine Literaturubersiecht Agfa Mitannon (Band II)), pp.126-156, 1961.
  • acylacetanilides such as benzoyl acetanilide and pivaloyl acetanilide are preferred.
  • magenta coupler residual groups are described in, for example, U.S. Patent Nos. 2,369,486, 2,343,703, 2,311,082, 2,600,788, 2,908,573, 3,062,653, 3,152,896, 3,519,429, 3,725,067 and 4,540,654; Japanese Patent O.P.I. Publication No. 59-162548/1984; and the above-given Agfa Mitannon (Band II), pp.126-156, 1961.
  • pyrazolones or pyrazoloazoles such as pyrazoloimidazole and pyrazolotriazole are preferred.
  • the releasable groups represented by X include, for example, a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic-oxy group, an acyloxy group, an alkylthio group, an arylthio group, a heterocyclic-thio group, a in which X represents a group consisting of the atoms necessary to form a 5- or 6-membered ring together with at least one of the atoms selected from the group consisting of the nitrogen atom contained in the formula, carbon atom, oxygen atom, nitrogen atom and sulfur atom, a monovalent group such as an acylamino group and a sulfonamido group, and a divalent group such as an alkylene group; provided, a dimer is formed by X in the case of a divalent group.
  • Halogen atoms chlorine atom, bromine atom and fluorine atom;
  • 2-equivalent yellow couplers those represented by the following formulas 2eq-2 and 2eq-3 are preferably used.
  • R 1 and R 2 represent each a hydrogen atom or a substituent; k and l are each an integer of 1 to 5, provided, when k and l are each not less than 2, R 1 and R 2 may be the same with or different from each other; and X is synonymous with X denoted in formula 2eq-1.
  • the substituents represented by R 1 and R 2 include, for example, a halogen atom or each of an alkyl group, a cycloalkyl group, an aryl group and a heterocyclic group capable of coupling directly or through a divalent atom or group.
  • divalent atoms or groups include, for example, an oxygen atom, a nitrogen atom, a sulfur atom and the groups of carbonyl amino, aminocarbonyl, sulfonylamino, aminosulfonyl, amino, carbonyl, carbonyloxy, oxycarbonyl, ureylene, thioureylene, thiocarbonylamino, sulfonyl and sulfonyloxy.
  • the above-given alkyl, cycloalkyl, aryl and heterocyclic groups include those each having a substituent.
  • a substituents include, for example, a halogen atom and the groups of nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxy, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamido, heterocyclic, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxy, imido and acyl.
  • X include those exemplified in formula 2eq-1 and, among them, an aryloxy group and (in which X is synonymous with the foregoing Xi) are preferable.
  • formula 2eq-2 there includes the case where a polymer not less than dimer is formed by R 1 or X and, in formula 2eq-3, there includes the case where a polymer not less than dimer is formed by R i , R 2 or X.
  • the preferable 2-equivalent magenta couplers include, for example, those represented by the following formulas 2eq-4, 2eq-5, 2eq-6 and 2eq-7.
  • R 3 represents a substituent; and R 1 , R 2 , X and l are each synonymous with R i , R 2 , X and l denoted in 2eq-2 and 2eq-3, respectively, provided that, when l is not less than 2, R 2 s may be the same with or different from each other.
  • R 1 and R 2 include those exemplified for R 1 and R 2 denoted in formula 2eq-3.
  • R 3 include, for example, each of the groups of alkyl, cycloalkyl, aryl and heterocyclic, provided, they include those each having a substituent.
  • substituents include, for example, those exemplified for the substituents which are each substituted to the groups given as the examples for R 1 and R 2 denoted in formula 2eq-2.
  • the examples of X include those exemplified in formula 2eq-1 and, among them, a halogen atom, an alkylthio group, an arylthio group, an aryloxy group, an acyloxy group, (in which X 1 is synonymous with the foregoing X 1 ), and an alkylene group are each preferable.
  • the preferable 2-equivalent cyan couplers include those represented by the following formulas 2eq-8, 2eq-9 and 2eq-10.
  • R 2 and R 3 are each synonymous with those denoted in 2eq-4; R 4 represents a substituent; m is an integer of 1 to 3; n is an integer of 1 or 2; and p is an integer of 1 to 5, provided, when m, n and p are each not less than 2, R 2 s may be the same with or different from each other.
  • R 2 and R 3 include, for example, those exemplified in formula 2eq-4, and R 4 includes, for example those exemplified for R 3 denoted in formula 2eq-4.
  • the examples of X include, those exemplified in formula 2eq-1 and, among them, a halogen atom, an alkoxy group, an aryloxy group and a sulfonamido group are particularly preferable.
  • formulas 2eq-8 and 2eq-10 there include the case where a polymer not less than a dimer is formed by R 2 , R 3 or X and, in formula 2eq-9, there includes the case where a polymer not less than a dimer is formed by R 2 , R 3 , R 4 or X.
  • the yellow couplers may be added in an amount within the range of, desirably, 5x10 -5 to 2x10- 3 mols/m 2 , more desirably, 1x10- 4 to 2x10- 3 mols/m 2 and, preferably, 2x10- 4 to 2x10- 3 mols/m 2 .
  • the magenta couplers may be added in an amount within the range of, desirably, 2x10 -5 to 1x10 -3 mols/m 2 , more desirably, 5x10 -5 to 1x10 -3 mols/m 2 and, preferably, 1x10 -4 to 1x10 -3 mols/m 2 .
  • the cyan couplers may be added in an amount within the range of, desirably, 5x10 -5 to 2x10 -3 mols/m 2 , more desirably, 1x10 -4 to 2x10 -3 mols/m 2 and, preferably, 2x10 -4 to 2x10 -3 mols/m 2 .
  • the light sensitive silver halide emulsion layers of the invention contains each a 2-equivalent coupler, and they are also allowed to contain each a 4-equivalent coupler in combination.
  • the 2-equivalent coupler content is within the range of 50 to 100 mol% of the whole coupler content and the 4-equivalent couplers occupy the rest. It is more desirable when the 2-equivalent coupler content is within the range of 70 to 100 mol% of the whole coupler content. It is preferable when the 2-equivalent coupler content is 100 mol% of the whole coupler content, that is to say, the whole coupler consist of 2- equivalent couplers.
  • the term, 'a 4-equivalent coupler' herein means a coupler having no substituent in the coupling position.
  • the yellow couplers include, preferably, an acylacetanilide of the pivalylacetanilode type or the benzoylacetanilide type.
  • the magenta couplers include, for example, an indazolone, a cyanoacetyl, a 5-pyrazolone, and a pyrazoloazole of the pyrazoloimidazole type. Among them, a 5-pyrazolone and a pyrazoloazole are preferable.
  • the cyan couplers include, preferably, a phenol and a naphthol.
  • the 4-equivalent couplers applicable in combination include, for example, those in which the coupling- positioned X denoted in the foregoing formulas 2eq-2 to 2eq-10 represents a hydrogen atom.
  • the examples of R 1 through R 4 include those exemplified in formulas 2eq-2 through 2eq-10. In each of the foregoing formulas, there include the cases where a polymer having not less than dimer is formed by R 1 through R 4 .
  • the additives applicable to the invention may be added in the dispersion method such as those described in RD 108119, XIV.
  • a light sensitive material may be provided thereto with the auxiliary layers such as a filtering layer and an intermediate layer, such as those described in, for example, the foregoing RD 308119.
  • the light sensitive materials of the invention can have a variety of layer arrangements such, as a regular layered arrangement, a reversed layer arrangement and a unit layer arrangement each described in, for example, the foregoing RD 308119, VII-K.
  • the effects of the invention can more excellently be displayed when a vinylsulfone type layer hardener is used in a light sensitive material.
  • the vinylsulfone type layer hardenrs herein mean the compounds each having a vinyl group coupled to a sulfonyl group or a group capable of forming a vinyl group coupled thereto. Among them, those having at least two groups each capable of forming a vinyl group coupled to a sulfonyl group or a vinyl group.
  • the compounds represented by the following formula VS-1 may preferably be used in the invention.
  • L represents a m-valent coupling group
  • n is an integer of 2 to 10, provided, when m is not less than 2, -S0 2 -Xs may be the same with or the different from each other.
  • An m-valent coupling group L is a m-valent group formed by a single coupling or plural combination couplings of, for example, an aliphatic hydrocarbon group such as an alkylene, alkylidene or an alkylidine group or the group formed by coupling the above-mentioned groups to each other, an aromatic hydrocarbon group such as an arylene group or the group formed by coupling them to each other, -O-, -NR'- in which R' represents a hydrogen atom or, preferably, an alkyl group having 1 to 15 carbon atoms, -S-,
  • the vinylsulfone type layer hardeners applicable to the invention include, for example, aromatic type compounds such as those described in German Patent No. 1,100,842; alkyl compounds each coupled with a hetero atom, such as those described in Japanese Patent Examined Publication Nos. 44-29622/1969, 47-25373/1972 and 47-24259/1972; sulfonamide ester type compounds such as those described in Japanese Patent Examined Publication No. 47-8736/1972; 1,3,5-tris [ ⁇ -(vinylsulfonyl)-propionyl]-hexahydro-S-triazine such as those described in Japanese Patent O.P.I. Publication No. 49-24435/1974; alkyl type compounds such as those described in Japanese Patent O.P.I. Publication No.s 51-44164/1976; and the compounds described in Japanese Patent O.P.I. Publication No. 59-18944/1984.
  • aromatic type compounds such as those described in German Patent No. 1,100,84
  • vinylsulfon type layer hardeners are used in a proportion within the range of 0.005 to 20% by weight and, preferably, 0.02 to 10% by weight to a binder such as gelatin to be used, after they are dissolved in water or an organic solvent.
  • the photographic layers to which these layer hardeners are to be added shall not specially be limited, but the hardeners may be added into, for example, the uppermost layer or the lowermost layer solely, or the whole photographic layer.
  • R 1 represents an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, an amino group, a carboxylic acid group including the salts thereof, or a sulfonic acid group including the salts thereof
  • R 2 and R 3 represent each a hydrogen atom, a halogen atom, an amino group, a nitro group, a hydroxyl group, an alkoxycarbonyl group, a carboxylic acid group including the salts thereof, or a sulfonic acid group including the salts thereof
  • M represents a hydrogen atom, an alkali metal or an ammonium group.
  • R 4 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenoalkyl group, -R 12- OR 13 or -CONHR' 4 (in which R 12 represents an alkylene group and, R 13 and R 14 represent each a hydrogen atom, an alkyl group or an arylalkyl group) or an arylalkyl group;
  • R 5 and R 6 represent each a hydrogen atom, a halogen atom, a halogenoalkyl group or an alkyl group;
  • R 7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenoalkyl group, arylalkyl group, -R 15 -OR 16 or -CONHR 17 (in which R 15 represents an alkylene group and, R 16 and R 17 represent each a hydrogen atom or an alkyl group); and
  • the typical examples of the compounds represented by formula B-1 include the following exemplified compounds.
  • the compounds represented by the above-given formula B-1 include some kinds of the known antiseptics such as tangerines which are available on the market readily for the skilled in the art.
  • the preferable include B-1-1, B-1-2, B-1-3, B-1-4 and B-1-5.
  • the compounds having formula B-1 applicable to the invention may be used in an amount within the range of, desirably, 0.03 to 50 g per liter of the stabilizer of the invention used, preferably, 0.12 to 10 g and, particularly, 0.15 to 5 g.
  • the compounds having formulas B-1 through B-3 may be used in an amount within the range of 0.1 mg to 500 mg per m 2 of a light sensitive material used and, preferably, 0.5 mg to 100 mg.
  • the compounds having formulas B-1 through B-3 may also be used independently or in combination.
  • the present invention can be applied to the color photographic light sensitive materials including, for example, color paper, color negative film, color reversal film, color reversal paper and direct-positive color paper each for general or cinematographic use; color film for cinematographic use; and color film for TV use.
  • a mutilayered color photographic light sensitive material sample No. 1 was prepared by forming the layers having the following compositions on a triacetyl cellulose film support, respectively, in the order from the support side.
  • the amounts of the materials added into the silver halide photographic light sensitive material are indicated in terms of grams per sq.meter of the light sensitive material, unless otherwise expressly stated, and the amounts of silver halides and colloidal silver are indicated in terms of the silver contents. However, the amounts of the sensitizing dyes used therein are indicated by the number of mols per mol of the silver halides contained in the same layer.
  • compositions Besides the above-given compositions, coating aid Su-1, dispersion aid Su-2, a viscosity controller, layer hardeners H-1 and H-2, stabilizer ST-1, antifoggant AF-1 and two kinds of AF-2 having Mw:10,000 and Mw:1,100,000 were added.
  • the emulsions each used in the above-prepared sample were a monodispersive emulsion having a low silver iodide content on the surface of the emulsion grains and were subjected to the optimum gold ⁇ sulfur sensitization in an ordinary sensitizing method.
  • the average grain size thereof is indicated by a grain size obtained by converting the grains into cubes.
  • Film samples Nos. 2 through 8 were each prepared by making use of the 2-equivalent couplers relating to the invention, as shown in Table 1.
  • the color developer, bleaching solution, fixing solution, stabilizing solution and their replenishers each used therein were as follows.
  • the automatic processor used in the continuous processing steps was that having a transport speed of 20m/min.
  • the tanks for the stabilizing bath were arranged in a three-tank counter-current system. Each of the tanks was provided with a thermostating-circulating filter and a replenishing inlet as well as with the same functions as those provided to the ordinary types of automatic processors for processing color negative films, which are generally available on the market.
  • 'one round' is defined as that an amount of a replenisher to a stabilizing bath reaches the same amount with the capacity of a stabilizing tank, the continuous processing was carried out up to three rounds in the combination shown in Table 2.
  • TEAC triethyl ammonium chloride
  • DTMAC dodecyl trimethyl ammonium chloride
  • LMTS sodium lauroylmethyl taurinate
  • DBSS sodium dodecylbenzene sulfinate.
  • every objective effect of the invention can excellently be displayed when using a 2-equivalent coupler in a light sensitive material, containing, in a fixing solution, ammonium ions in a proportion of not more than 50 mol% of the whole cation content of the fixing solution and containing, in a stabilizing solution, at least one kind of the compounds represented by the afore-given formula I or II.
  • a 2-equivalent coupler in a light sensitive material, containing, in a fixing solution, ammonium ions in a proportion of not more than 50 mol% of the whole cation content of the fixing solution and containing, in a stabilizing solution, at least one kind of the compounds represented by the afore-given formula I or II.
  • the stabilizing step was carried out in a 3-tank counter-current system in which the replenishments were made to the final tank of the stabilizing bath and the over-flow was flown into the tank precedent to the final tank. All the over-flows of the bleaching solution were flown into the bleach-fixing solution in the tank subsequent to the over-flown tank. The others including the film samples were subjected to the same experiments as in Example 1. The results thereof were almost the same as in Example 1.

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EP19910114954 1990-09-05 1991-09-04 Method for processing silver halide color photographic light sensitive materials Withdrawn EP0476434A3 (en)

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JP30829690A JPH04194855A (ja) 1990-09-05 1990-11-14 ハロゲン化銀カラー写真感光材料の処理方法
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0578309A2 (fr) * 1992-07-04 1994-01-12 Kodak Limited Méthode pour fixer un matériau photographique
EP0712040A2 (fr) * 1994-11-11 1996-05-15 Konica Corporation Méthode de traitement d'un matériau photographique à l'halogénure d'argent sensible à la lumière
US5968715A (en) * 1994-11-11 1999-10-19 Konica Corporation Method for processing silver halide photographic light-sensitive material
EP1141774A1 (fr) * 2000-01-06 2001-10-10 Trebla Chemical Company Concentrats liquides a dilution unitaire composes d'un agent de blanchiment et d'un agent de fixation

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JPS5156228A (ja) * 1974-11-12 1976-05-17 Mitsubishi Paper Mills Ltd Harogenkaginkaraashashinkankozairyono shorihoho
EP0168263A2 (fr) * 1984-07-13 1986-01-15 Konica Corporation Procédé de traitement d'un matériau photographique à l'halogénure d'argent sensible à la lumière
GB2165954A (en) * 1984-08-31 1986-04-23 Fuji Photo Film Co Ltd Method for processing of silver halide color photographic materials
EP0217643A2 (fr) * 1985-09-27 1987-04-08 Konica Corporation Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
JPS62196660A (ja) * 1986-02-24 1987-08-31 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
EP0395442A2 (fr) * 1989-04-28 1990-10-31 Konica Corporation Agent stabilisant pour matériau photographique à halogénure d'argent et méthode pour traiter le matériau photosensible par ce stabilisateur

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EP0168263A2 (fr) * 1984-07-13 1986-01-15 Konica Corporation Procédé de traitement d'un matériau photographique à l'halogénure d'argent sensible à la lumière
GB2165954A (en) * 1984-08-31 1986-04-23 Fuji Photo Film Co Ltd Method for processing of silver halide color photographic materials
EP0217643A2 (fr) * 1985-09-27 1987-04-08 Konica Corporation Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
JPS62196660A (ja) * 1986-02-24 1987-08-31 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
EP0395442A2 (fr) * 1989-04-28 1990-10-31 Konica Corporation Agent stabilisant pour matériau photographique à halogénure d'argent et méthode pour traiter le matériau photosensible par ce stabilisateur

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0578309A2 (fr) * 1992-07-04 1994-01-12 Kodak Limited Méthode pour fixer un matériau photographique
EP0578309A3 (fr) * 1992-07-04 1994-03-16 Kodak Ltd
US5389501A (en) * 1992-07-04 1995-02-14 Eastman Kodak Company Method of fixing a photographic material
EP0712040A2 (fr) * 1994-11-11 1996-05-15 Konica Corporation Méthode de traitement d'un matériau photographique à l'halogénure d'argent sensible à la lumière
EP0712040A3 (fr) * 1994-11-11 1997-04-16 Konishiroku Photo Ind Méthode de traitement d'un matériau photographique à l'halogénure d'argent sensible à la lumière
US5968715A (en) * 1994-11-11 1999-10-19 Konica Corporation Method for processing silver halide photographic light-sensitive material
EP1141774A1 (fr) * 2000-01-06 2001-10-10 Trebla Chemical Company Concentrats liquides a dilution unitaire composes d'un agent de blanchiment et d'un agent de fixation
EP1141774A4 (fr) * 2000-01-06 2003-06-25 Trebla Chemical Company Concentrats liquides a dilution unitaire composes d'un agent de blanchiment et d'un agent de fixation

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