US3241966A - Bleach fixing of photographic silver images - Google Patents
Bleach fixing of photographic silver images Download PDFInfo
- Publication number
- US3241966A US3241966A US140170A US14017061A US3241966A US 3241966 A US3241966 A US 3241966A US 140170 A US140170 A US 140170A US 14017061 A US14017061 A US 14017061A US 3241966 A US3241966 A US 3241966A
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- United States
- Prior art keywords
- fixing
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- molecular weight
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- 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.)
- Expired - Lifetime
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- 239000007844 bleaching agent Substances 0.000 title claims description 29
- 229910052709 silver Inorganic materials 0.000 title claims description 10
- 239000004332 silver Substances 0.000 title claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title description 5
- -1 SILVER HALIDE Chemical class 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 150000007513 acids Chemical class 0.000 claims description 10
- 238000004061 bleaching Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 21
- 239000007859 condensation product Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 16
- 229950006389 thiodiglycol Drugs 0.000 description 16
- 239000005864 Sulphur Substances 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 13
- 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 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 150000003568 thioethers Chemical class 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 229960001484 edetic acid Drugs 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ATTZFSUZZUNHBP-UHFFFAOYSA-N Piperonyl sulfoxide Chemical compound CCCCCCCCS(=O)C(C)CC1=CC=C2OCOC2=C1 ATTZFSUZZUNHBP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004133 Sodium thiosulphate Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003435 aroyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920006295 polythiol Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- YAHSFLRMWJLNER-UHFFFAOYSA-N 1-n,4-n-diethylbenzene-1,4-diamine;sulfuric acid Chemical compound OS(O)(=O)=O.CCNC1=CC=C(NCC)C=C1 YAHSFLRMWJLNER-UHFFFAOYSA-N 0.000 description 1
- DLLMHEDYJQACRM-UHFFFAOYSA-N 2-(carboxymethyldisulfanyl)acetic acid Chemical compound OC(=O)CSSCC(O)=O DLLMHEDYJQACRM-UHFFFAOYSA-N 0.000 description 1
- ZIUZDRMIXJKUNY-UHFFFAOYSA-N 3-[2-carboxyethyl(ethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CC)CCC(O)=O ZIUZDRMIXJKUNY-UHFFFAOYSA-N 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KYNFOMQIXZUKRK-UHFFFAOYSA-N bishydroxyethyldisulfide Natural products OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- FXDWOKJYEDVJME-UHFFFAOYSA-N ethene;2-sulfanylacetic acid Chemical compound C=C.OC(=O)CS.OC(=O)CS FXDWOKJYEDVJME-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 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
- GLZWNFNQMJAZGY-UHFFFAOYSA-N octaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCO GLZWNFNQMJAZGY-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 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
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- G03C7/421—Additives other than bleaching or fixing agents
Definitions
- This invention relates to a process for bleach fixing of photographic silver images as well as to a bleach fixing bath.
- R R and R represent hydrocarbon radicals which may be substituted and R may also represent hydrogen, and in which R R and R represent bivalent hydrocarbon radicals which may again be substituted.
- suitable organic acids are ethylenediamine tetra-acetic acid, nitrilotriacetic acid, malonic acid, ethyl malonic acid, tartaric acid, malic acid, fumaric acid, diglycolic acid, ethyliminodipropionic acid, ethylene dithioglycolic acid and dithioglycolic acid.
- These bleach fix baths are highly stable and are used, in particular, for the production of multicoloured images by the colour development process. Nevertheless, these baths have the disadvantage that they do not always completely bleach out the silver images at the areas of highest density,
- R represents a hydrogen atom or a substituted or unsubstituted alkyl, aryl, aralkyl, acyl, aroyl or heterocyclic radical; R and R which may be the same or different, each represent a hydrogen atom, a substituted or unsubstituted alkyl, aryl, aralkyl, acyl, aroyl or heterocyclic radical or the group(CH .Cl-I .O) ,R wherein R is a hydrogen atom or a substituent suitable for the etherification or esterification of an OH group and x, y, 2: and n are integers.
- water-soluble polyethylene oxides which increase the bleaching capacity of bleach fix baths are polyethylene oxides consisting of from 10 to 120 mols of ethylene oxide; reaction products of fatty alcohols, for example oleyl alcohol, with from 60 to 100 mols of ethylene oxide; reaction products of lauric acid with from 10 to 20 mols of ethylene oxide; reaction products of trimethylol propane with ethylene oxide, which have an average molecular weight of 4000; reaction products of ammonia with from 20 to 30 mols of ethylene oxide; and reaction products of dimethylamine with from 50 to mols of ethylene oxide.
- polyethylene oxides consisting of from 10 to 120 mols of ethylene oxide
- reaction products of fatty alcohols for example oleyl alcohol, with from 60 to 100 mols of ethylene oxide
- reaction products of lauric acid with from 10 to 20 mols of ethylene oxide
- reaction products of trimethylol propane with ethylene oxide which have an average molecular weight of 4000
- reaction products of ammonia with
- R, R, R and R' represent bivalent organic radicals With 210 carbon atoms which may be substituted, in represents an integer from 0-100, n and p an integer from 1-100, Y stands for a radical selected from the group consisting of and mixtures thereof wherein R" stands for a lower aliphatic radical having 1-3 carbon atoms and X represents a hydrogen atom or an aliphatic radical which may be substituted for improving the solubility of said compounds e.g. by hydroxyl, cyano, amino, carboxyl, sulfo, or a radical of an acid of phosphorus. X may further stand for an acyl radical derived from an aliphatic monoor dicarboxylic acid.
- Aliphatic, aromatic or mixed aliphatic-aromatic thioethers have proved suitable. Aliphatic thioethers which contain a plurality of thioether groupings in the molecule are preferred, however, because of their greater effectiveness. Furthermore, some of the sulphur atoms may be oxidised to sulphine or sulphonyl groups or some of the sulphur atoms may be treated with an alkylating agent to form sulphonium groups.
- thioethers are condensates of 6,5- and y,' -dihydroxyalkyl sulphides with polyalklyene glycols, particularly the co-condensates of thiodiglycol and its alkyl-substituted products with polyethylene and/or polypropylene glycols, or the hydroxyethylation products and/or the propoxylation products of monoand polyvalent alcohols which contain OH groups or other oxygen atoms as solubilizing groups.
- Derivatives of the aforementioned polythioethers can also be used with success, for example co-condensates of the aforementioned type wherein some of the sulphur atoms have been oxidized to form sulphoxide or sulphonyl groups or in which some of the sulphur atoms have been converted by alkylation agents into sulphonium groups, or in which the OH groups have been Wholly or partially esterified or etherified.
- Dithiodiglycol HOCH CH SSCH CH OH (15) A condensation product prepared from 0.94 mol of thiodiglycol and 1 mol of polyethylene oxide having a molecular weight of 680, the terminal OH-groups of which being etherified with acrylonitrile and the nitrile groups saponified to form terminal B-carboxyethyl-groups.
- a condensation product being produced from 10 mols of [3,,B-dimethyl-thioglycol and 1 mol of polyethylene oxide having a molecular weight of 1700, the terminal OH- groups of which are reacted with butane sultone to form terminal sulfobutyl groups.
- a condensation product prepared from 10 mols of thiodiglycol and 1 mol of polyethylene oxide with a molecular weight of 1700, the terminal OH-groups of which being transformed with thionylchloride into the corresponding chloride which is reacted with triethylphosphite to form terminal phosphoric acid groups.
- a condensation product prepared from 10 mols of thiodiglycol and 1 mol of a co-polymerisate of 1 mol of propylene oxide and 9 mols of polyethylene oxide having a molecular weight of 1700.
- the difference of 0.6 between the maximum and minimum values of the densities behind a blue filter represents a measure of the unbleached residual image of the field in question of a photometric test wedge processed with a bleach fix bath without an additive.
- Table 2 shows the corresponding density values which were obtained in a series of experiments with polyethylene oxides with and Without sulphur.
- the amount of polythioether being added was always 0.01 g. per liter of bleach fix bath.
- Example 1 A photometric test wedge is exposed on an ordinary commercial two-layer negative colour film. The film is then developed at 18 C. for five minutes in a colour developer of the following composition:
- Example 2 An ordinary commercial hard grade colour paper is exposed behind a blue colour separation wedge and de veloped in the colour developer employed in Example 1. The sample is then treated for 5 minutes in a stop fix bath which has been prepared by dissolving 5 g. of anhydrous sodium acetate, 10 g. of sodium bisulphate and 120 g. of anhydrous sodium thiosulphate in 600 ml. of water and making up to 1 liter with water. The pH value of the bath is 6.0.
- the sample is passed into the bleach fix bath employed in Example 1 without intermediate washing. If 1.0 g. of a condensate of molecular weight 1700 and containing 3.8% of sulphur and which has been prepared from 1.27 mols of thiodiglycol and 1 mol of a polyethylene oxide of molecular weight 1130 is added to the bleach fix bath a perfectly bleached yellow wedge is obtained after 8 minutes.
- any water-soluble thiosulphates may be used as fixing agents such as alkali thiosulphates or ammonium thiosulphate.
- the bleach fixing bath may contain as stabilising agents any water-soluble sulfite, bisulfite or metasulfite.
- the bleach fixing bath may have an additional content of water-soluble iodides as described in copending application Ser. No. 95,735, filed March 14, 1961, by Bernard Morcher, Karl Frank and Max Heilmann.
- the photographic material which shall be treated by the bleach fixing bath according to the invention may be developed by means of any developer composition known per se.
- the pH-value of the bleach fixing bath according to the invention may range approximately from 5 to 8.
- the amounts of the sulphur containing polyalkylene-oxides being added to the bleach fixing bath according to the invention it is self-evident that smaller amounts than 0.01 g./l. of the bleach fixing bath are less eifective. Higher amounts may be added.
- the upper limit of the amount to be added is given by the solubility of said compounds, which depends on the molecular weight, the content of water-solubilizing groups and so on.
- a process for the bleaching and fixing of a photo graphic silver halide emulsion which comprises subjecting the said emulsion to treatment with a fixing-bleaching composition
- a fixing-bleaching composition comprising (a) a conventional bleaching agent of the group consisting of complex salts of trivalent iron and an acid of the group consisting of polycarboxylic acids and nitrogen-containing polycarboxylic acids, and
- R, R, R" and R' are each a radical of the group consisting of alkylene radicals having up to 10 carbon atoms and phenylene, m is an integer from 0 to 100, n and p are each an integer from 1 to 100, Y is a radical of the group consisting of in which R"" is a lower aliphatic radical having up to 3 carbon atoms and X is a radical of the group consisting of (I) hydrogen, (II) alkyl containing up to 10 carbon atoms, (III) alkyl containing up to 10 carbon atoms and containing a substituent of the group consisting of cyano, amino, carboxyl, sulfo and radicals derived from acids of phosphorous, (IV) aryl, (V) aryl radicals containing a substitutent of the group consisting of amino, carboxyl, sulfo and radicals derived from acids of phosphorus, and (VI) acyl radicals of aliphatic
- a bleaching and fixing composition for treating photographic silver halide emulsions comprising (a) a conventional bleaching agent of the group consisting of complex salts of trivalent iron and an acid of the group consisting of polycarboxylic acids and nitrogen-containing polycarboxylic acids, (b) a conventional fixing agent consisting of a watersoluble salt of thiosulfuric acid, and (c) in dissolved form at least 0.1 gram per liter of a substance of the group consisting of polyalkylene oxides having the formula:
- R, R, R" and R are each a radical of the group consisting of alkylene radicals having up to 10 carbon atoms and phenylene, m is an integer from 0 to 100, n and p are each an integer from 1 to 100, Y is a radical of the group consisting of in which R"" is a lower aliphatic radical having up to 3 carbon atoms and X is a radical of the group consisting of (I) hydrogen, (II) alkyl containing up to 10 carbon atoms and (III) alkyl containing up to 10 carbon atoms and containing a substituent of the group consisting of cyano, amino, carboxyl, sulfo and radicals derived from acids of phosphorus, (IV) aryl, (V) aryl radicals containing a substituent of the group consisting of aminq, carboxyl, sulfo and radicals derived from acids of phosphorus, and (VI) acyl radicals of aliphatic
- a bleaching and fixing composition for the treatment of photographic silver halide emulsions comprising an aqueous solution containing the following substances in approximately the quantities specified per liter of solution:
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Description
United States Patent OfiFice 3,241,966 Patented Mar. 22, 1966 3,241,966 BLEACH FllXlNG F PHOTOGRAPH-lit} SILVER WAGES Max Heilrnann, Cologne-Flittard, Hanswilli von Brachel,
@oiogne-Snlz, and Hans Holtschmidt, Cologne-Stammhelm, Germany, assignors to Agfa Alitiengesellschaft, Leverlrusen, Germany, a corporation of Germany No Drawing. Filed .lune 9, 1961, Ser. No. 140,170 Claims priority, application Germany, June 14, 1960,
3 Claims. ((11. 9660) This invention relates to a process for bleach fixing of photographic silver images as well as to a bleach fixing bath.
According to German Patent Specification No. 866,605 the bleach fixing of photographic silver images is achieved by means of a bleach fix bath containing in addition to the known fixing agents for silver halide, a complex salt of trivalent iron with an organic acid of the following general formulae:
and
R R and R represent hydrocarbon radicals which may be substituted and R may also represent hydrogen, and in which R R and R represent bivalent hydrocarbon radicals which may again be substituted. Examples of suitable organic acids are ethylenediamine tetra-acetic acid, nitrilotriacetic acid, malonic acid, ethyl malonic acid, tartaric acid, malic acid, fumaric acid, diglycolic acid, ethyliminodipropionic acid, ethylene dithioglycolic acid and dithioglycolic acid. These bleach fix baths are highly stable and are used, in particular, for the production of multicoloured images by the colour development process. Nevertheless, these baths have the disadvantage that they do not always completely bleach out the silver images at the areas of highest density,
It is known from German patent specification No. 966,410 that it is possible to improve the effectiveness of the aforementioned bleach fix baths without affecting their stability by adding a polyethylene oxide and/ or a derivative thereof to them. For this purpose, water-soluble polyethylene oxides are used, for example, polyethylene oxides of the general formulae:
(GHQ-0112.0):
moronrornoa h N(OHz.CHzO)zR s In these formulae, R represents a hydrogen atom or a substituted or unsubstituted alkyl, aryl, aralkyl, acyl, aroyl or heterocyclic radical; R and R which may be the same or different, each represent a hydrogen atom, a substituted or unsubstituted alkyl, aryl, aralkyl, acyl, aroyl or heterocyclic radical or the group(CH .Cl-I .O) ,R wherein R is a hydrogen atom or a substituent suitable for the etherification or esterification of an OH group and x, y, 2: and n are integers. Examples of water-soluble polyethylene oxides which increase the bleaching capacity of bleach fix baths are polyethylene oxides consisting of from 10 to 120 mols of ethylene oxide; reaction products of fatty alcohols, for example oleyl alcohol, with from 60 to 100 mols of ethylene oxide; reaction products of lauric acid with from 10 to 20 mols of ethylene oxide; reaction products of trimethylol propane with ethylene oxide, which have an average molecular weight of 4000; reaction products of ammonia with from 20 to 30 mols of ethylene oxide; and reaction products of dimethylamine with from 50 to mols of ethylene oxide.
It has now been found that the effectiveness of the bleach fix baths can be further improved, without affecting their stability, if a polyalkylene oxide is added to them in which some of the oxygen atoms are replaced by sulphur atoms. This class of substances may be characterised by the following general formula:
wherein R, R, R and R' represent bivalent organic radicals With 210 carbon atoms which may be substituted, in represents an integer from 0-100, n and p an integer from 1-100, Y stands for a radical selected from the group consisting of and mixtures thereof wherein R" stands for a lower aliphatic radical having 1-3 carbon atoms and X represents a hydrogen atom or an aliphatic radical which may be substituted for improving the solubility of said compounds e.g. by hydroxyl, cyano, amino, carboxyl, sulfo, or a radical of an acid of phosphorus. X may further stand for an acyl radical derived from an aliphatic monoor dicarboxylic acid.
Aliphatic, aromatic or mixed aliphatic-aromatic thioethers have proved suitable. Aliphatic thioethers which contain a plurality of thioether groupings in the molecule are preferred, however, because of their greater effectiveness. Furthermore, some of the sulphur atoms may be oxidised to sulphine or sulphonyl groups or some of the sulphur atoms may be treated with an alkylating agent to form sulphonium groups.
Examples of suitable thioethers are condensates of 6,5- and y,' -dihydroxyalkyl sulphides with polyalklyene glycols, particularly the co-condensates of thiodiglycol and its alkyl-substituted products with polyethylene and/or polypropylene glycols, or the hydroxyethylation products and/or the propoxylation products of monoand polyvalent alcohols which contain OH groups or other oxygen atoms as solubilizing groups. Derivatives of the aforementioned polythioethers can also be used with success, for example co-condensates of the aforementioned type wherein some of the sulphur atoms have been oxidized to form sulphoxide or sulphonyl groups or in which some of the sulphur atoms have been converted by alkylation agents into sulphonium groups, or in which the OH groups have been Wholly or partially esterified or etherified.
Some of these substances and a process for the production thereof are described in United States Patent Specifications Nos. 2,484,369 and 2,518,245 and in French Patent Specification 1,201,171.
Examples of such thioethers are:
(1) A condensation product containing 3.8% of sulphur, having a molecular weight of 1700 and which has been prepared from 1 mol of a polyethylene oxide having a molecular weight of 1130 and 1.27 mols of thiodiglycol.
(2) A condensation product containing 3.8% of sulphur, having a molecular Weight of 1540 and which has been prepared from 1 mol of a polyethylene oxide having a molecular weight of 680 and 0.94 mol of thiodiglycol.
(3) A condensation product containing 3.7% of sulphur, having a molecular weight of 740 and which has been prepared from 1 mol of octaethylene glycol and 0.54 mol of thiodiglycol.
(4) A condensation product as recited under heading 2 in which the OH groups have been converted into the semi-ester with maleic anhydride.
(5) A condensation product as recited under heading 2 in which the OH-groups have been esterified with acetic acid.
(6) A condensation product having a molecular weight of 4000 and which has been prepared from mols of thiodiglycol and 1 mol of a polyethylene oxide having a molecular weight of 1700, the terminal groups of the condensation product being esterified with maleic anhydride.
(7) A condensation product having a molecular weight of 4000 and containing 10% of sulphur, 20% of which has been converted into the methosulphate with dimethyl sulphate, said condensation product having been prepared from 10 mols of thiodiglycol and 1 mol of a polyethylene oxide having a molecular weight of 1700.
(8) A condensation product having a molecular weight of 4000 and containing 10% of sulphur, 40% of which has been converted into the sulphoxide, said condensation product having been prepared from 10 mols of thiodiglycol and 1 mol of a polyethylene oxide having a molecular weight of 1700.
(9) A thioether having terminal butyl groups, a molecular weight of approximately 2400 and containing 3% of sulphur, the thioether having been produced by the condensation of 1 mol of diethylene glycol monobutyl ether with 3 mols of thiodiglycol and 0.5 mol of a polyethylene oxide of molecular weight 1750.
(10) A polyether thioether having a molecular weight of 3000 and containing 3.3% of sulphur, said polyether having been produced by the co-polymerisation of 0.03 mol of butane-1,4-diol, 2 mols of ethylene oxide and 0.1 mol of ethylene sulphide.
(11) A polyether thioether having a molecular weight of approximately 3500 and containing 9% of sulphur, said polyether thioether having been produced by the copolymerisation of 0.03 mol of butane-1,4-diol, 2 mols of ethylene oxide and 0.4 mol of ethylene sulphide.
(12) A condensation product having a molecular weight of 4000 and which has been produced from one mol of a polyethylene oxide of molecular weight 680 and 0.76 mol of thiodiglycol, the terminal OH groups in the condensation product having been etherified by the addition of acrylonitrile in the presence of an alkali.
(13) A thioether having terminal amino groups and which has been produced by the hydrogenation of the product recited under heading 12.
(14) Dithiodiglycol HOCH CH SSCH CH OH (15) A condensation product prepared from 0.94 mol of thiodiglycol and 1 mol of polyethylene oxide having a molecular weight of 680, the terminal OH-groups of which being etherified with acrylonitrile and the nitrile groups saponified to form terminal B-carboxyethyl-groups.
(16) A condensation product being produced from 10 mols of [3,,B-dimethyl-thioglycol and 1 mol of polyethylene oxide having a molecular weight of 1700, the terminal OH- groups of which are reacted with butane sultone to form terminal sulfobutyl groups.
(17) A condensation product prepared from 10 mols of thiodiglycol and 1 mol of polyethylene oxide with a molecular weight of 1700, the terminal OH-groups of which being transformed with thionylchloride into the corresponding chloride which is reacted with triethylphosphite to form terminal phosphoric acid groups.
(18) A condensation product prepared from 10 mols of thiodiglycol and 1 mol of a co-polymerisate of 1 mol of propylene oxide and 9 mols of polyethylene oxide having a molecular weight of 1700.
19) A condensation product having a molecular weight of 5200 and being prepared from 1 mol of oxethylated TABLE 1 Processing of the film with a Density behind a bleach fix bath: blue filter Without polyethylene oxide 2.70 With 0.1 g. polyethylene oxide 2.35 With 0.5 g. polyethylene oxide 2.20 With 1.0 g. polyethylene oxide 2.15 With 2.5 g. polyethylene oxide 2.10
The difference of 0.6 between the maximum and minimum values of the densities behind a blue filter represents a measure of the unbleached residual image of the field in question of a photometric test wedge processed with a bleach fix bath without an additive.
From Table 1 it can be seen that an addition of at least 1 g. of polyethylene oxide is necessary in order to permit bleaching of the residual image.
Table 2 shows the corresponding density values which were obtained in a series of experiments with polyethylene oxides with and Without sulphur. The amount of polythioether being added was always 0.01 g. per liter of bleach fix bath.
It is readily apparent from Table 2 that the same bleaching effect is obtained with a considerably smaller quantity of polyethylene oxide containing sulphur than in the case of the polyethylene oxides which contain no sulphur.
TABLE 2 Processing of the film with Density behind a a bleach fix bath: blue filter Without additive 2.7 With 1 g. polyethylene oxide 2.15 With 0.01 g. of condensation:
Product No. 1 2.08 Product No. 2 2.2 Product No. 3 2.10 Product No. 4 2.15 Product No. 5 2.30 Product No. 6 2.13 Product No. 7 2.16 Product No. 8 2.25 Product No. 9 2.15 Product No. 10 2.15 Product No. 11 2.05 Product No. 12 2.14 Product No. 13 2.15
Example 1 A photometric test wedge is exposed on an ordinary commercial two-layer negative colour film. The film is then developed at 18 C. for five minutes in a colour developer of the following composition:
2.75 g. diethyl-p-phenylenediamine sulphate 1.2 g. hydroxylamine sulfate 2 g. sodium sulphite (anhydrous) 2 g. sodium hexametaphosphate g. potassium carbonate 2 g. potassium bromide The film is then washed for 15 minutes in running water, bleached and fixed in a bath of the following composition:
40 g. of the sodium salt of the iron (III) complex of ethylenediamine tetra-acetic acid 9 g. of the tetrasodium salt of ethylenediamine tetra-acetic acid containing about 30% active ethylenediamine tetra-acetic acid (Trilon B of the BASF) 3.78 g. of free ethylenediamine tetra-acetic acid g. of sodium sulphite 200 g. of crystalline sodium thiosulphate Water to make up to 1 litre If 0.0 1 g. of a condensate of molecular weight 1700 and containing 3.8% of sulphur and which has been prepared from 1.27 mols of thiodiglycol and 1 mol of a polyethylene oxide of molecular weight 1130 is added to this bleach fix bath per litre, a film is obtained after 8 minutes which is free from any residual image.
If this additive is omitted, then a film which displays a considerable residual image is obtained after the bleach fix.
Example 2 An ordinary commercial hard grade colour paper is exposed behind a blue colour separation wedge and de veloped in the colour developer employed in Example 1. The sample is then treated for 5 minutes in a stop fix bath which has been prepared by dissolving 5 g. of anhydrous sodium acetate, 10 g. of sodium bisulphate and 120 g. of anhydrous sodium thiosulphate in 600 ml. of water and making up to 1 liter with water. The pH value of the bath is 6.0.
The sample is passed into the bleach fix bath employed in Example 1 without intermediate washing. If 1.0 g. of a condensate of molecular weight 1700 and containing 3.8% of sulphur and which has been prepared from 1.27 mols of thiodiglycol and 1 mol of a polyethylene oxide of molecular weight 1130 is added to the bleach fix bath a perfectly bleached yellow wedge is obtained after 8 minutes.
If 1.0 g. of a sulphur-free polyethylene oxide, for ex ample an addition product of 1 mol of ammonia and from to mols of ethylene oxide is added instead of the polyethylene thioether containing sulphur, the yellow wedge still displays considerable remains of the silver image after a reaction time of 12 minutes.
Having thus described our invention we now state that we believe our invention to be capable of numerous variations. For example any water-soluble thiosulphates may be used as fixing agents such as alkali thiosulphates or ammonium thiosulphate. The bleach fixing bath may contain as stabilising agents any water-soluble sulfite, bisulfite or metasulfite. Furthermore the bleach fixing bath may have an additional content of water-soluble iodides as described in copending application Ser. No. 95,735, filed March 14, 1961, by Bernard Morcher, Karl Frank and Max Heilmann.
Moreover it is clear to those skilled in the art that the photographic material which shall be treated by the bleach fixing bath according to the invention may be developed by means of any developer composition known per se.
The pH-value of the bleach fixing bath according to the invention may range approximately from 5 to 8.
As to the amounts of the sulphur containing polyalkylene-oxides being added to the bleach fixing bath according to the invention it is self-evident that smaller amounts than 0.01 g./l. of the bleach fixing bath are less eifective. Higher amounts may be added. The upper limit of the amount to be added is given by the solubility of said compounds, which depends on the molecular weight, the content of water-solubilizing groups and so on.
We claim:
1. In a process for the bleaching and fixing of a photo graphic silver halide emulsion which comprises subjecting the said emulsion to treatment with a fixing-bleaching composition comprising (a) a conventional bleaching agent of the group consisting of complex salts of trivalent iron and an acid of the group consisting of polycarboxylic acids and nitrogen-containing polycarboxylic acids, and
6 (b) a conventional fixing agent consisting of a watersoluble salt of thiosulfuric acid,
the improvement of subjecting the said emulsion to treatment with a fixing-bleach composition which contains in dissolved form, in addition to the two foregoing conventional ingredients, at least 0.01 gram per liter of a sub!- stance of the group consisting of polyalkylene oxides having the formula:
wherein R, R, R" and R' are each a radical of the group consisting of alkylene radicals having up to 10 carbon atoms and phenylene, m is an integer from 0 to 100, n and p are each an integer from 1 to 100, Y is a radical of the group consisting of in which R"" is a lower aliphatic radical having up to 3 carbon atoms and X is a radical of the group consisting of (I) hydrogen, (II) alkyl containing up to 10 carbon atoms, (III) alkyl containing up to 10 carbon atoms and containing a substituent of the group consisting of cyano, amino, carboxyl, sulfo and radicals derived from acids of phosphorous, (IV) aryl, (V) aryl radicals containing a substitutent of the group consisting of amino, carboxyl, sulfo and radicals derived from acids of phosphorus, and (VI) acyl radicals of aliphatic monocarboxylic acids and aliphatic dicarboxylic acids, and mixtures thereof.
2. A bleaching and fixing composition for treating photographic silver halide emulsions comprising (a) a conventional bleaching agent of the group consisting of complex salts of trivalent iron and an acid of the group consisting of polycarboxylic acids and nitrogen-containing polycarboxylic acids, (b) a conventional fixing agent consisting of a watersoluble salt of thiosulfuric acid, and (c) in dissolved form at least 0.1 gram per liter of a substance of the group consisting of polyalkylene oxides having the formula:
wherein R, R, R" and R are each a radical of the group consisting of alkylene radicals having up to 10 carbon atoms and phenylene, m is an integer from 0 to 100, n and p are each an integer from 1 to 100, Y is a radical of the group consisting of in which R"" is a lower aliphatic radical having up to 3 carbon atoms and X is a radical of the group consisting of (I) hydrogen, (II) alkyl containing up to 10 carbon atoms and (III) alkyl containing up to 10 carbon atoms and containing a substituent of the group consisting of cyano, amino, carboxyl, sulfo and radicals derived from acids of phosphorus, (IV) aryl, (V) aryl radicals containing a substituent of the group consisting of aminq, carboxyl, sulfo and radicals derived from acids of phosphorus, and (VI) acyl radicals of aliphatic monocarboxylic acids and aliphatic dicarboxylic acids, and mixtures thereof.
3. A bleaching and fixing composition for the treatment of photographic silver halide emulsions comprising an aqueous solution containing the following substances in approximately the quantities specified per liter of solution:
(i) 40 grams of the sodium salt of the ferric complex of ethylenediaminetetraacetic acid,
(ii) 9 grams of the tetrasodi-um salt of ethylenediaminetetraacetic acid containing approximately 30% by weight of active ethylenediaminetetraacetic acid,
8,241,966 7 8 (iii) 3.78 grams of ethylenediaminetetraacetic acid, References Cited by the Examiner (iv) 10 grams of anhydrous sodium sulfite, (v) 200 grams of sodium thiosulfate pentahydrate, and FOREIGN PATENTS (vi) 001 gram of condensation product having a mo- 5451083 8/1957 Canadalecular Weight of 1700 and containing 3.8% by 5 866,605 2/1953 Germany' weight of sulfur that was prepared from thiodiglycol 966,410 8/1957' Germanyand polyethylene oxide having a molecular weight of 1300 in the proportions of 1.27 mols of thiodiglycol NORMAN TORCHIN Pfimm'y Examine'l' per mol of the polyethylene oxide. HAROLD N. BURSTEIN, Examiner.
Claims (1)
1. IN A PROCESS FOR THE BLEACHING AND FIXING OF A PHOTOGRAPHIC SILVER HALIDE EMULSION WHICH COMPRISES SUBJECTING THE SAID EMULSION TO TREATMENT WITH A FIXING-BLEACHING COMPOSITION COMPRISING (A) A CONVENTIONAL BLEACHING AGENT OF THE GROUP CONSISTING OF COMPLEX SALTS OF TRIVALENT IRON AND AN ACID OF THE GROUP CONSISTING OF POLYCARBOXYLIC ACIDS AND NITROGEN-CONTAINING POLYCARBOXYLIC ACIDS, AND (B) A CONVENTIONAL FIXING AGENT CONSISTING OF A WATERSOLUBLE SALT OF THIOSULFURIC ACID, THE IMPROVEMENT OF SUBJECTING THE SAID EMULSION TO TREATMENT WITH A FIXING-BLEACH COMPOSITION WHICH CONTAINS IN DISSOLVED FORM, IN ADDITION TO THE TWO FOREGOING CONVENTIONAL INGREDIENTS, AT LEAST 0.01 GRAM PER LITER OF A SUBSTANCE OF THE GROUP CONSISTING OF POLYALKYLENE OXIDES HAVING THE FORMULA:
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEA34882A DE1146363B (en) | 1960-06-14 | 1960-06-14 | Process for bleach-fixing silver photographic images |
Publications (1)
Publication Number | Publication Date |
---|---|
US3241966A true US3241966A (en) | 1966-03-22 |
Family
ID=6928758
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US140170A Expired - Lifetime US3241966A (en) | 1960-06-14 | 1961-06-09 | Bleach fixing of photographic silver images |
Country Status (4)
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US (1) | US3241966A (en) |
BE (1) | BE604974A (en) |
DE (1) | DE1146363B (en) |
GB (1) | GB933008A (en) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3769014A (en) * | 1971-04-19 | 1973-10-30 | Eastman Kodak Co | Beta-disulfone silver halide solubilizing agents |
US3833376A (en) * | 1972-11-24 | 1974-09-03 | Minnesota Mining & Mfg | Color development process and compositions |
JPS49107737A (en) * | 1973-02-19 | 1974-10-14 | ||
US3907568A (en) * | 1971-10-22 | 1975-09-23 | Fuji Photo Film Co Ltd | Process for regenerating blixing solution for color photographic processing |
US4201585A (en) * | 1977-10-28 | 1980-05-06 | Agfa-Gevaert, N.V. | Photographic bleach compositions containing bleach-accelerating compounds |
US4294914A (en) * | 1978-09-14 | 1981-10-13 | Eastman Kodak Company | Photographic bleach compositions and methods of photographic processing |
US4446225A (en) * | 1982-03-25 | 1984-05-01 | Fuji Photo Film Co., Ltd. | Method for processing color photographic light-sensitive material |
US4451132A (en) * | 1981-12-17 | 1984-05-29 | Fuji Photo Film Co., Ltd. | Color photographic processing apparatus including a reverse osmosis apparatus |
EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
EP0200206A2 (en) | 1985-04-30 | 1986-11-05 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0201027A2 (en) | 1985-04-30 | 1986-11-12 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0202784A2 (en) | 1985-04-23 | 1986-11-26 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0209118A2 (en) | 1985-07-17 | 1987-01-21 | Konica Corporation | Silver halide photographic material |
DE3642244A1 (en) * | 1985-12-11 | 1987-06-19 | Fuji Photo Film Co Ltd | COLOR PHOTOGRAPHIC SILVER HALOGENID MATERIAL AND METHOD FOR TREATING IT |
US4745048A (en) * | 1985-06-07 | 1988-05-17 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material and method of processing the same using an improved desilvering accelerator |
EP0458277A2 (en) * | 1990-05-21 | 1991-11-27 | Fuji Photo Film Co., Ltd. | Composition having a fixing ability for photography and method for processing photographic materials with the same |
US5266449A (en) * | 1991-11-13 | 1993-11-30 | Agfa Gevaert Ag | Bleaching bath |
US5633124A (en) * | 1992-05-08 | 1997-05-27 | Eastman Kodak Company | Acceleration of silver removal by thioether compounds |
US6824965B2 (en) | 2000-08-04 | 2004-11-30 | Agfa-Gevaert | Bleach bath |
WO2012035314A1 (en) | 2010-09-17 | 2012-03-22 | Fujifilm Manufacturing Europe Bv | Photographic paper |
WO2021213762A1 (en) | 2020-04-24 | 2021-10-28 | Fujifilm Manufacturing Europe Bv | Photographic paper |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE866605C (en) * | 1944-11-27 | 1953-02-12 | Bayer Ag | Process for making photographic attenuator and bleach-fix baths |
DE966410C (en) * | 1953-05-13 | 1957-08-01 | Agfa Ag | Process for bleach-fixing silver photographic images |
CA545083A (en) * | 1957-08-20 | M. Mader Paul | Removing silver and silver halide from photographic emulsions |
-
0
- BE BE604974D patent/BE604974A/xx unknown
-
1960
- 1960-06-14 DE DEA34882A patent/DE1146363B/en active Pending
-
1961
- 1961-06-09 US US140170A patent/US3241966A/en not_active Expired - Lifetime
- 1961-06-14 GB GB21536/61A patent/GB933008A/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA545083A (en) * | 1957-08-20 | M. Mader Paul | Removing silver and silver halide from photographic emulsions | |
DE866605C (en) * | 1944-11-27 | 1953-02-12 | Bayer Ag | Process for making photographic attenuator and bleach-fix baths |
DE966410C (en) * | 1953-05-13 | 1957-08-01 | Agfa Ag | Process for bleach-fixing silver photographic images |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3769014A (en) * | 1971-04-19 | 1973-10-30 | Eastman Kodak Co | Beta-disulfone silver halide solubilizing agents |
US3907568A (en) * | 1971-10-22 | 1975-09-23 | Fuji Photo Film Co Ltd | Process for regenerating blixing solution for color photographic processing |
US3833376A (en) * | 1972-11-24 | 1974-09-03 | Minnesota Mining & Mfg | Color development process and compositions |
JPS49107737A (en) * | 1973-02-19 | 1974-10-14 | ||
JPS5810741B2 (en) * | 1973-02-19 | 1983-02-26 | コニカ株式会社 | Processing liquid for silver halide photographic materials |
US4201585A (en) * | 1977-10-28 | 1980-05-06 | Agfa-Gevaert, N.V. | Photographic bleach compositions containing bleach-accelerating compounds |
US4294914A (en) * | 1978-09-14 | 1981-10-13 | Eastman Kodak Company | Photographic bleach compositions and methods of photographic processing |
US4451132A (en) * | 1981-12-17 | 1984-05-29 | Fuji Photo Film Co., Ltd. | Color photographic processing apparatus including a reverse osmosis apparatus |
US4446225A (en) * | 1982-03-25 | 1984-05-01 | Fuji Photo Film Co., Ltd. | Method for processing color photographic light-sensitive material |
EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
EP0202784A2 (en) | 1985-04-23 | 1986-11-26 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0200206A2 (en) | 1985-04-30 | 1986-11-05 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0201027A2 (en) | 1985-04-30 | 1986-11-12 | Konica Corporation | Silver halide photographic light-sensitive material |
US4745048A (en) * | 1985-06-07 | 1988-05-17 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material and method of processing the same using an improved desilvering accelerator |
EP0209118A2 (en) | 1985-07-17 | 1987-01-21 | Konica Corporation | Silver halide photographic material |
DE3642244C2 (en) * | 1985-12-11 | 1998-07-02 | Fuji Photo Film Co Ltd | Color photographic silver halide recording material |
DE3642244A1 (en) * | 1985-12-11 | 1987-06-19 | Fuji Photo Film Co Ltd | COLOR PHOTOGRAPHIC SILVER HALOGENID MATERIAL AND METHOD FOR TREATING IT |
US4780403A (en) * | 1985-12-11 | 1988-10-25 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material containing disulfide type bleach accelerator |
EP0458277A2 (en) * | 1990-05-21 | 1991-11-27 | Fuji Photo Film Co., Ltd. | Composition having a fixing ability for photography and method for processing photographic materials with the same |
US5429914A (en) * | 1990-05-21 | 1995-07-04 | Fuji Photo Film Co., Ltd. | Composition having a fixing ability for photography and method for processing photographic materials with the same |
EP0458277A3 (en) * | 1990-05-21 | 1991-12-18 | Fuji Photo Film Co., Ltd. | Composition having a fixing ability for photography and method for processing photographic materials with the same |
US5266449A (en) * | 1991-11-13 | 1993-11-30 | Agfa Gevaert Ag | Bleaching bath |
US5633124A (en) * | 1992-05-08 | 1997-05-27 | Eastman Kodak Company | Acceleration of silver removal by thioether compounds |
US6824965B2 (en) | 2000-08-04 | 2004-11-30 | Agfa-Gevaert | Bleach bath |
WO2012035314A1 (en) | 2010-09-17 | 2012-03-22 | Fujifilm Manufacturing Europe Bv | Photographic paper |
WO2021213762A1 (en) | 2020-04-24 | 2021-10-28 | Fujifilm Manufacturing Europe Bv | Photographic paper |
Also Published As
Publication number | Publication date |
---|---|
DE1146363B (en) | 1963-03-28 |
BE604974A (en) | |
GB933008A (en) | 1963-07-31 |
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