EP0329088A2 - Procédé de traitement et solution de blanchiment pour des matériaux photographiques couleur à l'halogénure d'argent sensible à la lumière - Google Patents

Procédé de traitement et solution de blanchiment pour des matériaux photographiques couleur à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0329088A2
EP0329088A2 EP89102530A EP89102530A EP0329088A2 EP 0329088 A2 EP0329088 A2 EP 0329088A2 EP 89102530 A EP89102530 A EP 89102530A EP 89102530 A EP89102530 A EP 89102530A EP 0329088 A2 EP0329088 A2 EP 0329088A2
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Prior art keywords
group
mol
acid
bleaching solution
bleaching
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EP89102530A
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German (de)
English (en)
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EP0329088A3 (en
EP0329088B1 (fr
Inventor
Satoru Kuse
Masao Ishikawa
Shigeharu Koboshi
Masayuki Kurematsu
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Konica Minolta Inc
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Konica Minolta Inc
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Priority claimed from JP63315958A external-priority patent/JP2689153B2/ja
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Publication of EP0329088A3 publication Critical patent/EP0329088A3/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
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents

Definitions

  • the present invention relates to a processing method for silver halide color photographic light-sensitive materials (hereinafter also simply referred to as "light-sensitive meterials”) and a bleaching solution suitable for said processing method, specifically to a processing method and bleaching solution permitting sufficient desilvering in a short time and prevention of bleach fogging; this art can function well even in use for silver-rich high-sensitivity light-sensitive materials.
  • Light-sensitive material processing basically comprises color developing and desilvering processes; desilvering comprises bleaching and fixing processes or a bleach-fixing process. Rinsing, stabilization and other processes may be added.
  • ferricyanates, bichromates, and other inorganic oxidizing agents have conventionally been widely used to bleach image silver.
  • ferricyanates and bichromates are undersirable in preventing environmental pollution in that they may be decomposed by light to produce harmful cyan ions or hexavalent chromium ions, though they are relatively high in image silver bleaching power.
  • Another drawback is that it is difficult to regenerate fro reusing these processing solutions without discarding the waste liquid after processing.
  • processing solutions containing metal complex salts of organic acids, such as aminopolycarboxylic acid, as oxidizing agent have become used.
  • processing solutions are faulty in that the bleaching rate (oxidation rate) of image silver (metallic silver) formed in the developing process is low due to weak oxidation power.
  • iron (III) complex salt of ethylenediaminetetraacetic acid considered relatively strong in bleaching power among metal complex salts of aminopolycarboxylic acid, is now in practical use in bleaching solutions and bleach-fixers, but it is faulty in that bleaching power is insufficient and much time is taken in the bleaching process when used for high-sensitivity silver halide color photographic light-sensitive materials composed mainly of a silver bromide or silver iodobromide emulsion, specifically silver-rich color paper for picture taking and color negative and color reversal films for picture taking which contain silver iodide.
  • a ferrous complex salt of organic acid formed in bleaching developed silver e.g. iron (II) complex salt of ethylenediaminetetraacetic acid
  • iron (III) complex salt of ethylenediaminetetraacetic acid i.e. ferric complex salt of organic acid
  • a ragenerating agent is added to replenish the deficient components, then the solution is used as a replenisher.
  • compact-labos also called minilabos
  • minilabos have become widely established with the aim of reducing processing time for silver halide color photographic light-sensitive materials and delivery cost; in these labos, there are severe needs of process simplification and reduction of developing machine installation space, so regeneration is unsuitable since it necessitates troublesome procedures and maintenance, as well as additional processing space.
  • ferric complex salts of 1,3-propanediaminetetraacetic acid disclosed in the above literature, are faulty in that bleach fogging occurs when it is used to bleach silver-rich high-sensitivity light-sensitive materials for a long time. Accordingly, the use of these salts or mixtures as bleaching agents causes bleach fogging in color-sensitized high-sensitivity light-sensitive materials composed mainly of a silver chloroiodide or silver iodobromide emulsion, specifically ultrahigh-speed (e.g.
  • the object of the present invention is to provide a processing method with inhibited bleach fogging and a bleaching solution which functions well in embodying said processing method.
  • the above object of the invention is achieved by a method for processing a silver halide color photographic light-sensitive material comprising steps of developing the light-sensitive material with a color developer, bleaching, immediately after the developing step, the light sensitive material with a bleaching solution, and treating, after the bleaching step, the light-sensitive material with a solution having fixing capability, wherein the bleaching solution comprises at least one of ferric complex salts of compounds represented by the following Formula A or B in an amount of at least 0.01 mol per liter of the bleaching solution and a buffer agent capable of adjusting pH value to 3 to 7; and pH value of the bleaching solution is held within the range of from 3 to 7; wherein A, through A are each a -CH2OH group, a -COOM group, or a -PO3M1M2 group, which may be the same with or different from each other, M, M1 and M3 are each a hydrogen atom, a sodium atom, a potassium atom or an ammonium group; X is a substituted or
  • a bleaching treatment is carried out and a treatment with a fixer or a bleach-fixer is performed following to the bleaching treatment.
  • the desired effect can be displayed when the bleaching solution contains both a particular ferric complex salt of organic acid and a buffer agent capable of adjusting to pH 3 to 7, so that and a pH value of the solution is kept at pH 3 to 7.
  • a buffer agent capable of adjusting to pH 3 to 7, so that and a pH value of the solution is kept at pH 3 to 7.
  • A1 through A4 independently represent -CH2OH, -COOM or -PO3M1M2 whether identical or not; M, M1 and M2 independently represent a hydrogen atom, sodium, potassium or ammonium; X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms such as propylene, butylene, trimethylene, tetramethylene, pentamethylene; the substituent includes hydroxyl group and alkyl groups having 1 to 3 carbon atoms.
  • These compounds (A-1) through (A-12) may be arbitrarily used in the form of sodium, potassium or ammonium salts. From the veiwpoint of the desired effect of the invention and solubility, it is preferable to use ammonium salts of ferric complex salts of these compounds.
  • (A-1), (A-4), (A-7) and (A-9) are preferably used for the present invention; (A-1) is especially preferable.
  • A1 through A4 have the same definitions as above; n represents any one of the integers 1 through 8; B1 and B2 independently represent a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms such as ethylene, propylene, butylene, pentamethylene; the substituent includes hydroxyl group and lower alkyls having 1 to 3 carbon atoms such a methyl, ethyl, propyl group.
  • These compounds (B-1) through (B-7) may be arbitrarily used in the form of sodium, potassium or ammonium salts. From the veiwpoint of the desired effect and solubility, it is preferable to use ammonium salts of ferric complex salts of these compounds.
  • (B-1), (B-4) and (B-7) are preferably used for the present invention; (B-1) is especially preferable.
  • Ferric complex salts of these compounds of Formulae A or B are used at ratios of at least 0.1 mol per l bleaching solution, preferably 0.01 to 1.0 mol/l, more preferably 0.1 to 1.0 mol/l, ideally 0.15 to 0.8 mol/l. From the viewpoint of cost and solubility, it is preferable to limit the amount of ferric complex salts of compounds of Formula A or B in the above range.
  • bleaching agents preferably used in combination with compounds of Formula A or B in the bleaching solution of the present invention include the following compounds.
  • A′-1, A′-2, A′-7 and A′-12 are especially preferable.
  • aminopolycarboxylic acids may be used in the form of iron (III) complex salts or bound in a solution with iron (III) salts, e.g. ferric sulfate, ferric chloride, ferric acetate, ferric sulfate, ferric ammonium sulfate and ferric phosphate, to form iron (III) ion complex salts.
  • iron (III) salts e.g. ferric sulfate, ferric chloride, ferric acetate, ferric sulfate, ferric ammonium sulfate and ferric phosphate
  • iron (III) salts e.g. ferric sulfate, ferric chloride, ferric acetate, ferric sulfate, ferric ammonium sulfate and ferric phosphate
  • iron (III) salts e.g. ferric sulfate, ferric chloride, ferric acetate, ferric sulfate, ferric ammoni
  • aminopolycarboxylic acids may be used in excess of the level necessary to form iron (III) ion complex salts.
  • Aminopolycarboxylic acids and iron complex salts may be used in the form of ammonium, sodium, potassium or triethanolamine salts, or in combination.
  • bleaching solutions containing the above iron (III) ion complex(es) may contain metal ion complex salts of cobalt, copper, nickel, zinc and other metals as well.
  • buffer agent capable of adjusting to pH 3 to 7 used for the present invention is defined as a buffer agent which necessitates the addition of K2CO3 at ratios of over 5 g/l to adjust the aqueous solution containing a given amount of the buffer to pH 3 to 7.
  • buffers include the organic compounds represented by the following Formula I, II or III, and inorganic compounds having at least one nitrogen, phosphorus or boron atom.
  • Formula I A-COOH Wherein A represents a hydrogen atom or organic group.
  • Formula II B-PO3H2 Wherein B represents a hydrogen atom or organic group.
  • C′, D and E independently represent a hydrogen atom or organic group, and at least one of C′, D and E represent an organic compound group.
  • buff agents preferably used for the present invention are listed below.
  • the preferable fatty acid compounds include acrylic acid, adipinic acid, acetylenedicarboxylic acid, acetoacetic acid, azelaic acid, isocrotonic acid, isopropylmalonic acid, isobutyric acid, itachonic acid, isovaleric acid, ethylmalonic acid, capronic acid, formic acid, valeric acid, citric acid, glycolic acid, glutaric acid, crotonic acid, chlorofumaric acid, ⁇ -chloropropionic acid, gluconic acid, glyceric acid, ⁇ -chloropropionic acid, succinic acid, cyanoacetic acid, diethylacetic acid, diethylmalonic acid, dichloroacetic acid, citraconic acid, dimethylmalonic acid, oxalic acid, d-tartaric acid, meso-tartaric acid, trichlorolactic acid, tricarbarylic acid, trimethylacetic acid, lactic
  • the preferable acids having a cyclic structure include ascorbic acid, atropic acid, allocinnamic acid, benzoic acid, isophthalic acid, oxybenzoic acid (m-, p-), chlorobenzoic acid (o-, m-, p-), chlorophenylacetic acid (o-, m-, p-), cinnamic acid, salicylic acid, dioxybenzoic acid (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5), cyclobutane-1,1-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid (trans-, cis-), cyclopropane-1,1-dicarboxylic acid, cycropropane-1,2-dicarboxylic acid (trans-, cis-), cyclohexane-1,1-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid (trans
  • the preferable amine compounds include isoamylamine, isobutylamine, isopropylamine, ethylamine, ethylenediamine, diisoamylmaine, diisobutylamine, diethylamine, diethylenetriamine, dipropylamine, dimethylamine, tetraethylenepentaamine, tetramethylenediamine, triethylamine, trimethylamine, trimethyldiamine, m-butylamine, sec-butylamine, tert-butylamine, tert-butylamine, m-propylamine, pentamethylenediamine, hexamethylenetetraamine, quinoline, o-toluidine, aminobenzenesulfonic acid (o-, m-, p-), N-methylbenzylamine, methylbenzylamine (o-, m-, p-), 2-methylpiperidine, N-methoxybenzylamine, methoxybenzy
  • the preferable inorganic acids include nitrous acid, phosphorous acid, hypophosphorous acid, boric acid, phosphoric acid, pyrophosphoric acid, triphosphoric acid, metatriphosphoric acid, polyphosphoric acid, and polymetaphosphoric acid.
  • the other preferable compounds include N-(2-acetamido)iminodiacetic acid, N-(2-acetamido)-2-aminoethanesulfonic acid, bis(2-hydroxyethyl)iminotris-(hydroxymethyl)methane, 2-(N-morpholino)ethanesulfonic acid, 3-(N-morpholino)-2-hydroxypropanesulfonic acid, piperazine-N,N′-bis(2-ethanesulfonic acid), ethylenediaminediacetic acid, ethylenediamine-2-propionic acid, and ⁇ -aminoethyliminodiacetic acid; also included are organic phosphoric acids such as amino-methylphosphono-N,N-diacetic acid, 2-phosphonoethyliminodiacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and and the following:
  • fatty acids, cyclic acids, amine compounds and inorganic salts are preferable; fatty acids and amine compounds are more preferable; lower carboxylic acids, specifically those having 2 to 6 carbon atoms, are still more preferable.
  • these buffer compounds be added to the bleaching solution at 0.01 to 3.0 mol/l, more preferably 0.02 to 2.0 mol/l most preferably 0.1 to 2.0 mol/l. From the viewpoint of cost, solubility and bleaching performance, it is preferable to establish an upper limit of the amount of a buffer agent of the invention in the above-mentioned range.
  • acetic acid is very effective for solution stability or preventive effect on suspended solids in the range of from 0.5 to 3 mol/l, preferably 0.8 to 2 mol/l.
  • the pH of a bleaching agent of the present invention is in the range of from 3 to 7; from the viewpoint of the effect of the invention, it is preferable that the pH be in the range of from 4 to 6, ideally 4.5 to 5.8.
  • a bleaching solution of the present invention at 5 to 80°C, more preferably 20 to 45°C, still more preferably 25 to 42°C.
  • the amount of replenisher for a bleaching solution of the invention be 20 to 500 ml per m2 light-sensitive material, more preferably 30 to 350 ml, still more preferably 40 to 300 ml, ideally 50 to 250 ml.
  • halides such as ammonium bromide and ammonium chloride to a bleaching sulution of the invention; these halides are preferably added at 0.1 to 5 mol/l, more preferably 0.3 to 3 mol/l.
  • a bleaching agent of the present invention may contain various brightening agents, defoaming agents and surfactants.
  • Fixing agents include compounds which react with silver halide to form a water-soluble complex salt, e.g. thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate; thiocyanates such as potassium thiosyanate, sodium thiocyanate and ammonium thiocyanate; thioureas; thioethers, and halides such as iodides.
  • thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate
  • thiocyanates such as potassium thiosyanate, sodium thiocyanate and ammonium thiocyanate
  • thioureas such as thioethers
  • halides such as iodides.
  • the fixer and bleach-fixer may contain one or more pH buffers comprising various acids and salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, as well as fixing agent.
  • pH buffers comprising various acids and salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, as well as fixing agent.
  • a rehalogenating agent including, alkali halide and ammonium halide, such as potassium bromide, sodium bromide, sodium chloride, or ammonium bromide.
  • a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, or ammonium bromide.
  • substances known to be usually added to the fixer and bleach-fixer such as pH buffers, e.g. borates, oxalates, acetates, carbonates, phosphates; alkylamines and polyethyleneoxides.
  • the above fixing agents are normally used at over 0.1 mol per l processing solution; from the viewpoint of the desired effect of the invention, it is preferable to use these agents in the range of from 0.6 to 4 mols, more preferably 0.9 to 3.0 mols, still more preferably 1.1 to 2.0 mols.
  • aminocarboxylic acid and aminophosphonic acid respectively mean an amino compound having at least 2 carboxyl groups and an amino compound having at least 2 phosphon groups; they are preferably represented by the following Formulae XII and XIII, respectively.
  • E represents a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, -R83OR83OR83-, or -R83ZR83-;
  • Z represents N-R83-A6 or N-A6;
  • R79 through R83 independently represent a substituted or unsubstituted alkylene group;
  • A2 through A6 independently represent a hydrogen atom -OH, -COOM, or -pO3M2;
  • M represents a hydrogen atom or alkali metal atom.
  • XII-1, XII-2, XII-4, XII-6, XII-7, XII-10, XII-19, XIII-1, and XIII-5 are especially preferable for the desired effect of the present invention; particularly, XII-4 is still more preferable.
  • ferric complex salts of organic acids of the present invention are used in the form of free acids, alkali metal salts such as sodium salts, potassium salts and lithium salts, ammonium salts, or water-soluble amine salts such as triethanolamine salts; potassium salts, sodium salts, and ammonium salts are preferably used.
  • alkali metal salts such as sodium salts, potassium salts and lithium salts, ammonium salts, or water-soluble amine salts such as triethanolamine salts
  • potassium salts, sodium salts, and ammonium salts are preferably used.
  • These ferric complex salts may be used singly or in combination. Any amount of use may be chosen according to the silver content, silver halide composition etc. of the light-sensitive material to be processed; for example, these salts can be used at more than 0.01 mol per l bleach-fixer, preferably 0.05 to 1.0 mol. When these salts are used in replenishers, it is desirable to use them at the upper limit of solubility to minimize the
  • air or oxygen blowing may be conducted in the processing bath and replenisher storage tank, or a suitable oxidizing agent, such as hydrogen peroxide, bromate or persulfate may be added to increase bleacher or bleach-fixer activities.
  • a suitable oxidizing agent such as hydrogen peroxide, bromate or persulfate may be added to increase bleacher or bleach-fixer activities.
  • silver may be recovered from the fixer or bleach-fixer by a known method.
  • methods which serve well for this purpose include the electrolysis method of French Patent No. 2,299,667, precipitation method of Japanese Patent Publication Open to Public Inspection No. 73037/1977, West German Patent No. 2,311,220, ion exchange method of Japanese Patent Publication Open to Public Inspection No. 17114/1976, West Germany Patent No. 2,548,237 and metal replacement method of British Patent No. 1,353,805.
  • In-line silver recovery from the tank solution is preferable, since rapid processing is facilitated, but silver may be recovered from overflow waste liquid and then regenerated.
  • the desired effect of the invention is enhanced when the fixer or bleach-fixer of the invention is replenished at less than 800 ml per m2 light-sensitive material; a noticeable effect is obtained at 20 to 650 ml, particularly 30 to 400 ml per m2 light-sensitive material.
  • fixer or bleach-fixer contains 0.1 to 1.0 g/l of iodide (e.g. ammonium iodide, potassium iodide, sodium iodide, lithium iodide) and/or thiocyanate (e.g. sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate).
  • iodide e.g. ammonium iodide, potassium iodide, sodium iodide, lithium iodide
  • thiocyanate e.g. sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate.
  • fixer and bleach-fixer at pH 4 to 8, more preferably 5 to 7.5.
  • the fixer and bleach-fixer of the present invention may contain sulfites and sulfite-releasing compounds; examples of the sulfite and the sulfite-releasing compounds include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogensulfite, potassium hydrogensulfite, sodium hydrogensulfite, potassium metabisulfite, sodium metabisulfite, and ammonium metabisulfite, and the compounds represented by the following Formula S-1 or S-2 are also included.
  • R17 represents a hydrogen atom or alkyl group having 1 to 5 carbon atoms
  • R18 represents an alkyl group having 1 to 5 carbon atoms which includes substituted ones
  • M represent an alkalimetal atom
  • R19 and R20 independently represent a hydrogen atom or alkyl group having 1 to 5 carbon atoms which includes substituted ones
  • n represents the integer 0 to 4.
  • these bisulfites and bisulfite-releasing compounds at ratios of at least 0.1 mol, as calculated as sulfite, per l fixer or bleach-fixer, preferably 0.12 to 0.65 mol/l, more preferably 0.15 to 0.50 mol/l, still more preferably 0.20 to 0.40 mol/l.
  • the above-given mol numbers of sulfite of sulfite-releasing compound is mentioned in terms of mol numbers of sulfite.
  • total processing time for the bleaching solution and the solution with fixing capability, such as fixer or bleach-fixer, of the present invention be not more than 3 min 45 sec, more preferably 20 sec to 3 min 20 sec, still more preferably 40 sec to 3 min, most preferably 60 sec to 2 min 40 sec for the desired effect of the invention.
  • Bleaching time can be arbitrarily chosen in the above range of total time; for the desired purpose of the invention, it is preferable that bleaching time be not more than 1 min 30 sec, more preferably 10 to 70 sec, still more preferably 20 to 55 sec.
  • Processing time for the processing solution with fixing capability can be arbitrarily chosen in the above range of total time; it is preferable that the processing time be not more than 3 min 10 sec, more preferably 10 sec to 2 min 40 sec, still more preferably 20 sec to 2 min 10 sec.
  • Another preferred mode of the processing method of the invention is that in which partial or entire portion of overflow liquid of th color developer is flown into the bleacher; sludge formation in the bleacher is reduced when a given amount of the color developer is flown into the bleacher.
  • the color developer relating the present invention may contain alkali agents usually used in developers, e.g. sodium hydroxide, optassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate and borax, and may also contain various additives such as benzyl alcohol; alkali metal halides such as potassium bromide, potassium chloride; developing regulating agents such as citrazinic acid and preservatives such as hydroxylamine and sulfites.
  • alkali agents usually used in developers e.g. sodium hydroxide, optassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate and borax, and may also contain various additives such as benzyl alcohol; alkali metal halides such as potassium bromide, potassium chloride; developing regulating agents such as citrazinic acid and preservatives such as hydroxylamine and sulfites.
  • defoaming agents such as methanol, dimethylformamide and dimethylsulfoxide may be contained as appropriate.
  • the developer relating the present invention usually has a pH of over 7, preferably about 9 to 13.
  • the color developer used for the present invention may contain antioxidants such as hydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose, and pyrogallol-1,3-dimethylether.
  • antioxidants such as hydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose, and pyrogallol-1,3-dimethylether.
  • various chelating agents may be used in combination as sequestering agents.
  • chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid; organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid; aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) and ethylenediaminetetraphosphoric acid; oxycarbocylic 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 color developer used in the present invention contain a color developing agent at a concentration of not less than 1.5 x 10 ⁇ 2 mol/l, more preferably not less than 2.0 x 10 ⁇ 2 mol/l.
  • the desired effect is especially enhanced when processing with a stabilizer is conducted after processing with a fixer or bleach-fixer.
  • the amount of stabilizer replenisher is 1 to 80 times, preferably 2 to 60 times the amount of solution transferred from the preceding bath per unit area of the color photographic light-sensitive material for picture taking; it is preferable that the preceding bath component, namely bleach-fixer or fixer, concentration of the stabilizer by less than 1/500, more preferably less than 1/1000 in the final chamber of the stabilizer tank. From the viewpoint of reduction of environmental pollution and lengthening storage life of the solution, it is preferable to compose the stabilization tank so that the concentration is 1/500 to 1/100000, more preferably 1/2000 to 1/50000.
  • the stabilization tank be composed of more than one chambers, more preferably 2 to 6 chambers.
  • the stabilization tank is preferable to provide 2 to 6 chambers for the stabilization tank and use the counter current method in which the solution is supplied to the posterion bath and overflown the solution from the preceding bath.
  • the tank be composed of 2 or 3 chambers, more preferably 2 chambers.
  • the flow-in amount varies with the type of light-sensitive material, transport rate and method, and light-sensitive material surface squeezing method of automatic developing machine; in the case of color light-sensitive materials for picture taking or ordinary color roll films, the flow-in amount is usually 50 to 150 ml/m2 the effect of the present invention becomes more noticeable under this condition when the amount of replenisher is 50 ml to 4.0 l/m2, and it becomes still more noticeable when the amount of replenisher is 200 to 1500 ml/m2.
  • Treatment temperature with the stabilizer is 15 to 60°C, preferably 20 to 45°C.
  • the stabilizer of the present invention may contain various chelating agents, described in detail in the specification for Japanese Patent Application 63-46919/1988 by the present applicant, pp. 73 - 82.
  • the stabilizer preferably used for the invention have a pH value of 4.0 to 9.0, more preferably 4.5 to 9.0, still more preferably 5.0 to 8.5.
  • Any generally known alkali or acid can be used as pH adjuster in stabilizers preferably used for the present invention.
  • Stabilizers preferably used for the present invention may be added with salts of organic acids, e.g. citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid; pH adjusters, e.g. phosphates, borates, hydrochloric acid, sulfates; surfactants;; preservatives; and salts of metals such as Bi, Mg, Zn, Ni, Al, Sn, Ti, and Zr. These substances may be used in any combination in any amount, as long as the stabilizing bath relating the present invention is kept at constant pH and neither stability of color photographic images nor precipitation during storage is not adversely affected.
  • organic acids e.g. citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid
  • pH adjusters e.g. phosphates, borates, hydrochloric acid, sulfates
  • surfactants e.g. phosphates, borates, hydrochlor
  • the fungicides preferably used in stabilizers relating the present invention are hydroxybenzoic acid esters, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds, active halogen-releasing compounds, and benztriazole compounds.
  • silver may be recovered from the stabilizer as well by a method for silver recovery from fixer and bleach-fixer.
  • the stabilizer relating the present invention may be subjected to ion exchange resin contact, electrodialysis (cf. Japanese Patent Application No. 96352/1984), reverse osmosis (cf. Japanese Patent Application No. 96532/1984) etc.
  • deionized water for the stabilizer relating the present invention, since the antifungal property, stability and image storage property of the stabilizer are improved.
  • Any means of deionization can be used, as long as the dielectric constant of treated water is below 50 ⁇ s/cm, or the Ca/Mg ion concentration is below 5 ppm; for example, treatment using ion exchange resin or reverse osmosis membrane is preferably used singly or in combination. Ion exchange resins and reverse osmosis membranes are described in detail in Kokai-giho No. 87-1984; it is preferable to use strongly acidic H-type cation exchange resin and strongly alkaline OH-type anion exchange resin in combination.
  • the salt concentration of the stabilizer be below 1000 ppm, more preferably below 800 ppm.
  • processing time for the stabilizer is not more than 1 min, preferably not more than 1 min 30 sec, more preferably not more than 1 min.
  • the average silver iodide content of the entire silver halide emulsion be 0.1 to 15 mol%, more preferably 0.5 to 12 mol%, still more preferably 3 to 10 mol%.
  • the average grain size of the entire silver halide emulsion in the light-sensitive material there is no limitation on the average grain size of the entire silver halide emulsion in the light-sensitive material, but it is preferable that the average grain size be not more than 2.0 ⁇ m, more preferably 0.1 to 1.0 ⁇ m, still more preferably 0.2 to 0.6 ⁇ m.
  • the thickness of emulsion side there is a lower limit of the total dry thickness of all hydrophilic collid layers in the light-sensitive material, hereinafter referred to as the thickness of emulsion side, depending on the silver halide emulsion, couplers, oils, additives etc. contained in the layer; it is preferably that the thickness of emulsion side be 10 to 50 ⁇ m, more preferably 15 to 30 ⁇ m.
  • the distance between the uppermost surface of the emulsion side layer and the lowermost surface of the emulsion layer nearest the support be not less than 14 ⁇ m, and the distance between the uppermost surface and the lowermost surface of the emulsion layer which is different in color sensitivity from the emulsion layer nearest the support and which is second nearest the support be not less than 10 ⁇ m.
  • the light-sensitive material for the present invention is of the coupler-in-emulsion type (cf. US Patent Nos. 2,376,679 and 2,801,171), in which couplers are contained in the light-sensitive material; any coupler generally known in the relevant field can be used.
  • Examples of cyan coupler include compounds having a naphthol or phenol structure as the base structure and which form indoaniline dye via coupling.
  • Examples of magenta coupler include compounds having a 5-pyrazolone ring with active methylene group as the skeletal structure and pyrazoloazole compounds.
  • Examples of yellow coupler include compounds having a benzoylacetoanilide, pivalylacetoanilide or acylacetoanilide structure with an active methylene ring. In these couplers, whether a substituent is contained at the coupling site. As stated above, both 2-equivalent and 4-equivalent couplers can be used.
  • the cyan couplers are represented by the following Formulae C-A, C-B, and C-C.
  • R1 represents an alkyl group, alkenyl group, cycloalkyo group, aryl group or heterocyclic group
  • Y represents a group represented by in which R2 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group
  • R3 represents a hydrogen atom or group for R2; R2 and R3 may be identical or not, and may link together to form a 5- to 6-membered heterocycle
  • Z represents a hydrogen atom or group capable of being split off by the coupling reaction with the oxidation product of the aromatic primary amine-type color developing agent.
  • R1 represents -COHR4R5, -NHCOR4, -NHCOOR6, -NHSO2R6, -HNCONR4R5 or NHSO2NR4R5;
  • R2 represents a monovalent group;
  • R3 represents a substituent;
  • X represents a hydrogen atom or group which capable of being split off by the reaction with the oxidation product of the aromatic primary amine-type color developing agent;
  • l represents an integer 0 or 1;
  • m represents an integer 0 to 3;
  • R4 and R5 independently represent a hydrogen atom, aromatic group, aliphatic group or heterocyclic group;
  • R6 represents an aromatic group, aliphatic group or heterocyclic group; when m is 2 or 3, the R3 units may be identical or not, and may link together to form a ring;
  • R4 and R5, R2 and R3, R2, and X may link together to form a ring; provided that when l is 0, m represents 0, R1 represents -CONHR7
  • Y represents a group wherein R1 and R2 independently represent an alkyl group, preferably having 1 to 20 carbon atoms, e.g. methyl, ethyl, t-butyl, dodecyl; alkenyl group, preferably having 2 to 20 carbon atoms, e.g. aryl group, heptadecenyl group; cycloalkyl group; preferably 5- to 7-membered cycloalkyl group, e.g. cycloalkyl; aryl group, e.g.
  • R3 represents a hydrogen atom or group for R2; R2 and R3 may link together to form a 5- or 6-membered heterocycle.
  • any substituent may be introduced to R1 and R2; examples of the substituent include alkyl groups having 1 to 10 carbon atoms, e.g. methyl, i-propyl, i-butyl, t-butyl, t-octyl; aryl groups, e.g.
  • R1 represents a balast groups essential to provide a nondiffusion property for the cyan couplers of these Formulae and cyan dyes formed therefrom, preferably an alkyl group having 4 to 30 carbon atoms, aryl group, alkeny group, cycloalkyl group or heterocyclic group; examples include normal or branched alkyl groups such as groups of t-butyl, n-octyl, t-octyl, n-dodecyl, and 5- or 6-membered heterocyclid rings.
  • Z represents a hydrogen atom or group capable of being split off upon the coupling reaction with the oxidation product of N-hydroxyalkyl-substituted p-phenylenediamine derivative-type color developing agent.
  • halogen atoms e.g. chlorine, bromine, fluorine, substituted or unsubstituted alkoxy groups, aryloxy groups, heterocyclic oxy groups, acylocy groups, carbamoyloxy groups, sulfonyloxy groups, alkylthio groups, arylthio groups, heterocyclic thio groups, and sulfonamide groups; more specific examples include groups described in US Patent No.
  • R4 represents a substituted or unsubstituted aryl group, preferably a phenyl group.
  • the substituent for the aryl group includes -SO2R5 halogen atoms such as fluorine, chlorine, bromine; -CF3, -NO2, -CN, -COR5, -COOR5, -SO2OR5,
  • R5 represents an alkyl group, preferably having 1 to 20 carbon atoms, e.g. methyl, ethyl, t-butyl, dodecyl; alkenyl group, preferably having 2 to 20 carbon atoms, e.g. allyl group, heptadecenyl group; cycloalkyl group, preferably having 5- to 7-member, e.g. cyclohexyl group; or aryl groups, e.g. phenyl group, tolyl group, naphthyl group; R6 represents a hydrogen atom or group for R5.
  • the compounds of Formula C-D preferred for cyan couplers for the present invention have a substituted or unsubstituted phenyl group for R4, and the substituent in the phenyl group is cyano, nitro, -SO2R7, R7 represents an alkyl group, halogen atom, or trifluoromethyl.
  • Z and R1 each have the same definition as in Formulae C-A and C-B.
  • the balast groups preferable for R1 are represented by the following Formula C-E.
  • J represents an oxygen atom, sulfur atom or sulfonyl group
  • k represents the integer 0 to 4
  • l represents 0 or 1
  • R9 units may be identical or not
  • R8 represents a normal or branched alkylene group having 1 to 20 carbon atoms which may have aryl group etc. as a substituent
  • R9 represents a monovalent group, preferably a hydrogen atom, halogen atom, e.g. chlorine, bromide
  • alkyl group preferably a normal or branched alkyl group having 1 to 20 carbon atoms, e.g.
  • aryl group e.g. phenyl group
  • heterocyclic group e.g. nitrogen-containing heterocyclic group
  • alkocy group preferably normal or branched alkoxy group having 1 to 20 carbon atoms, e.g. methoxy, ethyoxy, t-butyloxy, octyloxy, decyloxy, dodecyloxy
  • aryloxy group e.g.
  • phenoxy group hydroxy group; acyloxy group; preferably alkylcarbonyloxy group, arylcarbonyloxy group, e.g. acetoxy group, benzoloxy group; carboxyl alkyloxycarbonyl group, normal or branched alkylcarbonyl group preferably having 1 to 20 carbon atoms, preferably phenoxycarbonyl group; alkylthio group; acyl group preferably having 1 to 20 carbon atoms; acylamino group, normal or branched alkylcarbamide group preferably having 1 to 20 carbon atoms; benzenecarbamide group; sulfonamide group, preferably normal or branched alkylsulfonamide or benzenesulfonamide group having 1 to 20 carbon atoms; carbamoyl group; normal or branched alkylaminocarbonyl or phenylaminocarbonyl group preferably having 1 to 20 carbon atoms; sulfamoyl group; normal or
  • the groups represented by R2 through R7 in Formula C-C each include substituted groups.
  • R6 aliphatic groups having 1 to 30 carbon atoms, aromatic groups having 1 to 30 carbon atoms, and heterocyclic groups having 1 to 30 carbon atoms are preferable; for R4 and R5, hydrogen atom and the groups preferable for R6 are preferred.
  • R2 is preferable a hydrogen atom bound to NH directly via NH, CO or SO2, aliphatic group having 1 to 30 carbon atoms, aromatic group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms, -OR8, -COR8, -PO( ⁇ OR10)2, -PO( ⁇ R10)2, -CO2R10, -SO2R10 or -SO2OR10 in which R8, R9 and R10 each have the same definition as R4, R5 and R6; R8 and R9 may link together to form a heterocycle.
  • R7 preferably represents an aromatic group having 6 to 30 carbon atoms; typical examples of the substituent for R7 include halogen atoms, hydroxy group, amino group, carboxyl group, sulfon group, cyano group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, sliphatic group, and aliphatic oxycarbonyl group.
  • the substituents may link together to form a ring, such as dioxamethylene group.
  • Typical examples of the group for R3 include halogen atom, hydroxy group, amino group, carboxyl group, sulfon group, cyano group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, and imide group.
  • the number of carbon atoms contained in R3 is preferably 0 to 30.
  • R1 preferably represents -CONR4R5, m preferably represents 0, R2 preferably represents -COR8, -COOR10, -SO2R10, -CONR8R9, or -SO2NR8R9 in direct bond to NH, more preferably -COOR10, -SOR8, or -SO2R10, most preferably -COOR10.
  • l preferably represents 0.
  • Examples of the coupler represented by Formula C-C are given in Japanese Patent Publication Open to Public Inspection Nos. 60-237448/1985, 61-153640/1986, 65-145557/1986, 62-85242/1987, 48-15529/1973, 50-117422/1975, 52-18315/1977, 52-90932/1977, 53-52423/1978, 54-48237/1979, 54-66129/1979, 55-32071/1980, 55-65957/1980, 55-105226/1980, 56-1938/1981, 56-12643/1981, 56-27147/1981, and 58-95346/1983, and US Patent No. 3,488,193; these couplers can be synthesized by the methods described in these references.
  • coupler properties such as solubility, for example, the oil-in-water emulsifying dispersion method, using water-insoluble high boiling point organic solvent, the alkali dispersion method, in which the coupler is added in alkaline solution, the latex dispersion method, and the solid dispersion method, in which the coupler is directly added in a fine solid.
  • couplers are normally added at 1.0 x 10 ⁇ 3 to 1.0 mol per mol silver halide, preferably 5.0 x 10 ⁇ 3 to 8.0 x 10 ⁇ 1.
  • Typical examples of the coupler of Formula C-C include the examples given in Japanese Patent Application No. 63-46919/1988, pp. 124 - 142.
  • the cyan coupler is normally used at 1 x 10 ⁇ 3 to 1 mol per mol silver halide, preferably 5 x 10 ⁇ 3 to 1 - 8 x 10 ⁇ 1 mol.
  • At least one of the photographic structural layers for the light-sensitive material processed by the method of the invention particularly at least one of the green-sensitive emulsion layers, contain a magenta coupler represented by the following Formula M-1.
  • Z represents a nonmetal atom necessary to the formation of a nitrogen-containing heterocyclic ring, which may have a substituent
  • X represents a hydrogen atom or group capable being split off upon the reaction with the oxidation product of the color developing agent
  • R represents a hydrogen atom or substituent.
  • R there in no particular limitation on the choice of the substituent for R; typical examples include alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl and cycloalkyl groups; are also included halogen atoms, cycloalkenyl, alkinyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclic thio groups, as well as
  • the alkyl group for R preferably has 1 to 32 carbon atoms, and may be normal or branched.
  • the aryl group for R is preferably a phenyl group.
  • the acylamino group for R includes alkylcarbonylamino group and arylcarbonylamino group.
  • the sulfonamido group for R include alkylsulfonylamino group and arylsulfonylamino groups.
  • alkyl and aryl moieties of the alkylthio group and arylthio group for R include the above-mentioned alkyl groups and aryl groups for R.
  • the alkenyl group for R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, more preferably 5 to 7 carbon atoms; the alkenyl group may be normal or branched.
  • the cycloalkenyl group for R preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.
  • Examples of the sulfonyl group for R include alkylsulfonyl groups and arylsulfonyl groups; examples of the sulfinyl group include alkylsufinyl groups and arylsulfinyl groups; examples of the phosphonyl group include alkylphosphonyl groups and arylphosphonyl groups; examples of the acyl group include alkylcarboxy groups and arylcarboxy groups; examples of the carbamoyl group include alkylcarbamoyl groups and arylcarbamoyl groups; examples of the sulfamoyl group include alkylsulfamoyl groups and arylsulfamoyl groups; examples of the acyloxy group include alkylcarbonyloxy groups and arylcarbonyloxy groups; examples of the carbamoyloxy group include alkylcarbamoyloxy groups and arylcarbamoyloxy groups; examples
  • Examples of the group for X capable of being split off upon the reaction with the oxidation product of the color developing agent include halogen atoms such as chlorine, bromine, fluorine and groups such as alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxyxarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkyloxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxycarbonylthio, acylamino, sulfonamido, nitrogen-containing heterocycle bonded through N atom, alkyloxycarbonylthiamino, aryloxycarbonylamino, carboxyl, and wherein R1′ has the same definition as R above; Z′ has the same definition as Z above; R2′ and R3′ independently represent a hydrogen atom, aryl group, alkyl group or heterocyclic group. a halogen
  • Examples of the nitrogen-containing heterocycle formed by Z to Z′ include pyrazole rings, imidazole rings, triazole rings, and tetrazole rings; examples of the substituent which these rings may have include those mentioned for R above.
  • the compound represented by Formula M-I is more specifically exemplified by the compounds of the following Formulae M-II through M-VII.
  • R2 through R8 and X have the same definitions as R above.
  • R1, X and Z1 have the same definitions as R1, X and Z in Formula M-I.
  • magenta couplers represented by the above Formula M-II through V-VII the magenta couplers represented by Formula M-II is especially preferable.
  • R1 represents an alkylene group
  • R2 represents an alkyl group, cycloalkyl group or aryl group.
  • the alkylene group for R1 preferably has 2 or more carbon atoms, more preferably 3 to 6 carbon atoms in the normal chain moiety, and it does not matter whether the group itself is normal or branched.
  • the alkyl group for R2 preferably has 5 to 6 members.
  • R9, R10 and R11 independently have the same definision as R above.
  • R9, R10 and R11 may link together to form a saturated or unsaturated ring, e.g. cycloalkane, cycloalkene, heterocycle, which may further link with R11 to form a bridged hydrocarbon residue.
  • R9 through R11 are alkyl groups, or at least one of R9 through R11, e.g. R11, is a hydrogen atom, which links with the other groups R9 and R10 to form a cycloalkyl in cooperation with the root carbon atoms.
  • R9 through R11 are alkyl groups and the other one is a hydrogen atom or alkyl group.
  • R12 has the same definition as R above.
  • R12 a hydrogen atom or alkyl group is preferable.
  • magenta couplers preferably used for the present invention include the compounds 1 through 177 described in the specification for Japanese Patent Application No. 61-180310/1987, pp. 48 - 64, as well as compound Nos. 1 - 4, 6, 8 - 17, 19 - 24, 26 - 43, 45 - 59, 61 - 104, 106 - 121, 123 - 162 and 164 - 223 of the compounds described in the specification for Japanese Patent O.P.I. Publication No. 62-166339/1987.
  • magenta couplers can be synthesized in accordance with the Journal of the Chemical Society, Perkin, I (1977), pp. 2047 - 2052, US Patent No. 3,725,067, Japanese Patent Publication Open to Public Inspection Nos. 59-99437/1984, 58-42045/1983, 59-162548/1984, 59-171956/1984, 60-33552/1985, 60-43659/1985, 60-172982/1985 and 60-190779/1985.
  • magenta couplers are usually used at 1 x 10 ⁇ 3 to 1 mol, preferably 1 x 10 ⁇ 2 to 8 x 10 ⁇ 1 mol per mol silver halide.
  • magenta dye-forming couplers preferably used for the present invention are represented by the following Formula I
  • Ar represents a phenyl group, sepcifically a substituted phenyl group.
  • the substituents are halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, cyano groups, carbamoyl groups, sulfamoyl groups, sulfonyl groups, sulfonamido groups, and acylamino groups; the phenyl group for Ar may have two or more substituents. Examples of the substituent are given below.
  • Halogen atoms chlorine, bromine, fluorine.
  • Alkyl groups methyl group, ethyl group, isopropyl group, butyl group, t-butyl group, t-pentyl group etc.; particularly, alkyl groups having 1 to 5 carbon atoms are preferable.
  • Phenoxy group, ⁇ -naphthoxy group etc.; the aryl moiety may have a substituent mentioned for the phenyl group for Ar above.
  • Carbonyl groups with an alkyl group as mentioned above; alkoxycarbonyl groups having 1 to 5 carbon atoms in the alkyl moiety are preferable, e.g. methoxycarbonyl group and pentyloxycarbonyl group.
  • Alkylcarbamoyl groups such as carbamoyl group and dimethylcarbamoyl group.
  • Alkylsulfamoyl groups such as sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group and ethylsulfamoyl group.
  • Alkylsulfonyl groups such as methanesulfonyl group, ethanesulfonyl group and butanesulfonyl group, and arylsulfamoyl groups.
  • Alkylsulfonamido groups such as methanesulfonamido group and toluenesulfonamido group, and arylsulfonamido groups.
  • halogen atoms are preferable and chlorine atom is particularly preferable.
  • Y represents a group which is split when a dye is formed in coupling with the oxidation product of a p-phenylenediamine-type color developing agent.
  • Examples include halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, arylthio groups, alkylthio groups, and wherein Z represents an atomic group which cooperates with the nitrogen atom and atoms selected from carbon, oxygen, nitrogen and sulfur atoms to form a 5- or 6-membered ring. Specific examples are given below.
  • Halogen atoms Chlorine, bromine, fluorine.
  • Ethoxy group benzyloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group etc.
  • Phenoxy group 4-methoxyphenoxy group, 4-nitrophenoxy group etc.
  • Phenylthio group 2-butoxy-5-octylphenylthio group, 2,5-dihexyloxyphenylthio group etc.
  • R is an acylamino group
  • examples include acetamido group, isobutylamino group, benzamido group, 3-[ ⁇ -(2,4-di-tert-amylphenoxy)butylamido]benzamido groups, 3-[ ⁇ (2,4-di-tert-amylphenoxy)acetamido]benzamido group, 3-[ ⁇ -(3-pentadecylphenoxy)butylamido]benzamido group, ⁇ -(2,4-di-tert-amylphenoxy)butylamido group, ⁇ -(3-pentadecylphenoxy)butylamido group, hexadecaneamido group, isostearoylamino group, 3-(3-octadecenylsuccinimide)benzamido group and pivaloylamino group; when R is an anilino group, examples include anilino group, 2-ch
  • X represents a halogen atom, alkoxy group or alkyl group.
  • halogen atoms Chlorine, bromine, fluorine.
  • Alkoxy groups having 1 to 5 carbon atoms are preferable, e.g. methoxy group, ethoxy group, butoxy group, sec-butoxy group, iso-pentyloxy group.
  • Alkyl group having 1 to 5 carbon atoms are preferable, e.g. methyl group, ethyl group, isopropyl group, butyl group, t-butyl group, t-pentyl group.
  • Halogen atoms are especially preferable; chlorine is most preferable.
  • Examples of the group for R1 capable of bonding to a benzene ring as a substituent include halogen atoms and groups of
  • R′, R ⁇ , and R′′′ whether identical or not, independently represent a hydrogen atom, or an alkyl, alkenyl or aryl group which may has a substituent. Of these groups, R′CONH-, are preferable.
  • magenta couplers preferably used for the present invention are given in the specification for Japanese Patent O.P.I. Publication No. 61-289530/1986, pp. 42 - 51 and the specification for Japanese Patent O.P.I. Publication No. 61-50145/1986, pp. 39 - 46.
  • These couplers can easily be synthesized in accordance with the methods described in Japanese Patent O.P.I. Publication Nos. 56-38043/1981, 57-14837/1982, 57-204036/1982 and 58-14833/1983.
  • magenta couplers are preferably added at ratios of 0.005 to 2 moles, more preferably 0.01 to 1 mol per mol silver halide.
  • cyan couplers or magenta couplers may be used singly or in combination; it is also possible to use them in combination with one or more other cyan or magenta couplers.
  • the silver halide emulsions applicable to the present invention be in the form of tabular grains, and any silver halide can be used, including silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide.
  • any silver halide can be used, including silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide.
  • protective colloids for these silver halides various substances can be used, as well as natural substances such as gelatin.
  • the silver halide emulsion may contain ordinary photographic additives, such as stabilizing agents, sensitizing agents, hardeners, sensitizing dyes and surfactants.
  • Color negative films, color paper, color reversal films, color reversal paper and other light-sensitive materials can be used for the present invention.
  • the present invention provides a processing method free of bleach fogging and a bleaching solution which functions well in embodying said processing method.
  • the amounts of additives to silver halide photographic light-sensitive material are shown in g per m2; the amounts of silver halide and collodal silver are shown in terms of silver.
  • a multilayer color photographic light-sensitive material with high sensitivity comprising the following layers of the respective compositions was prepared on a cellulose triacetate film base.
  • Layer 1 Antihalation layer Black colloidal silver 0.2 Gelatin 1.7 Ultraviolet absorber (UV-1) 0.3 Colored coupler (CM-1) 0.2 Solvent for ultraviolet absorber dispersion (oil-1) 0.15 Solvent for ultraviolet absorber dispersion (oil-2) 0.15 Solvent for colored coupler dispersion (oil-3) 0.2
  • Layer 2 Interlayer Gelatin 1.2
  • Layer 3 1st red-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 1.0 Silver iodobromide emulsion (Em-2) 0.5 Gelatin 1.3 Sensitizing dye (S-1) 0.5 x 10 ⁇ 4 (mol/mol silver) Sensitizing dye (S-2) 2 x 10 ⁇ 4 (mol/mol silver) Sensitizing dye (S-3) 2 x 10 ⁇ 4 (mol
  • coating aid Su-1 dispersion aids Su-2 and Su-3, hardeners H-1 and H-2, stabilizer ST-1, and antifogging agents AF-1 and AF-2 were also added to each layer.
  • Monodisperse type emulsion having a relatively low silver iodide content in the surfacial portion of the silver halide grains with an average grain size of 0.8 ⁇ m and an average silver iodide content of 8.0%.
  • Monodispersed type emulsion having a relatively low silver iodide content in the surfacial portion of the silver halide grains, with an average grain size of 0.4 ⁇ m and an average silver iodide content of 7.0%.
  • Monodispersed type emulsion having a relatively low silver iodide content in the surfacial portion of the silver halide grains, with an average grain size of 1.6 ⁇ m and an average silver iodide content of 6.4%.
  • Monodispersed type emulsion having a relatively low silver iodide content in the surfacial portion of the silver halide grains, with an average grain size of 2.0 ⁇ m and an average silver iodide content of 7.0%.
  • the sample thus prepared was subjected to exposure to white light through an optical wedge and then developed as follows:
  • the processing solutions used had the following compositions:
  • Ferric ammonium salt of examplified compound A-1 150 g Compound shown in Table 1 (hereinafter simply referred to as Compound) 0.4 mol Ammonium bromide 150 g
  • a compound listed in Table 1 was added to the bleaching solution and processing was conducted; minimum densities for B (blue), G (green), and R (red) were measured using an optical densitomer PDA-65A (Konica Corporation).
  • processing was conducted under the following conditions (using bleaching solution No. 24).
  • Process Time Temperature Color developing 3 min 15 sec 38°C Stop 60 sec 20°C Washing 120 sec 35°C Bleaching 45 sec 37°C Fixing 90 sec 37°C Stabilization 60 sec 37°C Drying 60 sec 70°C
  • a stop solution was prepared as follows and used; the bleaching solution used was the same as the above-mentioned bleaching solution, but none of the compounds of Table 1 was added; the color developer, fixer, and stabilizer used were the same as above.
  • the following layers with the respective compositions were formed on a triacetyl cellulose film base in due order, starting at the base side, to prepare the multilayer color photographic light-sensitive material sample 2.
  • Layer 1 Antihalation layer (HC-1) Black colloidal silver 0.22 Ultraviolet absorber (UV-1) 0.20 Colored coupler (CC-1) 0.05 Colored coupler (CM-2) 0.05 High boiling point solvent (oil-1) 0.20 Gelatin 1.4
  • Layer 2 Interlayer (IL-1) Ultraviolet absorber (UV-1) 0.01 High boiling point solvent (oil-1) 0.01 Gelatin 1.4
  • Layer 3 Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-5) 1.0 Silver iodobromide emulsion (Em-6) 0.5 Sensitizing dye (S-1) 2.5 x 10 ⁇ 4 (mol/mol silver) Sensitizing dye (S-3) 2.5 x 10 ⁇ 4 (mol/mol silver) Sensitizing dye (S-2) 0.5 x 10 ⁇ 4 (mol/mol silver) Cyan coupler (C-4) 1.2 Cyan coupler (C-1) 0.06 Colored cyan coupler (CC-
  • coating aid Su-1 dispersion aid Su-2
  • hardeners H-1 and H-2 preservative DI-1
  • stabilizer ST-1 preservative DI-1
  • anti-fogging agents AF-1 and AF-2 were also added to each layer.
  • Monodisperse type emulsion having a relatively low silver iodide content in the surface portion of the silver halide grains with an average grain size of 0.46 ⁇ m and an average silver iodide content of 7.5%.
  • Monodisperse type emulsion having a relatively low silver iodide content in the surface portion of the silver halide grains, with an average grain size of 0.78 ⁇ m and an average silver iodide content of 6.0%.
  • Monodisperse type emulsion having a relatively low silver iodide content in the surfacial portion of the silver halide grains, with an average grain size of 0.95 ⁇ m and an average silver iodide content of 8.0%.
  • Em-5, Em-7 and Em-8 are silver iodobromide emulsions composed mainly of octahedral grains, with multilayer structures as prepared in accordance with Japanese Patenet Publication Open to Inspection Nos. 60-138538/1985 and 61-245151/1986.
  • Em-5 through Em-8 the average value of grain diameter/grain thickness was 1.0, with the width of variation of grain distribution of 14, 10, 12, and 12%, respectively.
  • the sample thus prepared was subjected to exposure to white light through and optical wedge and then developed as follows:
  • the tank solutions used had the same compositions as Example 1; replenishers of the following compositions were also used for running processing.
  • fixer replenisher and stabilizer replenisher used were the same as in Example 1.
  • Process Processing time Processing temperature
  • Replenisher amount Color developing 3 min 15 sec 38°C 12 ml Bleaching 45 sec 37°C 1.5 ml Fixing 1 min 30 sec 37°C 10 ml Stabilization 60 sec 37°C 10 ml Drying 60 sec 70°C - (The amounts of replenishers are shown in ml per 100 cm2 light-sensitive material.)
  • Running processing was conducted until the bleaching solution replenisher amount became two times the capacity of the bleaching tank in 40 days. After completion of running processing, the film sample was measured in the same manner as Example 1, except that running processing was conducted in the absence/presence of 0.4 mol/l citric acid or 1.5 mol/l acetic acid, with the amount of bleacher replenisher varied to 0.75, 1.5, 5, and 10 ml per 100 cm2.
  • Example 2 experiments were conducted in the same manner as Example 1, but the color developing tank, bleaching tank, fixing tank and stabilizing tank were each provided with a vinyl chloride nozzle having an opening of a 0.5 mm diameter and an Iwake magnet pump MD-15 was used to jet the processing solutions to the surface of light-sensitive emulsion; the bleaching tank alone was subjected to aeration at a rate such that the volume of air equaled the capacity of the bleaching tank in 2 minutes. Aeration was continued during the light-sensitive material was loaded in the automatic developer.
  • a vinyl chloride nozzle having an opening of a 0.5 mm diameter
  • an Iwake magnet pump MD-15 was used to jet the processing solutions to the surface of light-sensitive emulsion
  • the bleaching tank alone was subjected to aeration at a rate such that the volume of air equaled the capacity of the bleaching tank in 2 minutes. Aeration was continued during the light-sensitive material was loaded in the automatic developer.
  • Table 15 Experiment No. Compound added to bleaching solution Amount of replenisher Bleach fogging (minimum density) Tank solution surface appearance B G R 101 Not added 0.75 1.17 0.75 0.63 +++ 102 1.5 1.06 0.72 0.57 +++ 103 5.0 1.03 0.69 0.54 ++ 104 10.0 1.01 0.68 0.52 + 105 Citric acid, 0.4 mol/l 0.75 0.85 0.59 0.45 + 106 1.5 0.83 0.58 0.44 + 107 5.0 0.81 0.57 0.43 - 108 10.0 0.81 0.57 0.43 - 109 Acetic acid, 1.5 mol/l 0.75 0.87 0.60 0.46 - 110 1.5 0.86 0.59 0.45 - 111 5.0 0.85 0.59 0.45 - 112 10.0 0.85 0.59 0.45 - Note: The evaluation criteria for tank solution surface appearance were the same as in Example 1.
  • Example 2 Experiments were conducted in the same manner as Example 1, but the color developing agent 4-amino-3-methyl-N-ethyl-N-( ⁇ -hydroxylethyl)aniline sulfate was present in the color developer in the amounts shown in Table 16, and processing time was varied as shown in Table 16. Processing time was adjusted so that sensitometry results agreed with each other.
  • Bleaching was conducted in the absence/presence of 0.8 mol/l citric acid in the bleaching solution.
  • magenta dye determined with green light
  • Table 19 Sample No. Magenta coupler G (minimum density) Succinic acid No added 4-1 M-4 0.57 0.68 4-2 M-5 0.58 0.69 4-3 M-6 0.57 0.68 4-4 M-7 0.57 0.68 4-5 M-8 0.57 0.68 4-6 M-9 0.58 0.69 4-7 M-10 0.58 0.69 4-8 M coupler-1, for comparison 0.65 0.74 4-9 M coupler-2, for comparison 0.63 0.71
  • magenta bleach fogging was mitigated by alternating magneta couplers by the magenta couplers preferred for the present invention.
  • the magneta couplers listed in Table 19 have the following Formulae:
  • the present invention is very effective when a ferric complex salt of A-1, as the bleaching agent, is present at more than 0.2 mol/l or when the molar ratio of ferric complex salt of aminopolycarboxylic acid contained as the bleaching agent, relative to A′-1, not represented by Formula A, exceeds 40%.
  • Example 1 The light-sensitive material of Example 1 was developed using the processes and processing solutions shown below.
  • Process Processing time Processing temperature Color developing 1 min 40 sec 39.8°C Bleaching 50 sec 38°C Fixing 50 sec 38°C Still water bath 50 sec 38°C Stabilization 50 sec 38°C Drying 90 sec 70°C
  • the processing solutions used had the following compositions:
  • Potassium carbonate 30 g Sodium hydrogencarbonate 2.5 g Potassium sulfite 4 g Diethylenetriaminepentaacetic acid 3.0g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino-3-methyl-N-ethyl-N-( ⁇ -hydroxylethyl)aniline sulfate 15.0 g Potassium hydroxide 1.2 g
  • a buffer of the present invention be present at ratios of over 0.1 mol/l when a ferric salt of a compound represented by Formula A or B is present at 0.3 to 1 mol per l bleaching solution.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP89102530A 1988-02-15 1989-02-14 Procédé de traitement et solution de blanchiment pour des matériaux photographiques couleur à l'halogénure d'argent sensible à la lumière Expired - Lifetime EP0329088B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP32501/88 1988-02-15
JP3250188 1988-02-15
JP7278188 1988-03-25
JP72781/88 1988-03-25
JP63315958A JP2689153B2 (ja) 1988-03-25 1988-12-13 ハロゲン化銀カラー写真感光材料の処理方法及び漂白液
JP315958/88 1988-12-13

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EP0329088A2 true EP0329088A2 (fr) 1989-08-23
EP0329088A3 EP0329088A3 (en) 1990-06-13
EP0329088B1 EP0329088B1 (fr) 1997-04-23

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0334317A2 (fr) * 1988-03-25 1989-09-27 Konica Corporation Composition pour traiter un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0353738A2 (fr) * 1988-08-05 1990-02-07 Fuji Photo Film Co., Ltd. Méthode de traitement d'un matériau photographique couleur à l'halogénure d'argent
EP0450293A2 (fr) * 1990-02-21 1991-10-09 Konica Corporation Solution de blanchiment pour matériau d'halogÀ©nure d'argent pour la photographie en couleurs et procédé de traitement en utilisant la même
EP0466510A1 (fr) * 1990-07-13 1992-01-15 Konica Corporation Solution de traitement et procédé de traitement d'un matériau à l'halogénure d'argent pour la photographie en couleur
EP0466372A1 (fr) * 1990-06-29 1992-01-15 Konica Corporation Procédé de traitement des matériaux photosensibles pour la photographie en couleur
EP0501479A1 (fr) * 1991-02-28 1992-09-02 Fuji Photo Film Co., Ltd. Solution de blanchiment et procédé de traitement d'un matériau photographique à l'halogénure d'argent pour la photographie en couleur
EP0534086A1 (fr) * 1991-07-26 1993-03-31 Konica Corporation Solution de blanchiment pour procédé photographique en couleurs
EP0546778A1 (fr) * 1991-12-13 1993-06-16 Konica Corporation Agent solide de traitement pour matériau photographique à l'halogénure d'argent sensible à la lumière
US5232822A (en) * 1988-10-15 1993-08-03 Konica Corporation Method for processing light-sensitive silver halide color photographic material
EP0553569A1 (fr) * 1991-12-27 1993-08-04 Konica Corporation Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent sensible à la lumière
EP0556782A1 (fr) * 1992-02-17 1993-08-25 Konica Corporation Solution de blanchiment ou de blanchiment-fixage et méthode de traitement de matériaux photographiques couleur à l'halogénure d'argent sensibles à la lumière utilisant cette solution
EP0602600A2 (fr) * 1992-12-14 1994-06-22 Eastman Kodak Company Compositions photographiques de blanchiment contenant persulphate avec catalyseurs ferriques
EP0657777A2 (fr) * 1993-12-07 1995-06-14 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent
US5521056A (en) * 1995-01-10 1996-05-28 Eastman Kodak Company Photographic peracid bleaching composition and processing method using ternary iron carboxylate complexes as catalysts in peracid bleaching solutions
US5582958A (en) * 1995-01-10 1996-12-10 Eastman Kodak Company Photographic bleaching composition and processing method using ternary iron carboxylate complexes as bleaching agents
EP0871065A1 (fr) * 1997-04-07 1998-10-14 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
US5976772A (en) * 1996-10-10 1999-11-02 Agfa Gevaert Ag Bleach-fixing bath for color photographic material
US6096487A (en) * 1997-02-13 2000-08-01 Eastman Kodak Company Cyan dye recovery using ferric aminopolycarboxylic acid bleaching composition
EP1403705A2 (fr) * 2002-09-27 2004-03-31 Eastman Kodak Company Composition de blanchiment photographique sans odeur et traitement des matériaux photographiques en couleur
US7160674B2 (en) 2003-08-29 2007-01-09 A&O Imagining Solutions Gmbh Photographic chemicals bundle

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0158369A2 (fr) * 1981-07-21 1985-10-16 Konica Corporation Méthode de stabilisation d'un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
DE3518257A1 (de) * 1984-05-21 1985-11-21 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Verfahren zur verarbeitung eines lichtempfindlichen farbphotographischen materials
JPS62222252A (ja) * 1986-03-24 1987-09-30 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
EP0293729A1 (fr) * 1987-05-25 1988-12-07 Konica Corporation Composition contenant un complexe de sel ferrique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0158369A2 (fr) * 1981-07-21 1985-10-16 Konica Corporation Méthode de stabilisation d'un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
DE3518257A1 (de) * 1984-05-21 1985-11-21 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Verfahren zur verarbeitung eines lichtempfindlichen farbphotographischen materials
JPS62222252A (ja) * 1986-03-24 1987-09-30 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
EP0293729A1 (fr) * 1987-05-25 1988-12-07 Konica Corporation Composition contenant un complexe de sel ferrique

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0334317A3 (en) * 1988-03-25 1990-05-30 Konica Corporation Composition for processing silver halide color photographic light-sensitive material
EP0334317A2 (fr) * 1988-03-25 1989-09-27 Konica Corporation Composition pour traiter un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0353738A2 (fr) * 1988-08-05 1990-02-07 Fuji Photo Film Co., Ltd. Méthode de traitement d'un matériau photographique couleur à l'halogénure d'argent
EP0353738B1 (fr) * 1988-08-05 1996-05-22 Fuji Photo Film Co., Ltd. Méthode de traitement d'un matériau photographique couleur à l'halogénure d'argent
US5232822A (en) * 1988-10-15 1993-08-03 Konica Corporation Method for processing light-sensitive silver halide color photographic material
EP0450293A2 (fr) * 1990-02-21 1991-10-09 Konica Corporation Solution de blanchiment pour matériau d'halogÀ©nure d'argent pour la photographie en couleurs et procédé de traitement en utilisant la même
EP0450293A3 (en) * 1990-02-21 1993-02-10 Konica Corporation Bleaching solution for light-sensitive silver halide color photographic material and processing method using the same
EP0466372A1 (fr) * 1990-06-29 1992-01-15 Konica Corporation Procédé de traitement des matériaux photosensibles pour la photographie en couleur
US5204228A (en) * 1990-06-29 1993-04-20 Konica Corporation Method of processing silver halide color photographic light-sensitive materials
EP0466510A1 (fr) * 1990-07-13 1992-01-15 Konica Corporation Solution de traitement et procédé de traitement d'un matériau à l'halogénure d'argent pour la photographie en couleur
US5246821A (en) * 1991-02-28 1993-09-21 Fuji Photo Film Co., Ltd. Bleaching solution for processing a silver halide color photographic material and a processing method using the same
EP0501479A1 (fr) * 1991-02-28 1992-09-02 Fuji Photo Film Co., Ltd. Solution de blanchiment et procédé de traitement d'un matériau photographique à l'halogénure d'argent pour la photographie en couleur
EP0534086A1 (fr) * 1991-07-26 1993-03-31 Konica Corporation Solution de blanchiment pour procédé photographique en couleurs
EP0546778A1 (fr) * 1991-12-13 1993-06-16 Konica Corporation Agent solide de traitement pour matériau photographique à l'halogénure d'argent sensible à la lumière
EP0553569A1 (fr) * 1991-12-27 1993-08-04 Konica Corporation Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent sensible à la lumière
US5580705A (en) * 1991-12-27 1996-12-03 Konica Corporation Method of bleaching silver halide color photographic light-sensitive materials using particular ferric chelates
EP0556782A1 (fr) * 1992-02-17 1993-08-25 Konica Corporation Solution de blanchiment ou de blanchiment-fixage et méthode de traitement de matériaux photographiques couleur à l'halogénure d'argent sensibles à la lumière utilisant cette solution
US5635341A (en) * 1992-02-17 1997-06-03 Konica Corporation Bleach or bleach-fixer and method for processing silver halide color photographic light-sensitive materials by use thereof
EP0602600A3 (fr) * 1992-12-14 1995-04-19 Eastman Kodak Co Compositions photographiques de blanchiment contenant persulphate avec catalyseurs ferriques.
US5536625A (en) * 1992-12-14 1996-07-16 Eastman Kodak Company Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts
EP0602600A2 (fr) * 1992-12-14 1994-06-22 Eastman Kodak Company Compositions photographiques de blanchiment contenant persulphate avec catalyseurs ferriques
US5460924A (en) * 1992-12-14 1995-10-24 Eastman Kodak Company Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts
US5627015A (en) * 1993-12-07 1997-05-06 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
EP0657777A2 (fr) * 1993-12-07 1995-06-14 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent
EP0657777A3 (fr) * 1993-12-07 1995-09-13 Fuji Photo Film Co Ltd Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent.
US5582958A (en) * 1995-01-10 1996-12-10 Eastman Kodak Company Photographic bleaching composition and processing method using ternary iron carboxylate complexes as bleaching agents
US5521056A (en) * 1995-01-10 1996-05-28 Eastman Kodak Company Photographic peracid bleaching composition and processing method using ternary iron carboxylate complexes as catalysts in peracid bleaching solutions
US5976772A (en) * 1996-10-10 1999-11-02 Agfa Gevaert Ag Bleach-fixing bath for color photographic material
US6096487A (en) * 1997-02-13 2000-08-01 Eastman Kodak Company Cyan dye recovery using ferric aminopolycarboxylic acid bleaching composition
EP0871065A1 (fr) * 1997-04-07 1998-10-14 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP1403705A2 (fr) * 2002-09-27 2004-03-31 Eastman Kodak Company Composition de blanchiment photographique sans odeur et traitement des matériaux photographiques en couleur
EP1403705A3 (fr) * 2002-09-27 2004-04-21 Eastman Kodak Company Composition de blanchiment photographique sans odeur et traitement des matériaux photographiques en couleur
US7160674B2 (en) 2003-08-29 2007-01-09 A&O Imagining Solutions Gmbh Photographic chemicals bundle

Also Published As

Publication number Publication date
DE68927983T2 (de) 1997-10-09
EP0329088A3 (en) 1990-06-13
EP0329088B1 (fr) 1997-04-23
CA1336480C (fr) 1995-08-01
DE68927983D1 (de) 1997-05-28

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