US3241966A - Bleach fixing of photographic silver images - Google Patents

Bleach fixing of photographic silver images Download PDF

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Publication number
US3241966A
US3241966A US140170A US14017061A US3241966A US 3241966 A US3241966 A US 3241966A US 140170 A US140170 A US 140170A US 14017061 A US14017061 A US 14017061A US 3241966 A US3241966 A US 3241966A
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United States
Prior art keywords
fixing
group
molecular weight
acid
mol
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Expired - Lifetime
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US140170A
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English (en)
Inventor
Heilmann Max
Brachel Hanswilli Von
Holtschmidt Hans
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Agfa Gevaert NV
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Agfa 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
    • 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 to a process for bleach fixing of photographic silver images as well as to a bleach fixing bath.
  • R R and R represent hydrocarbon radicals which may be substituted and R may also represent hydrogen, and in which R R and R represent bivalent hydrocarbon radicals which may again be substituted.
  • suitable organic acids are ethylenediamine tetra-acetic acid, nitrilotriacetic acid, malonic acid, ethyl malonic acid, tartaric acid, malic acid, fumaric acid, diglycolic acid, ethyliminodipropionic acid, ethylene dithioglycolic acid and dithioglycolic acid.
  • These bleach fix baths are highly stable and are used, in particular, for the production of multicoloured images by the colour development process. Nevertheless, these baths have the disadvantage that they do not always completely bleach out the silver images at the areas of highest density,
  • R represents a hydrogen atom or a substituted or unsubstituted alkyl, aryl, aralkyl, acyl, aroyl or heterocyclic radical; R and R which may be the same or different, each represent a hydrogen atom, a substituted or unsubstituted alkyl, aryl, aralkyl, acyl, aroyl or heterocyclic radical or the group(CH .Cl-I .O) ,R wherein R is a hydrogen atom or a substituent suitable for the etherification or esterification of an OH group and x, y, 2: and n are integers.
  • water-soluble polyethylene oxides which increase the bleaching capacity of bleach fix baths are polyethylene oxides consisting of from 10 to 120 mols of ethylene oxide; reaction products of fatty alcohols, for example oleyl alcohol, with from 60 to 100 mols of ethylene oxide; reaction products of lauric acid with from 10 to 20 mols of ethylene oxide; reaction products of trimethylol propane with ethylene oxide, which have an average molecular weight of 4000; reaction products of ammonia with from 20 to 30 mols of ethylene oxide; and reaction products of dimethylamine with from 50 to mols of ethylene oxide.
  • polyethylene oxides consisting of from 10 to 120 mols of ethylene oxide
  • reaction products of fatty alcohols for example oleyl alcohol, with from 60 to 100 mols of ethylene oxide
  • reaction products of lauric acid with from 10 to 20 mols of ethylene oxide
  • reaction products of trimethylol propane with ethylene oxide which have an average molecular weight of 4000
  • reaction products of ammonia with
  • R, R, R and R' represent bivalent organic radicals With 210 carbon atoms which may be substituted, in represents an integer from 0-100, n and p an integer from 1-100, Y stands for a radical selected from the group consisting of and mixtures thereof wherein R" stands for a lower aliphatic radical having 1-3 carbon atoms and X represents a hydrogen atom or an aliphatic radical which may be substituted for improving the solubility of said compounds e.g. by hydroxyl, cyano, amino, carboxyl, sulfo, or a radical of an acid of phosphorus. X may further stand for an acyl radical derived from an aliphatic monoor dicarboxylic acid.
  • Aliphatic, aromatic or mixed aliphatic-aromatic thioethers have proved suitable. Aliphatic thioethers which contain a plurality of thioether groupings in the molecule are preferred, however, because of their greater effectiveness. Furthermore, some of the sulphur atoms may be oxidised to sulphine or sulphonyl groups or some of the sulphur atoms may be treated with an alkylating agent to form sulphonium groups.
  • thioethers are condensates of 6,5- and y,' -dihydroxyalkyl sulphides with polyalklyene glycols, particularly the co-condensates of thiodiglycol and its alkyl-substituted products with polyethylene and/or polypropylene glycols, or the hydroxyethylation products and/or the propoxylation products of monoand polyvalent alcohols which contain OH groups or other oxygen atoms as solubilizing groups.
  • Derivatives of the aforementioned polythioethers can also be used with success, for example co-condensates of the aforementioned type wherein some of the sulphur atoms have been oxidized to form sulphoxide or sulphonyl groups or in which some of the sulphur atoms have been converted by alkylation agents into sulphonium groups, or in which the OH groups have been Wholly or partially esterified or etherified.
  • Dithiodiglycol HOCH CH SSCH CH OH (15) A condensation product prepared from 0.94 mol of thiodiglycol and 1 mol of polyethylene oxide having a molecular weight of 680, the terminal OH-groups of which being etherified with acrylonitrile and the nitrile groups saponified to form terminal B-carboxyethyl-groups.
  • a condensation product being produced from 10 mols of [3,,B-dimethyl-thioglycol and 1 mol of polyethylene oxide having a molecular weight of 1700, the terminal OH- groups of which are reacted with butane sultone to form terminal sulfobutyl groups.
  • a condensation product prepared from 10 mols of thiodiglycol and 1 mol of polyethylene oxide with a molecular weight of 1700, the terminal OH-groups of which being transformed with thionylchloride into the corresponding chloride which is reacted with triethylphosphite to form terminal phosphoric acid groups.
  • a condensation product prepared from 10 mols of thiodiglycol and 1 mol of a co-polymerisate of 1 mol of propylene oxide and 9 mols of polyethylene oxide having a molecular weight of 1700.
  • the difference of 0.6 between the maximum and minimum values of the densities behind a blue filter represents a measure of the unbleached residual image of the field in question of a photometric test wedge processed with a bleach fix bath without an additive.
  • Table 2 shows the corresponding density values which were obtained in a series of experiments with polyethylene oxides with and Without sulphur.
  • the amount of polythioether being added was always 0.01 g. per liter of bleach fix bath.
  • Example 1 A photometric test wedge is exposed on an ordinary commercial two-layer negative colour film. The film is then developed at 18 C. for five minutes in a colour developer of the following composition:
  • Example 2 An ordinary commercial hard grade colour paper is exposed behind a blue colour separation wedge and de veloped in the colour developer employed in Example 1. The sample is then treated for 5 minutes in a stop fix bath which has been prepared by dissolving 5 g. of anhydrous sodium acetate, 10 g. of sodium bisulphate and 120 g. of anhydrous sodium thiosulphate in 600 ml. of water and making up to 1 liter with water. The pH value of the bath is 6.0.
  • the sample is passed into the bleach fix bath employed in Example 1 without intermediate washing. If 1.0 g. of a condensate of molecular weight 1700 and containing 3.8% of sulphur and which has been prepared from 1.27 mols of thiodiglycol and 1 mol of a polyethylene oxide of molecular weight 1130 is added to the bleach fix bath a perfectly bleached yellow wedge is obtained after 8 minutes.
  • any water-soluble thiosulphates may be used as fixing agents such as alkali thiosulphates or ammonium thiosulphate.
  • the bleach fixing bath may contain as stabilising agents any water-soluble sulfite, bisulfite or metasulfite.
  • the bleach fixing bath may have an additional content of water-soluble iodides as described in copending application Ser. No. 95,735, filed March 14, 1961, by Bernard Morcher, Karl Frank and Max Heilmann.
  • the photographic material which shall be treated by the bleach fixing bath according to the invention may be developed by means of any developer composition known per se.
  • the pH-value of the bleach fixing bath according to the invention may range approximately from 5 to 8.
  • the amounts of the sulphur containing polyalkylene-oxides being added to the bleach fixing bath according to the invention it is self-evident that smaller amounts than 0.01 g./l. of the bleach fixing bath are less eifective. Higher amounts may be added.
  • the upper limit of the amount to be added is given by the solubility of said compounds, which depends on the molecular weight, the content of water-solubilizing groups and so on.
  • a process for the bleaching and fixing of a photo graphic silver halide emulsion which comprises subjecting the said emulsion to treatment with a fixing-bleaching composition
  • a fixing-bleaching composition comprising (a) a conventional bleaching agent of the group consisting of complex salts of trivalent iron and an acid of the group consisting of polycarboxylic acids and nitrogen-containing polycarboxylic acids, and
  • R, R, R" and R' are each a radical of the group consisting of alkylene radicals having up to 10 carbon atoms and phenylene, m is an integer from 0 to 100, n and p are each an integer from 1 to 100, Y is a radical of the group consisting of in which R"" is a lower aliphatic radical having up to 3 carbon atoms and X is a radical of the group consisting of (I) hydrogen, (II) alkyl containing up to 10 carbon atoms, (III) alkyl containing up to 10 carbon atoms and containing a substituent of the group consisting of cyano, amino, carboxyl, sulfo and radicals derived from acids of phosphorous, (IV) aryl, (V) aryl radicals containing a substitutent of the group consisting of amino, carboxyl, sulfo and radicals derived from acids of phosphorus, and (VI) acyl radicals of aliphatic
  • a bleaching and fixing composition for treating photographic silver halide emulsions comprising (a) a conventional bleaching agent of the group consisting of complex salts of trivalent iron and an acid of the group consisting of polycarboxylic acids and nitrogen-containing polycarboxylic acids, (b) a conventional fixing agent consisting of a watersoluble salt of thiosulfuric acid, and (c) in dissolved form at least 0.1 gram per liter of a substance of the group consisting of polyalkylene oxides having the formula:
  • R, R, R" and R are each a radical of the group consisting of alkylene radicals having up to 10 carbon atoms and phenylene, m is an integer from 0 to 100, n and p are each an integer from 1 to 100, Y is a radical of the group consisting of in which R"" is a lower aliphatic radical having up to 3 carbon atoms and X is a radical of the group consisting of (I) hydrogen, (II) alkyl containing up to 10 carbon atoms and (III) alkyl containing up to 10 carbon atoms and containing a substituent of the group consisting of cyano, amino, carboxyl, sulfo and radicals derived from acids of phosphorus, (IV) aryl, (V) aryl radicals containing a substituent of the group consisting of aminq, carboxyl, sulfo and radicals derived from acids of phosphorus, and (VI) acyl radicals of aliphatic
  • a bleaching and fixing composition for the treatment of photographic silver halide emulsions comprising an aqueous solution containing the following substances in approximately the quantities specified per liter of solution:

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US140170A 1960-06-14 1961-06-09 Bleach fixing of photographic silver images Expired - Lifetime US3241966A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA34882A DE1146363B (de) 1960-06-14 1960-06-14 Verfahren zum Bleichfixieren von photographischen Silberbildern

Publications (1)

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US3241966A true US3241966A (en) 1966-03-22

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BE (1) BE604974A (is")
DE (1) DE1146363B (is")
GB (1) GB933008A (is")

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3769014A (en) * 1971-04-19 1973-10-30 Eastman Kodak Co Beta-disulfone silver halide solubilizing agents
US3833376A (en) * 1972-11-24 1974-09-03 Minnesota Mining & Mfg Color development process and compositions
JPS49107737A (is") * 1973-02-19 1974-10-14
US3907568A (en) * 1971-10-22 1975-09-23 Fuji Photo Film Co Ltd Process for regenerating blixing solution for color photographic processing
US4201585A (en) * 1977-10-28 1980-05-06 Agfa-Gevaert, N.V. Photographic bleach compositions containing bleach-accelerating compounds
US4294914A (en) * 1978-09-14 1981-10-13 Eastman Kodak Company Photographic bleach compositions and methods of photographic processing
US4446225A (en) * 1982-03-25 1984-05-01 Fuji Photo Film Co., Ltd. Method for processing color photographic light-sensitive material
US4451132A (en) * 1981-12-17 1984-05-29 Fuji Photo Film Co., Ltd. Color photographic processing apparatus including a reverse osmosis apparatus
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP0200206A2 (en) 1985-04-30 1986-11-05 Konica Corporation Silver halide photographic light-sensitive material
EP0201027A2 (en) 1985-04-30 1986-11-12 Konica Corporation Silver halide photographic light-sensitive material
EP0202784A2 (en) 1985-04-23 1986-11-26 Konica Corporation Silver halide photographic light-sensitive material
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
DE3642244A1 (de) * 1985-12-11 1987-06-19 Fuji Photo Film Co Ltd Farbphotographisches silberhalogenidmaterial und verfahren zu dessen behandlung
US4745048A (en) * 1985-06-07 1988-05-17 Fuji Photo Film Co., Ltd. Silver halide color photographic material and method of processing the same using an improved desilvering accelerator
EP0458277A3 (en) * 1990-05-21 1991-12-18 Fuji Photo Film Co., Ltd. Composition having a fixing ability for photography and method for processing photographic materials with the same
US5266449A (en) * 1991-11-13 1993-11-30 Agfa Gevaert Ag Bleaching bath
US5633124A (en) * 1992-05-08 1997-05-27 Eastman Kodak Company Acceleration of silver removal by thioether compounds
US6824965B2 (en) 2000-08-04 2004-11-30 Agfa-Gevaert Bleach bath
WO2012035314A1 (en) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Photographic paper
WO2021213762A1 (en) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Photographic paper

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE866605C (de) * 1944-11-27 1953-02-12 Bayer Ag Verfahren zur Herstellung photographischer Abschwaecher- und Bleichfixierbaeder
DE966410C (de) * 1953-05-13 1957-08-01 Agfa Ag Verfahren zum Bleichfixieren von photographischen Silberbildern
CA545083A (en) * 1957-08-20 M. Mader Paul Removing silver and silver halide from photographic emulsions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA545083A (en) * 1957-08-20 M. Mader Paul Removing silver and silver halide from photographic emulsions
DE866605C (de) * 1944-11-27 1953-02-12 Bayer Ag Verfahren zur Herstellung photographischer Abschwaecher- und Bleichfixierbaeder
DE966410C (de) * 1953-05-13 1957-08-01 Agfa Ag Verfahren zum Bleichfixieren von photographischen Silberbildern

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3769014A (en) * 1971-04-19 1973-10-30 Eastman Kodak Co Beta-disulfone silver halide solubilizing agents
US3907568A (en) * 1971-10-22 1975-09-23 Fuji Photo Film Co Ltd Process for regenerating blixing solution for color photographic processing
US3833376A (en) * 1972-11-24 1974-09-03 Minnesota Mining & Mfg Color development process and compositions
JPS49107737A (is") * 1973-02-19 1974-10-14
US4201585A (en) * 1977-10-28 1980-05-06 Agfa-Gevaert, N.V. Photographic bleach compositions containing bleach-accelerating compounds
US4294914A (en) * 1978-09-14 1981-10-13 Eastman Kodak Company Photographic bleach compositions and methods of photographic processing
US4451132A (en) * 1981-12-17 1984-05-29 Fuji Photo Film Co., Ltd. Color photographic processing apparatus including a reverse osmosis apparatus
US4446225A (en) * 1982-03-25 1984-05-01 Fuji Photo Film Co., Ltd. Method for processing color photographic light-sensitive material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP0202784A2 (en) 1985-04-23 1986-11-26 Konica Corporation Silver halide photographic light-sensitive material
EP0200206A2 (en) 1985-04-30 1986-11-05 Konica Corporation Silver halide photographic light-sensitive material
EP0201027A2 (en) 1985-04-30 1986-11-12 Konica Corporation Silver halide photographic light-sensitive material
US4745048A (en) * 1985-06-07 1988-05-17 Fuji Photo Film Co., Ltd. Silver halide color photographic material and method of processing the same using an improved desilvering accelerator
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
DE3642244A1 (de) * 1985-12-11 1987-06-19 Fuji Photo Film Co Ltd Farbphotographisches silberhalogenidmaterial und verfahren zu dessen behandlung
US4780403A (en) * 1985-12-11 1988-10-25 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing disulfide type bleach accelerator
DE3642244C2 (de) * 1985-12-11 1998-07-02 Fuji Photo Film Co Ltd Farbphotographisches Silberhalogenidaufzeichnungsmaterial
EP0458277A3 (en) * 1990-05-21 1991-12-18 Fuji Photo Film Co., Ltd. Composition having a fixing ability for photography and method for processing photographic materials with the same
US5429914A (en) * 1990-05-21 1995-07-04 Fuji Photo Film Co., Ltd. Composition having a fixing ability for photography and method for processing photographic materials with the same
US5266449A (en) * 1991-11-13 1993-11-30 Agfa Gevaert Ag Bleaching bath
US5633124A (en) * 1992-05-08 1997-05-27 Eastman Kodak Company Acceleration of silver removal by thioether compounds
US6824965B2 (en) 2000-08-04 2004-11-30 Agfa-Gevaert Bleach bath
WO2012035314A1 (en) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Photographic paper
WO2021213762A1 (en) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Photographic paper

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Publication number Publication date
BE604974A (is")
GB933008A (en) 1963-07-31
DE1146363B (de) 1963-03-28

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