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WO1992007300A1 - Solution de blanchiment photographique - Google Patents

Solution de blanchiment photographique Download PDF

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Publication number
WO1992007300A1
WO1992007300A1 PCT/EP1991/001973 EP9101973W WO9207300A1 WO 1992007300 A1 WO1992007300 A1 WO 1992007300A1 EP 9101973 W EP9101973 W EP 9101973W WO 9207300 A1 WO9207300 A1 WO 9207300A1
Authority
WO
WIPO (PCT)
Prior art keywords
bleach
hydrogen peroxide
photographic
silver
bleach solution
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.)
Ceased
Application number
PCT/EP1991/001973
Other languages
English (en)
Inventor
John Richard Fyson
Peter Douglas Marsden
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.)
Kodak Ltd
Eastman Kodak Co
Original Assignee
Kodak Ltd
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kodak Ltd, Eastman Kodak Co filed Critical Kodak Ltd
Priority to EP91918048A priority Critical patent/EP0506909B1/fr
Priority to DE69127189T priority patent/DE69127189T2/de
Priority to JP3517045A priority patent/JP3045311B2/ja
Publication of WO1992007300A1 publication Critical patent/WO1992007300A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/40—Chemically transforming developed images
    • G03C5/44—Bleaching; Bleach-fixing

Definitions

  • This invention relates to photographic bleach compositions for use in photographic colour processing.
  • peroxy compounds eg hydrogen peroxide or a compound capable of releasing hydrogen peroxide
  • bleach solutions consisting of some 50 ml/1 30% hydrogen peroxide solution and 30 ml/1 concentrated acetic acid. Such solutions however do not bleach the entire amount of silver present.
  • US specification 4 454 224 describes an improvement on the above in which the bleach solution further contains a polyacetic acid and is alkaline having a pH of 7 or more.
  • Other peroxide bleach solutions must contain an organic metal complex salt, eg US specification 4 301 236, while others must employ a bleach accelerator eg, Japanese specifications 611250647A and 611261739A. In spite of all these suggestions no such solution has ever been used commercially.
  • Another objective of the present invention is to produce a bleach solution whose effluent is much more environmentally acceptable than currently used bleaches which contain ferricyanides or EDTA-type metal complexing agents and their complexes with, say, iron.
  • a photographic bleach solution comprising hydrogen peroxide, or a compound which releases hydrogen peroxide, and halide ions and which has a pH in the range of 5 to 11 , preferably 5 to 10.
  • the halide ions are preferably chloride.
  • the time of treatment in the present bleach solution is preferably more than 20 seconds, especially in the range 20 to 40 seconds. Thus the preferred time of treatment in the bleach bath is in the range 20 to 40 seconds.
  • the bleach solution has an alkali or buffer to maintain the pH within the stated range.
  • suitable materials include an alkali metal carbonate or a carbonate/hydrogen carbonate buffer, a phosphate buffer or an amine/borate buffer.
  • the relationship between the halide ion concentration and the pH is important and this relationship is shown in Fig 1 of the accompanying drawings which is a plot of lines of equal processing time on a pH versus potassium chloride concentration.
  • the area to the left of the 20 second line is not the preferred area to work within as bubble formation and damage to the gelatin layers can occur.
  • the preferred area is that lying between the 20 second line and the 40 second line.
  • the bleach solutions of the present invention may be used with any type of photographic silver halide colour material. Such materials and their possible constituents are described, for example, in Research Disclosure Item 308119, December 1989 published by Kenneth Mason Publications, Emsworth, Hants, United Kingdom. However, materials based on predominantly silver chloride emulsions are preferred.
  • the present invention also provides a method of photographic colour processing which comprises a bleach step wherein the bleach solution comprises hydrogen peroxide, or a compound which releases hydrogen peroxide, and halide ions and which has a pH in the range of 5 to 11 , preferably 5 to 10.
  • the bleach step may directly follow the developing or redox amplification stages or an intermediate stop bath may be employed.
  • An important consideration is whether unexposed (Dmin) areas produce unwanted dye by oxidation of developing agent carried over into the bleach bath. In both Examples below there is no significant increase in Dmin even though no stop bath was used.
  • the bleach solution may be used after a redox amplification step.
  • Redox amplification processes have been described, for example in British Specification Nos. 1,268,126, 1,399,481, 1,403,418 and 1,560,572.
  • colour materials are developed to produce a silver image (which may contain only small amounts of silver) and then treated with a redox amplifying solution (or developer-amplifier) to form a dye image.
  • the redox amplifying solution contains a reducing agent, for example a colour developing agent, and an oxidising agent which will oxidise the colour developing agent in the presence of the silver image which acts as a catalyst.
  • the photographic material used in such a process may be a conventional coupler-containing silver halide material or an image transfer material containing redox dye releasers.
  • Oxidised colour developer reacts with a colour coupler (usually contained in the photographic material photographic material) to form image dye.
  • the amount of dye formed depends on the time of treatment or the availability of colour coupler rather than the amount of silver in the image as is the case in conventional colour development processes.
  • suitable oxidising agents include peroxy compounds including hydrogen peroxide, cobalt (III) complexes including cobalt hexammine complexes, and periodates. Mixtures of such compounds can also be used.
  • a particular application of this technology is in the processing of silver chloride colour paper, especially such paper with low silver levels, for example at levels of total silver halide coverage below 200 mg/m 2 , preferably below 160 mg/m 2 and especially 140 mg/m 2 (as silver).
  • the photographic material to be processed preferably contains low levels of silver and is preferably based on emulsions which comprise at least 80%, preferably at least 90% silver chloride and especially substantially pure silver chloride.
  • a redox amplification bath was made up as follows:
  • a bleach solution was made up as follows:
  • pH Values were adjusted to between 5 and 10 using potassium carbonate or sulphuric acid as required.
  • a colour photographic paper comprising silver chloride emulsions and a total silver coverage of about 140 mg/m 2 was exposed to white light for 10 seconds and then developed for 45 seconds at 35"C. The paper was then immersed in the bleach solution and the silver loss followed by observing the transmitted infra-red density. The time of bleaching was taken as the time taken to reach a point at which the density no longer changed. The results are shown in Figure 1 of the accompanying drawings in which pH and KC1 content are plotted as "*". Samples of some runs where bleaching took place in less than 45 seconds were analysed and the residual silver was found to be less than 2 mg/m 2 thus confirming that effective bleaching had taken place.
  • Bleach tim ⁇ exp(7-42x[KCI] + O. ⁇ xpH - 2.2x[KCI]xpH + 97.3x[KCI] 2 - 45.4x[KCI] 3 ) sees.
  • the units for the concentrations shown in brackets are g/litre.
  • the curves on Fig 1 were drawn using this equation.
  • a bleach solution was made as follows:
  • a piece of conventional silver chloride-based photographic colour paper (containing a total silver coverage of 700 mg/m 2 ) was exposed to room light for 10 seconds, developed for 45 seconds in a conventional colour developer and plunged into the bleach solution. The silver loss was followed as described above. Bleaching was complete in 90 seconds. This shows that the bleach solution is useful for a photographic colour paper of conventional silver coverage.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Exposure Control For Cameras (AREA)
  • Stroboscope Apparatuses (AREA)
  • Studio Devices (AREA)

Abstract

Procédé de développement photographique couleur qui comprend une étape de blanchiment, la soution de blanchiment comprenant du peroxyde d'hydrogène ou un composé libérant du peroxyde d'hydrogène, et des ions halogénure, et possédant un pH compris entre 5 et 11. Des solutions de blanchiment du procédé sont aussi décrites.
PCT/EP1991/001973 1990-10-19 1991-10-17 Solution de blanchiment photographique Ceased WO1992007300A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP91918048A EP0506909B1 (fr) 1990-10-19 1991-10-17 Solution de blanchiment photographique
DE69127189T DE69127189T2 (de) 1990-10-19 1991-10-17 Photographische bleichlösung
JP3517045A JP3045311B2 (ja) 1990-10-19 1991-10-17 写真カラー処理方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909022749A GB9022749D0 (en) 1990-10-19 1990-10-19 Photographic bleach solution
GB9022749.7 1990-10-19

Publications (1)

Publication Number Publication Date
WO1992007300A1 true WO1992007300A1 (fr) 1992-04-30

Family

ID=10683999

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/001973 Ceased WO1992007300A1 (fr) 1990-10-19 1991-10-17 Solution de blanchiment photographique

Country Status (5)

Country Link
EP (1) EP0506909B1 (fr)
JP (1) JP3045311B2 (fr)
DE (1) DE69127189T2 (fr)
GB (1) GB9022749D0 (fr)
WO (1) WO1992007300A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5451491A (en) * 1992-12-29 1995-09-19 Eastman Kodak Company Method of bleaching and fixing a color photographic element using a peracid bleach and a low ammonium fixer
US5541041A (en) * 1995-04-17 1996-07-30 Eastman Kodak Company Stabilized peroxide bleaching solutions containing multiple chelating ligands and their use for processing of photographic elements
US5550009A (en) * 1995-04-17 1996-08-27 Eastman Kodak Company Stabilized peroxide bleaching solutions and their use for processing of photographic elements
EP0729065A1 (fr) * 1995-02-21 1996-08-28 Eastman Kodak Company Composition à base de péroxyde et procédé pour la traitement d'éléments photographiques couleurs à l'halogénure d'argent
US5554491A (en) * 1995-03-21 1996-09-10 Eastman Kodak Company Use of an alkaline prebath to activate an acidic peroxide bleach solution for processing color photographic elements
EP0747764A1 (fr) * 1995-05-26 1996-12-11 Eastman Kodak Company Procédé de traitement de produits photographiques au chlorure d'argent dont la sensibilité est convenable pour l'utilisation dans une caméra, lequel procédé utilisant des solutions de blanchiment à base de péroxyde
EP0758762A1 (fr) * 1995-08-12 1997-02-19 Kodak Limited Procédé de traitement de matériaux photographiques à l'halogénure d'argent
US5614355A (en) * 1995-02-21 1997-03-25 Eastman Kodak Company Peroxide composition and method for processing color photographic elements containing predominantly chloride silver halide emulsions
EP0779247A1 (fr) 1995-12-16 1997-06-18 Kodak Limited Procédé pour traiter les effluents des procédés de développement photographique
US5641616A (en) * 1994-04-20 1997-06-24 Eastman Kodak Company Non-rehalogenating bleaching composition and its use to process silver halide photographic elements
US5641615A (en) * 1994-04-20 1997-06-24 Eastman Kodak Company Processing silver halide photographic elements with a non-rehalogenating peroxide bleaching composition
US5691118A (en) * 1996-10-10 1997-11-25 Eastman Kodak Company Color paper processing using two acidic stop solutions before and after bleaching
US5763147A (en) * 1995-02-21 1998-06-09 Eastman Kodak Company Method for processing high silver bromide color negative photographic films using a peroxide bleaching composition
US5773202A (en) * 1995-02-21 1998-06-30 Haye; Shirleyanne Elizabeth Method for processing color photographic films using a peroxide bleaching composition
US6703192B1 (en) 2003-02-28 2004-03-09 Eastman Kodak Company Photographic peracid bleaching composition, processing kit, and method of use

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9516580D0 (en) 1995-08-12 1995-10-11 Kodak Ltd Method of processing photographic silver halide materials

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4277556A (en) * 1976-08-18 1981-07-07 Konishiroku Photo Industry Co., Ltd. Process for treating light-sensitive silver halide color photographic materials
US4301236A (en) * 1979-01-23 1981-11-17 Fuji Photo Film Co., Ltd. Photographic bleach solutions
WO1987006361A2 (fr) * 1986-04-18 1987-10-22 Eastman Kodak Company Compositions photographiques de fixation de blanchiment
EP0428101A1 (fr) * 1989-11-13 1991-05-22 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique en couleur à l'halogénure d'argent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4277556A (en) * 1976-08-18 1981-07-07 Konishiroku Photo Industry Co., Ltd. Process for treating light-sensitive silver halide color photographic materials
US4301236A (en) * 1979-01-23 1981-11-17 Fuji Photo Film Co., Ltd. Photographic bleach solutions
WO1987006361A2 (fr) * 1986-04-18 1987-10-22 Eastman Kodak Company Compositions photographiques de fixation de blanchiment
EP0428101A1 (fr) * 1989-11-13 1991-05-22 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique en couleur à l'halogénure d'argent

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5451491A (en) * 1992-12-29 1995-09-19 Eastman Kodak Company Method of bleaching and fixing a color photographic element using a peracid bleach and a low ammonium fixer
US5641615A (en) * 1994-04-20 1997-06-24 Eastman Kodak Company Processing silver halide photographic elements with a non-rehalogenating peroxide bleaching composition
US5641616A (en) * 1994-04-20 1997-06-24 Eastman Kodak Company Non-rehalogenating bleaching composition and its use to process silver halide photographic elements
US5614355A (en) * 1995-02-21 1997-03-25 Eastman Kodak Company Peroxide composition and method for processing color photographic elements containing predominantly chloride silver halide emulsions
US5773202A (en) * 1995-02-21 1998-06-30 Haye; Shirleyanne Elizabeth Method for processing color photographic films using a peroxide bleaching composition
US5763147A (en) * 1995-02-21 1998-06-09 Eastman Kodak Company Method for processing high silver bromide color negative photographic films using a peroxide bleaching composition
EP0729065A1 (fr) * 1995-02-21 1996-08-28 Eastman Kodak Company Composition à base de péroxyde et procédé pour la traitement d'éléments photographiques couleurs à l'halogénure d'argent
US5554491A (en) * 1995-03-21 1996-09-10 Eastman Kodak Company Use of an alkaline prebath to activate an acidic peroxide bleach solution for processing color photographic elements
EP0733946A1 (fr) * 1995-03-21 1996-09-25 Eastman Kodak Company Utilisation d'un prébain pour activer une solution de blanchiment au peroxyde acide dans le traitement d'éléments photographiques couleurs
US5550009A (en) * 1995-04-17 1996-08-27 Eastman Kodak Company Stabilized peroxide bleaching solutions and their use for processing of photographic elements
US5541041A (en) * 1995-04-17 1996-07-30 Eastman Kodak Company Stabilized peroxide bleaching solutions containing multiple chelating ligands and their use for processing of photographic elements
EP0747764A1 (fr) * 1995-05-26 1996-12-11 Eastman Kodak Company Procédé de traitement de produits photographiques au chlorure d'argent dont la sensibilité est convenable pour l'utilisation dans une caméra, lequel procédé utilisant des solutions de blanchiment à base de péroxyde
EP0758762A1 (fr) * 1995-08-12 1997-02-19 Kodak Limited Procédé de traitement de matériaux photographiques à l'halogénure d'argent
US5670300A (en) * 1995-08-12 1997-09-23 Eastman Kodak Company Method of processing photographic silver halide materials
EP0779247A1 (fr) 1995-12-16 1997-06-18 Kodak Limited Procédé pour traiter les effluents des procédés de développement photographique
US5719010A (en) * 1995-12-16 1998-02-17 Eastman Kodak Company Treatment method for treating effluents from a photographic development process
US5691118A (en) * 1996-10-10 1997-11-25 Eastman Kodak Company Color paper processing using two acidic stop solutions before and after bleaching
US6703192B1 (en) 2003-02-28 2004-03-09 Eastman Kodak Company Photographic peracid bleaching composition, processing kit, and method of use
US6852477B2 (en) 2003-02-28 2005-02-08 Eastman Kodak Company Photographic peracid bleaching composition, processing kit, and method of use

Also Published As

Publication number Publication date
DE69127189D1 (de) 1997-09-11
DE69127189T2 (de) 1998-03-12
EP0506909A1 (fr) 1992-10-07
GB9022749D0 (en) 1990-12-05
JP3045311B2 (ja) 2000-05-29
EP0506909B1 (fr) 1997-08-06
JPH05505475A (ja) 1993-08-12

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