EP0965883A1 - Ecological cleaning liquid for photographic processor - Google Patents
Ecological cleaning liquid for photographic processor Download PDFInfo
- Publication number
- EP0965883A1 EP0965883A1 EP98202038A EP98202038A EP0965883A1 EP 0965883 A1 EP0965883 A1 EP 0965883A1 EP 98202038 A EP98202038 A EP 98202038A EP 98202038 A EP98202038 A EP 98202038A EP 0965883 A1 EP0965883 A1 EP 0965883A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver
- cleaning
- iii
- salt
- mole
- 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- Withdrawn
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- 238000004140 cleaning Methods 0.000 title claims abstract description 62
- 239000007788 liquid Substances 0.000 title abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 41
- 239000004332 silver Substances 0.000 claims abstract description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 monophosphate salt Chemical class 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013522 chelant Substances 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 13
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- KZTASAUPEDXWMQ-UHFFFAOYSA-N azane;iron(3+) Chemical compound N.[Fe+3] KZTASAUPEDXWMQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 2
- VAVPGQSSOJBZIP-UHFFFAOYSA-N sodium;iron(3+) Chemical compound [Na+].[Fe+3] VAVPGQSSOJBZIP-UHFFFAOYSA-N 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical group [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000004285 Potassium sulphite Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- PDHFSBXFZGYBIP-UHFFFAOYSA-N 2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethanol Chemical group OCCSCCSCCO PDHFSBXFZGYBIP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 241001139947 Mida Species 0.000 description 1
- 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 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001447 alkali salts Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- YNNGZCVDIREDDK-UHFFFAOYSA-N aminocarbamodithioic acid Chemical compound NNC(S)=S YNNGZCVDIREDDK-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000012928 buffer substance Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229960002433 cysteine Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- SNWIYIPDTCGIMP-UHFFFAOYSA-N dihydroxy sulfate Chemical compound OOS(=O)(=O)OO SNWIYIPDTCGIMP-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000004712 monophosphates Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000004395 organic heterocyclic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 229940075931 sodium dithionate 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
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- G03C11/00—Auxiliary processes in photography
- G03C11/005—Cleaning photographic processing and manufacturing apparatus
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3427—Organic compounds containing sulfur containing thiol, mercapto or sulfide groups, e.g. thioethers or mercaptales
Definitions
- the present invention deals with an improved ecological one-step cleaning liquid for photographic processing equipment.
- deposits can form on the walls of the various processor tanks and on the mechanical roller/belt system used to transport the photographic silver halide material through the processor. These deposits are likely to soil the next sheets or stripes of processed film or paper.
- the deposits can be metallic silver, commonly referred to as “silver sludge", insoluble silver salts and alkali metal salts.
- the deposits in the fixer tank can be silver salts, alkali metal salts, aluminum oxides and elemental sulphur.
- the deposits in the wash tanks can be alkali metal salts, gelatin and gelatin by-products which induce the growth of fungi and algae.
- the prior art utilizes different cleaning compositions for the various tanks.
- the developer tank requires a combination of a strong oxidizing agent and a silver solvent system.
- Commonly used prior art cleaning solutions contained chromate salts such as dichromate combined with sulphuric or sulphamic acid (see e.g. DE 1068840). Consecutively a neutralizer such as an alkali bisulfite solution was used to remove residual chromate salts.
- a strong caustic solution is used to dissolve the salts and silver complexes.
- the algae and fungi slime in the wash tanks can be cleaned by a chlorine bleach such as a hypochlorite solution. From a modern ecological point of view all the chemicals cited above are agressive and hazardous to the environment.
- Chromium is recognized as a pollutant and a potential carcinogen.
- Caustic solutions are very injurious to the eyes and skin.
- the hypochlorite solution for cleaning the wash tank can react with residual caustic solution, used for the fixer, giving rise to the formation of toxic gaseous chlorine.
- the cleaning composition contains hydrogen ions, ammonium ions and sulphate ions.
- it is composed of sulphuric acid, ferric ammonium sulphate and water.
- CA 734388 a five-steps process is disclosed for cleaning successively all sections of an automatic processor.
- an aqueous solution with a pH of at most 1.0 and containing cerium(IV) ions is used, which however is corrosive.
- US 4,021,264 silver deposits are removed with an aqueous solution containing an alkali mono- or di-peroxysulphate, an alkali bisulphate and thiourea.
- the latter substance can cause photographic fog.
- a cleaning liquid containing a peroxydisulphate compound, an iron(III) salt and optionally an activator.
- JP-A 58-048052 describes an acidic cleaning solutiuon containing iodide or bromide ions.
- the cleaning composition comprises water, a hydroxycarboxylic acid such as citric acid or tartaric acid, and a peroxymonosulphate compound.
- a method for cleaning photographic treating equipment with a solution containing an aminopolycarboxylic acid ferric chelate and a silver complexing agent is disclosed in JP-A 2-311845.
- a two-steps cleaning metod is described using a first composition containing a chelate of an iron(III) salt plus a complexing agent, and a second composition which comprises water, an acid or acid anhydride, a surfactant and a water soluble solvent.
- the aqueous cleaning composition contains a peroxocompound, preferably sodium persulphate; in most examples sulfamic acid is also present.
- the present invention extends the teachings on cleaning liquids for photographic processors. It is an object of the present invention to provide an
- an aqueous cleaning composition for a photographic processor comprising,
- a monophosphate salt e.g. an alkali monophosphate salt, is also present in the cleaning composition.
- a principal ingredient of the cleaning composition according to the present invention is an aminopolycarboxylic acid chelate of an iron(III) salt.
- This compound will take care of the oxidation of the metallic silver sludge to silver ions.
- Suitable chelating agents for iron(III) ions are EDTA, DTPA, hydroxy(EDTA), PDTA, MIDA, ADA and NTA.
- the four latter compounds show the advantage of being biodegradable.
- Preferred compounds are sodium iron(III) EDTA, and ammonium iron(III) EDTA.
- the most preferred compound is ammonium iron(III) EDTA.
- the concentration of the iron complex salt must be at least 0.01 mole/l in order to be effective, and is preferably comprised between 0.025 and 0.2 mole/l.
- Suitable silver complexing agents include sodium-, potassium-, and ammonium thiosulphate; sodium-, potassium- or ammonium thiocyanate; sodium dithionate; alkyl alkanolamines; alkyl amines; thiourea; alkyl thiourea; cysteine HCl; ammonium dithiocarbamate.
- the most preferred silver complexing agent is ammonium thiosulphate.
- Another preferred silver complexing agent is dithiaoctanediol.
- the concentration of the silver complexing agent must be at least 0.05 mole/l.
- An essential ingredient of the cleaning composition according to the present invention is a silver oxidizing accelerator belonging to a specific chemical class.
- This compound is an organic heterocyclic compound having at least two nitrogen atoms in the heterocyclic nucleus and carrying a mercapto group.
- Highly preferred silver oxidation accelerators according to the defined class include the compounds of following table 1 :
- the most preferred silver oxidation accelerator is 3-mercapto-1,2,4-triazole (compound 3).
- the concentration of the silver oxidation accelerator in the cleaning solution must be at least 0.001 mole/l, and is preferably comprised between 0.005 and 0.05 mole/l.
- a silver oxidation accelerator as defined above it was necessary to use high concentrations of the chelated iron(III) salt, and the presence of a monophosphate salt was indispensable. Thanks to the presence of the silver oxidation accelerator moderate concentrations of the chelated iron(III) salt can be used and the presence of a monophosphate salt becomes optional.
- a monophosphate salt is present preferably in a concentration between 0.02 and 0.15 mole/l.
- the monophosphate ion functions as a supplementary oxidation accelerator and at the same time as a buffer substance.
- the monophosphate salt is an alkali salt, e.g. potassium monophosphate or sodium monophosphate.
- the cleaning solution can further optionally contain several other kinds of ingredients.
- the composition can contain minor amounts of inorganic or organic acids, such as acetic acid and/or citric acid, in order to adjust the pH of the cleaning solution and strenghten the buffer capacity.
- the pH of the cleaning composition is preferably comprised between 4 and 7.
- the solution can further contain a sequestering agent for complexing calcium and magnesium ions originating from hard water.
- the solution can further contain sulphite ions, preferably potassium sulphite. It assures the stabilisation of the thiosulphate.
- the solution can further contain one or more surfactants in order to assure good spreading activity on processor surfaces and good dispersion of silver deposits.
- a practical cleaning test is performed as follows.
- An automatic Rapiline 66 processor (registered trademark of Agfa-Gevaert N.V.) was filled with a conventional hydroquinone/Phenidone developer and a conventional fixer.
- About 80 m 2 of negative working red sensitive imagesetting film was processed with 50 ml/m 2 replenishment in dark light conditions to obtain clear film and to contaminate as much as possible the developer with dissolved silver halide.
- the cleaning solution was put in (ready-for-use, as concentrate, or as powder) and the processor ran for 15 minutes with the cleaning solution at 23°C. Thereafter the cleaning solution was drained and the developing tank was rinsed twice with tap water at room temperature. There is no second cleaning phase necessary. The tank was drained and the rollers, guiding plates and walls where controlled on remaining black silver deposit. The results where quoted from 0 to 5 according to an arbitrary scale. Zero means that no remaining silver deposit was found. Five means no reduction in silver deposit with regard to the start of the cleaning.
- a typical developer tank consists of the tank and the developer rack.
- the developer rack has the transport function for the immersed photographic material. This means that the possible appearance of scratches, guiding plate marks and roller marks is dependent on the quality of the rack.
- the entrance and the exit roller pair are the places where silver sludge contamination is most apparent, but the bottom guiding plate and rollers are the most contaminated ones.
- the most common places where silver sludge is transferred on the photographic material are the rollers (cause pressure and slip) and the guiding plates (cause abration due to direct contact). To prevent this heavily disturbing problem chemical cleaning of the developer is necessary as decribed here.
- Racks are to complex to clean mechanically. Also in closed tank and small guiding sleeves systems chemical cleaning at the spot is the only solution.
- This example illustrates the efficiency of the presence of several different silver oxidation accelerators and compares there activity by means of a bleach-fix test.
- This test is performed as follows. After 25 s of immersion in bright light in a conventional developer, and immersion in a fixer in an automatic Rapiline 66 processor of the photographic red sensitive, negative working recording paper Alliance HNp, having a silver coverage of 2.2 g/m 2 , a maximum density of above 2.00 is reached. The roll material was cut in small strips of about 3x10cm. The strips where partially immersed in 250ml of different stirred cleaning solutions at room temperature. The time of immersion was 60, 50, 40, 30, 20, 10 and 0 seconds respectively.
- the strips where rinsed in tap water (stop function) and consequetively rinsed in fixer and tap water, and dried.
- the reflection density was measured with a MacBeth RD918 densitometer to follow the bleach-fixing activity and the results where put in a graph.
- the (interpolated) time to reach a density of 0.5 was taken as representative. A time shorter than 40 seconds is considered as good.
- the actual cleaning compositions contained 0.194 mole/l ammonium Fe(III)EDTA, 0.336 mole/l ammonium thiosulphate, 0.083 mole/l potassium sulphite, 0.022 mole/l of Na-sequestrene, and 0.01 mol/l of the different silver oxidation accelerators.
- the pH was adjusted to 5.5 with acetic acid.
- the interpolated times to reach a reflection density of 0.5 are illustrated in following table 2a.
- compound No. time (s) D 0.5 cmpd 1 38 cmpd 2 29 cmpd 3 33 cmpd 4 36 cmpd 5 36 cmpd 6 38 cmpd 7 36 cmpd 8 28 cmpd 9 29 - (blank) 47
- Table 2b shows the bleach-fix speed of a liquid containing compound 3 compared to a blank containing no oxidation accelerator.
- time s
- Density blade
- Density cmpd 3
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Abstract
An improved ecological one-step cleaning liquid for
photographic processing equipment is disclosed. The aqueous solution
comprises (1) an aminopolycarboxylic acid chelate of an iron(III)
salt, (2) a silver complexing agent, and (3) a silver oxidation
accelerator of a particular type. Preferably, also a monophosphate
salt is present.
Description
The present invention deals with an improved ecological one-step
cleaning liquid for photographic processing equipment.
As it is well known conventional black-and-white photographic
processing involves the consecutive use of at least three solutions
being a developer which reduces the silver halide grains carrying a
latent image to metallic silver, a fixing solution to remove
undeveloped silver halide, and finally a wash tank to remove
residual fixer. In manual tray processing a stop bath can be
inserted between developer and fixer to arrest the developer, but
this is usually omitted in an automatic mechanical processor by
providing the fixer with a high buffering capacity.
After prolonged continuous processing unwanted deposits can
form on the walls of the various processor tanks and on the
mechanical roller/belt system used to transport the photographic
silver halide material through the processor. These deposits are
likely to soil the next sheets or stripes of processed film or
paper. In the developer tank the deposits can be metallic silver,
commonly referred to as "silver sludge", insoluble silver salts and
alkali metal salts. In the fixer tank the deposits can be silver
salts, alkali metal salts, aluminum oxides and elemental sulphur.
Finally, the deposits in the wash tanks can be alkali metal salts,
gelatin and gelatin by-products which induce the growth of fungi and
algae.
The prior art utilizes different cleaning compositions for the
various tanks. The developer tank requires a combination of a strong
oxidizing agent and a silver solvent system. Commonly used prior art
cleaning solutions contained chromate salts such as dichromate
combined with sulphuric or sulphamic acid (see e.g. DE 1068840).
Consecutively a neutralizer such as an alkali bisulfite solution was
used to remove residual chromate salts. In cleaning the fixer tank a
strong caustic solution is used to dissolve the salts and silver
complexes. The algae and fungi slime in the wash tanks can be
cleaned by a chlorine bleach such as a hypochlorite solution. From a
modern ecological point of view all the chemicals cited above are
agressive and hazardous to the environment. Chromium is recognized
as a pollutant and a potential carcinogen. Caustic solutions are
very injurious to the eyes and skin. The hypochlorite solution for
cleaning the wash tank can react with residual caustic solution,
used for the fixer, giving rise to the formation of toxic gaseous
chlorine.
Various alternatives have been formulated in the prior art to
substitute the cleaning chemicals described above.
According to US 3,625,908 the cleaning composition contains
hydrogen ions, ammonium ions and sulphate ions. In the preferred
embodiment it is composed of sulphuric acid, ferric ammonium
sulphate and water. In CA 734388 a five-steps process is disclosed
for cleaning successively all sections of an automatic processor.
According to DE 2429833 an aqueous solution with a pH of at most 1.0
and containing cerium(IV) ions is used, which however is corrosive.
In US 4,021,264 silver deposits are removed with an aqueous solution
containing an alkali mono- or di-peroxysulphate, an alkali
bisulphate and thiourea. However, the latter substance can cause
photographic fog. In DE 2756010 a cleaning liquid is disclosed
containing a peroxydisulphate compound, an iron(III) salt and
optionally an activator. JP-A 58-048052 describes an acidic cleaning
solutiuon containing iodide or bromide ions. According to US
4,678,597 the cleaning composition comprises water, a
hydroxycarboxylic acid such as citric acid or tartaric acid, and a
peroxymonosulphate compound. A method for cleaning photographic
treating equipment with a solution containing an aminopolycarboxylic
acid ferric chelate and a silver complexing agent is disclosed in
JP-A 2-311845. In US 5,266,121 a two-steps cleaning metod is
described using a first composition containing a chelate of an
iron(III) salt plus a complexing agent, and a second composition
which comprises water, an acid or acid anhydride, a surfactant and a
water soluble solvent. In US 5,441,665 the aqueous cleaning
composition contains a peroxocompound, preferably sodium persulphate;
in most examples sulfamic acid is also present.
The present invention extends the teachings on cleaning liquids
for photographic processors.
It is an object of the present invention to provide an
ecologically acceptable cleaning composition for a photographic
processor.
It is a further object of the present invention to provide a
cleaning composition for a photographic processor with reduced
cleaning time.
It is still a further object of the present invention to
provide a cleaning composition which is suitable for cleaning the
developer tank in just one step.
The above mentioned objects are realised by providing an
aqueous cleaning composition for a photographic processor
comprising,
In a preferred embodiment also a monophosphate salt, e.g. an
alkali monophosphate salt, is also present in the cleaning
composition.
A principal ingredient of the cleaning composition according to
the present invention is an aminopolycarboxylic acid chelate of an
iron(III) salt. This compound will take care of the oxidation of the
metallic silver sludge to silver ions. Suitable chelating agents for
iron(III) ions are EDTA, DTPA, hydroxy(EDTA), PDTA, MIDA, ADA and
NTA. The four latter compounds show the advantage of being
biodegradable. Preferred compounds are sodium iron(III) EDTA, and
ammonium iron(III) EDTA. The most preferred compound is ammonium
iron(III) EDTA. The concentration of the iron complex salt must be
at least 0.01 mole/l in order to be effective, and is preferably
comprised between 0.025 and 0.2 mole/l.
Suitable silver complexing agents include sodium-, potassium-,
and ammonium thiosulphate; sodium-, potassium- or ammonium
thiocyanate; sodium dithionate; alkyl alkanolamines; alkyl amines;
thiourea; alkyl thiourea; cysteine HCl; ammonium dithiocarbamate.
The most preferred silver complexing agent is ammonium thiosulphate.
Another preferred silver complexing agent is dithiaoctanediol. The
concentration of the silver complexing agent must be at least 0.05
mole/l.
An essential ingredient of the cleaning composition according
to the present invention is a silver oxidizing accelerator belonging
to a specific chemical class. This compound is an organic
heterocyclic compound having at least two nitrogen atoms in the
heterocyclic nucleus and carrying a mercapto group. Highly preferred
silver oxidation accelerators according to the defined class include
the compounds of following table 1 :
The most preferred silver oxidation accelerator is 3-mercapto-1,2,4-triazole
(compound 3).
The concentration of the silver oxidation accelerator in the
cleaning solution must be at least 0.001 mole/l, and is preferably
comprised between 0.005 and 0.05 mole/l.
It was found experimentally that when a silver oxidation
accelerator as defined above was omitted it was necessary to use
high concentrations of the chelated iron(III) salt, and the presence
of a monophosphate salt was indispensable. Thanks to the presence of
the silver oxidation accelerator moderate concentrations of the
chelated iron(III) salt can be used and the presence of a
monophosphate salt becomes optional. However, in a preferred
embodiment of the present invention a monophosphate salt is present
preferably in a concentration between 0.02 and 0.15 mole/l. The
monophosphate ion functions as a supplementary oxidation accelerator
and at the same time as a buffer substance. Preferably the
monophosphate salt is an alkali salt, e.g. potassium monophosphate
or sodium monophosphate.
The cleaning solution can further optionally contain several
other kinds of ingredients.
The composition can contain minor amounts of inorganic or
organic acids, such as acetic acid and/or citric acid, in order to
adjust the pH of the cleaning solution and strenghten the buffer
capacity. The pH of the cleaning composition is preferably comprised
between 4 and 7.
The solution can further contain a sequestering agent for
complexing calcium and magnesium ions originating from hard water.
The solution can further contain sulphite ions, preferably
potassium sulphite. It assures the stabilisation of the
thiosulphate.
The solution can further contain one or more surfactants in
order to assure good spreading activity on processor surfaces and
good dispersion of silver deposits.
A practical cleaning test is performed as follows. An automatic
Rapiline 66 processor (registered trademark of Agfa-Gevaert N.V.)
was filled with a conventional hydroquinone/Phenidone developer and
a conventional fixer. About 80 m2 of negative working red sensitive
imagesetting film was processed with 50 ml/m2 replenishment in dark
light conditions to obtain clear film and to contaminate as much as
possible the developer with dissolved silver halide. After a period
of sedimentation (1-3 days) the developing tank, rollers, guiding
plates and walls were completely turned black and gray ("silver
mirror" effect). Than the developer tank was drained. The cleaning
solution was put in (ready-for-use, as concentrate, or as powder)
and the processor ran for 15 minutes with the cleaning solution at
23°C. Thereafter the cleaning solution was drained and the developing
tank was rinsed twice with tap water at room temperature. There is
no second cleaning phase necessary. The tank was drained and the
rollers, guiding plates and walls where controlled on remaining
black silver deposit. The results where quoted from 0 to 5 according
to an arbitrary scale. Zero means that no remaining silver deposit
was found. Five means no reduction in silver deposit with regard to
the start of the cleaning.
The cleaning system described is suitable for all types of
photographic processors. A typical developer tank consists of the
tank and the developer rack. In the tank there are sensors, heating
elements, drain and replenishing pipes and circulation holes. The
corners and surface around these elements are very hard to clean
mechanically; only chemical cleaning is effective. The developer
rack has the transport function for the immersed photographic
material. This means that the possible appearance of scratches,
guiding plate marks and roller marks is dependent on the quality of
the rack. The entrance and the exit roller pair are the places where
silver sludge contamination is most apparent, but the bottom guiding
plate and rollers are the most contaminated ones. The most common
places where silver sludge is transferred on the photographic
material are the rollers (cause pressure and slip) and the guiding
plates (cause abration due to direct contact). To prevent this
heavily disturbing problem chemical cleaning of the developer is
necessary as decribed here. Racks are to complex to clean
mechanically. Also in closed tank and small guiding sleeves systems
chemical cleaning at the spot is the only solution.
The present invention will now be illustrated by the following
examples without however being limited thereto.
This example illustrates the efficiency of the presence of
several different silver oxidation accelerators and compares there
activity by means of a bleach-fix test. This test is performed as
follows. After 25 s of immersion in bright light in a conventional
developer, and immersion in a fixer in an automatic Rapiline 66
processor of the photographic red sensitive, negative working
recording paper Alliance HNp, having a silver coverage of 2.2 g/m2,
a maximum density of above 2.00 is reached. The roll material was
cut in small strips of about 3x10cm. The strips where partially
immersed in 250ml of different stirred cleaning solutions at room
temperature. The time of immersion was 60, 50, 40, 30, 20, 10 and 0
seconds respectively. The strips where rinsed in tap water (stop
function) and consequetively rinsed in fixer and tap water, and
dried. The reflection density was measured with a MacBeth RD918
densitometer to follow the bleach-fixing activity and the results
where put in a graph. The (interpolated) time to reach a density of
0.5 was taken as representative. A time shorter than 40 seconds is
considered as good.
The actual cleaning compositions contained 0.194 mole/l
ammonium Fe(III)EDTA, 0.336 mole/l ammonium thiosulphate, 0.083
mole/l potassium sulphite, 0.022 mole/l of Na-sequestrene, and 0.01
mol/l of the different silver oxidation accelerators. The pH was
adjusted to 5.5 with acetic acid. The interpolated times to reach a
reflection density of 0.5 are illustrated in following table 2a.
compound No. | time (s) D=0.5 |
cmpd 1 | 38 |
cmpd 2 | 29 |
cmpd 3 | 33 |
cmpd 4 | 36 |
cmpd 5 | 36 |
cmpd 6 | 38 |
cmpd 7 | 36 |
cmpd 8 | 28 |
cmpd 9 | 29 |
- (blank) | 47 |
The table shows that all the tested compound are effective
(time to reach D=0.5 smaller than 40 s).
Table 2b shows the bleach-fix speed of a liquid containing
compound 3 compared to a blank containing no oxidation accelerator.
time (s) | Density (blank) | Density (cmpd 3) |
0 | 2.04 | 2.02 |
10 | 1.89 | 1.71 |
20 | 1.34 | 1.17 |
30 | 1.05 | 0.55 |
40 | 0.66 | 0.38 |
50 | 0.43 | 0.39 |
It is clear from table 2b that the bleach-fixing is performed
faster with a liquid containing compound 3.
As comparison we give hereinafter the results of the bleach-fix
test (densities) performed with two prior art cleaning liquids the
oxidation step of which was based on bichromate (cleaning liquid A)
and on persulphate (cleaning liquid B) respectively. In both cases a
second step being a complexing step was necessary.
bleachfix time | cl. liq. A | cl. liq. B |
10.s | 0.35 | 1.99 |
20.s | 0.35 | 2.01 |
30 s | 0.35 | 1.97 |
40 s | 0.37 | 1.94 |
60.s | 0.34 | 1.85 |
t(D=0.5)= | <10 s | >60 s |
Tank cleaning: | 0 (15'/23°C) | 5 (arbitrary scale) |
The molar compositions of cleaning liquid A and cleaning liquid B
were as follows :
compound | conc mole/l | conc mole/l |
H2SO4 | 0.108 | 0 |
sulfaminic acid | 0.268 | 0 |
K2Cr2O7 | 0.041 | 0 |
NaOH | 0 | 0.100 |
CH3COOH | 0 | 0.347 |
Hydroquinone | 0 | 0.036 |
KBr | 0 | 0.084 |
ammoniumpersulphate | 0 | 0.132 |
compound | conc mole/l | conc mole/l |
(NH4)2S2O3 | 0.925 | 0.701 |
Na2SO3 | 0.086 | 0 |
H3BO3 | 0.081 | 0 |
CH3COONa | 0.103 | 0 |
CH3COOH | 0.138 | 0 |
One sees that the bleach-fixing speed is all right for the
cleaning liquid based on bichromate, which however is unecologig,
but much too slow for the liquid based on persulphate. However, both
comparative systems show the disadvantage of requiring a second step
being a complexing phase.
In example 2 the cleaning efficiency of cleaning solutions
having different compositions are compared. The results are
summarized in tables 3a and 3b.
ingredient | molar concentrations | |||||||
C1 | C2 | I1 | I2 | I3 | I4 | I5 | I6 | |
Na-sequestrene | 0.022 | = | = | = | = | = | = | = |
K2SO3 | 0.083 | = | = | = | = | = | = | = |
cpd 3 | - | - | 0.050 | 0.050 | 0.030 | 0.010 | 0.005 | 0.010 |
HAc | 0.606 | 0.606 | 0.628 | 0.491 | 0.471 | 0.471 | 0.626 | 0.583 |
(NH4)2S2O3 | 0.336 | 0.637 | 0.336 | = | = | = | = | = |
NaH2PO4.2aq | 0.096 | = | = | = | = | = | = | 0 |
NH4Fe(III)EDTA | 0.388 | = | = | = | = | = | = | = |
pH | 5.11 | 5.11 | 5.11 | 5.50 | 5.50 | 5.50 | 5.11 | 5.50 |
cleaning quality | 3 | 5 | 0 | 0 | 0 | 0 | 0 | 0.5 |
As already explained above the quality of the cleaning is
qualitatively rated by an arbitrary scale ranging from 0 (very good)
to 5 (very bad). It is clear from the table that the comparison
examples (C1 and C2) containing no silver oxidation accelerator show
a worse cleaning result than the invention examples (I1-I6). The
example containing no sodium monophosphate gives a slightly worse
result than the corresponding probe containing monophosphate.
ingredients | molar concentration | |||||
I6 | I7 | I8 | I9 | I10 | C3 | |
Na-sequestrene | 0.022 | = | = | = | = | = |
K2SO3 | 0.083 | = | = | = | = | = |
cmpd 3 | 0.010 | 0.005 | 0.010 | = | = | = |
HAc | 0.538 | 0.223 | 0.208 | 0.163 | 0.147 | 0.270 |
(NH4)2S2O3 | 0.336 | = | = | = | = | = |
NaH2PO4.2aq | 0 | 0.032 | 0.096 | = | = | = |
NH4Fe(III)EDTA | 0.388 | 0.194 | 0.097 | 0.048 | 0.024 | 0.006 |
pH | 5.50 | 4.45 | 5.50 | = | = | = |
cleaning quality | 0.5 | 0.5 | 0 | 0 | 0 | 3 |
It is clear from table 3b that the presence and the
concentration of the iron(III) complex salt is of crucial importance
for the quality of the cleaning. A concentration as low as 0.006 is
ineffective (comparison example C3). The examples without or with a
low concentration on sodium monophosphate show again a slightly
worse behaviour even at relative high concentrations of
NH4Fe(III)EDTA.
Claims (6)
- An aqueous cleaning composition for a photographic processor comprising,(1) an aminopolycarboxylic acid chelate of an iron(III) salt in a concentration of at least 0.01 mole/l,(2) a silver complexing agent in a concentration of at least 0.05 mole/l,(3) a heterocyclic silver oxidation accelerating compound having at least two nitrogen atoms in the heterocyclic nucleus and carrying a mercapto group, in a concentration of at least 0.001 mole/l.
- An aqueous cleaning composition according to claim 1 wherein said aminopolycarboxylic acid chelate of an iron(III) salt is an EDTA chelate.
- An aqueous cleaning composition according to claim 2 wherein said EDTA chelate is chosen from ammonium iron(III) EDTA and sodium iron(III) EDTA.
- An aqueous cleaning composition according to any of claims 1 to 3 wherein said silver compexing agent is a thiosulphate.
- An aqueous cleaning composition according to any of claims 1 to 4 wherein said silver oxidation accelerating compound is 3-mercapto-1,2,4-triazole.
- An aqueous cleaning composition according to any of claims 1 to 5 wherein said composition further contains a monophosphate salt.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP98202038A EP0965883A1 (en) | 1998-06-18 | 1998-06-18 | Ecological cleaning liquid for photographic processor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98202038A EP0965883A1 (en) | 1998-06-18 | 1998-06-18 | Ecological cleaning liquid for photographic processor |
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Publication Number | Publication Date |
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ID=8233826
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113900349A (en) * | 2021-10-25 | 2022-01-07 | 陕西师范大学 | Method for removing silver mirror on surface layer of black and white negative film |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH490696A (en) * | 1965-06-11 | 1970-05-15 | Agfa Gevaert Ag | Process for producing color photographic images |
DE2102713A1 (en) * | 1971-01-21 | 1972-08-10 | Agfa-Gevaert Ag, 5090 Leverkusen | Hardening bleach-fix baths |
FR2241095A1 (en) * | 1973-08-16 | 1975-03-14 | Eastman Kodak Co | |
US4914009A (en) * | 1986-06-30 | 1990-04-03 | Fuji Photo Film Co., Ltd. | Process for forming direct positive color image comprising the use of bleach accelerators |
DE4034873A1 (en) * | 1990-11-02 | 1992-05-07 | Wolfen Filmfab Ag | Photographic colour bleaching bath prodn. - by adding accelerator of 3-mercapto-s-triazole to conc soln., for silver halide gelatin emulsion |
US5266121A (en) * | 1992-08-12 | 1993-11-30 | Helion Industries, Inc. | Method of cleaning photographic processing equipment |
US5464727A (en) * | 1995-02-08 | 1995-11-07 | Eastman Kodak Company | Cleaning of emulsion manufacturing apparatus |
US5476593A (en) * | 1994-12-08 | 1995-12-19 | Eastman Kodak Company | Method for flushing an undesired precipitate from apparatus surfaces |
-
1998
- 1998-06-18 EP EP98202038A patent/EP0965883A1/en not_active Withdrawn
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH490696A (en) * | 1965-06-11 | 1970-05-15 | Agfa Gevaert Ag | Process for producing color photographic images |
DE2102713A1 (en) * | 1971-01-21 | 1972-08-10 | Agfa-Gevaert Ag, 5090 Leverkusen | Hardening bleach-fix baths |
FR2241095A1 (en) * | 1973-08-16 | 1975-03-14 | Eastman Kodak Co | |
US4914009A (en) * | 1986-06-30 | 1990-04-03 | Fuji Photo Film Co., Ltd. | Process for forming direct positive color image comprising the use of bleach accelerators |
DE4034873A1 (en) * | 1990-11-02 | 1992-05-07 | Wolfen Filmfab Ag | Photographic colour bleaching bath prodn. - by adding accelerator of 3-mercapto-s-triazole to conc soln., for silver halide gelatin emulsion |
US5266121A (en) * | 1992-08-12 | 1993-11-30 | Helion Industries, Inc. | Method of cleaning photographic processing equipment |
US5476593A (en) * | 1994-12-08 | 1995-12-19 | Eastman Kodak Company | Method for flushing an undesired precipitate from apparatus surfaces |
US5464727A (en) * | 1995-02-08 | 1995-11-07 | Eastman Kodak Company | Cleaning of emulsion manufacturing apparatus |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113900349A (en) * | 2021-10-25 | 2022-01-07 | 陕西师范大学 | Method for removing silver mirror on surface layer of black and white negative film |
CN113900349B (en) * | 2021-10-25 | 2023-08-18 | 陕西师范大学 | Method for removing silver mirror on surface layer of black-and-white negative film |
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