US3542555A - Photographic silver halide elements containing tetrakisazo dyes - Google Patents
Photographic silver halide elements containing tetrakisazo dyes Download PDFInfo
- Publication number
- US3542555A US3542555A US668174A US3542555DA US3542555A US 3542555 A US3542555 A US 3542555A US 668174 A US668174 A US 668174A US 3542555D A US3542555D A US 3542555DA US 3542555 A US3542555 A US 3542555A
- Authority
- US
- United States
- Prior art keywords
- dye
- dyes
- silver
- tetrakisazo
- silver halide
- 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
- 239000000975 dye Substances 0.000 title description 59
- 229910052709 silver Inorganic materials 0.000 title description 41
- 239000004332 silver Substances 0.000 title description 41
- -1 silver halide Chemical class 0.000 title description 32
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 24
- 239000010410 layer Substances 0.000 description 18
- 238000004061 bleaching Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 239000000987 azo dye Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000007844 bleaching agent Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 150000008049 diazo compounds Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 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 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 150000004780 naphthols Chemical class 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- AJIRUIWLEVHQMU-UHFFFAOYSA-N 3-aminophenazin-2-ol Chemical compound C1=CC=C2N=C(C=C(C(N)=C3)O)C3=NC2=C1 AJIRUIWLEVHQMU-UHFFFAOYSA-N 0.000 description 2
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229940061610 sulfonated phenol Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- USWINTIHFQKJTR-UHFFFAOYSA-N 3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(O)=CC2=C1 USWINTIHFQKJTR-UHFFFAOYSA-N 0.000 description 1
- DACUJXBUANTBKE-UHFFFAOYSA-N 4-acetamido-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(NC(=O)C)=CC(S(O)(=O)=O)=CC2=C1 DACUJXBUANTBKE-UHFFFAOYSA-N 0.000 description 1
- GPLYAUJTVOYYTL-UHFFFAOYSA-N 4-amino-2-hydroxybenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(O)=C1 GPLYAUJTVOYYTL-UHFFFAOYSA-N 0.000 description 1
- LRDIEHDJWYRVPT-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 LRDIEHDJWYRVPT-UHFFFAOYSA-N 0.000 description 1
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- HGWQOFDAUWCQDA-UHFFFAOYSA-N 4-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(O)=CC=C(S(O)(=O)=O)C2=C1 HGWQOFDAUWCQDA-UHFFFAOYSA-N 0.000 description 1
- ASFYHTGWWLFSDZ-UHFFFAOYSA-N 5-chloro-2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(Cl)C=C1S(O)(=O)=O ASFYHTGWWLFSDZ-UHFFFAOYSA-N 0.000 description 1
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 241000933336 Ziziphus rignonii Species 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000005421 aryl sulfonamido group Chemical group 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical compound S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NRZRRZAVMCAKEP-UHFFFAOYSA-N naphthionic acid Chemical compound C1=CC=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 NRZRRZAVMCAKEP-UHFFFAOYSA-N 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002988 phenazines Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 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
- 230000033458 reproduction Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001429 visible spectrum 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
- G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
- G03C7/29—Azo dyes therefor
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
- C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
- C09B43/14—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents with phosgene or thiophosgene
Definitions
- This invention relates to photography, and in particular, to dyes which are readily bleached in the presence of a silver image and to photographic elements and processes utilizing such dyes.
- a support material is coated with a light-sensitive layer that contains a silver halide emulsion and a bleachable azo dye.
- a typical multicolor element involves three such light-sensitive layers sensitized to red, green and blue light and having in association therewith, respectively, amounts of bleachable cyan colored, magenta colored and yellow colored azo dyes.
- bleachable cyan colored, magenta colored and yellow colored azo dyes After an imagewise exposure, such elements, both single color and multicolor, are developed in a typical black-and-white developer solution to product photographic silver images in the areas which have been impinged upon by activating radiation.
- bleaching solutions can be either alkaline, such as a sodium hydroxide solution of stannous chloride, or acidic, such as acidic thiourea.
- Another object of this invention is to provide, for photographic purposes, novel azo dyes which are readily bleached by both acidic and alkaline bleaching solutions in the presence of a silver image.
- An additional object of the present invention is to provide new photographic elements which, when processed by acidic or alkaline dye-bleach techniques, produce positive colored dye images.
- Still another object of this invention is to provide a new photographic dye-bleach process.
- the objects of the present invention are acCOmplished with tetrakisazo dyes which are readily bleached in the presence of a silver image.
- tetrakisazo dyes can be coated upon a support, contiguous to the silver halide of a silver halide emulsion, to form a light-sensitive photographic element which can be processed by known dyebleach techniques to provide positive dye images.
- the tetrakisazo dyes of this invention include dyes having the formula:
- R represents a ureylene radical
- each of R through R represents a phenylene radical
- each of R thorugh R represents either a monovalent sulfonated aryl alcohol radical or a monovalent sulfonated aryl amine radical.
- radiacls described herein and designated by R through R can be substituted.
- Typical substituents are, for example, hydroxyl radicals; halogen atoms such as bromine, iodine and chlorine; alkyl radiacls having 1 to about 14 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, octyl dodecyl, tetradecyl and the like; alkoxy radicals having from 1 to about 12 carbon atoms such as methoxy, ethoxy, propoxy, octoxy, dodecoxy and the like; and carboxylic acid ester radicals having from 1 to about 14 carbon atoms such as propionoyloxy, benzoyloxy, octanoyloxy, decanoyloxy, lauroyloxy and the like acyloxy and aracyloxy, radicals.
- substituents include sulfamino, aryl sulfonamido and other substituted amino radicals such as alkacylamino, acetamino for example, and aracylamino radicals such as benzoylamino.
- the nonvalent sulfonated aryl alcohol radicals and arylamine radicals, as represented by R R R and R are typically mono or disulfonated and can be additionally substituted.
- Typical sulfonated aryl alcohols are, for example, sulfonated phenols.
- phenols can be substituted with either a halogen atom, an alkyl radical such as methyl, ethyl, propyl, isopropyl, hexyl, octyl, dodecyl and the like alkyl radicals, generally varying between 1 and 14 carbon atoms, or an amino radical such as those described above for'R through R
- alkyl radical such as methyl, ethyl, propyl, isopropyl, hexyl, octyl, dodecyl and the like alkyl radicals, generally varying between 1 and 14 carbon atoms, or an amino radical such as those described above for'R through R
- Other typical sulfonated aryl alcohols are sulfonated naphthols.
- Paricular illustrations of subsituents typically attached to the sulfonated naphthols are an amino radical and substituted amino radicals such as acylamino, alkylamin
- Typical monovalent, sulfonated arylamines useful in this invention include such compounds as sulfonated phenylamines and sulfonated naphthylamines. Illustrative of such compounds are 1-aminonaphthalene-4-sulfonic acid and 1-aminobenzene-4-sulfonic acid. Additionally, the amino group can be advantageously substituted in a similar fashion to the amino groups noted hereinabove, with such typical substituents as alkyl groups, acyl groups, alkacyl groups and aracyl groups.
- the tetrakisazo dyes of the present invention are susceptible of preparation by well-known chemical syntheses.
- the dyes can be formed by first tetraazotizing a di-(4-aminophenyl) methylbenzene which essentially constitutes one-half of a final symmetrical tetraamine, which tetraazotized diamine is then coupled with, for example, a sulfonated phenol, naphthol or naphthylamine such as those described herein, to produce a diazo compound having two azo linkages.
- the tetrakisazo dyes of this invention are then obtained by linking two units of the described diazo compound by a urea residue.
- a typical method is to obtain free amino substitution on the carbon atoms between which the two diazo units will be linked, such as by the reduction of a nitro group.
- the diazo compound can then be reacted with phosgene in the presence of sodium carbonate until a test for free amino is no longer positive, thus forming the desired tetrakisazo dye.
- the dye so obtained is then typically salted out of solution by treatment with, for example, sodium chloride and purified by known techniques, typically filtration and washing in a solvent such as ethyl alcohol.
- a tetraamine can be preformed and then coupled with the desired sulfonated phenol or sulfonated naphthol to form the tetrakisazo dye directly, thus avoiding the necessity to subsequently join two diazo compounds. Purification can be obtained in the fashion described herein.
- Tetrakisazo dyes which are so produced can, depending upon the structure of the chromophoric chain, absorb light at essentially any point along the entire visible spectrum and are advantageously employed in the preparation of photographic layers and elements which can be developed by well-known dye-bleach techniques to produce positive, monochromatic or polychromatic dye images.
- Such photographic elements are prepared by coating a support with at least one light-sensitive layer which typically includes a silver halide emulsion and at least one of the tetrakisazo dyes of this invention.
- the silver halide emulsion and subject tetrakisazo dye can be coated in separate, but contiguous layers.
- any of the conventional photographic silver halides can be used such as silver bromide, silver chloride, silver bromoiodide, silver chlorobromoiodide etc.
- dye solubility or dye migration makes it advantageous, whether because of the dye characteristics or the type of dye-bleach system, a polymeric mordanting material can be used in the dye-containing layers to inhibit such dye migration.
- Typical such materials are cationic mordants like poly(styrene-maleimide) mordants as described in US. Ser. No. 655,758, filed July 25, 1967 and presently copending herewith or poly-a-methyl-allyl-N-guanidyl ketimine glycolate, described in United States Pat. 2,882,156.
- azo dyes which are bleachable in the presence of a silver image can be utilized conjunctively with the subject tetrakisazo dyes to produce the described photo graphic elements.
- additional azo dyes are those derived from 4,4'-di(p-aminobenzoylamino)diphenyl-3,3-disulfonic acid by tetraazotization and cou pling with suitable couplers, such as the sulfonated aryl alcohols and sulfonated arylamines described herein. Any known coupler, however, can be used, and the dyes so produced can range in color from yellow to magenta.
- Coating can be accomplished by a wide variety of techniques known to those skilled in the art, with doctor blade coating and hopper coating being typically employed means.
- the dye is preferably incorporated in an amount ranging from about 2.5 mg. to about 50 mg. per mg. of hydrophilic binder material.
- concentration of silver halide is susceptible of wide variation, but need only be sufficient to provide a silver image which will permit advantageous bleaching, since the subject dyes are bleached in situ with a photographic silver image.
- a silver coverage of about 20 to 30 mg./ft. is sufficient to promote suitable dye bleaching, and the additional silver halide is present to provide suflicient photosensitivity.
- silver coverages of from about 50 mg./ft. to about mg./ft. are used; coverages of 200 mg./ft. and higher can be used, but such heavy silver coverages are not generally practical since, in most mases, an excess of unreacted silver halide is obtained.
- the support upon which the light-sensitive layer or layers are coated can be extensively varied according to usual practice.
- Conventional polymeric film supports for example, cellulose esters such as cellulose acetate, cellulose nitrate and cellulose acetate butyrate and also poly (ethylene terephthalate) are advantageously employed.
- the subject photographic elements can involve a support coated with one of the above-described light-sensitive layers. Such a layer is advantageously colored with at least one of the subject bleachable tetrakisazo dyes, and when such a photographic elements is imagewise exposed and bleached by well-known techniques of the photographic dye-bleach art, a positive, monochromatic dye image of the original is produced.
- a photo graphic element prepared as described above can involve multiple light-sensitive layers to prepare a multicolor silver dye-bleach element.
- Such an element typically includes three silver halide emulsion layers separately sensitized to red, green and blue light radiation and having associated therewith, respectively, a bleachable cyan, magenta and yellow colored azo dye.
- the tetrakisazo dyes of this invention can be advantageously used in the same or different layers with other azo dyes, such as monoazo, diazo and triazo dyes.
- azo dyes such as monoazo, diazo and triazo dyes.
- Processing comprehends first developing a negative silver image by treating the imagewise exposed element in a black-and-white silver halide developer solution, and second, treating the photographic element bearing a negative silver image with a bleaching composition which causes the reduction of the subject tetrakisazo dyes to colorless products.
- Bleaching solutions can be either alkaline or acidic in characted.
- a typical alkaline bleaching solution is stannite (alkaline stannous chloride) which operates to reductively destroy an azo dye, such as the subject dyes, in the presence of silver as a catalyst.
- Acidic bleaching solutions utilize the photographic silver image as the reducing agent. Additionally, complexing agents such as thiourea can be added to increase the reducing power of the metallic silver, and accelerators such as phenazines can be present in acidic bleaching solutions to hasten the operation by their catalytic action.
- a typical acid bleaching composition has the formula Concentrated HCl: 100 ml.
- a dye of the invention is prepared according to the procedure described in Example 1, except that one mole of (4,4'-diaminodiphenyl-4"-nitrophenyl) methane is coupled with two moles of NW acid (l-naphthol-4-sulfonic acid.
- NW acid l-naphthol-4-sulfonic acid.
- One mole of an orange colored tetrakisazo dye results, having the formula:
- a photographic element is prepared by coating poly- (ethylene-terephthalate) film support .material with a light-sensitive emulsion layer comprising gelatin coated at a coverage of 300 mg./ft. silverbromoiodide coated at a silver coverage of 125 mg./ft. and the magentacolored tetrakisazo dye described in Example I coated at a coverage of 30 mg./ft. The coating is then dried.
- the photographic element so prepared is exposed in an Eastman 1B sensitometer through a standard .15 log E step wedge and is then developed in a black-and-white developer having the formula Elon: 3 g.
- dye-bleaching is accomplished by a 30 second immersion in a solution of 10 percent aqueous sodium hydroxide to which is added 10 g./liter of stannous chloride. Ferricyanide bleaching and fixation in hypo remove residual silver. After the dyebleaching, the developed coating exhibits a positive magenta dye image corresponding in dye density to the step wedge increments.
- EXAMPLE ]lV Another photographic element is prepared and exposed according to the procedure described in Example III, except that the tetrakisazo dye used is the orange colored dye described in Example II. It is developed in a blackand-White developer as in Example III. Dye-bleaching is accomplished by a 30 second immersion in a solution having the formula Thiourea: 125 g. 2-hydroxy-3-aminophenazine: .15 g. Concentrated H01: ml. Distilled water to make 1 liter.
- Ferricyanide bleaching and fixation in hypo remove residual silver After such processing, a positive, orange colored dye image is produced, corresponding in dye density to the step-wedge increments.
- a photographic element comprising a support having coated thereon at least one light-sensitive layer comprising silver halide emulsion and a bleachable tetrakisazo dye having the formula:
- R is a ureylene radical
- each of R through R is a phenylene radical
- each of R through R is a rnonovalent radical selected from the group consisting of a sulfonated 1- nalphtiiol radical and a sulfonated l-naphthylamine ra ica 2.
- a photographic element as described in claim 1, 5 NZN wherein the tetrakisazo dye has the formula:
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Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66817467A | 1967-09-15 | 1967-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3542555A true US3542555A (en) | 1970-11-24 |
Family
ID=24681296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US668174A Expired - Lifetime US3542555A (en) | 1967-09-15 | 1967-09-15 | Photographic silver halide elements containing tetrakisazo dyes |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3542555A (enrdf_load_stackoverflow) |
| BE (1) | BE720874A (enrdf_load_stackoverflow) |
| CH (1) | CH493865A (enrdf_load_stackoverflow) |
| FR (1) | FR1581356A (enrdf_load_stackoverflow) |
| GB (1) | GB1250767A (enrdf_load_stackoverflow) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3716368A (en) * | 1967-09-01 | 1973-02-13 | Ciba Geigy Ag | Photographic, light-sensitive material containing a trisazo dyestuff |
| CN105295425B (zh) * | 2015-11-11 | 2017-02-08 | 金华恒利康化工有限公司 | 一种环保型弱酸红染料及其制备方法 |
| WO2018085391A1 (en) * | 2016-11-01 | 2018-05-11 | Milliken & Company | Leuco polymers as bluing agents in laundry care compositions |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2739953A1 (de) * | 1977-09-05 | 1979-03-22 | Basf Ag | Verdoppelte triphenylmethanfarbstoffe |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2470769A (en) * | 1939-08-28 | 1949-05-24 | Chromogen Inc | Color photographic material and processes for producing same |
| US2644753A (en) * | 1948-11-05 | 1953-07-07 | Azo dyes and their use in color |
-
1967
- 1967-09-15 US US668174A patent/US3542555A/en not_active Expired - Lifetime
-
1968
- 1968-09-12 GB GB1250767D patent/GB1250767A/en not_active Expired
- 1968-09-13 BE BE720874D patent/BE720874A/xx unknown
- 1968-09-13 FR FR1581356D patent/FR1581356A/fr not_active Expired
- 1968-09-13 CH CH1374768A patent/CH493865A/fr not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2470769A (en) * | 1939-08-28 | 1949-05-24 | Chromogen Inc | Color photographic material and processes for producing same |
| US2644753A (en) * | 1948-11-05 | 1953-07-07 | Azo dyes and their use in color |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3716368A (en) * | 1967-09-01 | 1973-02-13 | Ciba Geigy Ag | Photographic, light-sensitive material containing a trisazo dyestuff |
| CN105295425B (zh) * | 2015-11-11 | 2017-02-08 | 金华恒利康化工有限公司 | 一种环保型弱酸红染料及其制备方法 |
| WO2018085391A1 (en) * | 2016-11-01 | 2018-05-11 | Milliken & Company | Leuco polymers as bluing agents in laundry care compositions |
| CN109890905A (zh) * | 2016-11-01 | 2019-06-14 | 美利肯公司 | 作为洗衣护理组合物中的上蓝剂的隐色聚合物 |
| CN109890905B (zh) * | 2016-11-01 | 2022-02-01 | 美利肯公司 | 作为洗衣护理组合物中的上蓝剂的隐色聚合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| BE720874A (enrdf_load_stackoverflow) | 1969-02-17 |
| FR1581356A (enrdf_load_stackoverflow) | 1969-09-12 |
| GB1250767A (enrdf_load_stackoverflow) | 1971-10-20 |
| CH493865A (fr) | 1970-07-15 |
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