US3748136A - Photographic silver bleaching solution - Google Patents
Photographic silver bleaching solution Download PDFInfo
- Publication number
- US3748136A US3748136A US00162611A US3748136DA US3748136A US 3748136 A US3748136 A US 3748136A US 00162611 A US00162611 A US 00162611A US 3748136D A US3748136D A US 3748136DA US 3748136 A US3748136 A US 3748136A
- Authority
- US
- United States
- Prior art keywords
- onium
- compounds
- bleaching
- stands
- compound
- 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
- 238000004061 bleaching Methods 0.000 title abstract description 38
- 229910052709 silver Inorganic materials 0.000 title abstract description 28
- 239000004332 silver Substances 0.000 title abstract description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title abstract description 24
- 150000004010 onium ions Chemical class 0.000 abstract description 46
- 238000000034 method Methods 0.000 abstract description 19
- 239000007800 oxidant agent Substances 0.000 abstract description 19
- 239000000243 solution Substances 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 29
- 125000004429 atom Chemical group 0.000 description 18
- 239000007844 bleaching agent Substances 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- -1 alkyl sulphate Chemical compound 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 6
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 3
- UOMQUZPKALKDCA-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UOMQUZPKALKDCA-UHFFFAOYSA-K 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229940126657 Compound 17 Drugs 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- FQRPXALREFKNJX-UHFFFAOYSA-M dimethyl(nonyl)sulfanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CCCCCCCCC[S+](C)C FQRPXALREFKNJX-UHFFFAOYSA-M 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 3
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical class C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- LZHIDNDUHUIYKG-UHFFFAOYSA-M dodecyl(trimethyl)azanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CCCCCCCCCCCC[N+](C)(C)C LZHIDNDUHUIYKG-UHFFFAOYSA-M 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000004693 imidazolium salts Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000004989 p-phenylenediamines Chemical class 0.000 description 2
- 125000005496 phosphonium group Chemical group 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- QUKZBUCPOSYYFO-UHFFFAOYSA-N 10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-ol Chemical compound C1CCCC2(C)C3CCC(C)(C(CC4)O)C4C3CCC21 QUKZBUCPOSYYFO-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- JHKKTXXMAQLGJB-UHFFFAOYSA-N 2-(methylamino)phenol Chemical compound CNC1=CC=CC=C1O JHKKTXXMAQLGJB-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- NBGQUWQFDPVHCQ-UHFFFAOYSA-M 4-methyl-4-octylmorpholin-4-ium;bromide Chemical compound [Br-].CCCCCCCC[N+]1(C)CCOCC1 NBGQUWQFDPVHCQ-UHFFFAOYSA-M 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-O 4-phenylpyridin-1-ium Chemical compound C1=CC=CC=C1C1=CC=[NH+]C=C1 JVZRCNQLWOELDU-UHFFFAOYSA-O 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 150000003868 ammonium compounds Chemical group 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 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
- 125000000732 arylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical compound C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- GLGSRACCZFMWDT-UHFFFAOYSA-N dilithium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Li+].[Li+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O GLGSRACCZFMWDT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- DRTCFOYIJNCGCX-UHFFFAOYSA-N ethene;iron(3+) Chemical group [Fe+3].C=C DRTCFOYIJNCGCX-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-O isoquinolin-2-ium Chemical compound C1=[NH+]C=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-O 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/40—Chemically transforming developed images
- G03C5/44—Bleaching; Bleach-fixing
Definitions
- oxidizing silver bleaching solutions are for instance used in so-called toning processes, in reversal processes, both colour and black-and-white, and in all other colour processes.
- oxidizing agents are used in said solutions such as water-soluble salts of the iron(III) ethylene diamine tetraacetic acid chelate, potassium dichromate, potassium hexacyanoferrate(III), potassium permanganate, cerium sulphate, etc.
- persulfates such as potassium, sodium, lithium and ammonium per'sulphate
- persulfates are not suitable for bleaching silver images because they are too slow silver bleaching agents.
- a method of bleaching a metallic silver containing photographic element by treatment of the said metallic silver containing element with a solution comprising a negatively charged oxidizing agent in the presence of onium compounds comprising no anionic group in their molecule, which means that betaine salts are excluded, the said onium compound being present in the said solution or in a solution with which the silver image is treated before the treatment with the bleaching solution.
- the invention further provides a photographic bleach solution which comprises a negatively charged oxidizing agent and such onium compound.
- the onium compounds used in accordance with the present invention include:
- each of R R R and R stands for alkyl or two of them together represent the atoms necessary to complete a saturated heterocyclic ring such as a morpholine and piperidine ring, provided that at least one of the alkyl groups on the onium atom comprises at least 4 C-atoms and at most 14 C-atoms, and the total sum of the C-atoms in all R-groups on the onium atom is comprised between 8 and 24, and
- X stands for an anion such as halide, p-toluene sulphonate,
- alkyl sulphate, perchlorate and persulphate
- Z stands for the atoms necessary to complete a cyclammonium nucleus which may carry substituents and fused-on rings, for example pyridinium, 4-phenylpyridinium, u-picolinium, quinolinium, isoquinolinium, benzoquinolinium, imidazolinium, thiazolinium, benzothiazolium, etc.,
- R stands for alkyl which, unless the cyclammonium nucleus completed by Z together with fused-on or substituent rings has at least 5 conjugated double bonds, comprises at least 8 C-atoms, and
- mono-onium compounds suitable for use according to the invention are:
- polyonium compounds suitable for being employed in accordance with the present invention those are included that contain an onium group selected from the group consisting of quaternary ammonium, quaternary phosphonium and ternary sulphonium, linked through its onium atom by at least one bivalent organic group, to the onium atom of another onium group selected from the group consisting of quaternary ammonium, quaternary phosphonium and ternary sulphonium groups.
- R R R and R stands for an alkyl group
- Y stands for a bivalent organic group for example alkylene, alkylene interrupted by one or more oxygen or sulphur atoms, arylene and alkylene-arylene-alkylene.
- polyonium compounds suitable for use according to the present invention are the compounds having the following formulae:
- oxido-reduction compounds which in oxidized form are onium compounds and which possess a polarographic half-wave potential measured at pH 3 in respect of the hydrogen electrode of at least 230 mv.
- pphenylene diamine derivatives such as N,N-dialkyl-pphenylene diamines, N,N'-tetraalkyl p phenylene diamines and l-alkyl--dialkylamino 1,2,3,4 tetrahydroquinolines can be most advantageously employed.
- oxide-reduction compounds are reversibly reducible dyestufi's such as Bindschedlers Green (CJI. 49,405), thiazine dyes for instance Methylene Blue (C.I. 52,015) and Lauths Violet (C.I. 52,000), as well as oxazine and phenazine dyes.
- These oxide-reduction compounds may be used in acidic bleaching solutions in their reduced form, in their oxidized form as well as in their semiquinone form since by the acidic medium they are always in oxidized form.
- the onium compounds employed according to the invention are present in the bleaching solution the moment upon which the metallic silver is bleached. Therefore, the onium compounds are preferably incorporated into the bleaching solution. However, they may also be used in solutions with which the photographic element comprising photographically formed metallic silver is treated before bleaching e.g. a stop bath, a stop-fixing bath and a mere acidic solution of the said onium compounds.
- the amount of onium compound used for accelerating the bleaching of metallic silver by means of negatively charged oxidizing agents may vary between very wide limits and depends on the particular onium compound used. The most suitable amount for the particular negatively charged oxidizing agent involved can be easily determined by some simple tests known to those skilled in the art.
- the ratio of negatively charged oxidizing agent to onium compound used according to the present invention is generally chosen so that the oxidizing agent strongly outweighs, even up to fifty times, the onium compound.
- the bleaching solutions used in conjunction with the onium compounds according to the present invention may comprise in addition to the negatively charged oxidizing agents any of the common ingredients used in such solutions including silver halide solvents such as sodium thiosulphate as is used for instance in bleach-fixing solutions, sodium sulphite, alkali metal halides particularly alkali metal bromides, water softeners, thickening agents, hardeners, optical brightening agents, etc.
- Any of the materials used in bleach baths can be used to obtain the desired pH-value e.g. sulphuric acid, sulphamic acid, hydrochloric acid, phosphoric acid, acetic acid, boric acid, citric acid, sodium citrate, monosodium phosphate, sodium bisulphate, etc.
- the pH of the bleach solutions generally fall between a range of from 2 to 9, a pH between 3 and 6 being generally preferred.
- EXAMPLE 1 Strips of positive fine grain film-type 5.61 available from Gevaert-Agfa N.V., Antwerp, Belgium, were overall exposed and developed in a conventional monomethylaminophenol/hydroquinone developer till a density of 2.40 was obtained whereupon the strips were fixed, washed and dried.
- Each of these strips was treated with a bleaching solution comprising per litre 45 g. of potassium persulphate and 2.5 g. of potassium bromide as well as 2.66 millimole of an onium compound as listed in the table below.
- the densities remaining after a treatment with the bleaching solution for 1 min., 3 min., 5 min. and 10 min. are listed in the table below.
- EXAMPLE 2 This example is analogous to Example 1, with the diiference that now the onium compounds listed in the table below were used.
- the densities remaining after a treatment with the bleaching solution for 1 min., 3 min., 5 min., and 7 min. are listed in the table below.
- EXAMPLE 6 formed upon colour development. This manifests itself in Strips of a film material as described in Example 1 were 6 acid 6.25 Ammonium thiosulphate 55 Sodium sulphite 5 Ammonium thiocyanate 2.5
- EXAMPLE 7 A positive multilayer tricolour film-material comprising in the blue-sensitive silver halide emulsion layer the yellow-forming colour coupler of the formula:
- the density of the image formed was then measured behind a blue, a green and a red filter and compared with the density of images formed under identical circumstances with the only difference that the bleaching bath contained one of the onium compounds listed in the table below.
- quaternary tetraalkyl phosphonium compounds quaternary tetraalkyl ammonium compounds and quaternary ammonium compounds in which the quaternary N-atom is a member of a heterocyclic ring system
- the onium compound is a quaternary ammonium compound in which the quaternary N-atom is a member of a heterocyclic ring system having at least 5 conjugated double bondsthe sum of the carbon atoms of the groups linked to the onium atom is comprised between 8 and 24 and at least one of the said groups has at least 4 and at most 14 Oatoms;
- the said negatively charged oxidizing agent is a persulphate, a dichromate or a water-soluble salt of iron(III) ethylene daimine tetraacetic acid chelate.
- Z stands for the atoms necessary to complete a cyclammonium group
- R stands for an alkyl group whic-hunless the cyclammonium group completed by Z has at least 5 conjugated double bondscomprises at least 8 C-atoms
- X stands for an anion
- each of R R R and R stands for an alkyl group, each of Q and Q the same or difierent, stands for S+, N+--R or P+--R wherein R stands for an alkyl group, each of Z, Z and Z stands for the atoms necessary to complete a cyclammonium group, Y stands for a bivalent organic group, and X stands for an anion.
- each of Z and Z stands for the atoms necessary to complete a pyridinium, thiazolium or imidazolium nucleus,
- each of R and R stands for an alkyl group or R together with R may be ethylene, trimethylene or tetramethylene when A is a chemical bond linking the 2- position of 2 to the 2-position of 2,
- X- stands for an anion.
- the said oxide-reduction compound is a N,N-tetraa1ky1-p-phenylene diamine or a l-alkyl-fi-dialkylamino-1,2,3,4#tetrahydroquinoline.
- a photographic bleach solution comprising a negatively charged oxidizing agent and an onium compound selected from the group consisting of:
- quaternary tetraalkyl phosphonium compounds quaternary tetraalkyl ammonium compounds and quaternary ammonium compounds in which the quaternary N-atom is a member of a heterocyclic ring system
- the onium compound is a quaternary ammonium compound in which the quaternary N-atom is a member of a heterocyclic ring system having at least conjugated double bondsthe sum of the carbon atoms of the groups linked to the onium atom is comprised between 8 and 24 and at least one of the said groups has at least 4 and at most 14 C-atoms;
- oxide-reduction compounds the oxidized forms of which are onium compounds and which possess a polarographic half-wave potential measured at pH 3 in respect of the hydrogen electrode of at least 230 mv.
- R R and R stands for an alkyl group or two of them together represent the atoms necessary to complete a saturated heterocyclic ring, at least one of the alkyl groups on the onium atom comprising at least 4 and at most 14 C-atoms and the sum of the C-atoms in all R-groups on the onium atom being comprised between 8 and 24, and X- stands for an anion.
- Z stands for the atoms necessary to complete a cyclammonium group
- R stands for an alkyl group which-unless the cyclammonium group completed by Z has at least 5 conjugdated double bondscomprises at least 8 C-atoms, an
- X- stands for an anion
- each of R R R R and R stands for an alkyl group
- each of Q and Q stands for 8+, N+R or P+R wherein R stands for an alkyl p,
- each of Z, Z and Z stands for the atoms necessary to complete a cyclammonium group
- Y stands for a bivalent organic group
- X stands for an anion
- each of Z and Z stands for the atoms necessary to complete a pyridinium, thiazolium or imidazolium nucleus,
- each of R and R stands for an alkyl group or R together with R may be ethylene, trimethylene, tetramethylene when A is a chemical bond linking the 2- position of Z to the 2-position of 2;
- X- stands for an anion.
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Abstract
A METHOD OF BLEACHING SILVER IMAGES IN PHOTOGRAPHIC ELEMENTS BY MEANS OF NEGATIVELY CHARGED OXIDIZING AGENTS IS DESCRIBED WHEREIN SAID BLEACHING IS ACCLELERATED BY THIS USE OF ONIUM COMPOUNDS IN THE BLEACHING SOLUTION OR IN A SOLUTION USED PRIOR TO THE BLEACHING SOLUTION. THE METHOD MAKES POSSIBLE TO USE AS OXIDIZING AGENTS THE INEXPENSIVE AND COLOURLESS PERSULPHATES WHICH ARE OTHERWISE TOO SLOW FOR SILVER BLEACHING.
Description
United States Patent 3,748,136 PHOTOGRAPHIC SILVER BLEACHING SOLUTION Josef Frans Willems, Wilrijk, Belgium, assignor to Agfa- Gevaert N.V., Mortsel, Belgium No Drawing. Filed July 14, 1971, Ser. No. 162,611 Claims priority, application Great Britain, Aug. 10, 1970, 38,508/ 70 Int. Cl. G03c 5/26, 5/32, 7/16 US. Cl. 96-60 R 7 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to the bleaching of metallic silver by means of oxidizing agents in processes where photographic silver images are produced that should be bleached away more particularly to methods for accelerating said bleaching and to solutions used in said methods.
In the production of photographic images it is often necessary or desirable to bleach a silver image formed upon exposure and development by treatment with an oxidizing solution. Such oxidizing silver bleaching solutions are for instance used in so-called toning processes, in reversal processes, both colour and black-and-white, and in all other colour processes. A wide variety of oxidizing agents are used in said solutions such as water-soluble salts of the iron(III) ethylene diamine tetraacetic acid chelate, potassium dichromate, potassium hexacyanoferrate(III), potassium permanganate, cerium sulphate, etc. Owing to their favourable redox potential and the fact that they are colourless and inexpensive, persulfates, such as potassium, sodium, lithium and ammonium per'sulphate, would be most desirable silver bleaching agents. However, persulphates are not suitable for bleaching silver images because they are too slow silver bleaching agents.
'It has now been found that silver bleaching by means of persulphates can be accelerated by the use of onium compounds as defined hereinafter. It was further found that said onium compounds do not only accelerate silver bleaching by means of persulphates but also silver bleaching by all kinds of negatively charged oxidizing agents such as dichromates for instance potassium, sodium and lithium dichromate and water-soluble salts of iron(III) ethylene diamine tetraacetic-acid chelate.
Theerfore, in accordance with the present invention there is provided a method of bleaching a metallic silver containing photographic element by treatment of the said metallic silver containing element with a solution comprising a negatively charged oxidizing agent in the presence of onium compounds comprising no anionic group in their molecule, which means that betaine salts are excluded, the said onium compound being present in the said solution or in a solution with which the silver image is treated before the treatment with the bleaching solution.
The invention further provides a photographic bleach solution which comprises a negatively charged oxidizing agent and such onium compound.
The onium compounds used in accordance with the present invention include:
(1) Basic mono-onium ternary trialkylsulphonium compounds, quaternary tetraalkyl phosphonium compounds, quaternary tetraalkyl ammonium compounds and 3,748,136 Patented July 24, 1973 quaternary ammonium compounds in which the quaternary N-atom is a member of a heterocyclic ring system, these onium compounds being characterised, unless the onium compound is a quaternary ammonium compound in which the quaternary N-atom is a member of a heterocyclic ring system having at least 5 conjugated double bonds, in that the sum of the carbon atoms of the groups linked to the onium atom is comprised between 8 and 24 and at least one of the said groups has at least 4 C-atoms and at most 14 C-atoms;
(2) Basic polyonium compounds;
(3) 'Oxido-reduction compounds the oxidized forms of which are onium compounds and which possess a polarographic half-wave potential measured at pH 3 in respect of the hydrogen electrode of at least 230 mv.
Among the mono-onium compounds suitable for being employed in practicing the present invention, those corresponding to the following general formulae are especially included:
wherein:
Q+ stands for S+ or N+-R each of R R R and R stands for alkyl or two of them together represent the atoms necessary to complete a saturated heterocyclic ring such as a morpholine and piperidine ring, provided that at least one of the alkyl groups on the onium atom comprises at least 4 C-atoms and at most 14 C-atoms, and the total sum of the C-atoms in all R-groups on the onium atom is comprised between 8 and 24, and
X stands for an anion such as halide, p-toluene sulphonate,
alkyl sulphate, perchlorate and persulphate;
wherein:
Z stands for the atoms necessary to complete a cyclammonium nucleus which may carry substituents and fused-on rings, for example pyridinium, 4-phenylpyridinium, u-picolinium, quinolinium, isoquinolinium, benzoquinolinium, imidazolinium, thiazolinium, benzothiazolium, etc.,
R stands for alkyl which, unless the cyclammonium nucleus completed by Z together with fused-on or substituent rings has at least 5 conjugated double bonds, comprises at least 8 C-atoms, and
X has the same significance as above.
Representative examples of mono-onium compounds suitable for use according to the invention are:
(1) l-m-nitrobenzyl-quinolinium chloride (2) l-dodecyl-pyridiniumchloride 3) Dodecyl trimethylammonium p-toluene sulphonate (4) Dimethyl-nonyl sulphonium p-toluene sulphonate (5) N-methyl N-octyl morpholinium bromide.
Among the polyonium compounds suitable for being employed in accordance with the present invention those are included that contain an onium group selected from the group consisting of quaternary ammonium, quaternary phosphonium and ternary sulphonium, linked through its onium atom by at least one bivalent organic group, to the onium atom of another onium group selected from the group consisting of quaternary ammonium, quaternary phosphonium and ternary sulphonium groups. These polyonium compounds can be represented by the following each of R R R and R stands for an alkyl group,
each of Q and Q the same or different, stands for 8+,
N+-R or P+-R wherein R stands for alkyl,
Z and X have the same significances as above,
each of Z and Z the same or different, have one of the significances given for Z, and
Y stands for a bivalent organic group for example alkylene, alkylene interrupted by one or more oxygen or sulphur atoms, arylene and alkylene-arylene-alkylene.
Other suitable polyonium compounds are the diquaternary ammonium compounds represented by the following general formula:
U l 2x- \N+ In in wherein:
Representative examples of polyonium compounds suitable for use according to the present invention are the compounds having the following formulae:
0,115] 2nic--sor (15) C Hs s if CH;
LL 2cH,so,-
Among the oxido-reduction compounds which in oxidized form are onium compounds and which possess a polarographic half-wave potential measured at pH 3 in respect of the hydrogen electrode of at least 230 mv., pphenylene diamine derivatives such as N,N-dialkyl-pphenylene diamines, N,N'-tetraalkyl p phenylene diamines and l-alkyl--dialkylamino 1,2,3,4 tetrahydroquinolines can be most advantageously employed.
Other suitable oxide-reduction compounds are reversibly reducible dyestufi's such as Bindschedlers Green (CJI. 49,405), thiazine dyes for instance Methylene Blue (C.I. 52,015) and Lauths Violet (C.I. 52,000), as well as oxazine and phenazine dyes. These oxide-reduction compounds may be used in acidic bleaching solutions in their reduced form, in their oxidized form as well as in their semiquinone form since by the acidic medium they are always in oxidized form.
In the method according to the present invention for accelerating the bleaching of metallic silver photographically formed in photographic silver halide elements by means of negatively charged oxidizing agents, it is essential that the onium compounds employed according to the invention are present in the bleaching solution the moment upon which the metallic silver is bleached. Therefore, the onium compounds are preferably incorporated into the bleaching solution. However, they may also be used in solutions with which the photographic element comprising photographically formed metallic silver is treated before bleaching e.g. a stop bath, a stop-fixing bath and a mere acidic solution of the said onium compounds.
The amount of onium compound used for accelerating the bleaching of metallic silver by means of negatively charged oxidizing agents may vary between very wide limits and depends on the particular onium compound used. The most suitable amount for the particular negatively charged oxidizing agent involved can be easily determined by some simple tests known to those skilled in the art. The ratio of negatively charged oxidizing agent to onium compound used according to the present invention is generally chosen so that the oxidizing agent strongly outweighs, even up to fifty times, the onium compound.
The bleaching solutions used in conjunction with the onium compounds according to the present invention may comprise in addition to the negatively charged oxidizing agents any of the common ingredients used in such solutions including silver halide solvents such as sodium thiosulphate as is used for instance in bleach-fixing solutions, sodium sulphite, alkali metal halides particularly alkali metal bromides, water softeners, thickening agents, hardeners, optical brightening agents, etc. Any of the materials used in bleach baths can be used to obtain the desired pH-value e.g. sulphuric acid, sulphamic acid, hydrochloric acid, phosphoric acid, acetic acid, boric acid, citric acid, sodium citrate, monosodium phosphate, sodium bisulphate, etc. The pH of the bleach solutions generally fall between a range of from 2 to 9, a pH between 3 and 6 being generally preferred.
The following examples illustrate the bleach-accelerating eifect of the onium compounds used according to the invention.
EXAMPLE 1 Strips of positive fine grain film-type 5.61 available from Gevaert-Agfa N.V., Antwerp, Belgium, were overall exposed and developed in a conventional monomethylaminophenol/hydroquinone developer till a density of 2.40 was obtained whereupon the strips were fixed, washed and dried.
Each of these strips was treated with a bleaching solution comprising per litre 45 g. of potassium persulphate and 2.5 g. of potassium bromide as well as 2.66 millimole of an onium compound as listed in the table below.
The densities remaining after a treatment with the bleaching solution for 1 min., 3 min., 5 min. and 10 min. are listed in the table below.
The above results clearly show that persulphates have only a very slow bleaching effect that can be accelerated by the use of the onium compounds.
EXAMPLE 2 This example is analogous to Example 1, with the diiference that now the onium compounds listed in the table below were used.
The results shown in the table below prove the bleachaccelerating effect of the onium compounds.
TABLE Density after- Onium compound added 1 min. 3 min. 5 mm. 10 min.
None 2. 34 2. 24 2. 14 1. Compound EXAMPLE 3 This example is analogous to Example 1, with the difference that now the oxido-reduction compounds listed in the table below were used instead of the onium compounds of Example 1.
The results listed below show the bleach-accelerating effect of the oxido-reduction compounds used.
This example is analogous to the preceding examples.
The results obtained by addition to the bleaching solution of the compounds listed in the table below are selfexplanatory. The results also show that the p-phenylene diamines may be added to the acidic bleaching solution under no matter what form.
8 to which per liter 2.66 millimole of an onium compound as listed in the table below was added.
The densities remaining after a treatment with the bleaching solution for 1 min., 3 min., 5 min., and 7 min. are listed in the table below.
TABLE Density after- Compound added 1 min. 3 min. 5 min. 7 min None 2. 12 1. 62 1. l 0. 48 Compound:
The above results show that the compounds of the invention also accelerate bleaching by means of iron(III) ethylene diamine tetraacetic acid.
TABLE Density after- Compound added 1 min. 3 min. min. 7 min. min. 283%.... 6 31%.? 5:53 i: l? l: 32 5: i8
NNHz-H2 s o. HsCa H O; 0 H; 2. 08 1. 42 0. 78 10. 4
N@NHCl HtCa C2Hs (reduced form) H O, C H 2.08 1. 42 0. 78 0. 14
N-- c104 mol 0.11
(semlquinone form) H5O: CzHs 2.08 1.42 0.78 0.14
WOW 20.0.- mol C2 li (oxidized form) EXAMPLE 5 5 Yellow forming colour couplers that are present in the In this example varying amounts of compound 17 are added to the bleach solution of Example 1.
The results attained are listed in the table below.
blue-sensitive silver halide emulsion layer of a photographic material give often rise to slow and difiicult bleaching by dichromate-baths of the metallic silver TABLE Compound 17 Density afterper litre bleach solution, g. 1 min. 3 min. 4 min. 5 min. 8 mm. 9 min. 10 min.
EXAMPLE 6 formed upon colour development. This manifests itself in Strips of a film material as described in Example 1 were 6 acid 6.25 Ammonium thiosulphate 55 Sodium sulphite 5 Ammonium thiocyanate 2.5
Water to make 1 litre.
high unwanted side-absorptions of the yellow dyestuft image formed.
The following examples illustrate the bleach accelerating effect of onium compounds when used together with bleaching solutions containing potassium dichromate as oxidizing agent.
EXAMPLE 7 A positive multilayer tricolour film-material comprising in the blue-sensitive silver halide emulsion layer the yellow-forming colour coupler of the formula:
S0111 OgNHCHs 2)u Ha was exposed through a blue filter and processed in the conventional way by the steps of treatment in a pre-bath, rinsing, colour development, fixing, rinsing, bleaching, rinsing, fixing and rinsing thus forming a yellow dyelmage.
Bleaching took place for 2 min. in a bath of the following composition:
G. Potassium bromide 20 Potassium dichromate 5 Potassium alum (crystalline) 40 Water to make 1000 ml. (average pH: 3.1).
The density of the image formed was then measured behind a blue, a green and a red filter and compared with the density of images formed under identical circumstances with the only difference that the bleaching bath contained one of the onium compounds listed in the table below.
The results obtained are listed in the table.
TABLE Density measured behind- Onium compound added per Blue Green Red liter of bleach bath filter filter filter None 2. 30 0. 60 0. 43 1 g. of compound 17..-- 2. 16 0. 40 0. 23 1 g. of compound 18 2.07 0. 34 0.18
EXAMPLE 8 Example 7 was repeated with the difference that the material now contained the yellow-forming colour coupler of the formula:
S 03H S O NHCHa HaCO- COCHzCONH- and bleaching took place once for 2 min. and once for 4 min. The results attained are listed in the following table.
1. Method of bleaching a developed metallic silver containing photographic element with a solution containing a negatively charged oxidizing agent said solution containing an onium compoud, or said developed element having been treated in a pre-bleaching bath, containing an onium compound, said onium compound comprising no anionic group in its molecule or a betaine structure and selected from the group consisting of:
(a) basic mono-onium trialkyl sulphonium compounds,
quaternary tetraalkyl phosphonium compounds, quaternary tetraalkyl ammonium compounds and quaternary ammonium compounds in which the quaternary N-atom is a member of a heterocyclic ring system, wherein-unless the onium compound is a quaternary ammonium compound in which the quaternary N-atom is a member of a heterocyclic ring system having at least 5 conjugated double bondsthe sum of the carbon atoms of the groups linked to the onium atom is comprised between 8 and 24 and at least one of the said groups has at least 4 and at most 14 Oatoms;
(b) basic polyonium compounds, and
(c) oxido-reduction compounds the oxidized forms of which are onium compounds and which possess a polarographic half-wave potential measured at pH 3 in respect of the hydrogen electrode of at least 230 2. Method according to claim 1, wherein the said onium compound is present in the said solution of negatively charged oxidizing agent.
3. Method according to claim 1, wherein the said onium compound is present in a solution with which the metallic silver containing element is treated before the said treatment wtih a solution of a negatively charged oxidizing agent.
4. Method according to claim 1, wherein the said negatively charged oxidizing agent is a persulphate, a dichromate or a water-soluble salt of iron(III) ethylene daimine tetraacetic acid chelate.
5. Method according to claim 1, wherein the said onium compound is a mono-onium compound corresponding to the formula:
ing to the formula:
Z: I:1'R5] X" wherein: Y
Z stands for the atoms necessary to complete a cyclammonium group,
R stands for an alkyl group whic-hunless the cyclammonium group completed by Z has at least 5 conjugated double bondscomprises at least 8 C-atoms, and
X" stands for an anion.
-7. Method according to claim 1, wherein the said onium compound is a polyonium compound corresponding to one of the following general formulae:
11 wherein: each of R R R and R stands for an alkyl group, each of Q and Q the same or difierent, stands for S+, N+--R or P+--R wherein R stands for an alkyl group, each of Z, Z and Z stands for the atoms necessary to complete a cyclammonium group, Y stands for a bivalent organic group, and X stands for an anion.
8. Method according to claim 1, wherein the said onium compound is a polyonium compound corresponding to the formula:
wherein:
each of Z and Z the same or difierent, stands for the atoms necessary to complete a pyridinium, thiazolium or imidazolium nucleus,
A stands for a chemical bond or the group --CH=CH,
each of R and R stands for an alkyl group or R together with R may be ethylene, trimethylene or tetramethylene when A is a chemical bond linking the 2- position of 2 to the 2-position of 2,, and X- stands for an anion.
9. Method according to claim 1, wherein the said onium compound is the oxidized form of an oxide-reduction compound which possesses a polarographic half-wave potential measured at pH 3 in respect of the hydrogen electrode of at least 230 mv.
10. Method according to claim 9, wherein the said oxide-reduction compound is a N,N-tetraa1ky1-p-phenylene diamine or a l-alkyl-fi-dialkylamino-1,2,3,4#tetrahydroquinoline.
11. A photographic bleach solution comprising a negatively charged oxidizing agent and an onium compound selected from the group consisting of:
(a) basic mono-onium trialkyl sulphonium compounds,
quaternary tetraalkyl phosphonium compounds, quaternary tetraalkyl ammonium compounds and quaternary ammonium compounds in which the quaternary N-atom is a member of a heterocyclic ring system, wherein-unless the onium compound is a quaternary ammonium compound in which the quaternary N-atom is a member of a heterocyclic ring system having at least conjugated double bondsthe sum of the carbon atoms of the groups linked to the onium atom is comprised between 8 and 24 and at least one of the said groups has at least 4 and at most 14 C-atoms;
(b) basic polyonium compounds, and
(c) oxide-reduction compounds the oxidized forms of which are onium compounds and which possess a polarographic half-wave potential measured at pH 3 in respect of the hydrogen electrode of at least 230 mv.
12. A photographic bleach solution to claim 11, wherein the said onium compound is a mono-onium compound corresponding to the formula:
wherein:
Q+ stands for S+ or N+R each of R, R R and R stands for an alkyl group or two of them together represent the atoms necessary to complete a saturated heterocyclic ring, at least one of the alkyl groups on the onium atom comprising at least 4 and at most 14 C-atoms and the sum of the C-atoms in all R-groups on the onium atom being comprised between 8 and 24, and X- stands for an anion.
13. A photographic bleach solution according to claim 11, wherein the said onium compound is a mono-onium compound corresponding to the formula:
wherein:
Z stands for the atoms necessary to complete a cyclammonium group,
R stands for an alkyl group which-unless the cyclammonium group completed by Z has at least 5 conjugdated double bondscomprises at least 8 C-atoms, an
X- stands for an anion.
14. A photographic bleach solution according to claim 11, wherein the said onium compound is a polyonium compound corresponding to one of the following general formulae:
N Z: 2X- \J 1 wherein:
each of R R R and R stands for an alkyl group,
each of Q and Q the same or different, stands for 8+, N+R or P+R wherein R stands for an alkyl p,
each of Z, Z and Z stands for the atoms necessary to complete a cyclammonium group,
Y stands for a bivalent organic group, and
X stands for an anion.
15. A photographic bleach solution according to claim 11, wherein the said onium compound is a polyonium compound corresponding to the formula:
wherein:
each of Z and Z the same or different, stands for the atoms necessary to complete a pyridinium, thiazolium or imidazolium nucleus,
A stands for a chemical bond or the group -CH=CH--,
each of R and R stands for an alkyl group or R together with R may be ethylene, trimethylene, tetramethylene when A is a chemical bond linking the 2- position of Z to the 2-position of 2;, and X- stands for an anion.
16. A photographic bleach solution according to claim 11, wherein the said onium compound is the oxidized form of an oxidoreduction compound which possesses a polarographic half-Wave potential measured at pH 3 in respect of the hydrogen electrode of at least 230 mv.
17. A photographic bleach solution according to claim 16, wherein the said oxido-reduction compound is a N,N'-
13 tetraalkyl-p-phenylene diamine or a 1-a1ky16-dia1kylamino-1,2,3,4-tetrahydroquino1ine.
References Cited UNITED STATES PATENTS McQueen 96-60 R Welliver et a1. 96-663 Chechak et a1 96-109 Stephen et a1 96-60 B F Yudelson et a l. 96-61 14 OTHER REFERENCES Mason, Photographic Processing Chemistry, 1966, Focal Press Limited, pp. 208-211.
5 NORMAN G. TORCHIN, Primary Examiner M. F. KELLEY, Assistant Examiner US. Cl. X.R.
10 96-22, 50 R, PT, 62, 61 UK
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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GB3850870A GB1358848A (en) | 1970-08-10 | 1970-08-10 | Silver bleaching solution |
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US3748136A true US3748136A (en) | 1973-07-24 |
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US00162611A Expired - Lifetime US3748136A (en) | 1970-08-10 | 1971-07-14 | Photographic silver bleaching solution |
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US (1) | US3748136A (en) |
BE (1) | BE770910A (en) |
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Cited By (9)
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US3870520A (en) * | 1972-10-05 | 1975-03-11 | Fuji Photo Film Co Ltd | Photographic processing composition |
US3945837A (en) * | 1972-07-15 | 1976-03-23 | Sakura Color Products Corporation | Ink composition |
US3948659A (en) * | 1973-03-09 | 1976-04-06 | Fuji Photo Film Co., Ltd. | Method of processing color photographic materials |
US4186008A (en) * | 1977-03-23 | 1980-01-29 | Ciba-Geigy Aktiengesellschaft | Method for processing silver dye-bleach materials |
US4246328A (en) * | 1976-09-06 | 1981-01-20 | Fuji Photo Film Co., Ltd. | Process of forming mask images |
US4508817A (en) * | 1983-05-20 | 1985-04-02 | Fuji Photo Film Co., Ltd. | Method of color photographic processing |
US4552834A (en) * | 1984-08-06 | 1985-11-12 | Eastman Kodak Company | Enhanced bleaching of photographic elements containing silver halide and adsorbed dye |
US5460924A (en) * | 1992-12-14 | 1995-10-24 | Eastman Kodak Company | Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts |
US5510232A (en) * | 1994-12-22 | 1996-04-23 | Eastman Kodak Company | Photographic processing composition and method using cationic hydroquinone as organic catalyst for persulfate bleaching agent |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5820424B2 (en) * | 1976-10-12 | 1983-04-22 | 富士写真フイルム株式会社 | Color image forming method |
JPS56146136A (en) * | 1980-04-15 | 1981-11-13 | Canon Inc | Fixing solution |
JP2591616B2 (en) | 1986-04-22 | 1997-03-19 | コニカ株式会社 | Processing method of silver halide photographic light-sensitive material in which fog is prevented |
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1970
- 1970-08-10 GB GB3850870A patent/GB1358848A/en not_active Expired
-
1971
- 1971-07-14 US US00162611A patent/US3748136A/en not_active Expired - Lifetime
- 1971-08-04 BE BE770910A patent/BE770910A/en unknown
- 1971-08-06 DE DE19712139401 patent/DE2139401A1/en active Pending
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3945837A (en) * | 1972-07-15 | 1976-03-23 | Sakura Color Products Corporation | Ink composition |
US3870520A (en) * | 1972-10-05 | 1975-03-11 | Fuji Photo Film Co Ltd | Photographic processing composition |
US3948659A (en) * | 1973-03-09 | 1976-04-06 | Fuji Photo Film Co., Ltd. | Method of processing color photographic materials |
US4246328A (en) * | 1976-09-06 | 1981-01-20 | Fuji Photo Film Co., Ltd. | Process of forming mask images |
US4186008A (en) * | 1977-03-23 | 1980-01-29 | Ciba-Geigy Aktiengesellschaft | Method for processing silver dye-bleach materials |
US4508817A (en) * | 1983-05-20 | 1985-04-02 | Fuji Photo Film Co., Ltd. | Method of color photographic processing |
US4552834A (en) * | 1984-08-06 | 1985-11-12 | Eastman Kodak Company | Enhanced bleaching of photographic elements containing silver halide and adsorbed dye |
US5460924A (en) * | 1992-12-14 | 1995-10-24 | Eastman Kodak Company | Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts |
US5536625A (en) * | 1992-12-14 | 1996-07-16 | Eastman Kodak Company | Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts |
US5510232A (en) * | 1994-12-22 | 1996-04-23 | Eastman Kodak Company | Photographic processing composition and method using cationic hydroquinone as organic catalyst for persulfate bleaching agent |
Also Published As
Publication number | Publication date |
---|---|
GB1358848A (en) | 1974-07-03 |
DE2139401A1 (en) | 1972-02-17 |
BE770910A (en) | 1972-02-04 |
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