EP0514457B1 - Solution de blanchiment photographique et son utilisation pour le traitement de photographies en couleurs - Google Patents

Solution de blanchiment photographique et son utilisation pour le traitement de photographies en couleurs Download PDF

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Publication number
EP0514457B1
EP0514457B1 EP91904196A EP91904196A EP0514457B1 EP 0514457 B1 EP0514457 B1 EP 0514457B1 EP 91904196 A EP91904196 A EP 91904196A EP 91904196 A EP91904196 A EP 91904196A EP 0514457 B1 EP0514457 B1 EP 0514457B1
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EP
European Patent Office
Prior art keywords
acid
bleaching solution
bleaching
photographic
potassium
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.)
Expired - Lifetime
Application number
EP91904196A
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German (de)
English (en)
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EP0514457A1 (fr
Inventor
David G. Foster
Keith H. Stephen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to AT91904196T priority Critical patent/ATE95323T1/de
Publication of EP0514457A1 publication Critical patent/EP0514457A1/fr
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Publication of EP0514457B1 publication Critical patent/EP0514457B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents

Definitions

  • This invention relates in general to photography and in particular to a novel bleaching solution for the bleaching of photographic elements. More specifically, this invention relates to an environmentally advantageous photographic bleaching solution which is useful in the color processing of photographic elements.
  • a suitable oxidizing agent commonly referred to as a bleaching agent
  • a fixing agent dissolving the silver halide so formed in a silver halide solvent
  • the bleaching agent and fixing agent can be combined in a bleach-fixing solution and the silver removed in one step by use of such solution.
  • bleaching agents are known for use in photographic processing, for example, ferricyanide bleaching agents, persulfate bleaching agents, dichromate bleaching agents, permanganate bleaching agents, ferric chloride, and water-soluble quinones.
  • ferric complex of an aminopolycarboxylic acid as a bleaching agent in photographic color processing. Such complexes are used in both bleaching compositions and bleach-fixing compositions.
  • a very large number of different compounds of the aminopolycarboxylic acid class are disclosed in the prior art as being useful photographic bleaching agents.
  • the usual commercial practice is to use an ammonium or alkali metal salt of a ferric complex of ethylenediamine-tetraacetic acid (EDTA) or of a ferric complex of propylenediaminetetraacetic acid (PDTA).
  • EDTA ethylenediamine-tetraacetic acid
  • PDTA propylenediaminetetraacetic acid
  • patent 4,268,618 which describes a photographic bleaching bath containing an organic acid iron (III) complex salt, an alkali metal or ammonium salt of bromic acid, a water-soluble halogenide, a compound of the formula X-(R')- n COOM or the formula and a compound of the formula and British patent 1,319,721 which describes a photographic bleaching bath which contains a complex ferric salt and an aliphatic dicarboxylic acid.
  • ferric complexes of an aminopolycarboxylic acid can be employed in photographic bleaching solutions in the form of ammonium or alkali metal salts such as sodium or potassium salts.
  • ammonium salts is undesirable from an environmental standpoint and the use of sodium salts provides an undesirably sluggish bleaching action.
  • photographic bleaching solutions which comprise a potassium salt of a ferric complex of an aminopolycarboxylic acid as the bleaching agent, since these solutions are both fast-acting and environmentally acceptable.
  • bleaching solution containing a potassium salt of a ferric complex of an aminopolycarboxylic acid.
  • a significant and highly undesirable increase in blue D min results from bleach induced dye formation.
  • bleach induced dye formation refers to reaction between the coupler and oxidized developing agent that takes place in the bleaching solution and leads to the generation of image dye and thus to stain formation.
  • an environmentally advantageous photographic bleaching solution for use in the color processing of photographic elements is an aqueous acidic solution which is substantially free of fixing agents, bromates and ammonium salts and comprises (1) as a bleaching agent, a potassium salt of a ferric complex of an aminpolycarboxylic acid, (2) as an agent which functions to convert silver to silver halide, a potassium halide, and (3) a sufficient amount of a water-soluble aliphatic carboxylic acid to inhibit bleach induced dye formation.
  • the present invention is based, in major part, on the unexpected discovery that water-soluble aliphatic carboxylic acids, when used in sufficient concentration, will effectively eliminate the problem of bleach induced dye formation and thus avoid unwanted staining that occurs in photographic processing. While water-soluble aliphatic carboyxlic acids have been commonly used in photographic bleach solutions heretofore, they have usually been used to adjust pH and use for this purpose does not require the high concentration of acid that is optimally used to effectively eliminate the problem of bleach induced dye formation.
  • the essential components of the novel bleaching solution of this invention are a potassium salt of a ferric complex of an aminopolycarboxylic acid, a potassium halide, and a water-soluble aliphatic carboxylic acid.
  • the potassium salt of the ferric complex of an aminopolycarboxylic acid can be employed in any effective amount, with useful amounts typically being at least 0.1 moles per liter of bleaching solution, and preferably at least 0.5 moles per liter.
  • useful ferric complexes include complexes of: nitrilotriacetic acid, ethylenediamine tetraacetic acid, propylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, ortho-diamine cyclohexane tetraacetic acid, ethylene glycol bis(aminoethyl ether) tetraacetic acid, diaminopropanol tetraacetic acid, N-(2-hydroxyethyl)ethylenediamine triacetic acid, ethyliminodipropionic acid, iminodiacetic acid, methyliminodiacetic acid, ethyliminodiacetic acid, and the like.
  • a mixture of bleaching agents is preferred over the use of individual bleaching agents, since a mixture can provide a desired level of bleaching power intermediate that of the individual bleaching agents of which it is composed.
  • particularly useful mixtures include a mixture of the ferric complex of ethylenediaminetetraacetic acid and the ferric complex of propylenediaminetetraacetic acid, a mixture of the ferric complex of ethylenediaminetetraacetic acid and the ferric complex of methyliminodiacetic acid, and a mixture of the ferric complex of iminodiacetic acid and the ferric complex of methyliminodiacetic acid.
  • Potassium halides useful in the bleaching solutions of this invention include potassium chloride and potassium bromide.
  • the potassium halide can be employed in any effective amount, with useful amounts typically being at least 0.1 moles per liter, and preferably at least 0.25 moles per liter.
  • Water-soluble aliphatic carboxylic acids useful in the bleaching solutions of this invention include all of the many members of this well-known class of acids, such as, for example: acetic acid citric acid propionic acid hydroxyacetic acid butyric acid malonic acid succinic acid, and the like.
  • the water-soluble aliphatic carboxylic acid is employed in an amount of at least 0.7 moles per liter of bleaching solution, and most preferably at least 0.9 moles per liter.
  • the bleaching solutions of this invention are aqueous acidic solutions preferably having a pH in the range of from about 4 to about 6.8 and most preferably in the range of from 4.5 to 5.5.
  • the bleaching solutions of this invention can contain other addenda known in the art to be useful in bleaching compositions, such as sequestering agents, sulfites, and non-chelated salts of aminopolycarboxylic acids.
  • compositions of this invention are bleaching solutions and not bleach-fixing solutions, and thus they are substantially free of fixing agents.
  • bleaching solution as used herein is intended to exclude bleach-fixing solutions.
  • the bleaching solutions of this invention are also substantially free of bromates such as are employed in U.S. patents 4,242,442 and 4,268,618.
  • a particularly useful sequestering agent which can be included in the bleaching solution of this invention to avoid the unwanted precipitation of salts is 1,3-diamino-2-propanol tetraacetic acid.
  • the bleaching solutions of this invention are especially useful in the color processing of photographic elements, including photographic films utilized in negative-positive processes or in color reversal processes.
  • Useful processes include a three-step process -- comprising the steps of color developing, bleaching and fixing -- and a six step process -- in which the film is processed in a first developer, a reversal bath, a color developer, a conditioning bath, a bleach bath and a fixing bath.
  • the processing is typically carried out using a color developing solution which contains a primary aromatic amino color developing agent.
  • These color developing agents are well known and widely used in a variety of color photographic processes. They include aminophenols and p-phenylenediamines.
  • aminophenol developing agents examples include o-aminophenol, p-aminophenol, 5-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene, and the like.
  • Particularly useful primary aromatic amino color developing agents are the p-phenylenediamines and especially the N-N-dialkyl-p-phenylenediamines in which the alkyl groups or the aromatic nucleus can be substituted or unsubstituted.
  • Examples of useful p-phenylenediamine color developing agents include: N-N-diethyl-p-phenylenediaminemonohydrochloride, 4-N,N-diethyl-2-methylphenylenediamine monohydrochloride, 4-(N-ethyl-N-2-methanesulfonylaminoethyl)-2-methylphenylenediamine sesquisulfate monohydrate, 4-(N-ethyl-N-2-hydroxyethyl)-2-methylphenylenediamine sulfate, 4-N,N-diethyl-2,2'-methanesulfonylaminoethylphenylenediamine hydrochloride, and the like.
  • color developing solutions typically contain a variety of other agents such as alkalies to control pH, bromides, iodides, benzyl alcohol, anti-oxidants, anti-foggants, solubilizing agents, brightening agents, and so forth.
  • Photographic color developing compositions are employed in the form of aqueous alkaline working solutions having a pH of above 7 and most typically in the range of from about 9 to about 13. To provide the necessary pH, they contain one or more of the well known and widely used pH buffering agents, such as the alkali metal carbonates or phosphates. Potassium carbonate is especially useful as a pH buffering agent.
  • the fixing bath converts all silver halide into soluble silver complexes which diffuse out of the emulsion layers.
  • Fixing bath retained within the layers of the photographic element is removed in a subsequent water washing step.
  • Thiosulfates including ammonium thiosulfate and alkali metal thiosulfates such as sodium thiosulfate and potassium thiosulfate, are particularly useful as fixing agents.
  • Other components of the fixing bath include preservatives and sequestering agents.
  • a commercially important process intended for use with color negative photographic elements which contain the couplers in the silver halide emulsion layers, or in layers contiguous thereto, utilizes, in order, the following processing baths: color developer, wash (optional), bleach, fix, wash and stabilizer.
  • processing baths color developer, wash (optional), bleach, fix, wash and stabilizer.
  • a commercially important process intended for use with color reversal photographic elements which contain the couplers in the silver halide emulsion layers, or in layers contiguous thereto utilizes, in order, the following processing baths: first developer, wash, reversal bath, color developer, bleach, fix, wash and stabilizer.
  • the first developer reduces the exposed silver halide to metallic silver;
  • the reversal bath nucleates the silver halide that remains after first development, the color developer converts the nucleated silver halide to metallic silver and forms the dye images,
  • the bleach converts all metallic silver to silver halide, the fix converts the silver halide into soluble silver complexes that are washed from the element, and the stabilizing bath improves image dye stability.
  • such a process is carried out using the novel bleaching solution described hereinabove.
  • novel bleaching solutions of the present invention can be utilized with any of a wide variety of photographic elements.
  • the photosensitive layers present in the photographic elements processed with the novel bleaching solutions of this invention can contain any of the conventional silver halides as the photosensitive material, for example, silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chloro-bromoiodide, and mixtures thereof.
  • These layers can contain conventional addenda and be coated on any of the photographic supports, such as, for example, cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polycarbonate film, polystyrene film, polyethylene terephthalate film, polymer-coated paper, and the like.
  • ferric complex of the aminopolycarboxylic acid it is generally convenient for the ferric complex of the aminopolycarboxylic acid to be formed in situ in the bleaching solution by reaction of a ferric salt, such as ferric sulfate or ferric nitrate, with an aminopolycarboxylic acid or mixture of aminopolycarboxylic acids.
  • a ferric salt such as ferric sulfate or ferric nitrate
  • potassium hydroxide is advantageously incorporated in the bleaching solution for the purpose of providing the desired potassium ions and maintaining the pH within the desired range.
  • the bleaching solution of this invention is free, or at least substantially free of ammonium salts, as the presence of ammonium ions in a photographic bleaching solution is environmentally disadvantageous.
  • the bleaching solution of this invention have a total iron content of less than 10 grams per liter. For environmental reasons, it is preferred to keep the total iron content of photographic bleaching solutions as low as possible.
  • Couplers having a low pKa tend to be completely ionized in water.
  • the activity of a coupler refers to its ability to form dye by reaction with oxidized developing agent. High activity couplers tend to produce very high D max values and are especially beneficial for this reason.
  • An aqueous acidic photographic bleaching solution was prepared in accordance with the following formulation:
  • the above-described bleaching solution was employed in the processing of a photographic negative-positive color film utilizing a conventional process comprising the steps of color developing, bleaching, fixing, washing and stabilizing.
  • the film contained a low pKa, high-activity yellow-dye-forming coupler of the formula: Contact with the bleaching solution was carried out at 33°C for 3 minutes.
  • the content of acetic acid in the bleaching solution was varied as indicated below, while all other factors were held constant, and for each sample of bleaching solution tested the blue D min was measured. Adjustment of pH of the bleach solution, necessitated by change in the acetic acid content, was accomplished by addition of sulfuric acid or potassium carbonate to give in each case a pH of 4.75.
  • the blue D min declines sharply as the acetic acid concentration is increased to a level of about 0.7 moles per liter of bleaching solution and then levels off. This results from the fact that, over the effective range, increasing the acetic acid level causes a corresponding decrease in bleach induced dye formation.
  • amounts of acetic acid of at least 0.7 moles per liter are preferred and, to provide added assurance of maintaining optimum conditions, amounts of at least 0.9 moles per liter are particularly preferred.
  • water-soluble aliphatic carboxylic acids, such as acetic acid to provide this improved result is clearly unexpected on the basis of what was known heretofore in the prior art.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

Une solution de blanchiment photographique avantageuse du point de vue de l'environnement et utile pour le traitement des couleurs d'éléments photographiques comprend: (1) comme agent de blanchiment un sel de potassium ou un complexe ferrique d'un acide aminopolycarboxylique; (2) comme agent de conversion de l'argent en halogénure d'argent un halogénure de potassium; et (3) comme inhibiteur de la formation de couleurs induite par le blanchiment un acide carboxylique aliphatique soluble dans l'eau. La solution de blanchiment est particulièrement utile pour traiter des éléments photographiques qui contiennent un copulant formateur de couleur jaune d'activité intense et de faible pKa, étant donné qu'il empêche de manière efficace l'augmentation indésirable de Dmin bleu qui peut se produire dans ces éléments par formation de couleur induite par le blanchiment.

Claims (7)

  1. Solution de blanchiment photographique acide aqueuse qui comprend un sel de potassium d'un complexe ferrique d'un acide aminopolycarboxylique, un halogénure de potassium et un acide carboxylique aliphatique soluble dans l'eau, et qui ne comprend pratiquement pas d'agents fixant, de bromate et de sels d'ammonium, la solution étant caractérisée en ce que la quantité d'acide carboxylique aliphatique soluble dans l'eau contenue dans la solution de blanchiment est d'au moins 0,7 mole par litre.
  2. Solution de blanchiment selon la revendication 1 dans laquelle le pH est compris entre 4 et 6,8, le sel de potassium d'un complexe ferrique d'un acide aminocarboxylique est présent en quantité d'au moins 0,1 mole par litre de solution de blanchiment, et l'halogénure de potassium est présent en quantité d'au moins 0,25 mole par litre de solution de blanchiment.
  3. Solution de blanchiment selon la revendication 1 ou 2 dans laquelle le complexe ferrique est un complexe ferrique d'acide éthylènediaminetétraacétique.
  4. Solution de blanchiment selon la revendication 1 ou 2 dans laquelle le complexe ferrique est un complexe ferrique d'acide propylènediaminetétraacétique.
  5. Solution de blanchiment selon la revendication 1 ou 2 dans laquelle la solution comprend des complexes ferriques des acides éthylènediaminetétraacétique et propylènediaminetétraacétique.
  6. Solution de blanchiment selon l'une quelconque des revendications précédentes 1 à 5 dans laquelle l'halogénure de potassium est le bromure de potassium.
  7. Solution de blanchiment selon l'une quelconque des revendications précédentes 1 à 6 dans laquelle l'acide carboxylique aliphatique soluble dans l'eau est l'acide acétique.
EP91904196A 1990-01-24 1991-01-18 Solution de blanchiment photographique et son utilisation pour le traitement de photographies en couleurs Expired - Lifetime EP0514457B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT91904196T ATE95323T1 (de) 1990-01-24 1991-01-18 Photographische bleichloesung und farbphotographische verarbeitung unter verwendung derselben.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US469102 1983-02-23
US46910290A 1990-01-24 1990-01-24

Publications (2)

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EP0514457A1 EP0514457A1 (fr) 1992-11-25
EP0514457B1 true EP0514457B1 (fr) 1993-09-29

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EP91904196A Expired - Lifetime EP0514457B1 (fr) 1990-01-24 1991-01-18 Solution de blanchiment photographique et son utilisation pour le traitement de photographies en couleurs

Country Status (5)

Country Link
EP (1) EP0514457B1 (fr)
JP (1) JPH0693108B2 (fr)
CA (1) CA2073765A1 (fr)
DE (1) DE69100446T2 (fr)
WO (1) WO1991011753A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04310950A (ja) * 1991-04-09 1992-11-02 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
EP0545464B1 (fr) * 1991-11-25 1998-10-14 Eastman Kodak Company Compositions améliorées de blanchiment photographique et procédés de traitement photographiques

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2021518A1 (de) * 1970-05-02 1971-12-02 Agfa Gevaert Ag Photographische Bleich- und Bleichfixierbaeder
JPS5023824A (fr) * 1973-07-02 1975-03-14
JPS5644424B2 (fr) * 1973-07-13 1981-10-19
JPS5555337A (en) * 1978-10-19 1980-04-23 Fuji Photo Film Co Ltd Processing method for silver halide color photographic material
JPS569744A (en) * 1979-07-05 1981-01-31 Fuji Photo Film Co Ltd Bleaching composition for photographic processing
JPS58116538A (ja) * 1981-12-29 1983-07-11 Fuji Photo Film Co Ltd カラ−写真処理方法

Also Published As

Publication number Publication date
EP0514457A1 (fr) 1992-11-25
DE69100446T2 (de) 1994-05-11
CA2073765A1 (fr) 1991-07-25
DE69100446D1 (de) 1993-11-04
JPH0693108B2 (ja) 1994-11-16
WO1991011753A1 (fr) 1991-08-08
JPH05503791A (ja) 1993-06-17

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