EP1172691A1 - Procédé et solutions de blanchiment pour le traitement de produits photographiques pour la préparation d'images suivant le procédé de blanchiment des couleurs à l'argent - Google Patents

Procédé et solutions de blanchiment pour le traitement de produits photographiques pour la préparation d'images suivant le procédé de blanchiment des couleurs à l'argent Download PDF

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Publication number
EP1172691A1
EP1172691A1 EP00810614A EP00810614A EP1172691A1 EP 1172691 A1 EP1172691 A1 EP 1172691A1 EP 00810614 A EP00810614 A EP 00810614A EP 00810614 A EP00810614 A EP 00810614A EP 1172691 A1 EP1172691 A1 EP 1172691A1
Authority
EP
European Patent Office
Prior art keywords
acid
bleaching
photographic silver
acid component
materials according
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.)
Withdrawn
Application number
EP00810614A
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German (de)
English (en)
Inventor
Pierre Dr. Favre
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.)
Ilford Imaging Switzerland GmbH
Original Assignee
Ilford Imaging Switzerland GmbH
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 Ilford Imaging Switzerland GmbH filed Critical Ilford Imaging Switzerland GmbH
Priority to EP00810614A priority Critical patent/EP1172691A1/fr
Publication of EP1172691A1 publication Critical patent/EP1172691A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/266—Supplying of photographic processing chemicals; Preparation or packaging thereof of solutions or concentrates
    • 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

Definitions

  • the invention relates to a new method for processing exposed and developed silver color bleaching materials and suitable for this process Preparations in the form of ready-to-use aqueous solutions or with Water-dilutable concentrates in liquid or solid form.
  • process steps (B) and (C), (C) and (D) or (B), (C) and (D) can be combined. Most common is the combination of process steps (B) and (C).
  • Those used for color and / or silver bleaching or combined bleaching Preparations are strongly acidic, i.e. H. they have a pH under 2, especially under 1. This pH value is set in the Usually with a single strong acid, primarily a mineral acid like Hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, Perchloric acid or phosphoric acid. Furthermore, strong ones organic acids, for example sulfamic acid, substituted sulfamic acid compounds, p-toluenesulfonic acid or other organic sulfonic acids are used become.
  • the acids can be the bleaching preparations directly as free acids or as adducts can be added with weak bases, as described in patent application EP 0'034'793 has been described.
  • the dye is generally bleached much faster than silver bleaching, especially in places that have the highest Contain a lot of metallic silver after the development step. Therefore the bleaching of the metallic silver at these points is generally the rate-determining one Factor that prevents the bleaching step from being shortened.
  • bleach accelerators generally quaternary ammonium salts or tertiary amines.
  • Patent applications DE 2'139'401, DE 2'651'969, DE 2'716'135 and EP 0'517'989 water-soluble phosphines are claimed as bleach accelerators.
  • the effectiveness this bleach accelerator depends very much on the external conditions from. Furthermore, some of the most effective bleach accelerators are very expensive or difficult to obtain.
  • the bleaching baths used today have the disadvantage that the speed bleaching is insufficient. This leads to an undesirably long treatment time at a relatively low temperature or to a high degree of corrosivity, high Evaporation and high oxidation at elevated temperature and reduced treatment time.
  • the aim of the present invention is to provide preparations for bleaching photographic silver color bleaching materials that allow the bleaching time respectively. Shorten processing time and / or the bleaching temperature resp. Lower processing temperature.
  • Another object of the invention is to provide preparations for bleaching photographic silver color bleaching materials that allow it without use of bleaching accelerators the same or shorter bleaching times with the same Temperature in comparison to known preparations containing bleach accelerators to reach.
  • Another object of the invention is to provide inexpensive preparations without bleach accelerator for bleaching photographic silver color bleaching materials, the other advantages, for example with regard to ecology, toxicity, ecotoxicity, Have solubility, stability and exploitability.
  • Another object of the invention are concentrates and partial concentrates for Production of ready-to-use aqueous bleaching preparations.
  • the present invention relates to a method for processing exposed and developed photographic silver color bleaching materials by the exposed and developed material treated with aqueous bleaching preparations becomes.
  • the invention is equally suitable for separate color and silver bleach baths as well as for combined color and silver bleach baths.
  • the main acid component is used to adjust the pH value of the bleaching bath to a value ⁇ 2, preferably ⁇ 1.
  • strong inorganic acids such as sulfuric acid, phosphoric acid, Hydrohalic acids or perchloric acid, sulfamic acid or substituted Sulfamic acid compounds, or strong organic sulfonic acids such as p-toluenesulfonic acid; or mixtures of these acids.
  • the purpose of the additive acid component is to increase the bleaching rate.
  • the acids of the additional acid component are organic sulfonic acids, preferred aromatic sulfonic acids. These aromatic sulfonic acids can be monosulfonic acids or be polysulfonic acids, they can be further unsubstituted or be substituted. Preferred substituents are alkyl having 1 to 3 carbon atoms, especially methyl; Halogen such as chlorine, bromine or iodine; Hydroxyl or with Alkyl with 1 to 3 carbon atoms substituted hydroxyl; unsubstituted carboxyl or carboxyl substituted with alkyl having 1 to 3 carbon atoms or Cyan.
  • the acids of the add acid component are different from those the main acid component.
  • organic sulfonic acids examples include benzenesulfonic acid, p-chlorobenzenesulfonic acid, p-hydroxybenzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid, 2-naphthalenesulfonic acid, 1-naphthalenesulfonic acid, 1-hydroxy-2-naphthalenesulfonic acid, 1-hydroxy-4-naphthalenesulfonic acid, 1,5-naphthalenedisulfonic acid and 1-hydroxy-3,6-naphthalenedisulfonic acid.
  • These acids can as free acids or as their salts, especially inorganic, in the Bleaching preparations are introduced.
  • the amount of acids in the additional acid component is 0.5 to 80 mole percent the amount of acids of the main acid component, preferably 2 to 50 mole percent from that.
  • Preferred acids of the additional acid component are p-toluenesulfonic acid, 1-naphthalenesulfonic acid and 2-naphthalenesulfonic acid or mixtures thereof.
  • a mixture of p-toluenesulfonic acid is particularly preferred as the additional acid component with 2-naphthalenesulfonic acid.
  • the baths used for color bleaching contain the most important components in addition to the mixture of a main acid component and an additional acid component a complexing agent b) for the silver and one or several color bleaching catalysts c).
  • the main bleaching catalysts used are diazine compounds such as pyrazine, Quinoxaline or phenazine and their derivatives are used.
  • suitable Bleaching catalysts are described, for example, in patent applications DE 735'672, DE 1'547'720, DE 2'144'297, DE 2'144'298, DE 2'722'776 and DE 2'722'777 Service.
  • a suitable complexing agent for silver is, for example, thiourea.
  • a water-soluble iodide is preferred
  • Sodium, potassium or ammonium iodide is used, such as this has been described in US Pat. No. 3,620,744: this makes enrichment more troublesome Prevents silver complexes in the bleaching bath.
  • an antioxidant must be used be used that prevents the oxidation of iodide to iodine.
  • Reductones or water-soluble mercapto compounds are advantageously used as antioxidants d).
  • Suitable reductones are in particular aci-reductones with a 3-carbonylidene (1,2) grouping such as reductin, triose reductone or preferably ascorbic acid.
  • Suitable mercapto compounds are e.g. B. thioglycerol or compounds of the formula HS-C x H 2x -B, preferably compounds of the formula HS-C m H 2m -COOH, where x is a number between 2 and 12, B is a sulfonic acid or carboxylic acid group and m is the number 3 or 4 mean.
  • antioxidants that can be used as antioxidants have been described in patent applications DE 2'258'076 and DE 2'423'814.
  • Further suitable antioxidants are alkali metal, alkaline earth metal or ammonium bisulfite adducts of organic carbonyl compounds, preferably alkali metal or ammonium bisulfite adducts of monoaldehydes with 1 to 4 carbon atoms or of dialdehydes with 2 to 5 carbon atoms, as described in the patent application DE 2,737,142.
  • the formaldehyde bisulfite adduct and the corresponding adducts of acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, glyoxal, malondialdehyde and glutardialdehyde are particularly preferred.
  • the tertiary water-soluble phosphines mentioned below as bleach accelerators can also be used simultaneously as antioxidants.
  • Hypophosphoric acid can also be used as an antioxidant, as has been described in GB 630,222.
  • Water-soluble aromatic mononitro- and dinitro compounds and anhraquinone sulfonic acid derivatives are used.
  • the use of such oxidizing agents serves in addition to the oxidation of the silver also to influence the color balance and to lower the gradation of the images produced in the silver color bleaching process, as in the patent applications DE 735'672, GB 45394190, GB 539'509 and JP 69-22673 has been.
  • the mononitro and dinitro compounds are preferably mono- or dinitrobenzenesulfonic acids, which are alkyl with 1 to 4 carbon atoms, Hydroxyl, amino or halogen (chlorine or bromine) can be substituted.
  • the Sulfonic acids are preferably added in the form of their readily soluble salts.
  • the sodium or potassium salts of o-nitrobenzenesulfonic acid are suitable, the m-nitrobenzenesulfonic acid, the 2,4-dinitrobenzenesulfonic acid, the 3,5-dinitrobenzenesulfonic acid, 3-nitro-4-chlorobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, 4-methyl-3,5-dinitrobenzenesulfonic acid, 3-chloro-2,5-dinitrobenzenesulfonic acid, 2-amino-4-nitrobenzenesulfonic acid, 2-amino-4-nitro-5-methoxybenzenesulfonic acid and 4-nitrophenolsulfonic acid.
  • bleach catalysts if they are nitrated benzenesulfonic acids, increase the bleaching rate when adding large amounts to the bleaching bath strong. But since, as mentioned before, they change the color balance a lot, are they as aromatic sulfonic acids in the sense of our invention in the Practice not useful.
  • Suitable bleaching accelerators f) are, for example, quaternary ammonium salts, as have been described in patent applications DE 2,139,401 and DE 2,716,135.
  • the quaternary, optionally substituted piperidine, piperazine, pyrazine, quinoline and pyridine compounds are preferred, the latter being particularly preferred.
  • Tetraalkylammonium compounds alkyl with 1 to 4 carbon atoms
  • alkylenediammonium compounds alkylene with 2 to 6 carbon atoms
  • bleach accelerators are water-soluble tertiary phosphines with at least a cyanoethyl group, as described in patent application DE 2,651,969 have been.
  • All baths can contain other additives such as hardening agents, wetting agents, contain optical brighteners or UV protection agents.
  • Baths of conventional composition can be used to develop silver are, for example, those used as developer hydroquinine or ascorbic acid and optionally additionally 1-phenyl-3-pyrazolidine. Possibly the developing bath already contains a bleaching catalyst.
  • the silver fixing bath can be composed in a known and customary manner.
  • Sodium thiosulfate or preferably ammonium thiosulfate, for example, serves as the fixing agent, optionally with additives such as sodium bisulfite and / or sodium metabisulfite.
  • the fixing bath can also be combined with the bleaching bath as a so-called Bleach-fix bath available.
  • the temperature of the bleaching baths is generally between 20 ° C and 90 ° C, preferably between 20 ° C and 60 ° C, but of course at a higher temperature the required processing time is shorter than at a lower temperature.
  • the Bleach baths are stable within the specified temperature range. In general become the aqueous bleaching preparations required for processing in the form of dilute aqueous solutions containing the components mentioned included, used. However, other methods are also conceivable, for example the application in paste form.
  • the aqueous bleaching preparation according to the present invention can for example from solid or liquid, especially aqueous concentrates of individual or all components a) to f) are produced.
  • aqueous concentrates of individual or all components a) to f) are produced.
  • One uses advantageously for example two liquid concentrates, one of which is the acid mixture a) and the oxidizing agent e) and the other the other components b), c), d) and f) contains, in the latter concentrate to improve solubility, in particular component c) an additional solvent such as ethyl or propyl alcohol, Ethylene glycol monomethyl or ethyl ether can be added.
  • This Concentrates and partial concentrates, which are also the subject of the present invention have excellent stability and are therefore longer Can be stored in time. These concentrates can optionally with water or with a mixture of water and an organic solvent become.
  • the concentrates of the individual or all components a) to c) and, if appropriate d), e) and f) or their combinations, for example from the components a) and e) and components b), c), d) and f) can be two to twenty times, preferably five to ten times the amount of the individual components included as previously indicated for the ready-to-use bleach baths has been. They are usually in the form of solid, liquid or pasty concentrates in front.
  • the inventive method for processing exposed and developed Silver color bleaching materials can be more positive in manufacturing Color images in automatic copying and recording machines or in high-speed processing other silver color bleaching materials can be used.
  • Photomechrome PMC 794 was used as the silver color bleaching material manufactured by ILFORD Imaging Switzerland GmbH, Marly, Switzerland and is distributed by PMI PLC, Bookham, Great Britain.
  • Test strips of this material are exposed to 1000 luxs of white light. With such overexposed material, the image whites can be improved and the accelerated bleaching of silver when using the inventive ones Bleaching baths are particularly well demonstrated.
  • Processing takes place in successive tanks at 30 ° C in 13 successive Tanks, with the first 2 tanks developer, the following 3 tanks Bleaching bath, the next tank of water, the following 3 tanks of fixer and the last 4 tanks contain water.
  • the residence time per bath is 14 seconds, which results in a total processing time of about 3 minutes.
  • the dwell time per bath is 21 seconds, which results in a total processing time of about 41 ⁇ 2 minutes.
  • BL-222 which is available from ILFORD Imaging Switzerland GmbH, was used as the comparative bleaching bath.
  • This bleaching bath has the composition given in Table 1: component Quantity (g / l) water 966.0 sulfuric acid 49.3 Irgasol P 0.1 Sodium salt of 3-mercaptopropyl sulfonic acid 5.2 2,3,6-Trimethylchinoxalin 1.5 potassium iodide 15.0 Sodium salt of m-nitrobenzenesulfonic acid 7.6
  • Irgasol P is a wetting agent that is available from Ciba Specialty Chemicals, Basel, Switzerland.
  • the organic sulfonic acids are added in different amounts to this bleaching bath, whereby bleaching baths according to our invention are obtained.
  • all bleaching baths are set to the same final weight.
  • a comparison bleaching bath is used in which only the amount of sulfuric acid is increased.
  • the exposed material samples as described above are processed and then the amount of silver Ag res (mg / m 2 ) still present in the material and the minimum visual density D vis are determined by X-ray analysis. In practice, processing is carried out at temperatures higher than 30 ° C. In practice, images with a minimum visual density D vis > 0.15 are unusable, since such visual density is perceived as extremely disruptive in the image whites. Under the experimental conditions described here, images with a minimum visual density> 0.40 are considered unusable.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP00810614A 2000-07-12 2000-07-12 Procédé et solutions de blanchiment pour le traitement de produits photographiques pour la préparation d'images suivant le procédé de blanchiment des couleurs à l'argent Withdrawn EP1172691A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP00810614A EP1172691A1 (fr) 2000-07-12 2000-07-12 Procédé et solutions de blanchiment pour le traitement de produits photographiques pour la préparation d'images suivant le procédé de blanchiment des couleurs à l'argent

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EP00810614A EP1172691A1 (fr) 2000-07-12 2000-07-12 Procédé et solutions de blanchiment pour le traitement de produits photographiques pour la préparation d'images suivant le procédé de blanchiment des couleurs à l'argent

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EP1172691A1 true EP1172691A1 (fr) 2002-01-16

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004063574A1 (de) * 2004-12-30 2006-07-13 Osram Opto Semiconductors Gmbh Leuchtvorrichtung mit mehreren Halbleiterlichtquellen

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2699394A (en) * 1950-12-15 1955-01-11 Gaspar Bela Production of photographic dye images
DE2600675A1 (de) * 1975-01-09 1976-07-15 Fuji Photo Film Co Ltd Katalysator zur beschleunigung der farbbleichung fuer das silberfarbbleichverfahren
US4186008A (en) * 1977-03-23 1980-01-29 Ciba-Geigy Aktiengesellschaft Method for processing silver dye-bleach materials
US4304846A (en) * 1979-02-09 1981-12-08 Ciba-Geigy Ag Method for processing silver dye-bleach materials
GB2265020A (en) * 1992-03-13 1993-09-15 Ilford Ag Silver halide emulsions with increased speed

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2699394A (en) * 1950-12-15 1955-01-11 Gaspar Bela Production of photographic dye images
DE2600675A1 (de) * 1975-01-09 1976-07-15 Fuji Photo Film Co Ltd Katalysator zur beschleunigung der farbbleichung fuer das silberfarbbleichverfahren
US4186008A (en) * 1977-03-23 1980-01-29 Ciba-Geigy Aktiengesellschaft Method for processing silver dye-bleach materials
US4304846A (en) * 1979-02-09 1981-12-08 Ciba-Geigy Ag Method for processing silver dye-bleach materials
GB2265020A (en) * 1992-03-13 1993-09-15 Ilford Ag Silver halide emulsions with increased speed

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004063574A1 (de) * 2004-12-30 2006-07-13 Osram Opto Semiconductors Gmbh Leuchtvorrichtung mit mehreren Halbleiterlichtquellen

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