US3264107A - Baths suitable for rehalogenating metallic silver in photographic materials - Google Patents

Baths suitable for rehalogenating metallic silver in photographic materials Download PDF

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Publication number
US3264107A
US3264107A US220156A US22015662A US3264107A US 3264107 A US3264107 A US 3264107A US 220156 A US220156 A US 220156A US 22015662 A US22015662 A US 22015662A US 3264107 A US3264107 A US 3264107A
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United States
Prior art keywords
bath
silver
acid
rehalogenating
metallic silver
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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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US220156A
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English (en)
Inventor
Wartburg Rene Von
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BASF Schweiz AG
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Ciba AG
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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
    • 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
    • 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
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials

Definitions

  • the material to be processed generally comprises a support on which are coated a plurality of light sensitive silver halide emulsions, which may be in the form of layers or granules and which contain bleachable dyestuffs in a difiusion-resistant form. After exposure, development and fixation, the dyestufis are bleached in dependence on the amount of silver locally present in the silver image. This is generally carried out in a bath which contains an acid, a substance capable of forming silver complexes, such as thiourea, and a bleaching catalyst.
  • the metallic silver is not completely oxidized, or impurities accompanying the silver are not completely removed, so that, after treatment in a fixing bath following upon the silver bleaching bath, there is left a residual density which becomes apparent in images to be viewed by reflected light as poor remission in the light areas of the image. While it is possible to improve the result by repeated alternate treatments with the silver bleaching bath and the fixing bath, this method is very troublesome, so that there is a need for a silver bleaching bath which completely oxidizes the metallic silver in a single, short treatment.
  • the present invention is based on the observation that a silver bleaching bath which contains a hydrohalic acid, a cupric salt and water-soluble aliphatic carboxylic acid converts metallic silver in a very short time and quantitatively into silver halide, even when the said silver bleaching bath is used after a dye bleaching bath that causes the silver to become less reactive. Accordingly, the invention provides for rehalogenating metallic silver in a photographic material, a bath which contains a cupric salt, a hydrohalic acid and a water-soluble aliphatic carboxylic acid.
  • hydrohalic acid there is preferably used hydrochloric or hydrobromic acid. While it is possible to form these acids by double decomposition, for example, by incorporating in the bath potassium bromide and sulfuric acid, the best results have been obtained with baths which contain no or a very small amount of metal ions, for example, alkali metal ions, other than the copper ions, and which are practically free from sulfate ions. Therefore baths which contain, instead of the often used copper sulfate, other copper salts, for example, copper acetate or copper nitrate, are preferred. The baths advantageously contain about 0.5 to 2.0 mols of the hydrohalic acid and about 0.1 to 1.0 mol of the copper salt per liter.
  • aliphatic carboxylic acids there may be mentioned, for example, unsaturated acids and polycarboxylic acids, though other acids may likewise be used, provided that they contain no basic substituents and are water-soluble.
  • the acids are advantageously composed exclusively of carbon, hydrogen and oxygen, and advantageously contain not more than 7 carbon atoms. It is of advantage to use acids capable of forming watersoluble copper compounds.
  • acetic acid As examples of such acids there may be mentioned: acetic acid, lactic acid, cyanoacetic acid, acrylic acid, succinic acid, tartaric acid, citric acid, and maleic acid.
  • these acids act, on one hand, as solvents or solution promoters for the products that passivate the metallic silver, such as dyestuff fission products and thiourea complexes, and radicals of bleaching catalysts or of filter dyestuffs.
  • these acids are capable of forming complexes with the copper ions, they are able to modify the oxidation conditions.
  • the acids give their optimum effect at a concentration ranging from about 1 to 15%, and preferably 2 to 12%.
  • the preferred silver bleaching baths of the invention are those which contain, per liter, about 0.5 to 2 mols of a hydrohalic acid, such as hydrochloric acid, 0.5 mol of a copper salt, such as copper nitrate, and about 2 to 12% of an aliphatic carboxylic acid, such as acrylic or citric acid.
  • a hydrohalic acid such as hydrochloric acid
  • a copper salt such as copper nitrate
  • an aliphatic carboxylic acid such as acrylic or citric acid
  • the baths can be further improved by adding thereto a small proportion of a surface-active agent, for example, a polyglycol ether of a higher fatty alcohol, and especially a fiuorinated aliphatic carboxylic acid such as described, for example, in U.S. specification No. 2,904,515.
  • a surface-active agent for example, a polyglycol ether of a higher fatty alcohol, and especially a fiuorinated aliphatic carboxylic acid such as described, for example, in U.S. specification No. 2,904,515.
  • the baths of the invention for rehalogenating metallic silver are suitable for use in all processes in which strongly acid baths are not harmful. They are therefore suitable for use in those color photographic processes in which dyestuffs are not decomposed by acid, more especially, for the silver dye bleaching process.
  • the baths of the invention are superior to the known silver bleaching baths. They bring about more rapidly the complete rehalogenation of metallic silver or complete removal of the impurities associated with the silver in multilayer materials to be viewed by reflected light so that, after subsequent removal of the silver halide in a fixing bath, clearer pictures and above all better whites, are obtained.
  • the azo-dyestuifs suitable for use in the silver dye bleaching process have in general a good resistance and satisfactory stability to the rehalogenation baths of the invention, but there are cases in which the dyestufis are adversely affected when the bath has a very high concentration of aliphaticcarboxylic acid.
  • the addition of an organic base or of a salt thereof to the rehalogenation bath protects the dyestuif from oxidation without impairing the action of the bath on the silver to be rehalogenated or on the dark impurities accompanying the silver.
  • Especially suitable bases are biguanides such, for example, as diphenyl-4:4'-dibiguanide, in a concentration below 1%. While baths containing no base give in many cases, though not always, satisfactory results, baths that contain a base as aforesaid are more generally applicable.
  • Example 1 A white-reflecting support was coated with a layer of a red-sensitized silver bromide emulsion containing a diffusion-resistant blue-green azo-dyestuff, this layer was coated with a green-sensitized silver bromide gelatine emulsion containing a diffusion-resistant purple aZo-dyestuff, the latter layer was coated with a yellow filter layer, and the filter layer was coated with the topmost layer of a non-sensitized silver bromide gelatine emulsion containing a diffusion-resistant yellow azo-dyestuif.
  • the material was exposed, developed, fixed and then bleached in a bath containing hydrochloric acid, sodium chloride, thiourea and 2:3-aminohydroxyphenazine, whereby all dyestuff in the areas that had been exposed to white light were destroyed.
  • the material was thoroughly washed and bleached for 10 minutes at 24 C. in one of the silver bleaching baths described below, once more washed, fixed, washed and dried. The densities of the exposed areas as viewed by -reflected light were then measured.
  • the log l /I value was found to be 0.32.
  • the known ferricyanide baths did not produce any more favorable results; above, all, they produced spotty images which made accurate measurements impossible.
  • baths C to M of the invention which had the same composition as bath (B) exc pt that the acetic acid was replaced by the additives specified.
  • concentrations specified are those that gave the optimum results in another series of tests:
  • Example 2 A material having the arrangement of layers described in Example 1, was made in which the green-sensitized layer contained a dyestuif of the formula SOaH lTIH:
  • Hydrochloric acid 37% strength -ml-.. Copper nitrate .3H O grams- Acrylic acid ml 125 Surface-active agent 0.1% ml 15 Diphenyl-4:4'-dibiguanide hydrochloride --grams-- 3 Water to make 1 liter.
  • a bath suitable for rehalogenating metallic silver in a photographic material which bath is substantially free from alkali metal ions and sulfate ions and which comprises a cupric salt, a hydrohalic acid and a watersoluble aliphatic carboxylic acid composed exclusively of carbon, hydrogen and oxygen.
  • a bath suitable for rehalogenating metallic silver in a photographic material which bath is substantially free from alkali metal ions and sulfate ions which comprises a cupric salt, a hydrohalic acid, a surface-active agent and a water-soluble aliphatic carboxylic acid composed exclusively of carbon, hydrogen and oxygen.
  • a bath suitable for rehalogenating metallic silver in a photographic material which bath is substantially free from alkali metal ions and sulfate ions and which comprises a cupric salt, a hydrohalic acid, a biguanide base and a water-soluble aliphatic carboxylic acid composed exclusively of carbon, hydrogen and oxygen.
  • a bath suitable for rehalogenating metallic silver in a photographic material which bath is substantially free from alkali metal ions and sulfate ions and which comprises a cupric salt, a hydrohalic acid and acetic acid.
  • a bath suitable for rehalogenating metallic silver in a photographic material which bath is substantially free from alkali metal ions and sulfate ions and which comprises a cupric salt, a hydrohalic acid and acrylic acid.
  • a bath suitable for rehalogenating metallic silver in a photographic material which bath is substantially free from alkali metal ions and sulfate ions and which comprises a cupric salt, a hydrohalic acid and citric acid.
  • a bath suitable for rehalogenating metallic silver in a photographic material which bath is substantially free from alkali metal ions and sulfate ions and which comprises a cu ric salt, a hydrohalic acid, a surface-active agent and acrylic acid.
  • a bath suitable for rehalogenating metallic silver in a photographic material which bath is substantially free from alkali metal ions and sulfate ions and which comprises a cupric salt, a hydrohalic acid, a surface-active agent and citric acid.
  • a bath suitable for rehalogenating metallic silver in a photographic material which bath is substantially free from alkali metal ions and sulfate ions and which comprises a cupric salt, a hydrohalic acid, a surfaceactive agent, diphenyl-4:4'-dibiguanide hydrochloride and acrylic acid.
  • the step which comprises carrying out the silver bleaching after the dye bleaching in a bath which comprises a cupric salt, a hydrohalic acid and a water-soluble aliphatic carboxylic acid.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US220156A 1961-09-08 1962-08-29 Baths suitable for rehalogenating metallic silver in photographic materials Expired - Lifetime US3264107A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1046561A CH405071A (de) 1961-09-08 1961-09-08 Bad zur Rehalogenierung metallischen Silbers

Publications (1)

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US3264107A true US3264107A (en) 1966-08-02

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US (1) US3264107A (ja)
BE (1) BE622239A (ja)
CH (1) CH405071A (ja)
DE (1) DE1154348B (ja)
ES (1) ES280611A1 (ja)
GB (1) GB949440A (ja)
NL (1) NL282992A (ja)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445925A (en) * 1993-04-13 1995-08-29 Eastman Kodak Company Method of forming a photographic color image
US5569443A (en) * 1994-11-18 1996-10-29 The Dow Chemical Company Method for removing hydrogen sulfide from a gas using polyamino disuccinic acid
US5585226A (en) * 1995-08-30 1996-12-17 Eastman Kodak Company Polyamino monoesuccinates for use in photographic processes
US5652085A (en) * 1995-08-30 1997-07-29 Eastman Kodak Company Succinic acid derivative degradable chelants, uses and composition thereof
US5716767A (en) * 1995-12-29 1998-02-10 Agfa-Gevaert Ag Bleaching bath for photographic black-&-white material
US5741555A (en) * 1995-05-22 1998-04-21 The Dow Chemical Company Succinic acid derivative degradable chelants, uses and compositions thereof
US5795681A (en) * 1994-07-09 1998-08-18 Mueller; Helmut Stabilization of holograms formed in gelatin

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2133255A (en) * 1937-05-19 1938-10-11 Percy A E Armstrong Process of electroplating copper
US2326055A (en) * 1940-10-10 1943-08-03 Eastman Kodak Co Dye bleaching process
US2350736A (en) * 1942-07-10 1944-06-06 Eastman Kodak Co Method of producing dye images
US2494068A (en) * 1946-06-03 1950-01-10 Eastman Kodak Co Photographic relief image
US2669519A (en) * 1952-04-26 1954-02-16 Seaplant Chemical Corp Gelling compositions
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
US2853443A (en) * 1956-04-25 1958-09-23 Westinghouse Electric Corp Addition agent for acid copper electrolytes
US2854386A (en) * 1955-02-07 1958-09-30 Aladdin Ind Inc Method of photographically printing conductive metallic patterns
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2133255A (en) * 1937-05-19 1938-10-11 Percy A E Armstrong Process of electroplating copper
US2326055A (en) * 1940-10-10 1943-08-03 Eastman Kodak Co Dye bleaching process
US2350736A (en) * 1942-07-10 1944-06-06 Eastman Kodak Co Method of producing dye images
US2494068A (en) * 1946-06-03 1950-01-10 Eastman Kodak Co Photographic relief image
US2669519A (en) * 1952-04-26 1954-02-16 Seaplant Chemical Corp Gelling compositions
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
US2854386A (en) * 1955-02-07 1958-09-30 Aladdin Ind Inc Method of photographically printing conductive metallic patterns
US2853443A (en) * 1956-04-25 1958-09-23 Westinghouse Electric Corp Addition agent for acid copper electrolytes
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445925A (en) * 1993-04-13 1995-08-29 Eastman Kodak Company Method of forming a photographic color image
US5859273A (en) * 1993-05-20 1999-01-12 The Dow Chemical Company Succinic acid derivative degradable chelants, uses and compositions thereof
US5795681A (en) * 1994-07-09 1998-08-18 Mueller; Helmut Stabilization of holograms formed in gelatin
US5569443A (en) * 1994-11-18 1996-10-29 The Dow Chemical Company Method for removing hydrogen sulfide from a gas using polyamino disuccinic acid
US5741555A (en) * 1995-05-22 1998-04-21 The Dow Chemical Company Succinic acid derivative degradable chelants, uses and compositions thereof
US5585226A (en) * 1995-08-30 1996-12-17 Eastman Kodak Company Polyamino monoesuccinates for use in photographic processes
US5652085A (en) * 1995-08-30 1997-07-29 Eastman Kodak Company Succinic acid derivative degradable chelants, uses and composition thereof
US5716767A (en) * 1995-12-29 1998-02-10 Agfa-Gevaert Ag Bleaching bath for photographic black-&-white material

Also Published As

Publication number Publication date
GB949440A (en) 1964-02-12
ES280611A1 (es) 1963-03-01
DE1154348B (de) 1963-09-12
NL282992A (ja)
BE622239A (ja)
CH405071A (de) 1965-12-31

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