US3293036A - Bleach-fix compositions and process for producing colored photographic images - Google Patents

Bleach-fix compositions and process for producing colored photographic images Download PDF

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Publication number
US3293036A
US3293036A US263391A US26339163A US3293036A US 3293036 A US3293036 A US 3293036A US 263391 A US263391 A US 263391A US 26339163 A US26339163 A US 26339163A US 3293036 A US3293036 A US 3293036A
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United States
Prior art keywords
fixing
color
bleach
bath
water
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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
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US263391A
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English (en)
Inventor
Meckl Heinz
Haseler Helmut
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Agfa Gevaert NV
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Agfa AG
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Publication date
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Publication of US3293036A publication Critical patent/US3293036A/en
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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421Additives other than bleaching or fixing agents

Definitions

  • the material after development generally is rinsed or treated in a stop fixing bath. Thereafter, the metallic silver formed in the development is oxidised in .a bleach-fixing Ibath. Generally, complexes of trivalent iron or cobalt are used as oxidising agents in this case. The silver compound formed is fixed together with the residual silver halide.
  • the rinsing and treatment with the stop-fixing bath between the developing bath and the bleach-fixing bath serves primarily for the removal of the excess developer substance and the alkali from the photographic layer. However, this is generally not achieved completely, so that certain proportions of developer substance pass into the oxidising bleach-fixing bath. In this bath, the developer is oxidised to form products which react with the color couplers incorporated into the photographic layers, so that more especially color fogging occurs in the uppermost layer.
  • a bleach-fixing bath in which on the one hand no color fogging occurs and, on the other hand, the density of the cyan dyestuff is not reduced.
  • a bleachfixing bat-h having a pH value below 7.0 has the disadvantage that it destroys more cyan dyestuff when fresh than when used.
  • the invention has for its object the solution of the last-mentioned problem.
  • water-soluble derivatives of these two compounds can also be used for the present purpose.
  • Example 1 A multi-layer color photographic material, containing 3-(p-stearylamino lbenzoylacetamino)-isophth-alic acid as a yellow color coupler, 1-(4'-phenoxy-3'sulphophenyl)- 3-heptadecyl-5-pyrazolone as a magenta color coupler and 1-hydroxy-4sulpho-2-naphtho ic acid octadecylamide as a cyan color coupler is developer in a developer having the following composition:
  • a color image is obtained without the slightest indication of a color fogging.
  • Example 2 The development takes place as indicated in Example 1 and the further processing is effected in a stop-fixing bath with the following composition:
  • the immediately following bleach-fixing bath has the following composition:
  • the color image obtained is completely free from color fogging.
  • the baths according to the invention can have a pH value between 7 and 9 and advantageously between 7.5 and 8.0.
  • the bleachfixing bath is advantageously followed by a rinsing and a stabilising bath which has a pH value of approximately 7.
  • a rinsing or a stop-fixing bath Interposed between the developing bath and the bleach-fixing bath is a rinsing or a stop-fixing bath, which has a pH value between 7.0 and 9.0, advantageously 7.0 and 8.0, or both.
  • suitable bleaching agents comprises complex salts of trivalent iron (German No. 866,605) or cobalt, as de'scnibed, for example, in German No. 9'5 4,475,
  • Diethylene triaminepentaacetic acid (HOOCCH NCH CH N- (CH COOH -CH CH N- (CH COOH) 2 Nitrilo-triacetie aoid N-(CH COOH) Ethylaminediprop-ionic acid (bis-(2-carboxyethyl)ethylamine);
  • Any water-soluble thiosulphate may be used as fixing agent such as alkali thiosulphates or ammonium thiosulphate.
  • the bleach-fixing bath may contain as stabilizing agents any water-soluble sulfite, bisulfiite or metasulfite. Furthermore the bleach-fixing bath may have an additional content of water-soluble iodides according to our copending application Ser. No. 95,735, now abandoned.
  • the photographic material which shall the treated according to the invention may be developed by means of any developer composition known per se.
  • the pH value of the bleach-fixing bath can be adjusted by the addition of phosphates, carbonates or borates of alkali or alkalineearth metals.
  • the reducing agent according to the invention should be added in an amount of between 0.2-5 g. per litre, preferably in an amount of 0.5-3 g. per litre.
  • the anion of the hydrazine respectively hydroxylamine salts to be used are not critical. Preferred are salts of the said compounds with acids such as sulphuric acid or hydrochloric acid.
  • a process for the production of a photographic image which comprises (a) imagewise exposure of a photographic multilayer color material comprising at least one light-sensitive silver halide emulsion layer which contains a color coupler capable of reacting with an oxidation product of a color-forming developer to form a dye.
  • a bleach-fixing bath containing (1) a bleaching agent selected from the group consisting of ferric and cob altic complex salts of a member selected from the group consisting of hydroxypolycarboxylic and aminopolycarboxylic acids, (2) a fixing agent consisting of a water-soluble salt of thiosulfuric acid, said fixing bath having a pH value of between 7 and 9,
  • the improvement according to which the simultaneously bleaching and fixing is accomplished in efiective contact with a reducing agent selected from the class consisting of a hydrazine salt, a water-soluble ihydroxylamine salt and formamidine-sulphinic acid.
  • a reducing agent selected from the class consisting of a hydrazine salt, a water-soluble ihydroxylamine salt and formamidine-sulphinic acid.
  • a composition for the simultaneous bleaching and fixing of an exposed and developed photographic color material comprising at least one light-sensitive silver halide emulsion layer which contains a color coupler capable of reacting with an oxidation product of a colorforming developer-to form a dye, which contains (1) a bleaching agent of the group consisting of ferric and co'baltic complex salts of a member selected from the group consisting of hydroxynolvcar-boxylic and aminopolycarboxylic acids,
  • a fixing agent consisting of a water-soluble salt of thiosulfuric acid
  • a reducing agent selected from the class consisting of a hydrazine salt, a water-soluble hydroxylamine salt and a formamidine-sulphinic acid in an amount of between 0.2 and 5 g. per liter of the composition.
  • composition as'defined in claim 3 containing the ferric complex salt of ethylenediaminetetraacetic acid as 6 bleaching agent (I) and sodium thiosulfate as the fixing 768,401 2/1957 Great Britain. agent (II). 774,194 5/ 1957 Great Britain.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US263391A 1962-04-05 1963-03-07 Bleach-fix compositions and process for producing colored photographic images Expired - Lifetime US3293036A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA39881A DE1155980B (de) 1962-04-05 1962-04-05 Verfahren zur Herstellung farbiger photographischer Bilder nach dem Farbentwicklungsverfahren

Publications (1)

Publication Number Publication Date
US3293036A true US3293036A (en) 1966-12-20

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Family Applications (1)

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US263391A Expired - Lifetime US3293036A (en) 1962-04-05 1963-03-07 Bleach-fix compositions and process for producing colored photographic images

Country Status (5)

Country Link
US (1) US3293036A (el)
BE (1) BE630320A (el)
CH (1) CH433982A (el)
DE (1) DE1155980B (el)
GB (1) GB988967A (el)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607277A (en) * 1967-10-14 1971-09-21 Agfa Gevaert Ag Photographic viscous processing
JPS4852233A (el) * 1971-11-01 1973-07-23
US3931004A (en) * 1972-04-21 1976-01-06 Fuji Photo Film Co., Ltd. Method of treating waste liquids from photographic processings
US4518680A (en) * 1983-02-17 1985-05-21 Konishiroku Photo Industry Co., Ltd. Bleach-fixing solution and processing of light-sensitive color photographic material by use thereof
US4828970A (en) * 1986-04-18 1989-05-09 Konishiroku Photo Industry Co., Ltd. Method for processing a light-sensitive silver halide color photographic material by controlling the pH value of the bleach fixing solution
US5006456A (en) * 1987-06-08 1991-04-09 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic light-sensitive materials using sulphinc acids and salts or their precursors
WO2001050196A1 (en) * 2000-01-06 2001-07-12 Trebla Chemical Company One-part bleach-fix liquid concentrates
EP1160622A1 (en) * 2000-05-27 2001-12-05 Agfa-Gevaert N.V. A bleach-fixing concentrate
US6455236B1 (en) * 2000-01-06 2002-09-24 Trebla Chemical Company One-part bleach-fix liquid concentrates

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE14362C (de) * C. MULLER in Fulda Schaftmaschine für Hoch- und Tieffach
GB768401A (en) * 1955-01-31 1957-02-13 Leonar Werke Ag Improvements in or relating to simultaneously developing and fixing or stabilizing photographic silver halide emulsions
GB774194A (en) * 1954-06-19 1957-05-08 Photo Chemical Company Ltd Improvements in photographic bleach-fix baths
GB777635A (en) * 1954-03-11 1957-06-26 Gevaert Photo Prod Nv Improvements in or relating to a process for simultaneously bleaching and fixing a photographic colour image

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE14362C (de) * C. MULLER in Fulda Schaftmaschine für Hoch- und Tieffach
GB777635A (en) * 1954-03-11 1957-06-26 Gevaert Photo Prod Nv Improvements in or relating to a process for simultaneously bleaching and fixing a photographic colour image
GB774194A (en) * 1954-06-19 1957-05-08 Photo Chemical Company Ltd Improvements in photographic bleach-fix baths
GB768401A (en) * 1955-01-31 1957-02-13 Leonar Werke Ag Improvements in or relating to simultaneously developing and fixing or stabilizing photographic silver halide emulsions

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607277A (en) * 1967-10-14 1971-09-21 Agfa Gevaert Ag Photographic viscous processing
JPS4852233A (el) * 1971-11-01 1973-07-23
JPS5123179B2 (el) * 1971-11-01 1976-07-15
US3931004A (en) * 1972-04-21 1976-01-06 Fuji Photo Film Co., Ltd. Method of treating waste liquids from photographic processings
US4518680A (en) * 1983-02-17 1985-05-21 Konishiroku Photo Industry Co., Ltd. Bleach-fixing solution and processing of light-sensitive color photographic material by use thereof
US4828970A (en) * 1986-04-18 1989-05-09 Konishiroku Photo Industry Co., Ltd. Method for processing a light-sensitive silver halide color photographic material by controlling the pH value of the bleach fixing solution
US5006456A (en) * 1987-06-08 1991-04-09 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic light-sensitive materials using sulphinc acids and salts or their precursors
WO2001050196A1 (en) * 2000-01-06 2001-07-12 Trebla Chemical Company One-part bleach-fix liquid concentrates
US6455236B1 (en) * 2000-01-06 2002-09-24 Trebla Chemical Company One-part bleach-fix liquid concentrates
EP1160622A1 (en) * 2000-05-27 2001-12-05 Agfa-Gevaert N.V. A bleach-fixing concentrate
US20040058283A1 (en) * 2000-05-27 2004-03-25 Gustav Tappe Bleach-fixing concentrate

Also Published As

Publication number Publication date
DE1155980B (de) 1963-10-17
GB988967A (en) 1965-04-14
CH433982A (de) 1967-04-15
BE630320A (el)

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