EP0569576B1 - Photographic bleach composition - Google Patents
Photographic bleach composition Download PDFInfo
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- 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
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- 239000007844 bleaching agent Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000003352 sequestering agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- 230000000536 complexating effect Effects 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- -1 alkali metal salt Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229960003330 pentetic acid Drugs 0.000 claims description 6
- 125000005499 phosphonyl group Chemical group 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 5
- 229920000388 Polyphosphate Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 239000001205 polyphosphate Substances 0.000 claims description 5
- 235000011176 polyphosphates Nutrition 0.000 claims description 5
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 claims description 3
- VZYDKJOUEPFKMW-UHFFFAOYSA-N 2,3-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=CC(S(O)(=O)=O)=C1O VZYDKJOUEPFKMW-UHFFFAOYSA-N 0.000 claims description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000011885 synergistic combination Substances 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 description 10
- 230000003019 stabilising effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000004061 bleaching Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- ISWQCIVKKSOKNN-UHFFFAOYSA-L Tiron Chemical compound [Na+].[Na+].OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O ISWQCIVKKSOKNN-UHFFFAOYSA-L 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 239000013068 control sample Substances 0.000 description 3
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LFMQNMXVVXHZCC-UHFFFAOYSA-N 1,3-benzothiazol-2-yl n,n-diethylcarbamodithioate Chemical compound C1=CC=C2SC(SC(=S)N(CC)CC)=NC2=C1 LFMQNMXVVXHZCC-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- CJAZCKUGLFWINJ-UHFFFAOYSA-N 3,4-dihydroxybenzene-1,2-disulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C(S(O)(=O)=O)=C1O CJAZCKUGLFWINJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004972 metal peroxides Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- G03C7/30—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)
- Detergent Compositions (AREA)
Abstract
Description
- This invention relates to photographic bleach compositions for use in photographic colour processing.
- There are a number of proposals in the art to use peroxy compounds, e.g. hydrogen peroxide or a compound capable of releasing hydrogen peroxide, in bleach compositions in conventional colour processes. 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. - In U.S.
specification 4 277 556 there are described bleach solutions having a pH between 2.0 and 5.5 consisting of a hydrogen peroxide solution and a mono- or dicarboxylic acid, or an alkylidene diphosphonic acid, typically 50ml/l 30% of hydrogen peroxide solution and 30 ml/l concentrated acetic acid. Such solutions however do not bleach the entire amount of silver present. U.S. Specification 4 454 224 describes an improvement on this in which the hydrogen peroxide bleach solution is alkaline having a pH of 7 or more and contains a polyacetic acid such as diethylenetriaminepentaacetic acid or 'DTPA'. This complexes with the silver ion formed by the oxidising action of the peroxy compound and the silver complex thus formed, being soluble in the photofixing composition, can then be readily removed. In spite of all these suggestions no such solution has ever been used commercially. There is further disclosed in European Patent Application Publication No. 0 428 101 Al an alkaline bleach solution containing a water-soluble chloride for producing rapid desilvering to which an organic phosphonic acid may be added to eliminate blister formation. - It has also been established that peroxide bleaches used for processes for low silver materials are unstable and decompose in a matter of days or even hours, becoming unusable. Complex metal ions, which are naturally present in the water used to make up the bleach or which leach out of the paper during processing, catalyse the decomposition of the peroxide in the bleach. In U.S.
Specification 4 454 224 it can be seen that 'DTPA' has little or no stabilising effect on the bleaching agent at the pH used. - It has now been found, however, that the addition of even a tiny amount of a combination of two or more sequestering agents which can complex with a transition metal ion, can significantly enhance the stability of peroxide bleaches at a particular pH range. This preservation of the active ingredient of the bleach causes a reduction in waste and is inexpensive compared to replacement of the solution.
- According to the present invention therefore there is provided 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 polyalkyl-carboxylic, -phosphonic or -sulphonic acid containing at least one amine group which has condensed with one or more alkyl hydrogens of the alkyl-carboxylic, -phosphonic or -sulphonic acid, such as a compound of formula (I) as defined hereinbelow or a salt thereof;
- an alkylidene -1, 1-diphosphonic acid, such as a compound of formula (II) as defined hereinbelow;
- a polyhydroxyphenyl such as a compound of formula (III) as defined hereinbelow; or
- a polyphosphate such as a compound of formula (IV), as defined hereinbelow, or an alkali metal salt thereof.
- If a single sequestering agent is used some stabilising effect occurs but this is surprisingly dependent upon the pH used. Thus although 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.
-
- wherein X1 and X2 may be 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, carboxyl, sulphonyl or phosphonyl group or the group Z,
- wherein Z =
- wherein a, b, c and d 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, carboxyl, sulphonyl or phosphonyl group or either X1 and/or X2 may be repeat units of A or B,
- Y is as defined for a, b, c and d or is the group Z or the group B,
- wherein X3 and X4 are the same or different and are as defined for X1 and X2 wherein the sum of m, n and r is an integer from 1 to 10 and
- wherein one or both of the hydrogen atoms in each of the (cH2)m,(CH2)n or (CH2)r groups may be replaced by a straight or branched chain alkyl group having 1 to 6 carbon atoms,
- with the proviso that at least one of X1, X2, X3 and X4 is or contains a carboxylic, sulphonyl or phosphonyl group, or a salt thereof.
- 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.
- In contrast, an alkylidene -1, 1-diphosphonic acid of formula (II)
HO(P(O)(OH)O-)nH (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. - However, according to the invention and for optimum bleaching efficiency a combination of two or more sequestering agents is used. Thus, although 'DTPA' has little effect at an alkaline pH, its combination with the effective 'HEPA' produces a further enhanced or 'synergistic' effect.
- 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.
- In a preferred aspect of this invention 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.
- In a most preferred aspect of this invention 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. Conveniently commercially available 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.
- 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.
- 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.
- The invention will now be described with reference to the following examples which in no way limit the scope of the invention.
- 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 - To this solution was added lml of water containing 0.1% by weight of each of the transition metals copper (II), iron (III) and manganese (II) as their sulphates, giving a final concentration of each of these metal ions of 1 ppm.
- To a 100ml sample of this bleach, 0.lml of 1-hydroxyethylidene-1,1-diphosphonic acid ('HEPA') was added. To another 100ml sample 0.1ml 80% diethylenetriaminepentaacetic acid ('DTPA') was added and to yet another 100ml sample 0.lml of each of 'HEPA' and 'DTPA' was added. A control sample of 100ml with no sequestering agent was also taken. The pH of each sample was adjusted to 8.0 with sodium hydroxide solution or dilute sulphuric acid as appropriate and the solutions transferred into clean brown glass bottles, which were kept in the dark at room temperature (about 20°C).
- At intervals 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.
- The results, which are shown graphically in Figure 1, show that 'HEPA' preserves the hydrogen peroxide to a substantial extent and an even greater improvement results by the addition of 'DTPA', indicating a synergistic effect between the sequestering agents, even though 'DTPA' on its own has little or no effect.
- Thus, whereas the relative peroxide concentration of the control sample and 'DTPA' falls to zero within 10 days, with both 'HEPA' and the combination of 'HEPA' and 'DTPA' very little peroxide is destabilised until three weeks have elapsed and there is still a residual effect after six weeks.
- In order to try the bleaching ability of the stored bleach it was tested as described in Example 2 of WO-A-92/07300. The time for bleaching increased by no more than 100% after one month, whereas a solution with no addenda was bleach-inactive in considerably less than one week.
- The above experiment was repeated with the pH, however, adjusted to 6.0 with sodium hydroxide solution or dilute sulphuric scid as appropriate, using separate samples of 'HEPA', 'DTPA', catechol disulphonate ('TIRON'™) and a polyphosphate ('QUADRAFOS'™), and also a control sample with no sequestering agent present.
- The results, which are shown graphically in Figure 2, show that each sequestering agent tested had a substantial peroxide stabilising effect when compared with the control, with 'DTPA' and 'TIRON'™ having negligible loss in effect even after 6 weeks, 'QUADRAFOS'™ retaining a good level for this time and 'HEPA' only falling to nil peroxide concentration after this 6 week period compared with 2 weeks for the control.
- The bleaching ability of the stored bleach was confirmed as described in Example 1.
Claims (16)
- 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 decomposition of the bleach, wherein the pH of the solution is in the alkaline range.
- A bleach solution as claimed in claim 1, wherein each sequestering agent is selected from a polyalkyl-carboxylic, -phosphonic or -sulphonic acid of formula (I)wherein X1 and X2 may be 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, carboxyl, sulphonyl or phosphonyl group or the group Z,wherein a, b, c and d 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, carboxyl, sulphonyl or phosphonyl group or either X1 and/or X2 may be repeat units of A or B,wherein X3 and X4 are the same or different and are as defined for X1 and X2 wherein the sum of m, n and r is an integer from 1 to 10 andwherein one or both of the hydrogen atoms in each of the (CH2)m,(CH2)n or (CH2)r groups may be replaced by a straight or branched chain alkyl group having 1 to 6 carbon atoms,with the proviso that at least one of X1, X2, X3 and X4 is or contains a carboxylic, sulphonyl or phosphonyl group, or a salt thereof;a diphosphonic acid of formula (II)
a polyhydroxyphenyl of formula (III)
HO(P(O)OH)0-)nH
wherein n is from 4 to 12
or an alkali metal salt thereof. - A bleach solution as claimed in claim 2, comprising a compound of formula (I), wherein at least one of X1, X2, X3 and X4 is a carboxylic acid group.
- A bleach solution as claimed in either of claims 2 and 3, comprising in combination 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.
- A bleach solution as claimed in any one of claims 2 to 4, wherein the polyalkylcarboxylic acid of formula (I) is diethylenetriaminepentaacetic acid.
- A bleach solution as claimed in either of claims 2 and 4, wherein the compound of formula (II) is 1-hydroxyethylidene-1,1-diphosphonic acid.
- A bleach solution as claimed in claim 2, wherein the compound of formula (III) is dihydroxyphenyl sulphonate.
- A bleach solution as claimed in either of claims 2 and 4 wherein in the compound of formula (IV) n is from 4 to 8.
- A bleach solution as claimed in any one of claims 2 to 6, wherein diethylenetriaminepentaacetic acid is combined with 1-hydroxyethylidene-1,1-diphosphonic acid in a synergistic combination.
- A bleach solution as claimed in any one of the preceding claims, wherein the ratio of any two components is in the range 1:1 to 1:10 by volume wherein either component may be present in the greater amount.
- A bleach solution as claimed in any one of the preceding claims, wherein each sequestering agent in the combination is added in an amount of from .005 to 5% by weight of bleach solution.
- A bleach solution as claimed in claim 11, wherein the sequestering agent is added in an amount of from 0.04% to 0.1% by weight of bleach solution.
- A bleach solution as claimed in any one of the preceding claims, wherein 30% hydrogen peroxide is used in an amount of from 20 to 100ml, preferably 50ml, per litre of solution.
- 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, wherein the pH of the solution is in the alkaline range.
- A method as claimed in claim 14, wherein the bleach solution is as claimed in any one of claims 1 to 13.
- The use of a bleach solution as claimed in any one of claims 1 to 13 in a method of photographic colour processing as claimed in claim 14.
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 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0569576A1 EP0569576A1 (en) | 1993-11-18 |
EP0569576B1 true EP0569576B1 (en) | 1997-08-06 |
Family
ID=10705611
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92924624A Expired - Lifetime EP0569576B1 (en) | 1991-12-03 | 1992-11-30 | Photographic bleach composition |
Country Status (5)
Country | Link |
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EP (1) | EP0569576B1 (en) |
JP (1) | JP3266259B2 (en) |
DE (1) | DE69221471T2 (en) |
GB (1) | GB9125687D0 (en) |
WO (1) | WO1993011459A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0679945B1 (en) * | 1994-04-20 | 1998-08-19 | Eastman Kodak Company | Processing of a silver halide photgraphic with a peroxide bleach composition |
US5783376A (en) * | 1994-04-20 | 1998-07-21 | Eastman Kodak Company | Sulfo-substituted carboxylates as buffers for photographic bleaches and bleach-fixes |
JP3455323B2 (en) * | 1994-04-20 | 2003-10-14 | イーストマン コダック カンパニー | Bleaching composition |
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 (en) | 2007-12-13 | 2013-03-18 | Akzo Nobel Nv | Stabilized hydrogen peroxide solutions |
Family Cites Families (3)
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 (en) * | 1981-07-21 | 1983-01-27 | Konishiroku Photo Ind Co Ltd | Method for stabilizing silver halide color photosensitive material |
US4933266A (en) * | 1988-03-01 | 1990-06-12 | Eastman Kodak Company | Photographic bleaching and bleach-fixing solutions |
-
1991
- 1991-12-03 GB GB919125687A patent/GB9125687D0/en active Pending
-
1992
- 1992-11-30 WO PCT/EP1992/002762 patent/WO1993011459A1/en active IP Right Grant
- 1992-11-30 JP JP50981993A patent/JP3266259B2/en not_active Expired - Fee Related
- 1992-11-30 EP EP92924624A patent/EP0569576B1/en not_active Expired - Lifetime
- 1992-11-30 DE DE69221471T patent/DE69221471T2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH06505573A (en) | 1994-06-23 |
WO1993011459A1 (en) | 1993-06-10 |
GB9125687D0 (en) | 1992-01-29 |
EP0569576A1 (en) | 1993-11-18 |
DE69221471T2 (en) | 1998-03-19 |
JP3266259B2 (en) | 2002-03-18 |
DE69221471D1 (en) | 1997-09-11 |
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