EP0270217B1 - Solution de blanchiment-fixage ayant un bon rendement de traitement et méthode de traitement d'un matériau sensible à la lumière l'utilisant - Google Patents

Solution de blanchiment-fixage ayant un bon rendement de traitement et méthode de traitement d'un matériau sensible à la lumière l'utilisant Download PDF

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Publication number
EP0270217B1
EP0270217B1 EP19870308819 EP87308819A EP0270217B1 EP 0270217 B1 EP0270217 B1 EP 0270217B1 EP 19870308819 EP19870308819 EP 19870308819 EP 87308819 A EP87308819 A EP 87308819A EP 0270217 B1 EP0270217 B1 EP 0270217B1
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Prior art keywords
bleach
group
general formula
carbon atoms
fixing solution
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EP19870308819
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German (de)
English (en)
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EP0270217A2 (fr
EP0270217A3 (en
Inventor
Naoki Takabayashi
Shigeharu Koboshi
Satoru Kuse
Kazuhiro Kobayashi
Moeko Higuchi
Hiroaki Kobayashi
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Konica Minolta Inc
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Konica Minolta Inc
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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

Definitions

  • This invention relates to a bleach-fixing solution, and particularly to a bleach-fixing solution that can achieve rapid processing when applied in a light-sensitive material for photographing.
  • the desilvering of light-sensitive materials for photographing in which a highly sensitive silver iodobromide-rich emulsion is used is carried out separately in a bleaching step and a fixing step.
  • DTPA ⁇ Fe complex salt a diethylenetriaminepentaacetic acid ferric complex salt
  • DTPA ⁇ Fe complex salt a diethylenetriaminepentaacetic acid ferric complex salt
  • the above DTPA ⁇ Fe complex salt can satisfy the above properties when used in the higher pH range, specifically, at about pH 7 to 9.
  • ammonia gas may be readily generated when used in such a pH range, so that there has been a problem undesirable from a viewpoint of the work environment if the developing is carried out in a small room.
  • EP-A-0 173 540 discloses a color forming method using a light-sensitive silver halide color photographic material having red, green and blue sensitive layers with a total thickness of 25 microns or less.
  • the method involves involves inagewise exposure folllowed by color development in the presence of a dye forming coupler.
  • the silver is removed from the developed material using a bleach-fixing solution.
  • the bleach-fixing solution may contain one or more organic acid ferric complexes such as ethylamine diamine tetraacetic acid and 1,2-diaminopropane tetraacetic acid.
  • the present inventors have continued further studies to find, as a result, that the lowering of the desilvering ability and the inferiority in the color reproduction that are considered to be caused by the above-mentioned accumulation of ferrous ions can be solved at the same time and the problem of the generation of ammonia gas can be solved by using a bleach-fixing solution having the pH aminopolycarboxylic ferric complex salt.
  • Some compounds of the compounds represented respectively by General Formulas (II) and (III) of this invention are known to be used in a bleach-fixing solution containing an ethylenediaminetetraacetic acid iron (III) complex (hereinafter "EDTA ⁇ Fe) as a bleaching agent, as disclosed, for example, in Japanese Publication No. 39985/1979/ However, it was revealed that such compounds may gradually release sulfite ions when used in the bleach-fixing solution containing the above EDTA ⁇ Fe, so that aldehydes or ketones may be accumulated and the desilvering speed may be gradually lowered.
  • EDTA ⁇ Fe ethylenediaminetetraacetic acid iron
  • a first object of this invention is to provide a bleach-fixing solution made feasible for rapid processing of a light-sensitive photographic material for photographing.
  • a second object of this invention is to provide a bleach-fixing solution free from generation of ammonia gas and desirable from the viewpoint of work environment.
  • a third object of this invention is further to provide a bleach-fixing solution that can delay the occurrence of the precipitation even during storage with time to attain a stable bleach-fixing performance.
  • a fourth object of this invention is to provide a bleach-fixing solution that can improve the bleach stain at a non-image portion of a light-sensitive material when the processing with low replenishment is carried out.
  • a bleach-fix solution for processing a light-sensitive silver halide photographic material for photographing wherein said solution has a pH ranging from between 3.0 to 6.8, contains a ferric complex salt having a ligand comprising a compound represented by the Formulas I-1 and I-2 shown below, and further contains at least one of;
  • R2 and R3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and M represents an alkali metal atom or an ammonium group,
  • R4 and R5 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; M represents an alkali metal atom or an ammonium group; and n represents an integer of 0 to 6,
  • R2 represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl-substituted alkyl group having 1 to 5 carbon atoms, or ( ⁇ CH2)n6COOH; and n4, n5 and n6 each represents an integer of 1 or 2,
  • n7 and n9 each represent an integer of 0 to 3
  • n8 represents an integer of 1 to 3, provided that the sum of n7, n8 and n9 is 2 or more
  • R3 and R4 each represent a hydrogen atom, a hydroxyl-substituted alkyl group having 1 to 3 carbon atoms, or a carboxyl-substituted alkyl group having 1 or 2 carbon atoms;
  • R5 and R6 each represent a hydrogen atom or a hydroxyl-substituted phenyl group;
  • R7, R8, R9 and R10 each represent a hydrogen atom or a hydroxyl-substituted alkyl group having 1 to 3 carbon atoms, provided that R7, R8, R9 and R10 each may combine to form a ring having 5 to 8 carbon atoms;
  • n10 and n11 each represent an integer of 1 to 3; and
  • n12 represents an integer of 0 to 4,
  • n13 represents an integer of 1 to 8.
  • the ferric complex salt having a ligand comprising the compound represented by the Formulas I-1 and I-2 may be used also in the form of a free acid (hydrogen salt), or may also be used in the form of a counter salt including alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amines, for example, triethanolamine.
  • alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amines, for example, triethanolamine.
  • Preferably used are a potassium salt, a sodium salt and an ammonium salt.
  • At least one of these ferric complex salts of this invention may be used, but two or more of these can also be used in combination. It is also possible to use them in combination with any ferric complex salts outside this invention.
  • the ferric complex salt can be used in any amount in the bleach-fixing solution of this invention so long as it is in an amount sufficient for obtaining the effect of this invention.
  • overly high concentration of the ferric complex salt may cause the deterioration of shelf stability of the bleach-fixing solution, and, on the other hand, overly low concentration of the ferric complex salt may cause the deterioration of desilvering performance and color reproduction performance.
  • it may be usually used preferably in the range of 0.02 to 1.30 mol/lit., more preferably 0.10 to 1.20 mol/lit.
  • the effect of this invention can be preferably exhibited when used in the range of 0.20 to 0.80 mol/lit.
  • the bleach-fixing solution of this invention may be appropriately in the pH range of pH 3.0 to 6.8, because sulfite gas may be generated at less than pH 3.0 and the effect of this invention may be insufficient if the pH is higher than 6.8. It can be used at any pH so long as it is used in this pH range, but is preferably used at pH 4.0 to 6.7, particularly preferably H 5.0 to 6.5, taking account of the solubility of various iron salts at low temperature the odor of the sulfite gas generated from sulfite ions in addition to desilvering performance and color reproduction.
  • the bleach-fixing solution of this invention may preferably contain a variety of sulfites therein, and these sulfites may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, etc.
  • At least one compound selected from the compounds represented respectively by General Formulas (II) and (III) may be used as a preservative in the bleach-fixing solution of this invention.
  • the alkyl group having 1 to 8 carbon atoms may preferably include an alkyl group having 1 to 4 carbon atoms.
  • One of the preferred compounds included in the carbonyl bisulfite addition compound represented by General Formula (II) is a compound wherein R2 is a hydrogen atom and R3 is an alkyl group having 1 to 4 carbon atoms, and another of them is a compound wherein R2 and R3 each are in alkyl group having 1 to 4 carbon atoms.
  • the alkyl group having 1 to 8 carbon atoms may preferably include an alkyl group having 1 or 2 carbon atoms.
  • n which represents an integer of 0 to 6, may preferably be an integer of 1 to 4.
  • One of the preferred compounds included in the carbonyl bis-sulfite addition compound represented by General Formula (III) is a compound wherein R4 and R5 each are a hydrogen atom and n is an integer of 1 to 4. Another of them is a compound wherein R4 and R5 each are an alkyl group having 1 or 2 carbon atoms and n is an integer of 1 to 4.
  • the polymer having a unit of a pyrrolidone nucleus in the molecular structure (hereinafter called "vinyl pyrrolidone polymer of this invention") will be described below.
  • the vinyl pyrrolidone polymer of this invention may comprise either a homopolymer of vinyl pyrrolidone alone or a copolymer thereof with additional copolymerizable monomer(s), but it is required to be water-soluble as a polymer.
  • the above additional monomer copolymerizable with vinyl pyrrolidone may typically include, for example, vinyl esters, acrylates, methacrylates, acrylic acids, methacrylic acid, styrene, etc.
  • the vinyl esters may include for example, vinyl acetate, vinyl propionate, vinyl butyrate.
  • the acrylic esters may include, for example, methyl ester, ethyl ester, butyl ester, 2-ethyl hexyl ester, etc.
  • the copolymerization ratio may preferably be selected in the range of 5 to 100 mol % based on the vinyl pyrrolidone.
  • the average molecular weight of the vinyl pyrrolidone polymer of this invention may preferably in the range of 500 to 800,000 more preferably 2,000 to 400,000
  • the determination of the average molecular weight of the polymer can be carried out according to a usual method, for example, according to the following:
  • Typical examples of the vinyl pyrrolidone polymer of this invention are shown below, but by no means limited to these.
  • the amount for the addition of the above vinyl pyrrolidone polymer of this invention may vary depending on the type of the polymer, the polymerization degree and so forth, but approximately may preferably in the range of 0.1 to 100 g, more preferably 0.2 to 50 g, still more preferably 0.3 to 20 g, and particularly preferably 0.5 to 10 g, per liter of the bleach-fixing solution of this invention.
  • the vinyl pyrrolidone polymer of this invention may be added in the bleach-fixing solution by, for example, adding it directly as it is in the form of powder, or may be added by dissolving it in a solvent such as water.
  • the above vinyl pyrrolidone polymer of this invention may be more preferably used for the purpose of better improving the shelf stability of the bleach-fixing solution, when a sulfite or a sulfite-releasable compound (for example, carbonyl bisulfite addition compounds disclosed in Japanese Patent Publication No. 38895/1979) is used in combination with it.
  • a sulfite or a sulfite-releasable compound for example, carbonyl bisulfite addition compounds disclosed in Japanese Patent Publication No. 38895/1979
  • the sulfite or the sulfite-releasable compound may preferably be contained in an amount of 1 x 10 ⁇ 3 mol or more per liter of the bleach-fixing solution of this invention. It may be used more preferably in an amount of not less than 0.02 mol and not more than 2.0 mols, still more preferably not less than 0.05 mol and not more than 1.3 mols, and most preferably not less than 0.09 mol and not more than 0.9 mol.
  • the above sulfite may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, etc.
  • the ferric complex salt having a ligand Comprising at least one of the compounds represented respectively by General Formulas (IV) to (VII) may be used also in the form of a free acid (hydrogen salt), or may also be used in the form of a counter salt including alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amine salts, for example, triethanolamine salt, etc.
  • alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amine salts, for example, triethanolamine salt, etc.
  • Preferably used are a potassium salt, a sodium salt and an ammonium salt.
  • the ferric complex salt having a ligand comprising the compound represented by Formulas I-1 and I-2 and ferric complex salt having a ligand comprising at least one of the compounds represented respectively by General Formulas (IV) to (VII) of this invention may preferably be in the range of 1 mol % to 95 mol %, more preferably 5 mol % to 90 mol %, and most preferably 10 mol % to 80 mol %, based on the total amount of these.
  • the ferric complex salt having a ligand comprising the compound represented by Formulas I-1 and I-2 and that having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII) of this invention can be used in any amount in the bleach-fixing solution of this invention so long as it is in an amount sufficient for obtaining the effect of this invention.
  • overly high concentration of the ferric complex salt may cause the deterioration of shelf stability of the bleach-fixing solution, and, on the other hand, overly low concentration of the ferric complex salt may cause the deterioration of desilvering performance and color reproduction performance.
  • the effect of this invention can be preferably exhibited when used in the range of 0.20 to 0.80 mol/lit.
  • ferric complex salt having a ligand comprising the compound represented by General Formula (I) and ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII) of this invention are used in combination, so that the shelf stability can be improved while maintaining the good desilvering and color reproduction performances inherent in the bleach-fixing solution of this invention.
  • the bleach-fixing solution of the present embodiment may preferably contain a sulfite and/or a sulfite-releasable compound in order to further improve the shelf stability.
  • a sulfite and/or a sulfite-releasable compound may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, formaldehyde bisulfite addition compounds, etc.
  • These compounds may be used in an amount of 0.001 mol to 2.0 mols, preferably 0.001 mol to 1.3 mols, most preferably 0.01 mol to 0.9 mol, per liter of the bleach-fixing solution of this invention.
  • the silver halide fixing agent to be contained in the bleach-fixing solution of this invention may include a compound capable of forming a water-soluble complex salt through the reaction with the silver halide used in usual fixing, typically including, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thioureas, thioethers, highly concentrated bromides, iodides, etc.
  • These fixing agents can be used in an amount of not less than 5 g/lit., preferably not less than 50 g/lit., or more preferably not less than 70 g/lit. and in the amount of the range they can be dissolved.
  • the bleach-fixing solution of this invention may contain various additives.
  • the additives are alkali halides or ammonium halides, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc.
  • the bleach-fixing solution of this invention may contain, alone or in combination of two or more of, pH buffering agents including boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium, carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It may further contain every kind of brightening agents, anti-foaming agents, surface active agents and mildewproofing agents.
  • pH buffering agents including boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium, carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It may further contain every kind of brightening agents, anti-foaming agents, surface active agents and mildewproofing agents.
  • organic chelating agents such as acetyl acetone, phosphonocarboxylic acid, pholyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopolycarboxylic acid, stabilizers such as nitroalcohol and nitrate, solubilizing agents such as alkanolamine, anti-stain agents such as organic amine, other additives, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide.
  • organic chelating agents such as acetyl acetone, phosphonocarboxylic acid, pholyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopolycarboxylic acid, stabilizers such as nitroalcohol and nitrate, solubilizing agents such as alkanolamine, anti-stain agents such as organic amine, other additives, and organic solvents
  • a bleach accelerator may preferably be used in the bleach-fixing solution of this invention.
  • the compounds described in Japanese Unexamined Patent Publication No. 19851/1987 and, to exhibit the effect of this invention with good results, the compounds represented respectively by General Formulas (A-I) to (A-Iv) shown below.
  • Q1 represents a group of atoms necessary for the formation of a nitrogen-containing heterocyclic ring (including those condensed with a saturated or unsaturated ring of 5 or 6 members); R1 represents a hydrogen atom, an alkali metal atom, or an alkyl group, provided that Q ⁇ have the same meaning as defined for Q1.
  • R2 and R3 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group.
  • R and R ⁇ each have the same meaning as R2 and R3, X ⁇ have the same meaning as X;
  • Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic group, an alkyl group or M represents a divalent metal atom;
  • R ⁇ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including those condensed with an unsaturated ring of 5 or 6 members) or an amino group; and
  • n1 to n6 and m1 to m5 each represent an integer of 1 to 6.
  • B represents an alkylene group having 1 to 6 carbon atoms
  • Y represents -N ⁇ or -CH ⁇
  • R4 and R5 each have the same meaning as R2 and R3, provided that R4 and R5 each may represent -B-SZ, or R2 and R3, and R4 and R5 each may combine to form a ring.
  • the compound represented by the above formula may include compounds of enol form and salts thereof.
  • R6 and R7 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group or -B1-S-Z1, provided that R6 and R7 may combine to form a ring.
  • Y1 represents ⁇ N- or ⁇ CH-;
  • B1 represents an alkylene group having 1 to 6 carbon atoms;
  • Z1 represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group, or and n7 represents an integer of 1 to 6.
  • Ar represents a divalent arylene group or a divalent organic group comprising the combination of an aryl group with an oxygen and/or an alkylene group;
  • B2 and B3 each represent a lower alkylene group;
  • R8, R9, R10 and R11 each represent a hydroxyl-substituted lower alkyl group;
  • x and y each represent 0 or 1.
  • G ⁇ represents an anion; and
  • z represents 0, 1 or 2.
  • the bleaching accelerator may preferably added in an amount ranging from about 0.01 to 100 g, more preferably 0.05 to 50 g, and particularly preferably 0.05 to 15 g, per liter of the bleach-fixing solution of this invention.
  • the bleach-fixing solution of this invention can preferably be also applied in the low replenishment processing.
  • iodide ions are accumulated in the bleach-fixing solution of this invention.
  • the bleach-fixing solution of this invention may cause substantially no lowering of the desilvering performance even by the accumulation of iodide ions, but also it may hardly cause surprisingly any density increase at a non-image portion (the so-called fogging) also when a light-sensitive material is dipped in the bleach-fixing solution without taking the step of rinsing such as washing with water after color developing processing.
  • the iodide ions may preferably be contained in the bleach-fixing solution in an amount of not less than 0.0005 mol/lit. More preferably, it may preferably contained in the bleached-fixing solution in an amount of not less than 0.001 mol/lit.
  • the processing time when using the bleach-fixing solution of this invention may be not longer than 3 minutes and 30 seconds without any problems, but may preferably be not longer than 3 minutes, more preferably in 2 minutes and 30 seconds.
  • the bleach-fixing solution of this invention may be used at a temperature of 80°C or less, desirably 55°C or less, and most preferably 45°C or less. It can also desirably be used while suppressing evaporation or the like.
  • the bleach-fixing solution of this invention can be applied in any light-sensitive silver halide photographic materials so long as they are light-sensitive photographic materials for photographing.
  • they may preferably be light-sensitive materials employing a highly sensitive silver iodobromide emulsion having a silver iodide content of not less than 0.5 mol %, more preferably not less than 1 mol % per liter.
  • the bleach-fixing solution of this invention may be used as a processing solution for bleach-fixing immediately after the color developing of the above light-sensitive silver halide photographic material for photographing, or, alternatively, used as a bleach-fixing solution after the color developing and after the processing such as washing, rinsing or stopping, or further may be used as a bleach-fixing solution after the pre-fixing was carried out after the color developing.
  • the processing by use of the bleach-fixing solution of this invention may be also followed by washing with water, and thereafter may be followed by stabilizing. It can be also applied in the multi-step counter current stabilizing technique in which the washing step is omitted or the amount of water for the washing is extremely reduced as disclosed in Japanese Unexamined Patent Publication No.
  • the silver halide emulsion for photographing that can be applied in this invention can be chemically sensitized according to a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.
  • An antifoggant, a stabilizer and so forth can be added in the silver halide emulsion.
  • a binder for the emulsion gelatin can be used advantageously.
  • Emulsion layers and other hydrophilic colloid layers can be hardened, and also can contain a plasticizer, a dispersion of a water-soluble or slightly soluble synthetic polymer (i.e., latex).
  • Couplers can be used in the emulsion layers of a light-sensitive color photographic material.
  • a compound capable of releasing photographically useful fragments such as development accelerators, bleaching accelerators, developers, silver halide solvents, color torning agents, hardening agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers through the coupling with a colored coupler, a competing coupler and an oxidized product of a developing agent.
  • the light-sensitive material can be provided with auxiliary layers such as a filter layer, a halation-preventive layer and an irradiation-preventive layer. These layers and/or emulsion layers may also contain a dye that may flow out from the light-sensitive material or may be bleached during development processing.
  • a matte agent, a lubricant, an image-stabilizing agent, a surface active agent, a color fog preventive agent, a development accelerator, a development retarder or a bleaching accelerator may be added in the light-sensitive material.
  • a support there can be used paper laminated with polyethylene or the like, a polyethylene terephthalate film, baryta paper, cellulose triacetate, etc.
  • a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 88 mg per 100 cm2.
  • the above emulsion layers comprised silver iodobromide having a silver iodide mol % of about 4.3 %, and there were used the following (Y-1) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the following (M-1) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the following (C-1) as a cyan coupler in the red-sensitive silver halide emulsion layer.
  • a sensitizing dye, a hardening agent and a spreading agent were added to the respective emulsion layers.
  • a light-sensitive silver halide color negative materials thus prepared was used as a sample. Using samples obtained by cutting the above sample into pieces and subjected to wedge exposure according a conventional method, processing was carried out according to the following steps with use of a processing apparatus for pieces (hereinafter called "hand developing").
  • the bleach-fixing solutions available after the above processing were stored with time for 1 week at 38°C under the open ratio of 10 cm2/lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution has an air contact area of 10 cm2 based on 1 liter of the bleach-fixing solution), and the above processing was again repeated with use of the bleach-fixing solutions available after storage.
  • the residual silver amount (mg/dm2) at the maximum density portion of the film samples was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photoelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
  • bleach-fixing solutions Nos. 1-1 and 2-1 used in the above Experiment 1 the types of the preservatives in the bleach-fixing solutions and the concentration for the addition were changed as shown in Table 3 below and the pH was adjusted to 6.0, to prepare bleach-fixing solutions Nos. 9-1 to 9-3 and Nos. 10-1 to 10-3.
  • the above bleach-fixing solutions the light-sensitive materials corresponding to those in Experiment 1 were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1.
  • the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 3.
  • the bleach-fixing solutions in which the organic acid which forms the comparative ferric complex salt and the preservative are used can delay the occurrence of precipitation to have good shelf stability even when stored with time, and also can achieve good desilvering performance and color reproduction performance of a dye image to be obtained by use of said solution.
  • the bleach-fixing solutions according to this invention in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing the bisulfite addition compound of this invention can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability.
  • the bleach-fixing solutions of this invention had no ammoniacal odor at all.
  • Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 1.
  • the bisulfite addition compound and exemplary compound No. II-4 in the bleach-fixing solutions were used in concentration of 0.25 mol/lit.
  • the types of the bleaching agents were selected as shown in Table 4, and the concentration of the bleaching agents was varied as shown in Table 4.
  • the pH of the bleach-fixing solutions was adjusted to 6.0
  • bleach-fixing solutions of this invention particularly those having the content of bleaching agent in the range of 0.02 mol/lit. to 1.30 mol.lit., preferably 0.10 to 1.20 mol/lit., and more preferably 0.20 to 0.8 mol/lit., are seen to be good bleach-fixing solutions that can have high desilvering and color reproduction performances and may not be sulfidized for a long period even if they are stored with time.
  • Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 1.
  • the preservative in bleach-fixing solution No. 1-1 used in Experiment 1 of Example 1 was replaced by exemplary compound No. II-6 (concentration: 0.2 mol/lit), the bleaching agent and the amount thereof were changed as shown in Table 5, and the concentration of KI in the bleach-fixing solutions was varied as shown in Table 5
  • the pH of the bleach-fixing solutions was adjusted to 6.0.
  • the samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as D R1 .
  • D R1 transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as D R2 .
  • the difference between D R1 and D R2 was determined ( ⁇ D R ) to evaluate the magenta stain.
  • Bleach-fixing solutions Nos. 1-11 to 1-16 and Nos. 2-21 to 2-26 were prepared in the same manner as in Experiment 1 of Example 1 except that, in the bleach-fixing solutions No. 1-1 and No. 2-1 prepared in Experiment 1 of Example 1, the pH was adjusted to 6.0 exemplary compound No. II-4 (concentration: 0.1 mol/lit.) was used as the preservative, and the bleaching accelerator was added as shown in Table 6 below.
  • the bleach-fixing solutions of this invention can maintain good effect in any of the desilvering performance, color reproduction performance and shelf stability even when stored.
  • the bleach-fixing solutions outside this invention which can be effective for any of the performances observed immediately after the solutions were prepared, result in further deterioration of the desilvering performance, color reproduction performance and shelf stability when they are stored.
  • a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 90 mg per 100 cm2.
  • the above emulsion layers comprised silver iodobromide having silver iodide mol % of about 4.1 %, and there were used the above (Y-l) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the above (M-l) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the above (C-l) as a cyan coupler in the red-sensitive silver halide emulsion layer.
  • conventional additives such as a sensitizing dye, a hardening agent and a spreading agent were added.
  • a light-sensitive silver halide color negative materials thus prepared was used as a sample.
  • the bleach-fixing solutions after the above processing were stored with time for 1 week at 38°C under the open ratio of 10 cm2/lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution have an air contact area of 10 cm2 based on 1 liter of the bleach-fixing solution), and the above processing was again repeated with use of the bleach-fixing solutions available after storage.
  • the residual silver amount (mg/dm2) at the maximum density portion of the film samples was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photoelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
  • Exemplary vinyl pyrrolidone polymer (2) in bleach-fixing solution No. 13 used in the above Experiment 1 was changed for a control, exemplary vinyl pyrrolidone polymers Nos. (1), (3) and (5), repsectively, and the pH was adjusted to 6.0, to prepare bleach-fixing solutions Nos. 16-1 to 16-5.
  • Light-sensitive materials corresponding to those in Experiment 1 and employing the above bleach-fixing solutions were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1.
  • the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 9.
  • the bleach-fixing solutions according to this invention in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing polyvinyl pyrrolidone of this invention can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability.
  • the bleach-fixing solutions of this invention had no ammoniacal odor at all.
  • Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 5.
  • the ammonium sulfite concentration in the bleach-fixing solutions was controlled to 12 g/lit.
  • the types of the bleaching agents were selected as shown in Table 10, and the concentration of the bleaching agents was varied as shown in Table 10.
  • the pH of the bleach-fixing solutions was adjusted to 6.0.
  • bleach-fixing solutions of this invention particularly those having the content of bleaching agent in the range of 0.02 mol/lit, to 1.30 mol/lit., preferably 0.10 to 1.20 mol/lit., and more preferably 0.20 to 0.8 mol/lit., are seen to be good bleach-fixing solutions that can have high desilvering and color reproduction performances and may not be sulfidized for a long period even if they are stored with a time.
  • Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 5.
  • the bleaching agent in bleach-fixing solution No. 11-1 used in Experiment 1 of Example 5 as the bleach-fixing solution and the amount thereof were changed as shown in Table 11, and the concentration of KI in the bleach-fixing solutions was varied as shown in Table 11.
  • the pH of the bleach-fixing solutions was adjusted to 6.0.
  • the samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as D R1 .
  • D R1 transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as D R2 .
  • the different between D R1 and D R2 was determined ( ⁇ D R ) to evaluate the magenta stain.
  • Bleach-fixing solutions Nos. 11-11 to 11-16 and Nos. 13-32 to 13-37 were prepared in the same manner as in Experiment 1 of Example 5 except that, in the bleach-fixing solutions Nos. 11-1 and No. 13-1 prepared in Experiment 1 of Example 5, the pH was adjusted to 6.0 and the bleaching accelerator was added as shown in Table 12 below.
  • the bleach-fixing solutions of this invention can maintain good effect in any of the desilvering performance, color reproduction performance and shelf stability even when stored.
  • the bleach-fixing solutions outside this invention which can be effective for any of the performances observed immediately after the solutions were prepared, result in further deterioration of the desilvering performance, color reproduction performance and shelf stability when they are stored.
  • a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 93 mg per 100 cm2.
  • the above emulsion layers comprised silver iodobromide having silver iodide mol % of about 5.0 %, and there were used the above (Y-l) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the above (M-l) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the above (C-l) as a cyan coupler in the red-sensitive silver halide emulsion layer.
  • a sensitizing dye, a hardening agent and a spreading agent were added to the respective emulsion layers.
  • a light-sensitive silver halide color negative materials thus prepared was used as a sample.
  • the bleach-fixing solutions available after the above processing were stored with time for 1 week at 38°C under the open ratio of 10 cm2/lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution have an air contact area of 10 cm2 based in 1 liter of the bleach-fixing solution, and the above processing was again repeated with use of the bleach-fixing solutions available after storage.
  • the residual silver amount (mg/dm2) at the maximum density portion of the film samples was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
  • the concentration and combination of the ferric complex salt comprising the organic acid in bleach-fixing solution No. 19 used in the above Experiment 1 was varied as shown in Table 15 below to prepare bleach-fixing solutions Nos. 22-1 to 24-10.
  • the light-sensitive materials corresponding to those in Experiment 1 were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1.
  • the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 15.
  • the bleach-fixing solutions according to this invention in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing a ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas of General Formulas (IV) to (VII) can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability.
  • the bleach-fixing solutions of this invention had no ammoniacal odor at all.
  • bleach-fixing solutions of this invention particularly those having the content of bleaching agent in the range of 0.02 mol/lit. to 1.30 mol/lit., preferably 0.10 to 1.20 mol/lit., and more preferably 0.20 to 0.8 mol/lit., are seen to be good bleach-fixing solutions that can have high desilvering and color reproduction performances and may not be sulfidized for a long period even if they are stored with time.
  • the samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as D R1 .
  • D R1 transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as D R2 .
  • the difference between D R1 and D R2 was determined ( ⁇ D R ) to evaluate the magenta stain. Results obtained are shown together in Table 19.
  • Bleach-fixing solutions Nos. 17-21 to 17-26 and Nos. 19-31 to 19-36 were prepared in the same manner as in Experiment 1 of Example 9 except that, in bleach-fixing solutions No. 17-1 and No. 19-1 prepared in Experiment 1 of Example 9, the pH was adjusted to 6.0 and the bleaching accelerator was added as shown in Table 20 below.
  • the bleach-fixing solutions of this invention can maintain good effect in any of the desilvering performance, color reproduction performance and shelf stability even when stored, even if the bleach-fixing time is shortened.
  • the bleach-fixing solutions outside this invention which can be effective for any of the performances observed immediately after the solutions were prepared, result in further deterioration of the desilvering performance, color reproduction performance and shelf stability when they are stored.

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Claims (16)

  1. Solution de blanchiment-fixage servant à traiter un matériau photographique photosensible à base d'halogénure d'argent pour photographie, dans laquelle ladite solution a un pH s'échelonnant de 3,0 à 6,8, contient un sel complexe ferrique renfermant un ligand comprenant un composé représenté par les formules I-1 et I-2 indiquées ci-dessous, et contient en outre au moins un des composés suivants :
    (i) au moins un des composés représentés respectivement par la formule générale (II) et la formule générale (III) indiquées ci-dessous;
    (ii) un polymère hydrosoluble renfermant, dans sa structure moléculaire, un motif de noyau pyrrolidone; et
    (iii) un sel complexe ferrique renfermant un ligand comprenant au moins un composé choisi parmi les composés représentés respectivement par les formules générales (IV) à (VII);
    Figure imgb0116
     formule générale (II) :
    Figure imgb0117
        dans laquelle R₂ et R₃ représentent un atome d'hydrogène ou un groupe alkyle comportant 1 à 8 atomes de carbone; et M représente un atome de métal alcalin ou un groupe ammonium,
    formule générale (III) :
    Figure imgb0118
        dans laquelle R₄ et R₅ représentent chacun un atome d'hydrogène ou un groupe alkyle comportant 1 à 8 atomes de carbone; M représente un atome de métal alcalin ou un groupe ammonium; et n représente un nombre entier de 0 à 6,
    formule générale (IV) :
    Figure imgb0119
        dans laquelle R₂ représente un groupe alkyle comportant 1 à 5 atomes de carbone, un groupe alkyle hydroxy-substitué comportant 1 à 5 atomes de carbone, ou (̵CH₂)n6COOH; et n₄, n₅ et n₆ représentent chacun le nombre entier 1 ou 2,
    formule générale (V) :
    Figure imgb0120
        dans laquelle n₇ et n₉ représentent chacun un nombre entier de 0 à 3, et n₈ représente un nombre entier de 1 à 3, à condition que la somme de n₇, n₈ et n₉ soit supérieure ou égale à 2,
    formule générale (VI) :
    Figure imgb0121
        dans laquelle R₃ et R₄ représentent chacun un atome d'hydrogène, un groupe alkyle hydroxy-substitué comportant 1 à 3 atomes de carbone, ou un groupe alkyle carboxy-substitué comportant 1 ou 2 atomes de carbone; R₅ et R₆ représentent chacun un atome d'hydrogène ou un groupe phényle hydroxy-substitué; R₇, R₈, R₉ et R₁₀ représentent chacun un atome d'hydrogène ou un groupe alkyle hydroxy-substitué comportant 1 à 3 atomes de carbone, à condition que R₇, R₈, R₉ et R₁₀ puissent chacun se combiner pour former un noyau possédant 5 à 8 atomes de carbone; n₁₀ et n₁₁ représentent chacun un nombre entier de 1 à 3; et n₁₂ représent un nombre entier de 0 à 4,
    formule générale (VII) :
    Figure imgb0122
        dans laquelle n₁₃ représente un nombre entier de 1 à 8.
  2. Solution de blanchiment-fixage selon la revendication 1, dans laquelle la solution possède un pH situé dans le domaine compris entre 4,0 et 6,7.
  3. Solution de blanchiment-fixage selon la revendication 2, dans laquelle la solution possède un pH situé dans le domaine compris entre 5,0 et 6,5.
  4. Solution de blanchiment-fixage selon la revendication 1, dans laquelle le sel complexe ferrique est contenu dans une proportion de 0,02 à 1,30 moles/litre.
  5. Solution de blanchiment-fixage selon la revendication 1, dans laquelle le sulfite est le sulfite d'ammonium, le sulfite de sodium, le sulfite de potassium, l'hydrogénosulfite de sodium, l'hydrogénosulfite de potassium ou le métabisulfite de sodium.
  6. Solution de blanchiment-fixage selon la revendication 1, dans laquelle le groupe alkyle représenté par R₂ et R₃ de formule générale (II) est un atome d'hydrogène ou un groupe alkyle comportant 1 à 4 atomes de carbone.
  7. Solution de blanchiment-fixage selon la revendication 1, dans laquelle le groupe alkyle représenté par R₄ et R₅ de formule générale (III) est un groupe alkyle comportant 1 à 2 atomes de carbone et n représente un nombre entier de 1 à 4.
  8. Solution de blanchiment-fixage selon la revendication 1, dans laquelle le composé choisi parmi les composés de formules générales (II) et (III) est contenu dans une proportion de 0,01 à 2 moles/litre.
  9. Solution de blanchiment-fixage selon la revendication 1, dans laquelle le polymère renfermant un motif de noyau pyrrolidone a une masse moléculaire moyenne de 500 à 800 000.
  10. Solution de blanchiment-fixage selon la revendication 1, dans laquelle le polymère renfermant un motif de noyau pyrrolidone est contenu dans une proportion de 0,1 à 100 g par litre de la solution de blanchiment-fixage.
  11. Solution de blanchiment-fixage selon la revendication 1, dans laquelle, lorsque la solution de blanchiment-fixage contient le polymère renfermant un motif de noyau pyrrolidone, la solution de blanchiment-fixage contient en outre un sulfite ou un composé libérant un sulfite, dans une proportion de 1 x 10⁻¹ mole/litre.
  12. Solution de blanchiment-fixage selon la revendication 1, dans laquelle le sel complexe ferrique renfermant un ligand comprenant au moins un composé choisi parmi les composés représentés respectivement par les formules générales (IV) à (VII) sont contenus dans une proportion de 1 à 95% en moles, rapportée à la quantité totale dudit sel complexe ferrique et du sel complexe ferrique renfermant un ligand comprenant un composé représenté par la formule générale (I).
  13. Solution de blanchiment-fixage selon la revendication 1, dans laquelle le sel complexe ferrique renfermant un ligand comprenant le composé représenté par la formule générale (I) et celui renfermant un ligand comprenant au moins un composé choisi parmi les composés représentés respectivement par les formules générales (IV) à (VII) sont contenus dans une proportion de 0,02 à 1,30 moles/litre au total.
  14. Solution de blanchiment-fixage selon la revendication 1, dans laquelle la solution de blanchiment-fixage contient aussi au moins un accélérateur de blanchiment choisi parmi les composés représentés par la formules générales (A-I) à (A-IV) indiquées ci-dessous :
    formule générale (A-I) :
    Figure imgb0123
     dans laquelle Q₁ représente un groupe d'atomes nécessaire à la formation d'un noyau hétérocyclique azoté (y compris ceux condensés avec un noyau saturé ou insaturé à 5 ou 6 chaînons); R₁ représente un atome d'hydrogène, un atome de métal alcalin,
    Figure imgb0124
     ou un groupe alkyle, à condition que Q' ait la même définition que Q₁ ci-dessus,
    formule générale (A-II) :
    Figure imgb0125
     dans laquelle R₂ et R₃ représentent chacun un atome d'hydrogène, un groupe alkyle comportant 1 à 6 atomes de carbone, un groupe hydroxyle, un groupe carboxyle, un groupe amino, un groupe acyle comportant 1 à 3 atomes de carbone, un groupe aryle ou un groupe alcényle; A représente un groupe de formule :
    Figure imgb0126
     -SZ
    ou un groupe résiduel hétérocyclique ayant la valence n₁ (y compris ceux condensés avec un noyau saturé ou insaturé à 5 ou 6 chaînons); et X représente =S, =O ou =NR''; formules dans lesquelles R et R' ont chacun la même signification que R₂ et R₃, X' a la même signification que X, Z représente un atome d'hydrogène, un atome de métal alcalin, un groupe ammonium, un groupe amino, un groupe hétérocyclique azoté, un groupe alkyle ou
    Figure imgb0127
     M représente un atome de métal divalent; R'' représente un atome d'hydrogène, un groupe alkyle comportant 1 à 6 atomes de carbone, un groupe cycloalkyle, un groupe aryle, un groupe résiduel hétérocyclique (y compris ceux condensés avec un noyau saturé ou insaturé à 5 ou 6 chaînons) ou un groupe amino; et n₁ à n₆ et m₁ à m₅ représentent chacun un nombre entier de 1 à 6; B représente un groupe alkylène comportant 1 à 6 atomes de carbone; Y représente -N〈 ou -CH〈, R₄ et R₅ ont chacun la même signification que R₂ et R₃, à condition que R₄ et R₅ puissent chacun représenter -B-SZ, ou R et R', R₂ et R₃, et que R₄ et R₅ puissent chacun se combiner pour former un noyau; le composé représenté par la formule générale (A-II) peut englober des composés de forme énol et leurs sels,
    formule générale (A-III) :
    Figure imgb0128
     dans laquelle R₆ et R₇ représentent chacun un atome d'hydrogène, un groupe alkyle comportant 1 à 6 atomes de carbone, un groupe hydroxyle, un groupe carboxyle, un groupe amino, un groupe acyle comportant 1 à 3 atomes de carbone, un groupe aryle, un groupe alcényle ou -B₁-S-Z₁, à condition que R₆ et R₇ puissent se combiner pour former un noyau, Y₁ représente 〉N- ou 〉CH-; B₁ représente un groupe alkylène comportant 1 à 6 atomes de carbone; Z₁ représente un atome d'hydrogène, un atome de métal alcalin, un groupe ammonium, un groupe amino, un groupe résiduel hétérocyclique azoté, ou
    Figure imgb0129
     et n₇ représente un nombre entier de 1 à 6,
    formule générale (IV) :
    Figure imgb0130
     dans laquelle Ar représente un groupe arylène divalent ou un groupe organique divalent comprenant la combinaison d'un groupe aryle avec un atome d'oxygène et/ou un groupe alkylène; B₂ et B₃ représentent chacun un groupe alkylène inférieur; R₈, R₉, R₁₀ et R₁₁ représentent chacun un groupe alkyle inférieur hydroxy-substitué; et x et y représentent chacun 0 ou 1; G' représente un anion; et z représente 0, 1 ou 2.
  15. Solution de blanchiment-fixage selon la revendication 14, dans laquelle l'accélérateur de blanchiment est contenu dans une proportion de 0,01 à 100 g par litre de solution de blanchiment-fixage.
  16. Procédé de traitement d'un matériau photographique photosensible à base d'halogénure d'argent pour photographie, qui comprend la réalisation du traitement avec une solution de blanchiment-fixage ayant un pH s'échelonnant de 3,0 à 6,8, contenant un sel complexe ferrique renfermant un ligand comprenant un composé représenté par les formules I-1 et I-2 indiquées ci-dessous, et contenant en outre au moins un des composés suivants :
    (i) au moins un des composés représentés respectivement par la formule générale (II) et la formule générale (III) indiquées ci-dessous;
    (ii) un polymère hydrosoluble renfermant, dans sa structure moléculaire, un motif de noyau pyrrolidone; et
    (iii) un sel complexe ferrique renfermant un ligand comprenant au moins un composé choisi parmi les composés représentés respectivement par les formules générales (IV) à (VII);
    Figure imgb0131
     formule générale (II) :
    Figure imgb0132
        dans laquelle R₂ et R₃ représentent un atome d'hydrogène ou un groupe alkyle comportant 1 à 8 atomes de carbone; et M représente un atome de métal alcalin ou un groupe ammonium,
    formule générale (III) :
    Figure imgb0133
        dans laquelle R₄ et R₅ représentent chacun un atome d'hydrogène ou un groupe alkyle comportant 1 à 8 atomes de carbone; M représente un atome de métal alcalin ou un groupe ammonium; et n représente un nombre entier de 0 à 6,
    formule générale (IV) :
    Figure imgb0134
        dans laquelle R₂ représente un groupe alkyle comportant 1 à 5 atomes de carbone, un groupe alkyle hydroxy-substitué comportant 1 à 5 atomes de carbone, ou (̵CH₂)n6COOH; et n₄, n₅ et n₆ représentent chacun le nombre entier 1 ou 2,
    formule générale (V) :
    Figure imgb0135
        dans laquelle n₇ et n₉ représentent chacun un nombre entier de 0 à 3, et n₈ représente un nombre entier de 1 à 3, à condition que la somme de n₇, n₈ et n₉ soit supérieure ou égale à 2,
    formule générale (VI) :
    Figure imgb0136
        dans laquelle R₃ et R₄ représentent chacun un atome d'hydrogène, un groupe alkyle hydroxy-substitué comportant 1 à 3 atomes de carbone, ou un groupe alkyle carboxy-substitué comportant 1 ou 2 atomes de carbone; R₅ et R₆ représentent chacun un atome d'hydrogène ou un groupe phényle hydroxy-substitué; R₇, R₈, R₉ et R₁₀ représentent chacun un atome d'hydrogène ou un groupe alkyle hydroxy-substitué comportant 1 à 3 atomes de carbone, à condition que R₇, R₈, R₉ et R₁₀ puissent chacun se combiner pour former un noyau possédant 5 à 8 atomes de carbone; n₁₀ et n₁₁ représentent chacun un nombre entier de 1 à 3; et n₁₂ représent un nombre entier de 0 à 4,
    formule générale (VII) :
    Figure imgb0137
        dans laquelle n₁₃ représente un nombre entier de 1 à 8.
EP19870308819 1986-10-08 1987-10-06 Solution de blanchiment-fixage ayant un bon rendement de traitement et méthode de traitement d'un matériau sensible à la lumière l'utilisant Expired - Lifetime EP0270217B1 (fr)

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JPS5814834A (ja) * 1981-07-21 1983-01-27 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の安定化処理方法
US4552834A (en) * 1984-08-06 1985-11-12 Eastman Kodak Company Enhanced bleaching of photographic elements containing silver halide and adsorbed dye
US4707434A (en) * 1984-08-20 1987-11-17 Konishiroku Photo Industry Co., Ltd. Color image forming method comprising processing with a bleach-fixing solution

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DE3786895D1 (de) 1993-09-09
EP0270217A2 (fr) 1988-06-08
EP0270217A3 (en) 1989-03-22

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