US3615493A - Method of processing color photographs by a silver dye-bleaching method - Google Patents
Method of processing color photographs by a silver dye-bleaching method Download PDFInfo
- Publication number
- US3615493A US3615493A US677726A US3615493DA US3615493A US 3615493 A US3615493 A US 3615493A US 677726 A US677726 A US 677726A US 3615493D A US3615493D A US 3615493DA US 3615493 A US3615493 A US 3615493A
- Authority
- US
- United States
- Prior art keywords
- dye
- dyes
- bleaching
- silver
- vinylpyrrolidone
- 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
Links
- 238000000034 method Methods 0.000 title claims description 31
- 229910052709 silver Inorganic materials 0.000 title abstract description 37
- 239000004332 silver Substances 0.000 title abstract description 37
- 238000004061 bleaching Methods 0.000 title abstract description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title abstract description 27
- 238000012545 processing Methods 0.000 title abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims description 20
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- QIFCIFLDTQJGHQ-UHFFFAOYSA-M potassium;2-phenylethenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 QIFCIFLDTQJGHQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 81
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 abstract description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- -1 silver halide Chemical class 0.000 description 18
- 239000000839 emulsion Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000001043 yellow dye Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001007 phthalocyanine dye Substances 0.000 description 3
- 239000000984 vat dye Substances 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000999 acridine dye Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 229940097275 indigo Drugs 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000001017 thiazole dye Substances 0.000 description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- JDASKPRUFDKACZ-UHFFFAOYSA-M 1-octadecylpyridin-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 JDASKPRUFDKACZ-UHFFFAOYSA-M 0.000 description 1
- MHOFGBJTSNWTDT-UHFFFAOYSA-M 2-[n-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazol-3-ium-2-yl)diazenyl]anilino]ethanol;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(CCO)CC)=CC=C1N=NC1=[N+](C)C2=CC=C(OC)C=C2S1 MHOFGBJTSNWTDT-UHFFFAOYSA-M 0.000 description 1
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- AKVUWTYSNLGBJY-UHFFFAOYSA-N 2-methyl-1-morpholin-4-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCOCC1 AKVUWTYSNLGBJY-UHFFFAOYSA-N 0.000 description 1
- SQHWUYVHKRVCMD-UHFFFAOYSA-N 2-n,2-n-dimethyl-10-phenylphenazin-10-ium-2,8-diamine;chloride Chemical compound [Cl-].C12=CC(N(C)C)=CC=C2N=C2C=CC(N)=CC2=[N+]1C1=CC=CC=C1 SQHWUYVHKRVCMD-UHFFFAOYSA-N 0.000 description 1
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 1
- JRMDFAKCPRMZKA-UHFFFAOYSA-N 6-n,6-n,2-trimethylacridin-10-ium-3,6-diamine;chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=NC3=CC([NH+](C)C)=CC=C3C=C21 JRMDFAKCPRMZKA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XKTMIJODWOEBKO-UHFFFAOYSA-M Guinee green B Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC=CC=2)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 XKTMIJODWOEBKO-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000083869 Polyommatus dorylas Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- KSCQDDRPFHTIRL-UHFFFAOYSA-N auramine O Chemical compound [H+].[Cl-].C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 KSCQDDRPFHTIRL-UHFFFAOYSA-N 0.000 description 1
- VADJQOXWNSPOQA-UHFFFAOYSA-L dichlorozinc;3-n,3-n,6-n,6-n-tetramethylacridine-3,6-diamine;hydrochloride Chemical compound Cl.[Cl-].[Cl-].[Zn+2].C1=CC(N(C)C)=CC2=NC3=CC(N(C)C)=CC=C3C=C21 VADJQOXWNSPOQA-UHFFFAOYSA-L 0.000 description 1
- NJDNXYGOVLYJHP-UHFFFAOYSA-L disodium;2-(3-oxido-6-oxoxanthen-9-yl)benzoate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=CC(=O)C=C2OC2=CC([O-])=CC=C21 NJDNXYGOVLYJHP-UHFFFAOYSA-L 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- NIILHKUNQFSIDT-UHFFFAOYSA-N methyl(tridecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCC[NH2+]C NIILHKUNQFSIDT-UHFFFAOYSA-N 0.000 description 1
- FTZOMWRBGAUFMT-UHFFFAOYSA-N n,2-dimethyl-4-[3-methyl-4-(methylamino)benzenecarboximidoyl]aniline Chemical compound C1=C(C)C(NC)=CC=C1C(=N)C1=CC=C(NC)C(C)=C1 FTZOMWRBGAUFMT-UHFFFAOYSA-N 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- SHXOKQKTZJXHHR-UHFFFAOYSA-N n,n-diethyl-5-iminobenzo[a]phenoxazin-9-amine;hydrochloride Chemical compound [Cl-].C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=[NH2+])C2=C1 SHXOKQKTZJXHHR-UHFFFAOYSA-N 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 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
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- FLOMHNPVJPAASA-UHFFFAOYSA-M sodium;3-[[4-(dimethylamino)phenyl]-[4-[methyl-[(3-sulfonatophenyl)methyl]amino]phenyl]methylidene]-6-dimethylazaniumylidenecyclohexa-1,4-diene-1-sulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1C(\C=1C=CC(=CC=1)N(C)CC=1C=C(C=CC=1)S([O-])(=O)=O)=C\1C=C(S([O-])(=O)=O)C(=[N+](C)C)C=C/1 FLOMHNPVJPAASA-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- JADVWWSKYZXRGX-UHFFFAOYSA-M thioflavine T Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C1=[N+](C)C2=CC=C(C)C=C2S1 JADVWWSKYZXRGX-UHFFFAOYSA-M 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- AICNZRYBCUSVMO-UHFFFAOYSA-M trimethyl(tridecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCC[N+](C)(C)C AICNZRYBCUSVMO-UHFFFAOYSA-M 0.000 description 1
- YXZRCLVVNRLPTP-UHFFFAOYSA-J turquoise blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Cu+2].NC1=NC(Cl)=NC(NC=2C=C(NS(=O)(=O)C3=CC=4C(=C5NC=4NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)NC=4NC(=C6C=C(C=CC6=4)S([O-])(=O)=O)NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)N5)C=C3)C(=CC=2)S([O-])(=O)=O)=N1 YXZRCLVVNRLPTP-UHFFFAOYSA-J 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001018 xanthene dye Substances 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
- G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
Definitions
- Leucobases of dyes can be used as dyes for photographic light-sensitive color film in a silver dyebleaching system, without accompanying formation of fog, by processing the film, after dye bleaching, in a cleaning bath containing a water-soluble N-vinylpyrrolidone polymer, a
- peregal or a lissolamine.
- the present invention relates to a method of processing color photographic materials by a silver dye-bleaching method and more particularly to a method of processing color photographs in which acleaning treatment is applied after silver dye bleaching.
- a unicolor image or a multiple color image can be formed.
- a dye used in such a silver dye bleaching method there is desired a dye which, (I) can be easily bleached by a bleaching bath in proportion to the photographic silver image, (2) becomes colorless by being completely bleached at a maximum silver image density, and (3) has high light fastness.
- azo dyes anthraquinone dyes, indigo dyes, phthalocyanine dyes, and the like.
- the silver dye-bleaching method using such dyes has the merit that the color image obtained is faster to light, chemicals (acid and alkali) and moisture and also has better saturation and sharpness than those obtained by the so-called color developing method, it has the fault that, since the dye has a color from the first, the dye absorbs light to be absorbed by the silver halide to some extent, and hence, a light-sensitive element having a high sensitivity cannot be obtained.
- Such a fault can be removed by using a colorless compound formed by the reduction of the dye, i.e., a leucobase of dye. That is, the dye is first incorporated in an emulsion as its leucobase, and then after exposure, it is colored by oxidation in an appropriate step. Thereafter, the dye thus colored is converted into the leucobase again at the silver image portion by the dye bleaching processing, and the leucobase is removed from the light-sensitive emulsion layer to provide a colored image.
- a colorless compound formed by the reduction of the dye i.e., a leucobase of dye. That is, the dye is first incorporated in an emulsion as its leucobase, and then after exposure, it is colored by oxidation in an appropriate step. Thereafter, the dye thus colored is converted into the leucobase again at the silver image portion by the dye bleaching processing, and the leucobase is removed from the light-sensitive emulsion layer to provide a colored image.
- the dye employed in the method is one capable of forming a stable leuco derivative by reduction, and also providing the original dye simply by the oxidation of the leuco derivative.
- the dye there are illustrated diphenylmethane dyes, triphenylmethane dyes, indigo dyes and other vat colors.
- an object of this invention is to provide a process of completely removing the leucobase of a dye in a light-sensitive emulsion layer in color photographic processings after subjecting the photographic light-sensitive color element containing the stable leucobase of dye to a silver dye bleaching process.
- the color element thus processed is further processed in a cleaning bath containing a polymer of water-soluble N- vinylpyrrolidone, a copolymer of water-soluble N-vinylpyrrolidone and another monomer, a peregal or a lissolamine, whereby the dye-bleached products remaining in the emulsion layer or emulsion layers, after the dye-bleaching procedure, are completely removed therefrom.
- copolymers of water-soluble N-vinylpyrrolidone and other monomer incorporated in the aforesaid cleaning bath there are illustrated copolymers of water-soluble N-vinylpyrrolidone and a vinyl ester, such as, vinyl acetate, vinyl propionate, or vinylbutyrate; an acrylic acid ester, such as a methyl ester, ethyl ester, butyl ester, or Z-ethyI-hexyl ester; a methacrylic acid ester, such as, methyl ester, ethyl ester, butyl ester, or 2-ethyl-hexyl ester; an acrylamide derivative, such as N-methylacrylar'nide, N-ethylacrylamide, N-N-diethylacrylamide, N-butylacrylamide, or acryloylmorpholine; and a methacrylamide derivative, such as, N
- copolymer having a monomer ratio to N-vinylpyrrolidone of 10-30 mol percent it'is very preferable to employ the copolymer having a monomer ratio to N-vinylpyrrolidone of 10-30 mol percent, but the invention shall not be limited to the preferred copolymer.
- Cop'olymers having any monomer ratios may be mula:
- RQ-O (CHgCH10)nH wherein R is an alkyl group and n is an integer indicating the polymerization degree of 'the ethyleneoxy group.
- Peregal O As the examples of the peregals, there are illustrated Peregal O, Peregal OK, Peregal ON, Peregal KBhe and Peregal C (trade names of LG. C0,).
- the lissolamines used in this invention there are illustrated octadecylpyridinium bromide and tridecyltrimethylammonium bromide.
- the compounds incorporated in the cleaning bath of this invention are not limited to only the above-mentioned compounds, but there may be used any water-soluble compounds within the above-described classes capable of completely removing from silver halide emulsion layers the dye-bleached products remaining in the emulsion layers after the dye-bleaching processing.
- the proportion of the water-soluble compound to be incorporated in the aforesaid cleaning bath of this invention may be varied widely according to the kind of compound, but is preferably from 5 to 50 g. and most preferably 10 to 30 g. per 1 liter of the cleaning bath. 7
- the process of this invention is particularly effective for processing a photographic light-sensitive color element containing a stable leucobase of dye or stable leucobases of dyes and photographic light-sensitive color elements to be processed by a silver dye bleaching, but may be effectively applied to the processing of other photographic light-sensitive elements containing azo dyes which are not converted into the stable leucobases for completely removing a small quantity of dye-bleached products remaining undecomposed therein after dye bleaching.
- sulfide dyes such as sulfide vat dye
- a vat dye such as solubilized vat dye
- a triarylmethane or diphenylmethane dye (4) an oxazine dye, an azine dye, thiazole dye, a quinoline dye, an acridinedye, an xanthene dye, and phthalocyanine dye.
- the following are practical examples of the effective dyes to be employed in the process of this invention, but the dyes to be used in this invention are not limited to them only.
- yellow dyes such as, Sulfur Yellow-2 of color index (C.l. No. 53,120, Sulfur Yellow-4 of C.l. No. 53,160, Sulfur Yellow-8 of C.l. No. 53,226. and the like; magenta dyes such as Sulfur Red-2 of C.l. No. 53,260 Sulfur Violet-l of C.l. No. 53,410, Sulfur Violet-4 ofC.I. No. 53,700, Sulfur Violet 3 ofC.I. No. 53,780, and the like; and cyan dyes such as Sulfur Blue-l4 of C.l. No. 53,400, Sulfur Green- 6 of C.l. No. 53,530, Sulfur Blue-l of C.l. No. 53,540 and the like.
- Sulfur Yellow-2 of color index C.l. No. 53,120, Sulfur Yellow-4 of C.l. No. 53,160, Sulfur Yellow-8 of C.l. No. 53,226. and
- yellow dyes such as, lndigosol Yellow HCGN ofC.I. No. 56,006, Indigosol Golden Yellow lGK of C.l. No. 59,101,1ndigosolYellow- 2GB of C.l. No. 61,726, Algosol Yellow GCA-CF of C.l. No. 67,301, lndigosol Yellow V of C.l. No. 60,531,1ndanthrene Yellow 461- of C.l. No. 68,420, ldanthrene Yellow G of C.l. No. 70,600, Mikethrene Yellow GC ofC.1. No. 67,300, lndanthrene Yellow of C.l. No.
- magenta dyes such as lndigosol Brilliant Pink IR of C.l. No. 73,361, lndigosol Violet lRHR of C.l. No. 73,386, lndigosol Violet R of C1.
- cyan dyes such as lndanthrene Turquoise Blue 3G'K of Cl. No. 67,915, lndanthrene Blue 56 of C.l. No. 69,845,1ndanthrene Blue GCD of C.l. No. 69,810 and the like.
- diphenylmethane dyes there are illustrated such yellow dyes, such as, Basic Yellow 2 of C.l. No. 41,000, Basic Yellow 3 of C.l. No. 41,005 and the like.
- triphenylmethane dyes there are illustrated magenta dyes, such as, Acid Blue 34 ofC.I. No. 42,561, Acid Violet 21 of C.l. No. 42,580 and the like and cyan dyes, such as, Basic Green 4 ofC.I. No. 42,000, Acid Green 11 of C.l. No. 49,039, Acid Green 13 of C.l. No. 42,046, Acid Green 3 ofC.I. No. 42,051 and the like.
- cyan dyes such as, Basic Blue 4 of C.l. No. 51,004, Basic Blue 12 of C.l. No. 51,180 and the like or magenta dyes such as Mordant Violet 50 of C.l. No. 51,055, Mordant Violet 35 of C.l. No. 51,025 and the like.
- magenta dyes such as, Basic Red 5 of C.l. No. 50,040, Basic Violet of C.l. No. 50,055, Basic Violet 5 C.l. No. 50,205, Basie Violet 8 of C.l. No. 50,210 and the like.
- thiazole dyes there are illustrated yellow dyes, such as, Basic Yellow 1 of C.l. No. 49,005 and the like.
- quinoline dyes there are illustrated yellow dyes, such as, Solvent Yellow 33 of C.l. No. 47,000.
- acridine dyes there are yellow dyes, such as, Basic Orange 14 of C.l. No. 46,005, Basic Yellow 7 of C.l. No. 46,020 and the like.
- magenta dyes such as, Basic Red 11 of C.l. No. 45,050, Basic Red 8 of C.l. No. 45,150. Basic Violet ll of C.l. No. 45,175 and the like, and also, as the phthalocyanine dyes there are illustrated Vat Blue 29 of C.l. No. 74,140, and the like.
- a secondary development may be conducted before the dye bleaching.
- Poly-N-vinylpyrrolidone 30.0 g. Sodium Sulfate (anhydrous) 20.0 g. Sodium Sulfate 30.0 Water To Make 1,000 ml.
- sodium sulfite was added to prevent the leucobases from being reduced in the processing and from being air-oxidized to form insoluble precipitates. Also, sodium sulfate was used to increase the effect of the cleaning procedure by salting out the complex salts of polyvinyl pyrrolidone and the leucobases.
- EXAMPLE 2 Ferric Chloride 27.0 g. Concentrated Hydrochloric Acid 20.0 ml. Potassium Bromide l0.0 g. Water to Make L000 ml.
- the developed silver was oxidized again to the silver halide, and, at the same time, the leucobases of dyes were colored by oxidation throughout the layers.
- the element was subjected, as in example 1, to dye bleaching processing in the cleaning bath, and silver bleaching.
- the clear colored image thus obtained was a positive image.
- EXAMPLE 3 The procedure as in example I was repeated, using as a cleaning bath a bath having the following composition Poly( NVinylpyrrolidone-Vinyl Acetate(8:2 Copolymcr) 10.0 g. Sodium Sull'tte (Anhydrous) 20.0 g. Sodium Sulfate 30.0 g. Water to Make L000 ml.
- EXAMPLE 5 The procedure of example I was repeated, using as the compound to be incorporated in the cleaning bath the following compounds, that is, Poly(N-Vinylpyrrolidone-Butylmethacrylate) (9:l copolymer), Poly(N-Vinylpyrrolidone- Acrylamide) (8:2 copolymer), Poly(N-Vinylpyrrolidoneacryloylmorpholine) (7:3 copolymer), Poly(N-Vinylpyrrolidone-potassium Styrenesulfonate) (8:2 copolymer), the Peregals, Octadecylpyrridinium Bromide, and Tridecylmethylammonium Bromide.
- Poly(N-Vinylpyrrolidone-Butylmethacrylate) 9:l copolymer
- Poly(N-Vinylpyrrolidone- Acrylamide) (8:2 copolymer
- the colored images obtained without using the foregoing cleaning baths had fog densities of higher than 0.2 in optical transmission density, whereas when the cleaning baths were used as in the examples, the fog density could be maintained at a level of less than 0.08.
- a photographic light-sensitive color element having on a support a single photographic silver halide emulsion layer containing a leucobase of a dye or multiple photographic silver halide emulsion layers containing leucobases of dyes,
- the rocess which comlprises, after dye bleaching cleaning the ligh -sensit1ve color e ement III a cleaning bah capab e of removing the leucobase material from the light-sensitive element, said cleaning bath containing from 5 to 50 grams per liter of a material selected from the group consisting of a water-soluble polymer of N-vinylpyrrolidone and a water soluble copolymer of N-vinylpyrrolidone. 2.
- copolymer of N-vinylpyrrolidone is selected from copolymers of N-vinylpyrrolidone and butylmethacrylate, copolymers of N-vinylpyrrolidone and acrylamide, copolymers of N-vinylpyrrolidone and acryloyomorpholine, and copolymers of N-vinylpyrrolidone and potassium styrenesulfonate.
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Abstract
Leucobases of dyes can be used as dyes for photographic lightsensitive color film in a silver dye-bleaching system, without accompanying formation of fog, by processing the film, after dye bleaching, in a cleaning bath containing a water-soluble Nvinylpyrrolidone polymer, a peregal, or a lissolamine.
Description
United States Patent Kanagawa, Japan [32] Priority Oct. 25, 1966 [3 3] Japan [54] METHOD OF PROCESSING COLOR PHOTOGRAPHS BY A SILVER DYE-BLEACHING METHOD 3 Claims, No Drawings s21 U.S.Cl 96/53 51 Int.Cl G03c7/00 [50] Field of Search [56] References Cited UNITED STATES PATENTS 2,263,012 11/1941 Schinzel 2,326,055 8/1943 Morris..... 2,376,297 5/1945 Weber 2,709,136 5/1955 Ganguin Primary ExaminerNorman G. Torchin Assistant Examiner-Mary F. Kelley Attorney-Sughrue, Rothwell, Mion, Zinn & Macpeak ABSTRACT: Leucobases of dyes can be used as dyes for photographic light-sensitive color film in a silver dyebleaching system, without accompanying formation of fog, by processing the film, after dye bleaching, in a cleaning bath containing a water-soluble N-vinylpyrrolidone polymer, a
peregal, or a lissolamine.
METHOD OF PROCESSING COLOR PHOTOGRAPHS BY A SILVER DYE-BLEACHING METHOD BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing color photographic materials by a silver dye-bleaching method and more particularly to a method of processing color photographs in which acleaning treatment is applied after silver dye bleaching.
2. Description of the Prior Art The formation of color photographic images by a silver dyebleaching method is based upon the fact that some kinds of dyes are destroyed by the presence of metallic silver. That is, silver'dye bleaching is generally carried out in the following manner. After light-exposing and developing a photographic gelatino silver halide emulsion layer, which has been uniformly colored by a suitable dye, such as, a light-sensitive color element having multiple silver halide layers each containing a yellow dye, a magenta dye, and a cyan dye respectively, the silver image thus formed is oxidized and simultaneously processed in a liquid containing an acid and a compound capable of forming a complex compound with silver ions, such as, thiourea, semicarbazide, thiosemicarbazide, potassium thiocyanate and the like. This has the action of reducing (bleaching) dyes at the silver image bearing portions or in a bleaching bath comprising an alkaline solution containing sodium sulfide, hydrosulfite, stannous chloride, thiourea and the like, and thereafter, the silver salt and remaining liquid are removed to provide a reversal dye image of the original silver image.
Therefore, by the aforesaid process, a unicolor image or a multiple color image can be formed. As a dye used in such a silver dye bleaching method, there is desired a dye which, (I) can be easily bleached by a bleaching bath in proportion to the photographic silver image, (2) becomes colorless by being completely bleached at a maximum silver image density, and (3) has high light fastness. For example, there are employed azo dyes, anthraquinone dyes, indigo dyes, phthalocyanine dyes, and the like. However, while the silver dye-bleaching method using such dyes has the merit that the color image obtained is faster to light, chemicals (acid and alkali) and moisture and also has better saturation and sharpness than those obtained by the so-called color developing method, it has the fault that, since the dye has a color from the first, the dye absorbs light to be absorbed by the silver halide to some extent, and hence, a light-sensitive element having a high sensitivity cannot be obtained.
Such a fault, however, can be removed by using a colorless compound formed by the reduction of the dye, i.e., a leucobase of dye. That is, the dye is first incorporated in an emulsion as its leucobase, and then after exposure, it is colored by oxidation in an appropriate step. Thereafter, the dye thus colored is converted into the leucobase again at the silver image portion by the dye bleaching processing, and the leucobase is removed from the light-sensitive emulsion layer to provide a colored image.
In other words, the dye employed in the method is one capable of forming a stable leuco derivative by reduction, and also providing the original dye simply by the oxidation of the leuco derivative. As typical examples of the dye, there are illustrated diphenylmethane dyes, triphenylmethane dyes, indigo dyes and other vat colors.
However, employing the aforesaid dyes capable of easily forming the leuco derivative, is accompanied by the following faults, as compared with the case of using dyes which do not form a stable leucobase, but are decomposed under usual conditions. That is, different from the case of azo dyes, dyes capable of forming stable leucobases are not decomposed by the dye-bleaching processing and stay as leucobases in the lightsensitive emulsion layer. If the leucobase is not completely removed from the light-sensitive emulsion layer, the leucobase is converted into the colored dye again by the subsequent silver dye-bleaching procedure or air oxidation, which causes fogs. Even though the light-sensitive emulsion layer containing such a leucobase is washed with water for a long period of time after dye bleaching, there remain fogs of an optical transmission density of higher than 0.2.
Therefore, an object of this invention is to provide a process of completely removing the leucobase of a dye in a light-sensitive emulsion layer in color photographic processings after subjecting the photographic light-sensitive color element containing the stable leucobase of dye to a silver dye bleaching process.
SUMMARY OF THE INVENTION Thus, according to the present invention, after processing by silver dye bleaching, a photographic light-sensitive color element, having on a support a monolayered or multiple layered silver halide emulsion layer containing the leucobases of dyes, the color element thus processed is further processed in a cleaning bath containing a polymer of water-soluble N- vinylpyrrolidone, a copolymer of water-soluble N-vinylpyrrolidone and another monomer, a peregal or a lissolamine, whereby the dye-bleached products remaining in the emulsion layer or emulsion layers, after the dye-bleaching procedure, are completely removed therefrom.
DETAILED DESCRIPTION OF THE INVENTION As the copolymer of water-soluble N-vinylpyrrolidone and other monomer incorporated in the aforesaid cleaning bath, there are illustrated copolymers of water-soluble N-vinylpyrrolidone and a vinyl ester, such as, vinyl acetate, vinyl propionate, or vinylbutyrate; an acrylic acid ester, such as a methyl ester, ethyl ester, butyl ester, or Z-ethyI-hexyl ester; a methacrylic acid ester, such as, methyl ester, ethyl ester, butyl ester, or 2-ethyl-hexyl ester; an acrylamide derivative, such as N-methylacrylar'nide, N-ethylacrylamide, N-N-diethylacrylamide, N-butylacrylamide, or acryloylmorpholine; and a methacrylamide derivative, such as, N-methylmethacrylamide, N-ethylmethacrylamide or methacryloylmorpholine. In this case, it'is very preferable to employ the copolymer having a monomer ratio to N-vinylpyrrolidone of 10-30 mol percent, but the invention shall not be limited to the preferred copolymer. Cop'olymers having any monomer ratios may be mula:
RO(CH CH O),,H or
RQ-O (CHgCH10)nH wherein R is an alkyl group and n is an integer indicating the polymerization degree of 'the ethyleneoxy group.
As the examples of the peregals, there are illustrated Peregal O, Peregal OK, Peregal ON, Peregal KBhe and Peregal C (trade names of LG. C0,).
Further, as the lissolamines used in this invention there are illustrated octadecylpyridinium bromide and tridecyltrimethylammonium bromide. However, it should be understood that the compounds incorporated in the cleaning bath of this invention are not limited to only the above-mentioned compounds, but there may be used any water-soluble compounds within the above-described classes capable of completely removing from silver halide emulsion layers the dye-bleached products remaining in the emulsion layers after the dye-bleaching processing.
The proportion of the water-soluble compound to be incorporated in the aforesaid cleaning bath of this invention may be varied widely according to the kind of compound, but is preferably from 5 to 50 g. and most preferably 10 to 30 g. per 1 liter of the cleaning bath. 7
Moreover, it is possible that instead of incorporating the aforesaid compound in the cleaning .bathof this invention,.the.
compound is previously incorporated in the emulsion layers, intermediate layers or a yellow filter layer of a photographic light-sensitive color element.
Further, the process of this invention is particularly effective for processing a photographic light-sensitive color element containing a stable leucobase of dye or stable leucobases of dyes and photographic light-sensitive color elements to be processed by a silver dye bleaching, but may be effectively applied to the processing of other photographic light-sensitive elements containing azo dyes which are not converted into the stable leucobases for completely removing a small quantity of dye-bleached products remaining undecomposed therein after dye bleaching.
As the dyes incorporated in the photographic light-sensitive color elements in a silver dye-bleaching method and capable of forming stable leucobases, there are illustrated, (1) sulfide dyes such as sulfide vat dye, (2) a vat dye, such as solubilized vat dye, (3) a triarylmethane or diphenylmethane dye, (4) an oxazine dye, an azine dye, thiazole dye, a quinoline dye, an acridinedye, an xanthene dye, and phthalocyanine dye. The following are practical examples of the effective dyes to be employed in the process of this invention, but the dyes to be used in this invention are not limited to them only.
Thus, as the sulfide dyes there are illustrated yellow dyes, such as, Sulfur Yellow-2 of color index (C.l. No. 53,120, Sulfur Yellow-4 of C.l. No. 53,160, Sulfur Yellow-8 of C.l. No. 53,226. and the like; magenta dyes such as Sulfur Red-2 of C.l. No. 53,260 Sulfur Violet-l of C.l. No. 53,410, Sulfur Violet-4 ofC.I. No. 53,700, Sulfur Violet 3 ofC.I. No. 53,780, and the like; and cyan dyes such as Sulfur Blue-l4 of C.l. No. 53,400, Sulfur Green- 6 of C.l. No. 53,530, Sulfur Blue-l of C.l. No. 53,540 and the like.
As the vat colors there are illustrated yellow dyes, such as, lndigosol Yellow HCGN ofC.I. No. 56,006, Indigosol Golden Yellow lGK of C.l. No. 59,101,1ndigosolYellow- 2GB of C.l. No. 61,726, Algosol Yellow GCA-CF of C.l. No. 67,301, lndigosol Yellow V of C.l. No. 60,531,1ndanthrene Yellow 461- of C.l. No. 68,420, ldanthrene Yellow G of C.l. No. 70,600, Mikethrene Yellow GC ofC.1. No. 67,300, lndanthrene Yellow of C.l. No. 68,405 and the like; magenta dyes such as lndigosol Brilliant Pink IR of C.l. No. 73,361, lndigosol Violet lRHR of C.l. No. 73,386, lndigosol Violet R of C1. No. 59,321, lndigosol Red Violet IRRL of C.l. No. 59,316, indigosol Red lFBB of C.l. No. 67,001, lndanthrene Red Violet of C.l. No. 67,895, Mikethrene Brilliant Violet BBK of C.l. No. 63,355, and the like; and cyan dyes such as lndanthrene Turquoise Blue 3G'K of Cl. No. 67,915, lndanthrene Blue 56 of C.l. No. 69,845,1ndanthrene Blue GCD of C.l. No. 69,810 and the like.
As the diphenylmethane dyes there are illustrated such yellow dyes, such as, Basic Yellow 2 of C.l. No. 41,000, Basic Yellow 3 of C.l. No. 41,005 and the like. As the triphenylmethane dyes there are illustrated magenta dyes, such as, Acid Blue 34 ofC.I. No. 42,561, Acid Violet 21 of C.l. No. 42,580 and the like and cyan dyes, such as, Basic Green 4 ofC.I. No. 42,000, Acid Green 11 of C.l. No. 49,039, Acid Green 13 of C.l. No. 42,046, Acid Green 3 ofC.I. No. 42,051 and the like.
Also, as the oxazine dyes, there may be used cyan dyes, such as, Basic Blue 4 of C.l. No. 51,004, Basic Blue 12 of C.l. No. 51,180 and the like or magenta dyes such as Mordant Violet 50 of C.l. No. 51,055, Mordant Violet 35 of C.l. No. 51,025 and the like.
As the azine dyes there are illustrated magenta dyes, such as, Basic Red 5 of C.l. No. 50,040, Basic Violet of C.l. No. 50,055, Basic Violet 5 C.l. No. 50,205, Basie Violet 8 of C.l. No. 50,210 and the like. As the thiazole dyes there are illustrated yellow dyes, such as, Basic Yellow 1 of C.l. No. 49,005 and the like. As quinoline dyes there are illustrated yellow dyes, such as, Solvent Yellow 33 of C.l. No. 47,000. As the acridine dyes there are yellow dyes, such as, Basic Orange 14 of C.l. No. 46,005, Basic Yellow 7 of C.l. No. 46,020 and the like.
Furthermore, as the zanthene dyes there may be used magenta dyes, such as, Basic Red 11 of C.l. No. 45,050, Basic Red 8 of C.l. No. 45,150. Basic Violet ll of C.l. No. 45,175 and the like, and also, as the phthalocyanine dyes there are illustrated Vat Blue 29 of C.l. No. 74,140, and the like.
Now, the practice of the invention will be explained with reference to the following examples:
EXAMPLE 1 Potassium Bichromate 5.0 g. Concentrated Sulfuric Acid 5.0 ml.
Water To Make 1,000 ml.
1n this way, the developed silver was removed from the lightsensitive emulsion layers and at the same time the leucobases of the dyes were uniformly oxidized and converted into the original dyes.
Thereafter, the element was processed for 4 minutes in a bath having the following composition:
Sodium Sulfite (anhydrous) Water To Make 50.0 g. 1,000 ml.
After washing with water for 4 minutes, the element was dye bleached for 7 minutes in a bath having the following composition:
Stannous Chloride 40.0 g. Sodium Hydroxide 50.0 g. Triethanolamine 100.0 ml. Anthraquinone 0.1 Water To Make 1,000 ml.
In this way, the dyes were reduced again to the leucobases at the portions bearing the remaining silver halides.
A secondary development may be conducted before the dye bleaching.
In this case, the reduction products remaining in the lightsensitive emulsion layers were completely removed therefrom by processing the element for 10 minutes in a cleaning bath having the following composition:
Poly-N-vinylpyrrolidone 30.0 g. Sodium Sulfate (anhydrous) 20.0 g. Sodium Sulfate 30.0 Water To Make 1,000 ml.
in the aforesaid cleaning bath of this example, sodium sulfite was added to prevent the leucobases from being reduced in the processing and from being air-oxidized to form insoluble precipitates. Also, sodium sulfate was used to increase the effect of the cleaning procedure by salting out the complex salts of polyvinyl pyrrolidone and the leucobases.
After washing with water for 10 minutes, the element was processed in a bath having the following composition, for 7 minutes:
Sodium Acetate (anhydrous) 20.0 g. Potassium Alum 30.0 g. Borax 10.0 g. Potassium Ferricyanide 30.0 g. Potassium Bromide 15.0 g. Water To Make 1,000 ml.
After washing with water for 4 minutes, the element was processed for 4 minutes in a conventional acid hardening fixing bath, washed with water sufficiently, and dried. The clear colored image thus obtained was a negative image.
EXAMPLE 2 Ferric Chloride 27.0 g. Concentrated Hydrochloric Acid 20.0 ml. Potassium Bromide l0.0 g. Water to Make L000 ml.
In this way, the developed silver was oxidized again to the silver halide, and, at the same time, the leucobases of dyes were colored by oxidation throughout the layers.
After washing with water, the element was subjected, as in example 1, to dye bleaching processing in the cleaning bath, and silver bleaching. The clear colored image thus obtained was a positive image.
EXAMPLE 3 The procedure as in example I was repeated, using as a cleaning bath a bath having the following composition Poly( NVinylpyrrolidone-Vinyl Acetate(8:2 Copolymcr) 10.0 g. Sodium Sull'tte (Anhydrous) 20.0 g. Sodium Sulfate 30.0 g. Water to Make L000 ml.
Results substantially similar to those of example 1 were obtained.
EXAMPLE 4 The same procedure as in example I was repeated, using as a cleaning bath a bath having the following composition:
Poly(N-Vinylpyrrolidone-Methyl Acrylatn) (3 :2 Copolyiner) l -s s- Sodium sulfite (anhydrous) 20.0 Sodium Sulfate 30.0 g. Water to Make L000 ml.
Results substantially similar to those of example l were obtained.
EXAMPLE 5 The procedure of example I was repeated, using as the compound to be incorporated in the cleaning bath the following compounds, that is, Poly(N-Vinylpyrrolidone-Butylmethacrylate) (9:l copolymer), Poly(N-Vinylpyrrolidone- Acrylamide) (8:2 copolymer), Poly(N-Vinylpyrrolidoneacryloylmorpholine) (7:3 copolymer), Poly(N-Vinylpyrrolidone-potassium Styrenesulfonate) (8:2 copolymer), the Peregals, Octadecylpyrridinium Bromide, and Tridecylmethylammonium Bromide.
In any case, the colored images obtained without using the foregoing cleaning baths had fog densities of higher than 0.2 in optical transmission density, whereas when the cleaning baths were used as in the examples, the fog density could be maintained at a level of less than 0.08.
What we claim is:
1. In a method of processing by a silver dye-bleaching technique, a photographic light-sensitive color element having on a support a single photographic silver halide emulsion layer containing a leucobase of a dye or multiple photographic silver halide emulsion layers containing leucobases of dyes,
the rocess which comlprises, after dye bleaching cleaning the ligh -sensit1ve color e ement III a cleaning bah capab e of removing the leucobase material from the light-sensitive element, said cleaning bath containing from 5 to 50 grams per liter of a material selected from the group consisting of a water-soluble polymer of N-vinylpyrrolidone and a water soluble copolymer of N-vinylpyrrolidone. 2. The process according to claim 1 wherein said copolymer of N-vinylpyrrolidone is selected from copolymers of N-vinylpyrrolidone and butylmethacrylate, copolymers of N-vinylpyrrolidone and acrylamide, copolymers of N-vinylpyrrolidone and acryloyomorpholine, and copolymers of N-vinylpyrrolidone and potassium styrenesulfonate.
3. The process according to claim 1 wherein said cleaning bath further contains sodium sulfite and sodium sulfate.
Claims (2)
- 2. The process according to claim 1 wherein said copolymer of N-vinylpyrrolidone is selected from copolymers of N-vinylpyrrolidone and butylmethacrylate, copolymers of N-vinylpyrrolidone and acrylamide, copolymers of N-vinylpyrrolidone and acryloyomorpholine, and copolymers of N-vinylpyrrolidone and potassium styrenesulfonate.
- 3. The process according to claim 1 wherein said cleaning bath further contains sodium sulfite and sodium sulfate.
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JP7036966 | 1966-10-25 |
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US3615493A true US3615493A (en) | 1971-10-26 |
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ID=13429440
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US677726A Expired - Lifetime US3615493A (en) | 1966-10-25 | 1967-10-24 | Method of processing color photographs by a silver dye-bleaching method |
Country Status (4)
Country | Link |
---|---|
US (1) | US3615493A (en) |
CH (1) | CH493008A (en) |
DE (1) | DE1597585C3 (en) |
GB (1) | GB1184445A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3837873A (en) * | 1972-05-31 | 1974-09-24 | Texas Instruments Inc | Compositions for use in forming a doped oxide film |
-
1967
- 1967-10-24 GB GB48330/67A patent/GB1184445A/en not_active Expired
- 1967-10-24 US US677726A patent/US3615493A/en not_active Expired - Lifetime
- 1967-10-25 CH CH1490267A patent/CH493008A/en not_active IP Right Cessation
- 1967-10-25 DE DE1597585A patent/DE1597585C3/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3837873A (en) * | 1972-05-31 | 1974-09-24 | Texas Instruments Inc | Compositions for use in forming a doped oxide film |
Also Published As
Publication number | Publication date |
---|---|
DE1597585C3 (en) | 1979-03-29 |
CH493008A (en) | 1970-06-30 |
DE1597585A1 (en) | 1970-06-11 |
DE1597585B2 (en) | 1978-07-27 |
GB1184445A (en) | 1970-03-18 |
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