EP0569576B1 - Photographisches bleichmittel - Google Patents

Photographisches bleichmittel Download PDF

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Publication number
EP0569576B1
EP0569576B1 EP92924624A EP92924624A EP0569576B1 EP 0569576 B1 EP0569576 B1 EP 0569576B1 EP 92924624 A EP92924624 A EP 92924624A EP 92924624 A EP92924624 A EP 92924624A EP 0569576 B1 EP0569576 B1 EP 0569576B1
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Prior art keywords
bleach
formula
bleach solution
solution
group
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English (en)
French (fr)
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EP0569576A1 (de
Inventor
John Richard C/O Kodak Limited Fyson
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Kodak Ltd
Eastman Kodak Co
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Kodak Ltd
Eastman Kodak Co
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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

Definitions

  • This invention relates to photographic bleach compositions for use in photographic colour processing.
  • peroxy compounds e.g. hydrogen peroxide or a compound capable of releasing hydrogen peroxide
  • Some peroxide bleach solutions must contain an organic metal complex salt e.g. US Specification 4 301 236, while others must employ a bleach accelerator e.g. Japanese specifications 611250647A and 611261739A.
  • a photographic bleach solution comprising hydrogen peroxide, or a compound capable of releasing hydrogen peroxide, and in combination two or more sequestering agents for complexing with a transition metal which will inhibit the decomposition of the bleach, wherein the pH of the solution is in the alkaline range.
  • Sequestering agents which may be suitable include two or more of the following:-
  • a single sequestering agent is used some stabilising effect occurs but this is surprisingly dependent upon the pH used.
  • a compound of formula (I) such as 'DTPA', has negligible effect at an alkaline pH, as mentioned hereinbefore, at a mildly acidic pH, for example pH 6.0, it can be highly effective in stabilising bleach.
  • a compound of formula (I) is represented by the structure.
  • Examples of compounds of formula (I) that are particularly suitable are ethylenediaminetetraacetic acid 'EDTA', propylenediaminetetraacetic acid 'PDTA', nitrilotriacetic acid 'NTA' but most preferably diethylenetriaminepentaacetic acid 'DTPA', these compounds generally being used in the form of their corresponding tetra- or penta-sodium salts.
  • X a hydrogen atom, a halogen atom or a hydroxyl group
  • Compounds of formula (III) and (IV) are both more effective in stabilising bleach at a mildly acidic pH, these compounds having the formulae represented hereinunder:- wherein R 1 , R 2 , R 3 and R 4 are the same or different and each is a hydrogen atom, a straight or branched chain alkyl group having 1 to 6 carbon atoms, a hydroxyl, sulphonyl or carboxyl group, especially dihydroxyphenyl sulphonate ('catechol' disulphonate 'CDS') or 'TIRON' and HO(P(O)(OH)O-) n H (IV) wherein n is from 4 to 12, preferably 4 to 8 or an alkali metal salt thereof, such as 'QUADRAFOS'TM or 'CALGON'TM.
  • a synergistic effect may be said to occur when at some time during the storage of the bleach solution the combined stabilising effect of two or more of the components is greater than the sum of the individual stabilising effects of the two or more components.
  • such an effect may result by the combination of a polyalkylcarboxylic acid of formula (I) or a salt thereof with a diphosphonic acid of formula (II) or a polyphosphate of formula (IV) or an alkali metal salt thereof.
  • the combination comprises diethylenetriaminepentaacetic acid, 'DTPA' or a salt thereof and 1-hydroxy-ethylidene-1,1diphosphonic acid, 'HEPA'.
  • the components may be combined with the ratio of any two components being in the range 1:1 to 1:10 by volume wherein either component may be present in the greater amount.
  • Each sequestering agent as a component in the synergistic combination is added in an amount of from .005 to 5% by weight of bleach solution, preferably from 0.04 to 0.1% by weight.
  • Compounds capable of releasing hydrogen peroxide include metal peroxides; compounds which include hydrogen peroxide in their crystal structure such as sodium percarbonate; other peroxy compounds such as sodium perborate and persulphate; or soluble organic peroxides, such as butyl peroxide or benzyl peroxide.
  • the hydrogen peroxide or a compound such as mentioned above is added in a sufficient quantity to enable the bleach step to take place in a suitable length of time.
  • 30% hydrogen peroxide is used in an amount of from 20 to 100 ml/litre bleach solution, preferably about 50ml/litre, but equivalent amounts of, for example, 8% or 3% hydrogen peroxide may also be used.
  • the bleach solution preferably has one or more acids, alkalis or buffers to maintain the pH at the required level, such as an alkali metal carbonate, carbonate/hydrogen carbonate buffer, phosphate buffer, amine/borate buffer, boric acid, or a carboxylic acid, such as acetic acid, propionic acid or glycollic acid.
  • acids, alkalis or buffers to maintain the pH at the required level, such as an alkali metal carbonate, carbonate/hydrogen carbonate buffer, phosphate buffer, amine/borate buffer, boric acid, or a carboxylic acid, such as acetic acid, propionic acid or glycollic acid.
  • the bleach solutions of the present invention may be used with any type of photographic silver halide colour material.
  • Such materials and their possible constituents are described, for example, in Research Disclosure Item 308119, December 1989, published by Kenneth Mason Publications, Emsworth, Hants., United Kingdom. However materials based on predominantly silver chloride emulsions are preferred.
  • the present invention also provides a method of photographic colour processing including a bleach step, which comprises the addition of hydrogen peroxide, or a compound capable of releasing hydrogen peroxide, and in combination two or more sequestering agents for complexing with a transition metal which will inhibit catalytic decomposition of the bleach.
  • a bleach step which comprises the addition of hydrogen peroxide, or a compound capable of releasing hydrogen peroxide, and in combination two or more sequestering agents for complexing with a transition metal which will inhibit catalytic decomposition of the bleach.
  • the bleach step may directly follow the developing or redox amplification stages or an intermediate stop bath may be employed.
  • the photographic material to be processed preferably contains low levels of silver and is preferably based on emulsions which comprise at least 80%, preferably at least 90%, silver chloride and especially substantially pure silver chloride.
  • a peroxide bleach suitable for use with a low silver paper material, was made up with the following formula: hydrogen peroxide 30% 50ml sodium hydrogen carbonate 25g potassium chloride 0.5g tap water to 1 litre
  • the amount of residual hydrogen peroxide was determined using the method outlined on page 363 of the 3rd edition of 'A Text-book of Quantitative Inorganic Analysis' by Vogel. The titration was made with 5g/l sodium thiosulphate. The residual peroxide was determined as the amount of this solution need to reach the end point.

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  • General Physics & Mathematics (AREA)
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Claims (16)

  1. photographische Bleichlösung, die Wasserstoffperoxid enthält oder eine Verbindung, die Wasserstoffperoxid freizusetzen vermag und in Kombination hiermit zwei oder mehrere Sequestriermittel zur Komplexbildung mit einem Übergangsmetall, welche die Zersetzung der Bleichlösung inhibiert, wobei der pH-Wert der Lösung im alkalischen Bereich liegt.
  2. Bleichlösung nach Anspruch 1, in der jedes Sequestriermittel ausgewählt ist aus einer Polyalkyl-carboxyl-, -phosphon- oder -sulfonsäure der Formel (I)
    Figure imgb0011
    worin X1 und X2 gleich oder verschieden sein können und jeweils stehen für ein Wasserstoffatom, eine geradkettige oder verzweigtkettige Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, eine Hydroxyl-, carboxyl-, Sulfonyl- oder Phosphonylgruppe oder die Gruppe Z,
    wobei Z =
    Figure imgb0012
    worin a, b, c und d gleich oder verschieden sind und jeweils stehen für ein Wasserstoffatom, eine geradkettige oder verzweigtkettige Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, eine Hydroxyl-, Carboxyl-, Sulfonyl- oder Phosphonylgruppe oder
    entweder X1 und/oder X2 können wiederkehrende Einheiten von A oder B sein,
    Y ist definiert wie für a, b, c und d angegeben oder steht für die Gruppe Z oder die Gruppe B,
    Figure imgb0013
     worin X3 und X4 gleich oder verschieden sind und definiert sind, wie für X1 und X2 angegeben,
    wobei die Summe von m, n und r eine ganze Zahl von 1 bis 10 ist, und
    worin ein oder beide der Wasserstoffatome in jeder der -(CH2)-m,-(CH2)-n oder -(CH2)-r-Gruppen ersetzt sein kann durch eine geradkettige oder verzweigtkettige Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, wobei gilt, daß mindestens einer der Reste X1, X2, X3 und X4 eine Carboxyl-, Sulfonyl- oder Phosphonylgruppe oder ein Salz hiervon ist oder eine solche enthält;
    einer Diphosphonsäure der Formel (II)
    Figure imgb0014
     worin X steht für ein Wasserstoffatom, ein Halogenatom oder eine Hydroxylgruppe und n steht für 0 bis 12;
    einem Polyhydroxyphenyl der Formel (III)
    Figure imgb0015
     worin R1, R2, R3 und R4 gleich oder verschieden sind und jeweils stehen für ein Wasserstoffatom, eine geradkettige oder verzweigtkettige Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, eine Hydroxyl-, Sulfonyl- oder Carboxylgruppe,
    und einem Polyphosphat der Formel (IV)

            HO(P(O)OH)O-)nH

       worin n steht für 4 bis 12
       oder einem Alkalimetallsalz hiervon.
  3. Bleichlösung nach Anspruch 2, mit einer Verbindung der Formel (I), worin mindestens einer der Reste X1, X2, X3 und X4 eine Carboxylsäuregruppe ist.
  4. Bleichlösung nach einem der Ansprüche 2 und 3, die in Kombination miteinander enthält eine Polyalkylcarboxylsäure der Formel (I), oder ein Salz hiervon, sowie eine Diphosphonsäure der Formel (II) oder ein Polyphosphat der Formel (IV) oder ein Alkalimetallsalz hiervon.
  5. Bleichlösung nach einem der Ansprüche 2 bis 4, in der die Polyalkylcarboxylsäure der Formel(I) Diethylentriaminpentaessigsäure ist.
  6. Bleichlösung nach einem der Ansprüche 2 und 4, in der die Verbindung der Formel (II) 1-Hydroxyethyliden-1,1-diphosphonsäure ist.
  7. Bleichlösung nach Anspruch 2, in der die Verbindung der Formel (III) Dihydroxyphenylsulfonat ist.
  8. Bleichlösung nach einem der Ansprüche 2 und 4, worin in der Verbindung der Formel (IV) n für 4 bis 8 steht.
  9. Bleichlösung nach einem der Ansprüche 2 bis 6, in der Diethylentriaminpentaessigsäure kombiniert ist mit 1-Hydroxyethyliden-1,1-diphosphonsäure in einer synergistischen Kombination.
  10. Bleichlösung nach einem der vorstehenden Ansprüche, in der das Verhältnis von beliebigen zwei Komponenten im Bereich von 1:1 bis 1:10 auf Volumenbasis liegt, wobei jede Komponente in der größeren Menge vorliegen kann.
  11. Bleichlösung nach einem der vorstehenden Ansprüche, in der jedes Sequestriermittel in der Kombination in einer Menge von 0,005 bis 5 Gew.-% der Bleichlösung zugegeben wird.
  12. Bleichlösung nach Anspruch 11, in der das Sequestriermittel in einer Menge von 0,04 bis 0,1 Gew.-% der Bleichlösung zugegeben wird.
  13. Bleichlösung nach einem der vorstehenden Ansprüche, in der 30 %-iges Wasserstoffperoxid in einer Menge von 20 bis 100 ml, vorzugsweise 50 ml, pro Liter Lösung verwendet wird.
  14. Verfahren zur farbphotographischen Entwicklung mit einer Bleichstufe, die die Zugabe von Wasserstoffperoxid oder einer Verbindung, die Wasserstoffperoxid freizusetzen vermag und in Kombination hiermit die Verwendung von zwei oder mehreren Sequestriermitteln zur Komplexbildung mit einem Übergangsmetall, die die katalytische Zersetzung des Bleichbades inhibiert, wobei der pH-Wert der Lösung im alkalischen Bereich liegt.
  15. Verfahren nach Anspruch 14, bei dem die Bleichlösung eine solche ist, wie sie in einem der Ansprüche 1 bis 13 beansprucht wird.
  16. Verwendung einer Bleichlösung nach einem der Ansprüche 1 bis 13, in einem Verfahren zur farbphotographischen Entwicklung, wie es in Anspruch 14 beansprucht wird.
EP92924624A 1991-12-03 1992-11-30 Photographisches bleichmittel Expired - Lifetime EP0569576B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9125687 1991-12-03
GB919125687A GB9125687D0 (en) 1991-12-03 1991-12-03 Photographic bleach composition
PCT/EP1992/002762 WO1993011459A1 (en) 1991-12-03 1992-11-30 Photographic bleach composition

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EP0569576A1 EP0569576A1 (de) 1993-11-18
EP0569576B1 true EP0569576B1 (de) 1997-08-06

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EP (1) EP0569576B1 (de)
JP (1) JP3266259B2 (de)
DE (1) DE69221471T2 (de)
GB (1) GB9125687D0 (de)
WO (1) WO1993011459A1 (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0679945B1 (de) * 1994-04-20 1998-08-19 Eastman Kodak Company Verarbeitung eines photographischen Silberhalogenidelement mit einer Wasserstoffperoxid-Bleichzusammensetzung
US5783376A (en) * 1994-04-20 1998-07-21 Eastman Kodak Company Sulfo-substituted carboxylates as buffers for photographic bleaches and bleach-fixes
JP3455323B2 (ja) * 1994-04-20 2003-10-14 イーストマン コダック カンパニー 漂白用組成物
US5763147A (en) * 1995-02-21 1998-06-09 Eastman Kodak Company Method for processing high silver bromide color negative photographic films using a peroxide bleaching composition
US5614355A (en) * 1995-02-21 1997-03-25 Eastman Kodak Company Peroxide composition and method for processing color photographic elements containing predominantly chloride silver halide emulsions
US5773202A (en) * 1995-02-21 1998-06-30 Haye; Shirleyanne Elizabeth Method for processing color photographic films using a peroxide bleaching composition
US5554491A (en) * 1995-03-21 1996-09-10 Eastman Kodak Company Use of an alkaline prebath to activate an acidic peroxide bleach solution for processing color photographic elements
US5541041A (en) * 1995-04-17 1996-07-30 Eastman Kodak Company Stabilized peroxide bleaching solutions containing multiple chelating ligands and their use for processing of photographic elements
US5550009A (en) * 1995-04-17 1996-08-27 Eastman Kodak Company Stabilized peroxide bleaching solutions and their use for processing of photographic elements
DK2225175T3 (da) 2007-12-13 2013-03-18 Akzo Nobel Nv Stabiliserede hydrogenperoxidopløsninger

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4277556A (en) * 1976-08-18 1981-07-07 Konishiroku Photo Industry Co., Ltd. Process for treating light-sensitive silver halide color photographic materials
JPS5814834A (ja) * 1981-07-21 1983-01-27 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の安定化処理方法
US4933266A (en) * 1988-03-01 1990-06-12 Eastman Kodak Company Photographic bleaching and bleach-fixing solutions

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JPH06505573A (ja) 1994-06-23
WO1993011459A1 (en) 1993-06-10
GB9125687D0 (en) 1992-01-29
EP0569576A1 (de) 1993-11-18
DE69221471T2 (de) 1998-03-19
JP3266259B2 (ja) 2002-03-18
DE69221471D1 (de) 1997-09-11

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