WO2001050196A1 - Concentres liquides de blanchiment-fixage a un composant - Google Patents

Concentres liquides de blanchiment-fixage a un composant Download PDF

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Publication number
WO2001050196A1
WO2001050196A1 PCT/US2000/034444 US0034444W WO0150196A1 WO 2001050196 A1 WO2001050196 A1 WO 2001050196A1 US 0034444 W US0034444 W US 0034444W WO 0150196 A1 WO0150196 A1 WO 0150196A1
Authority
WO
WIPO (PCT)
Prior art keywords
concentrate
phosphate
acid
fix
bleach
Prior art date
Application number
PCT/US2000/034444
Other languages
English (en)
Inventor
Laszlo Papai
Original Assignee
Trebla Chemical Company
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
Priority claimed from US09/477,565 external-priority patent/US6221570B1/en
Application filed by Trebla Chemical Company filed Critical Trebla Chemical Company
Priority to JP2001550492A priority Critical patent/JP2003529789A/ja
Priority to EP00989310A priority patent/EP1269260A4/fr
Priority to AU25830/01A priority patent/AU2583001A/en
Priority to BR0016922-6A priority patent/BR0016922A/pt
Priority to CA002396002A priority patent/CA2396002A1/fr
Publication of WO2001050196A1 publication Critical patent/WO2001050196A1/fr

Links

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
    • 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

Definitions

  • the bleaching and fixing concentrates are usually separated into two or more parts that are subsequently combined to form a working solution.
  • a two-part bleach-fixing liquid concentrate is disclosed in U.S. Patent No. 4,956,268 issued to Kiyoshi Nakazyo et al, wherein a first concentrate comprises a silver halide solvent and the second concentrate contains an oxidizing agent.
  • the components are packaged separately from each other to prevent chemical reactions that form undesirable reaction products, such as crystallized precipitates.
  • U.S. Patent No. 3,751,251 provides for a one-part liquid bleach-fix concentrated regenerator.
  • an aqueous solution of an aminopolycarboxylic acid and a thiosulfate ion are mixed with a sufficient amount of a sulfite ion, in the form of gaseous sulfur dioxide, to adjust the pH of the solution to between 5.4 and 6.0.
  • this product still has a limited shelf life due to undesirable crystal formation in the concentrate.
  • the bleaching agent may be selected from the group consisting of compounds of polyvalent metals such as iron, (III) , cobalt (III) , chromium (VI) , and copper (II) ; peracids; quinones; nitro compounds and mixtures thereof.
  • the compounds of the polyvalent metals may include iron (III) compounds such as ferric chloride; ferricyanide; bichromates; and organic complexes with aminopolycarboxylic acids, aminopolyphosphonic acids and organic phosphonic acids.
  • the polyvalent metal oxidizing agent does not precipitate out of the concentrate when a thiocyanate fixing agent is used as the sole fixing agent, or when combined with another fixing agent.
  • the shelf life of the concentrate increases as the amount of thiocyanate salt increases in the one-part bleach-fix liquid concentrate.
  • the thiocyanate salt in the one-part bleach-fix liquid concentrate is generally used in an amount greater than 0.1 mol/liter to less than 1 mole/liter of concentrate.
  • the present invention can include additional photographic processing agents; such as preservatives, alkaline agents, buffering agents, bleaching accelerators, brightening agents, anti-staining agents, defoaming agents, surfactants, fungicides, anticorrosion agents and organic solvents.
  • additional photographic processing agents such as preservatives, alkaline agents, buffering agents, bleaching accelerators, brightening agents, anti-staining agents, defoaming agents, surfactants, fungicides, anticorrosion agents and organic solvents.
  • the kit comprises a single package containing a concentrated aqueous solution comprising a bleaching agent, which oxidizes metallic silver, and at least a thiocyanate salt present in an amount sufficient to inhibit crystal formation in the one-part bleach-fix liquid concentrate.
  • the present invention provides for stabilizing one-part bleach-fix liquid concentrates by introducing a source of phosphate ions into the concentrates in amounts sufficient to inhibit crystal formation, and to maintain the concentrates within a range of pH values that are between about 4 and about 7.
  • the bleaching agent should be used in a sufficient amount to effectively oxidize any metallic silver remaining on the photographic material. More specifically, the bleaching agent may be present m an amount from about 10 percent to about 25 percent, and more preferably from about 15 percent to about 20 percent based on total weight of the concentrate. As described above, any remaining light-sensitive silver halide must be dissolved m a silver halide solvent, commonly referred to as a fixing agent. Because the silver halides are almost insoluble, they cannot be removed from the emulsion by water washing, but instead must be treated with a fixing agent, which reacts with the silver halides to form soluble complex salts. Thus, m addition to the bleaching agent, at least one fixing agent must be incorporated into the one-part bleach-fix liquid concentrates of the present invention.
  • any fixing agent that dissolves light-sensitive silver halides without affecting the silver image without causing excessive swelling or softening of the gelatin layer may be used.
  • Thiosulfates, thiocyanates, thioether compounds, thiourea, and thioglycolic acid are the most important with the proviso that wnen thiocyanate salt is used, it is used either alone or m combination with a different and distinct fixing agent.
  • any fixing agent other than a thiocyanate salt which acts as a silver halide solvent
  • thiosulfates such as sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, lithium thiosulfate, and guanidine thiosulfate, and more preferably, ammonium thiosulfate.
  • Ammonium thiosulfate is preferred because solutions containing this fixing agent show a higher rate of fixation than sodium thiosulfate solutions.
  • phosphoric acid prevents ferrous iron precipitation to such an extent that it can, by itself, stabilize the one-part bleach-fix concentrate to provide a concentrate with an increased shelf life capacity.
  • the one-part bleach-fix liquid concentrates of the present invention may be accomplished using tap, deionized, or sterilized water. Upon dilution to working strength solutions, the one-part bleach-fix liquid concentrates may be used effectively for bleaching and fixing photographic materials
  • agitation of the working solution ensures that more of the bleach-fix agents are available to the photographic materials being treated. This results in an increased bleaching and fixing rate. Agitation can be achieved by various techniques including injection of a jet flow of processing solution against the surface of the photosensitive material or increasing the rate of circulation flow through the entire processing solution.
  • the photographic material may be treated in bleach-fix working solution for generally up to 150 seconds, and preferably up to 60 seconds.
  • the components were added sequentially in a single vessel providing approximately 1 liter of the one-part concentrate of the present invention.
  • the vessel was placed in storage at ambient pressure and at a temperature of approximately 20°C.
  • the one-part liquid concentrate prepared according to the above formulation remained crystal free even after 14 months of storage.
  • one liter of a one- part concentrate was prepared without the addition of any thiocyanate salt according to the following formula:
  • the shelf life of the one- part bleach-fix liquid concentrates may exceed one year by the addition of at least 30 g of a thiocyanate salt.
  • a thiocyanate salt was added without the addition of another fixing agent the concentrate did not form crystals in two years.
  • high concentrations of thiocyanate salt may form toxic hydrogen cyanide gas during electrolytic recovery of silver from a spent bleach-fix solution.

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

Abstract

L'invention concerne des compositions et des procédés permettant de fabriquer des concentrés liquides stables de blanchiment-fixage appropriés pour être dilués dans des bains prêt à l'emploi, au moyen d'un agent oxydant métallique polyvalent de blanchiment-fixage, au moins un agent de fixation et une source d'ions phosphate. Afin d'empêcher qu'une précipitation ne se produise, ce qui arrive lorsqu'un agent de blanchiment à base de fer (III) est réduit par des composants du concentré, on ajoute des ions phosphate.
PCT/US2000/034444 2000-01-06 2000-12-18 Concentres liquides de blanchiment-fixage a un composant WO2001050196A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2001550492A JP2003529789A (ja) 2000-01-06 2000-12-18 一浴式漂白・定着濃縮液
EP00989310A EP1269260A4 (fr) 2000-01-06 2000-12-18 Concentres liquides de blanchiment-fixage a un composant
AU25830/01A AU2583001A (en) 2000-01-06 2000-12-18 One-part bleach-fix liquid concentrates
BR0016922-6A BR0016922A (pt) 2000-01-06 2000-12-18 Concentrado lìquido branqueador-fixador de parte única, método para preparar um agente branqueador e fixador de concentração de trabalho para processamento fotográfico, método para estabilizar o dito concentrado, kit de processamento fotográfico, e, solução útil para simultaneamente branquear e fixar um elemento fotográfico
CA002396002A CA2396002A1 (fr) 2000-01-06 2000-12-18 Concentres liquides de blanchiment-fixage a un composant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US09/477,565 US6221570B1 (en) 2000-01-06 2000-01-06 One-part bleach-fix liquid concentrates
US09/477,565 2000-01-06
US09/715,612 US6455236B1 (en) 2000-01-06 2000-11-17 One-part bleach-fix liquid concentrates
US09/715,612 2000-11-17

Publications (1)

Publication Number Publication Date
WO2001050196A1 true WO2001050196A1 (fr) 2001-07-12

Family

ID=27045599

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/034444 WO2001050196A1 (fr) 2000-01-06 2000-12-18 Concentres liquides de blanchiment-fixage a un composant

Country Status (6)

Country Link
EP (1) EP1269260A4 (fr)
JP (1) JP2003529789A (fr)
AU (1) AU2583001A (fr)
BR (1) BR0016922A (fr)
CA (1) CA2396002A1 (fr)
WO (1) WO2001050196A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1160622A1 (fr) * 2000-05-27 2001-12-05 Agfa-Gevaert N.V. Une solution concentrée de blanchiment-fixage
US6503002B1 (en) 1996-12-05 2003-01-07 Applied Science Fiction, Inc. Method and apparatus for reducing noise in electronic film development

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293036A (en) * 1962-04-05 1966-12-20 Agfa Ag Bleach-fix compositions and process for producing colored photographic images
US3702247A (en) * 1970-01-13 1972-11-07 Ilford Ltd Color photographic process using a bleach-fix solution containing a selenosulfate
US3879203A (en) * 1972-04-12 1975-04-22 Agfa Gevaert Ag Process for bleach-fixing color photographic silver halide material
US4814260A (en) * 1986-06-20 1989-03-21 Konishiroku Photo Industry Co., Ltd. Method of storing photographic processing solution in a package having specific oxygen permeability

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615507A (en) * 1968-12-13 1971-10-26 Eastman Kodak Co Photographic bleach-fix solutions
US3620725A (en) * 1969-01-23 1971-11-16 Technology Inc Rapid photographic development system
IL32940A (en) * 1969-03-20 1973-01-30 Kms Ind Inc Equipment and method for developing exposed color photographic emulsions
DE2506404A1 (de) * 1975-02-15 1976-08-26 Agfa Gevaert Ag Verfahren zur herstellung eines transparenten farbphotographischen bildes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293036A (en) * 1962-04-05 1966-12-20 Agfa Ag Bleach-fix compositions and process for producing colored photographic images
US3702247A (en) * 1970-01-13 1972-11-07 Ilford Ltd Color photographic process using a bleach-fix solution containing a selenosulfate
US3879203A (en) * 1972-04-12 1975-04-22 Agfa Gevaert Ag Process for bleach-fixing color photographic silver halide material
US4814260A (en) * 1986-06-20 1989-03-21 Konishiroku Photo Industry Co., Ltd. Method of storing photographic processing solution in a package having specific oxygen permeability

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1269260A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6503002B1 (en) 1996-12-05 2003-01-07 Applied Science Fiction, Inc. Method and apparatus for reducing noise in electronic film development
EP1160622A1 (fr) * 2000-05-27 2001-12-05 Agfa-Gevaert N.V. Une solution concentrée de blanchiment-fixage

Also Published As

Publication number Publication date
AU2583001A (en) 2001-07-16
CA2396002A1 (fr) 2001-07-12
EP1269260A1 (fr) 2003-01-02
JP2003529789A (ja) 2003-10-07
BR0016922A (pt) 2002-10-15
EP1269260A4 (fr) 2003-06-25

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