EP0283174A2 - Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent amélioré au point de vue de la restitution des couleurs - Google Patents

Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent amélioré au point de vue de la restitution des couleurs Download PDF

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Publication number
EP0283174A2
EP0283174A2 EP88301886A EP88301886A EP0283174A2 EP 0283174 A2 EP0283174 A2 EP 0283174A2 EP 88301886 A EP88301886 A EP 88301886A EP 88301886 A EP88301886 A EP 88301886A EP 0283174 A2 EP0283174 A2 EP 0283174A2
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EP
European Patent Office
Prior art keywords
acid
processing
silver halide
light
photographic material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP88301886A
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German (de)
English (en)
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EP0283174A3 (en
Inventor
Masao Ishikawa
Moeko Hagiwara
Shigeharu Koboshi
Naoki Takabayashi
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Konica Minolta Inc
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Konica Minolta Inc
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Priority claimed from JP62-94594A external-priority patent/JPH01558A/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0283174A2 publication Critical patent/EP0283174A2/fr
Publication of EP0283174A3 publication Critical patent/EP0283174A3/en
Withdrawn legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • This invention relates to a mehtod for processing a light-sensitive silver halide color photographic material and a processing solution to be used for the method, more particularly to a method for light-sensitive silver halide color photographic material which can be applied for a light-sensitive silver halide color photographic material of high sensitivity, high silver content to improve color restoration badness by supressing the leuco formation of cyan dye, and a processing solution to be used for said processing method.
  • color developing step exposed silver halide is reduced with a color developing agent to generate silver, and the color developing agent oxidized reacts with a color forming agent (coupler) to give a dye image.
  • color forming agent a color forming agent
  • desilverization through the action of an oxidizing agent (generally called bleaching agent), the silver generated in the color developing step is oxidized, and thereafter dissolved with a complexing agent of silver ions generally called fixing agent.
  • bleaching agent oxidizing agent
  • fixing agent a complexing agent of silver ions
  • the desilverization step as mentioned above may include the case in which it is carried out in two baths of a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, the case in which it is carried out in a bleach-fixing bath containing the bleaching agent and the fixing agent co-present therein, and further the case in which those baths are combined.
  • auxiliary steps for maintaining photographic, physical quality of the image, or for improving storability of the image, various auxiliary steps are included.
  • film hardening bath stopping bath, image stabilizing bath, water washing bath, etc.
  • bleaching agent in general, red prussiate, bichromate, ferric chloride, ferric complex of aminopoly­carboxylic acid, ferric complex of aminopolyphosphonic acid, persulfate, etc. have been known.
  • ferric complex of aminopolycarboxylic acid (typically ferric complex of ethylenediaminetetraaceic acid) has little problem in environmental pollution possesed by the above bleaching agents, and also no problem in storage, and therefore it is the bleaching agent practically applied most broadly at present time.
  • the bleaching power of ferric complex of amnopolycarboxylic acid cannot be necessarily said to be sufficient, and in the processing solution by use of this as the bleaching agent, although the desired object can be accomplished in the case of bleaching or bleach-fixing processing of a low sensitivity light-sensitive silver halide material composed mainly of silver chlorobromide emulsion, in the case of processing of a light-sensitive color photographic material of high sensitivity composed mainly of silver chlorobromoiodide or silver iodobromide emulsion, particularly, a color reversal light-sensitive material for photographing, a color negative light-­sensitive material for photographing by use of high silver content emulsion, there have been involved the drawbacks such that desilverization badness occurred, that color restoration badness frequently occurred, and that a long time is required for bleaching.
  • the method of lowering pH of the bleaching solution has the drawback that color restoration badness is liable to occur, although bleaching speed may be improved. Also, in the case of increasing the concentration of the bleaching agent, the same drawback as mentioned above is liable to occur, because it cannot be added in large amount due to the problem of precipitation of iron complex. Also, the method of adding a bleaching accelerator involves the drawback that it is liable to form a difficultly soluble silver complex with silver, and further that it is poorly soluble, and even if used, color restoration is not sufficient.
  • the present inventors have investigated variously on the above problems, and consequently found that the above coloration restoration badness is a problem generated commonly when a ferric complex of an aminopolycarboxylic acid and a ferric complex of an aminopolyphosphonic acid are used as the bleaching agent in the bleaching solution or the bleach-fixing solution in the desilverization step, which problem becomes particularly great as the result of the action of the ferric complex of aminopoly­carboxylic acid or amnopolyphosphonic acid as the oxidizing agent, whereby ferrous complex (complex ions) of aminopolycarboxylic acid or aminophosphonic acid formed by reduction of itself is accumulated in the processing solution or the light-sensitive material.
  • accumulation of the above ferrous complex ions depends on pH of the bleaching solution or bleach-fixing solution, and it has been found that formation of ferrous complex ions will occur more readily as the pH is higher. Further, it has been found that formation of ferrous complex ions, in addition to the phenomenon caused by decomposition of the ferric complex of aminopolycarboxy­lic acid or aminopolyphosphonic acid, when using a bleach-fixing solution, also occurs by reduction of the ferric complex ions with the sulfite contained as the preservative in the bleach-fixing solution, or alternatively the ferric complex itself is reduced by oxidizing silver by processing of a light-sensitive material of high silver content to become ferrous complex ions, whereby ferrous complex ions exist at high concentration in the coating of the light-sensitive photographic material during processing to covert cyan dye to leuco dye.
  • Color restoration badness due to such leuco formation of cyan dye has been particularly marked in a light-­sensitive color photographic material of high sensitivity, high silver content type with a thickness of 13 ⁇ m or more.
  • the ferrors complex ions in the coating of the light-sensitive photographic material formed in the bleaching reaction is remarkably inhibited in diffusion outside of the coating, whereby it may be considered that formation of leuco dye is increased to make greater the color restoration badness.
  • this method also oxidizes the sulfite which is a preservative, and therefore, although there is no danger when renewal ratio of the solution is relatively higher with relatively greater amount of processed amount as in the case of processing of color paper, etc., oxidation of the solution will proceed too far in the case of relatively smaller processing amount as in color nega, whereby the sulfite which is a preservative is oxidized and the thiosulfate decomposed to precipitate sulfur (sulfide) to form a precipitate, thus involving a danger of causing a vital inconvenience.
  • a first object of the present invention is to provide a method for processing a light-sensitive silver halide color photographic material by which leuco formation of cyan dye will occur with difficulty even in processing of a light-sensitive color photoraphic material, particularly a light-sensitive silver halide color photographic material having a high film thickness of the high sensitivity high silver amount type and a processing solution to be used for said processing method.
  • a second object of the present invention is to provide a method for developing a dye which can be practiced easily without problem in environmental pollution.
  • a method for processing a light-­sensitive silver halide color photographic material which comprises subjecting an exposed light-sensitive silver halide color photographic material to color developing processing and then applying at least desilverization processing, characterized in that the processing bath to be used in said desilverization processing contains a ferric complex of at least one compound selected from the compounds represented by the formula (I) and the formula (II) shown below, and after said desilverization processing, processing with an alkali bath having a pH of 8.0 or more and containing a buffering agent is performed, wherein L represents an alkylene group, a cycloalky­lene group, a phenylene group, -L8-O-L8-O-L8- or -L9-Z-L9-; where Z represents N-L10-R8, L1 to L13 each represent an alkylene group; R1 to R11 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (
  • the above objects can be accomplished further efficiently by (1) containing a chelating agent with a chelate stability constant with iron ions (logKMA) of 6 or more in the above alkali bath, (2) containing 1 x 10 ⁇ 3 mol or more of ferric complex of an aminopolycarboxylic acid per 1 liter of the bath in the above alkali bath, (3) containing an oxidizing agent in the above alkali bath.
  • a chelating agent with a chelate stability constant with iron ions (logKMA) of 6 or more in the above alkali bath containing 1 x 10 ⁇ 3 mol or more of ferric complex of an aminopolycarboxylic acid per 1 liter of the bath in the above alkali bath, (3) containing an oxidizing agent in the above alkali bath.
  • logKMA iron ions
  • ferric complex of the compound of the present invention after desilverization processing by use of a ferric complex of at least one compound selected from the compounds represented by the formula (I) and the formula (II) (hereinafter called ferric complex of the compound of the present invention) as the bleaching agent, by processing with an alkali bath with pH of 8.0 or higher, the ferrous complex ions of the compound of the present invention formed and accumulated by adsorption in the gelatin coating of the light-­sensitive silver halide color photographic maerial are desorbed, diffused quickly out of the above gelatin coating to make the atmosphere alkaline, whereby developing of cyan dye is remarkably accelerated to improve color restoration badness.
  • the desilverization processing applied after the color developing step can be any step, provided that the ferric complex of the compound of the preent invention is used as the bleaching agent, but a preferable representative desilverization step by application of the present invention is as exemplified below.
  • the ferric complex of the compound of the present invention is used as the bleaching agent.
  • the compound of the present inventon is at least one compound selected from the compounds represented by the formula (I) and the formula (II) shown below: wherein L represents an alkylene group, a cycloalkylene group, a phenylene group, -L8-O-L8-O-L8- or -L9-Z-L9-; where Z represents L1 to L13 each represent an alkylene group; R1 to R11 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt); with proviso that at least two of R1 to R4 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R5 to R7 is a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt).
  • the ferric complex of the compound of the present invention to be used in the processing solution having bleaching ability of the present invention is a complex of ferric ions (Fe3+) with a compound of the present invention.
  • aminopolycarboxylic acids are preferred, particularly preferably A-1 to A-3, A-8, A-13, A-14, A-17 to A-19, A-22, A-24 to A-27.
  • the ferric complex of the compound of the present invention to be used in the present invention may be used in the form of a complex, or a ferric ion complex may be formed in a solution by use of a ferric salt, for example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. together with the compound of the present invention.
  • a ferric salt for example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc.
  • a ferric salt for example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc.
  • ferric salt for example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc.
  • metal ion complex of metals other than iron such as cobalt, copper, nickel, etc. may be contained.
  • the above ferric complex of the compound of the present invention may be preferably in the range from 0.05 to 2 mol, more preferably from 0.1 to 1.0 mol, particularly preferably from 0.2 to 0.6 mol, per 1 liter of the solution having bleaching ability.
  • the bleaching solution when employing a bleaching solution, can contain, in addition to the ferric complex of the compound of the present invention as the above bleaching agent, any of known additives which can be used in conventional bleaching solution, including buffering agents comprising various salts of boric acid, borax, metaboric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc., halide compounds such as potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc.
  • buffering agents comprising various salts of boric acid, borax, metaboric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide,
  • the pH of the bleaching solution of the present invention may be preferably in the range from 4.0 to 8.0, more preferably from 5.0 to 6.5.
  • a bleach-fixing solution in the desilverization step of the present invention, in addition to the compounds which can be added in the above bleaching solution, there may be employed a compound capable of forming a water-­soluble complex through the reaction with a silver halide as used in conventional fixing processing as the silver halide fixing agent, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate and thiocyanate such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, thiourea, thioether, highly concentrated bromide, iodide, etc.
  • These fixing agents can be used in amounts within the range which can be solved of 5 g/liter or more, preferably 50 g/liter or more, more preferably 70 g/liter or more.
  • optical brighteners can be also contained. It is also possible to incorporate appropriately preservatives such as hydroxylamine, hydrazine, sulfite, metabisulfite, bisulfite adduct of aldehyde or ketone compound, etc.; organic chelating agents such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopoly­carboxylic acid, etc.
  • appropriately preservatives such as hydroxylamine, hydrazine, sulfite, metabisulfite, bisulfite adduct of aldehyde or ketone compound, etc.
  • organic chelating agents such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopoly­carbox
  • stabilizers such as nitro alcohol, nitrate, etc.; solubilizing agents such as alkanolamine, etc.; stain preventives such as organic amine, etc.; other additives; or organic solvents such as methanol, dimethylformamide, dimethyl sulfoxide, etc.
  • the pH of the bleach-fixing solution of the present invention may be preferably in the range from 3.0 to 9.8, more preferably from 5.6 to 8.5, particularly preferably from 6.0 to 8.3.
  • the fixing solution contains a fixing agent such as thiosulfate, thiocyanate, etc. as mentioned above for bleach-fixing solution as the silver halide fixing agent.
  • a fixing agent such as thiosulfate, thiocyanate, etc. as mentioned above for bleach-fixing solution as the silver halide fixing agent.
  • preservatives such as hydroxylamine, hydrazine, sulfite, metalbisulfite, bisulfite adducts of aldehyde or ketone compounds, etc.
  • further known additives conventionally used in fixing solution such as various pH buffering agents as mentioned for bleaching solution, halide compounds, etc. can be contained.
  • the pH of the fixing solution may be preferably in the range from 5.0 to 8.5, more preferably from 6.0 to 8.0.
  • a part or all of the bleaching bath overflow solution used which flow out from the bleaching bath as the result of addition of bleaching replenishing solution into the bleaching bath, and a part or all of the fixing bath overflow solution used which flow out from the fixing bath as the result of addition of fixing replenishing solution into the fixing bath, respectively can be introduced into the bleach-fixing bath.
  • overflow solutions from the both bleaching and fixing baths can be reutilized effectively, without giving bad influence on desilverization peformance, and also reduction in the total amount of replenishing solution is possible.
  • the light-sensitive silver halide color photographic material subjected to the above desilverization processing is processed in an alkali bath having pH of 8.0 or higher and containing a buffering agent.
  • processing in an alkali bath may be practiced continuously after the desilverization processing, as a matter of course, and also before the alkali bath processing, water washing, rinsing, and further the water washing substitutive stabilization which extremely reduces the amount of washing water, etc. may be applied.
  • the above alkali bath can be operated by maintaining its pH value at 8.0 or more, specifically pH 8.0 to 14.0, preferably 8.0 to 12.0, more preferably 8.5 to 12.0, most preferably 9.0 to 11.5
  • alkali processing solution having pH of 8.0 or higher and containing a buffering agent of the present invention (hereinafter called merely alkali bath of the present invention) is to be described.
  • any compound having stable buffering action in an aqueous solution of pH 8.0 or higher may be employed.
  • Specific examples may include inorganic salts such as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, boric acid, borax, sodium metaborate, sodium phosphate, potassium phosphate, sodium primary phosphate, etc.; amines such as ethanolamine, ethylenediamine, methylamine, trimethylamine, propylamine, etc.; amino acids such as hydroxyproline, leucine, glycine, alanine, aspartic acid, ⁇ -aminobutylacetic acid, etc.; various organic compounds such as sulfosalicylic acid, piperazine, guanidine, etc., and these can be used either alone or in combination.
  • the buffering agent to be used in the present invention in view of the cost, the color restoration badness improvement effect of the present invention, the pH maintenance effect during continuous use over a long term and further bad influence on other photographic performances, sodium carbonate, potassium carbonate, potassium bicarbonate, boric acid, borax, sodium metaborate, sodium phosphate, potassium phosphate, sodium primary phosphate, sulfosalicylic acid, etc. may be preferably used.
  • the buffering agetn may serve as an alkali agent, an alkali agent such as sodium hydroxide and potassium hydroxide may be added separately.
  • the amount of the above buffering agent used in the alkali bath of the present invention may differ greatly depending on the pH of the alkali bath, the kind of the buffering agent employed, and if it is used in too much amount, staining may be generated on the processed light-sensitive material, or if it is too small, the problem such as small buffering effect, etc. may ensue.
  • an amount ranging from 0.2 to 50 g per one liter of the alkali bath, more preferably 0.5 to 30 g may be employed.
  • the alkali bath processing in the present invention can be done without problem by use of one or multiple tanks, but preferably 1 to 2 tanks may be employed.
  • the alkali bath of the present invention may be used similarly as the manner in which other processing baths for photography are used, specifically with sufficient supply of a replenishing solution, but it is preferable to make the amount replenished minimum in view of environmental pollution, etc.
  • the amount of the processing solution carried over from the preceding bath into the alkali bath may differ depending on the kind of the light-sensitive material, the conveying speed and conveying sysem of the automatic developing machine, the squeezing system of the light-­sensitive material surface, etc., but in the present invention, the amount carried over may be preferably 25 ml/m2 to 150 ml/m2 with the unit area of the light-­sensitive material processed as the standard, and the replenished amount at which the effect of the present invention is more marked for the amount carried over may be in the range from 50 ml/m2 to 3.0 liter/m2, with the replenished amount with particularly remarkable effect being in the range from 100 ml/m2 to 950 ml/m2.
  • a chelating agent with a chelate stability constant with iron ions (logKMA) of 6 or more can be incorporated, whereby the effect of the present invention, specifically improvement of the color restoration badness can be effectively accomplished. Also, it has the effect of preventing effectively formation of hydroxides of soluble irons salts carried over into the alkali bath.
  • the chelate stability constant means the constant generally known by L.G. Sill, en. A.E. Martell, "Stability Constants of Metal-ion Complexes", The Chemical Society, London (1964), S. Chaberek, A.E. Martell, "Organic Sequestering Agents", Wiley (1959), etc.
  • chelating agents with chelate stability constant for iron ions of 6 or more there may be included organic carboxylic acid chelating agents, organic aminopolycarboxylic acids, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc.
  • the above iron ions mean both of ferric ions (Fe3+) and ferrous ions (Fe2+).
  • specific compound examples having chelate stability constant with iron ions of 6 or more may include the following compounds, which are not limitative of the present invention. That is, there are ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxy­ethylglycine, ethlenediaminediacetic acid, ethylene­diaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylimino­diacetic acid, diaminopropanolteraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediamine­tetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethyliden
  • the amount of the above chelating agent used in the present invention may be in the range from 0.01 to 50 g, preferably from 0.05 to 20 g, to give good results.
  • Particularly preferable compounds may include ferric sodium ethylene­diaminetetraacetate, ferric sodium diethylenetriamine­pentaacetate, ferric sodium propylenediaminetetraacetate, ferric sodium 1,2-diaminopropanetetraacetate, etc., and it may be added in an amount of 0.5 to 30 g, particularly preferably 2 to 15 g, per liter of the alkali bath.
  • an oxidizing agent for example, hydrogen peroxide, sodium percarbonate, sodium perborate, potassium persulfate, ammonium persulfate, sodium perchlorate, sodium hypochlorite, potassium hydrobromide, ammonium hydrobromide, sodium hydrobromide, etc.
  • the amount of the oxidizing agent may be preferably 0.01 g to 30 g/liter.
  • the above alkali bath processing may be the final step, or further water washing processing or processing with stabilizing processing substantially without use of washing water may be practiced.
  • the components in the stabilizing solution may comprise basically only water, but various compounds can be also added, and the compounds preferably used in the present invention may include formalin, surfactants, ammonium salts, chelating agent and metal salts.
  • an antifungal agent may be used, if necessary.
  • Useful antifungal agents may include hydroxybenzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, quaternary ammonium compounds, urea compounds, isooxazole compounds, propanolamine compounds, sulfamide derivatives, amino acid compounds, triazine compounds and benzotriazole compounds.
  • the light-sensitive silver halide color photographic material to be applied for the processing method of the present invention is not basically limited in its kind, but particularly effectively used in the present invention are high sensitivity photographic light-­sensitive materials having silver halide grains containing 0.5 mol% or more, preferably 3 to 10 mol% of silver iodide in at least one layer of the silver halide emulsion layers.
  • the sum of the dried film thicknesses of the all photographic constituent layers on the side having the silver halide emulsion layer on the support should be preferably 13 ⁇ m or more preferably 15 ⁇ m to 28 ⁇ m, more preferably 17 ⁇ m to 24 ⁇ m, and further a high silver content light-sensitive material in which the amount of the coated silver on the support may be 20 mg/100 cm2 or more, preferably 30 mg/100 cm2 to 80 mg/100 cm2, more preferably 40 mg/100 cm2 to 70 mg/100 cm2.
  • the silver halide emulsion of the light-sensitive silver halide color photographic material applicable for the present invention can be chemically sensitized in conventional manner, and optically sensitized to a desired wavelength region by use of a sensitizing dye.
  • silver halide emulsion antifoggant, stabilizer, etc.
  • binder for said emulsion gelatin may be advantageously used.
  • the emulsion or other hydrophilic colloid layers can be subjected to film hardening, and also plasticizers, dispersions of water-insoluble or difficultly soluble synsthetic polymers (latex) can be incorporated therein.
  • a coupler is used in the emulson layer of the light-sensitive material for color photography.
  • colored couplers having the effect of color correction, competitive couplers, and compounds releasing useful fragments for photography such as developing accelerator, bleaching accelerator, developer, silver halide solvent, color controller, film hardening agent, foggant, antifoggant, chemical sensitizer, spectral sensitizer and desensitizer through coupling with the oxidized product of a developing agent.
  • auxliary layers such as filter layer, halation preventive layer, irradiation preventive layer, etc. can be provided.
  • auxliary layers such as filter layer, halation preventive layer, irradiation preventive layer, etc.
  • a dye flowed out from the light-sensitive material or bleached during developing processing may be also contained.
  • matting agent lubricant, image stabilizer, surfactant, color antifoggant, developing accelerator, developing retarder or bleaching accelertor can be added.
  • papers lamianted with polyethylene, etc., polyethyleneterephthalate film, baryta paper, cellulose triacetate, etc. can be used.
  • This sample was cut into pieces, and by use of the piece to which wedge exposure was given in a conventional manner, processing was performed by use of a processing device for piece according to the following steps (hereinafter called hand developing processing).
  • the bleach-fixing solution for the color developing solution, the bleach-fixing solution, the alkali bath solution and the stabilizing solution, those shown below were used.
  • Ammonium ethylenediaminetetraacetate 2.0 g Ferric diammonium ethylenediamine­tetraacetate (complex of exemplary compound No. A-3) 150 g 70% Aqueous ammonium thiosulfate 250 ml Ammonium sulfite 10 g Mercaptobenztriazole 2.5 g Ammonia water 7.3 ml (made up to one liter with addition of water, and adjusted to pH as shown in Table 1 with acetic acid and ammonia water)
  • ferric diammonium ethylenediaminetetraacetate was reduced so as to form 40 g of ferrous diammonium ethyelenediaminetetraacetate, and again pH was adjusted as shown in Table 1.
  • Diethylenetriaminepentaacetic acid 2.0 g Buffering agent (kind is indicated in Table 3) 10 g Bleach-fixing solution in Example - 1 100 ml Made up to 1 l with addition of water, and adjusted to pH as shown in Table - 3.)
  • the alkali bath solution was stored in a glass beaker with an opening area of 15 cm2 (opening area per one liter of alkali bath) at 50 °C for 5 days and 10 days, respectively, and thereafter the same processing as above was conducted by use of the respective stored alkali bath solutions, and deterioration after storage with lapse of time of the alkali bath solution was observed.
  • Table 3 The results are also shown in Table 3.
  • Example - 1 The processing steps in Example - 1, namely the respective steps of 1. color developing, 2. bleach-fixing, 3. alkali bath and 4. stabilizing were replaced with the processing steps as shown in the following Table 4-1 and 4-2 to carry out experiments.
  • the bleach-fixing solution used was that of pH 6.5 in Example - 1, and the alkali bath used was similarly tht of pH 10.0.
  • Ammonium ethylenediaminetetraacetate 2.0 g Ferric diammonium ethylenediaminetetraacetate 100 g Ammonium bromide 130 g Mercaptobenztriazole 1.5 g Ammonia water 5.0 ml (made up to one liter with addition of water, and adjusted to pH 6.0 with ammonia wate or acetic acid)
  • Example - 1 Except for the above processing steps, the same experiments as in Example - 1 were conducted and color restoration ratio and desilverizability were examined. The results are shown in Table 5.
  • Example - 1 pH of the bleach-fixing solution was changed to 6.5, pH of the alkali bath to 10.0, and further the ferric complex of the aminopoly­carboxylic aicd or aminopolyphosphonic acid shown in the following Table 6 was used in place of ferric diammonium ethylenediaminetetraacetate as the aminopolycarboxylic acid in the bleach-fixing solution at the concentration shown in Table 6, and experiments were conducted following otherwise the same procedure as in Example - 1. The results are also shown in Table 6.
  • Example - 1 the light-sensitive materials shown in the following Table 8 with various film thicknesses of the light-sensitive materials to be processed (film thickness was changed by varying only gelatin amount) and coated silver amounts, and the experiments were conducted following otherwise the same procedure as in the experiment No. 1 - 24. However, experiments were also conducted for comparison using no alkali bath. The results are also shown in Table 8.
  • the effect is not greatly affected by the film thickness of the light-­sensitive material and the coated silver amount, and good effect of color restoration badness improvement can be obtained at a film thickness of 13 ⁇ m or more (color restoration badness is small at a film thickness of 13 ⁇ m or less). It can be appreciated that particularly great improvement effect can be obtained in the case of a film thickness of 16 ⁇ m or more, while greater improvement effect can be obtained as the coated silver amount is more.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP88301886A 1987-03-04 1988-03-03 Method for processing lightsensitive silver halide color photographic material improved in color restoration Withdrawn EP0283174A3 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP4946987 1987-03-04
JP49469/87 1987-03-04
JP62-94594A JPH01558A (ja) 1987-03-04 1987-04-17 復色不良が改良されるハロゲン化銀カラ−写真感光材料用処理液および該処理液を用いた処理方法
JP94594/87 1987-04-17

Publications (2)

Publication Number Publication Date
EP0283174A2 true EP0283174A2 (fr) 1988-09-21
EP0283174A3 EP0283174A3 (en) 1989-09-27

Family

ID=26389868

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88301886A Withdrawn EP0283174A3 (en) 1987-03-04 1988-03-03 Method for processing lightsensitive silver halide color photographic material improved in color restoration

Country Status (2)

Country Link
EP (1) EP0283174A3 (fr)
AU (1) AU611670B2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482915A1 (fr) * 1990-10-23 1992-04-29 Konica Corporation Procédé de traitement des matériaux photographiques à l'halogénure d'argent pour la photographie en couleur

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2622839B2 (ja) * 1987-05-25 1997-06-25 コニカ株式会社 漂白用パーツ組成物
EP0329051B1 (fr) * 1988-02-13 1995-08-02 Fuji Photo Film Co., Ltd. Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4601975A (en) * 1983-12-23 1986-07-22 Konishiroku Photo Industry Co., Ltd. Method for processing light-sensitive silver halide color photographic material
US4707434A (en) * 1984-08-20 1987-11-17 Konishiroku Photo Industry Co., Ltd. Color image forming method comprising processing with a bleach-fixing solution
AU599904B2 (en) * 1985-03-29 1990-08-02 Konishiroku Photo Industry Co., Ltd. Method of processing light-sensitive silver halide color photographic material
AU590557B2 (en) * 1985-04-25 1989-11-09 Konishiroku Photo Industry Co., Ltd. Processing method of light-sensitive silver halide color photographic material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482915A1 (fr) * 1990-10-23 1992-04-29 Konica Corporation Procédé de traitement des matériaux photographiques à l'halogénure d'argent pour la photographie en couleur

Also Published As

Publication number Publication date
JPS64558A (en) 1989-01-05
EP0283174A3 (en) 1989-09-27
AU1255688A (en) 1988-09-08
AU611670B2 (en) 1991-06-20

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