US3667950A - Bleach-fixing solution for color photography - Google Patents
Bleach-fixing solution for color photography Download PDFInfo
- Publication number
- US3667950A US3667950A US98881A US3667950DA US3667950A US 3667950 A US3667950 A US 3667950A US 98881 A US98881 A US 98881A US 3667950D A US3667950D A US 3667950DA US 3667950 A US3667950 A US 3667950A
- Authority
- US
- United States
- Prior art keywords
- bleach
- fixing
- solution
- group
- fixing solution
- 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
- 150000001875 compounds Chemical group 0.000 abstract description 43
- -1 METHYLOL GROUP Chemical group 0.000 abstract description 26
- 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 abstract description 16
- 239000000463 material Substances 0.000 abstract description 11
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 abstract description 8
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001299 aldehydes Chemical group 0.000 abstract description 4
- 238000004061 bleaching Methods 0.000 description 28
- 238000012545 processing Methods 0.000 description 25
- 238000000034 method Methods 0.000 description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 238000005406 washing Methods 0.000 description 14
- 125000003172 aldehyde group Chemical group 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000011161 development Methods 0.000 description 8
- 238000005562 fading Methods 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000003139 buffering effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- LKZCRGABYQYUFX-UHFFFAOYSA-L barium(2+);dithiocyanate Chemical compound [Ba+2].[S-]C#N.[S-]C#N LKZCRGABYQYUFX-UHFFFAOYSA-L 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- YARHBRUWMYJLHY-UHFFFAOYSA-Q triazanium;iron(3+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YARHBRUWMYJLHY-UHFFFAOYSA-Q 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- NCNYEGJDGNOYJX-NSCUHMNNSA-N (e)-2,3-dibromo-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Br)=C(/Br)C=O NCNYEGJDGNOYJX-NSCUHMNNSA-N 0.000 description 1
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- XJBNELXWSXDUFP-UHFFFAOYSA-N 1,1,3-tris(hydroxymethyl)urea Chemical compound OCNC(=O)N(CO)CO XJBNELXWSXDUFP-UHFFFAOYSA-N 0.000 description 1
- QAGFPFWZCJWYRP-UHFFFAOYSA-N 1,1-bis(hydroxymethyl)urea Chemical compound NC(=O)N(CO)CO QAGFPFWZCJWYRP-UHFFFAOYSA-N 0.000 description 1
- DZNJSBHVDXLTIK-UHFFFAOYSA-N 1-(hydroxymethyl)imidazolidine-2,4-dione Chemical compound OCN1CC(=O)NC1=O DZNJSBHVDXLTIK-UHFFFAOYSA-N 0.000 description 1
- XFIZJENETBUYNB-UHFFFAOYSA-N 1-cyano-2-(hydroxymethyl)guanidine Chemical compound N#CNC(N)=NCO XFIZJENETBUYNB-UHFFFAOYSA-N 0.000 description 1
- AQOMATUINIDHTE-UHFFFAOYSA-N 1-hydroxy-1-methyl-3-(methylcarbamoyl)urea Chemical compound ON(C(=O)NC(=O)NC)C AQOMATUINIDHTE-UHFFFAOYSA-N 0.000 description 1
- ICVIFRMLTBUBGF-UHFFFAOYSA-N 2,2,6,6-tetrakis(hydroxymethyl)cyclohexan-1-ol Chemical compound OCC1(CO)CCCC(CO)(CO)C1O ICVIFRMLTBUBGF-UHFFFAOYSA-N 0.000 description 1
- RWGPAMBILZOZBK-UHFFFAOYSA-N 2-(2-oxoethoxy)acetaldehyde Chemical compound O=CCOCC=O RWGPAMBILZOZBK-UHFFFAOYSA-N 0.000 description 1
- LOTYADDQWWVBDJ-UHFFFAOYSA-N 2-methyl-2-nitropropane-1,3-diol Chemical compound OCC(C)(CO)[N+]([O-])=O LOTYADDQWWVBDJ-UHFFFAOYSA-N 0.000 description 1
- KIPMDPDAFINLIV-UHFFFAOYSA-N 2-nitroethanol Chemical class OCC[N+]([O-])=O KIPMDPDAFINLIV-UHFFFAOYSA-N 0.000 description 1
- WACQLQIAUWURGA-UHFFFAOYSA-N 3-hydroxy-2,2-bis(hydroxymethyl)propanoic acid Chemical compound OCC(CO)(CO)C(O)=O WACQLQIAUWURGA-UHFFFAOYSA-N 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
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical group [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PKDBSOOYVOEUQR-UHFFFAOYSA-N mucobromic acid Natural products OC1OC(=O)C(Br)=C1Br PKDBSOOYVOEUQR-UHFFFAOYSA-N 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- ZUZQXHSOEZUAIS-UHFFFAOYSA-N nitric acid;6-nitro-1h-benzimidazole Chemical compound O[N+]([O-])=O.[O-][N+](=O)C1=CC=C2N=CNC2=C1 ZUZQXHSOEZUAIS-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical group [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
- IJNJLGFTSIAHEA-UHFFFAOYSA-N prop-2-ynal Chemical compound O=CC#C IJNJLGFTSIAHEA-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
- G03C7/421—Additives other than bleaching or fixing agents
Definitions
- a single bleach-fixing solution for color photographic light-sensitive materials comprising a ferricyanide and a thiocyanate and containing at least one compound having an aldehyde group or a methylol group is disclosed.
- the present invention relates to an improved bleachfixing (blixing, solution in color photographic processings.
- the processings for color photographic materials include the steps of color development, stopping, first fixing, bleaching, second fixing, hardening, stabilizing, and the like, but such processings as they are usually practiced are simplified and the period of time for processing is shortened by conducting the stopping step and the first fixing step, the bleaching step and the second fixing step, or the second fixing step and the hardening step, in one bath. Further, such a technique is closely connected with the elements used for each light sensitive material.
- the present invention provides an improved bleachfixing solution for the color photographic processings as described above.
- Typical bleaching solutions for color photographic materials are a bleaching solution in which a water-soluble iron complex salt of ethylene diamine tetraacetic acid is used as the oxidizing agent and a bleaching solution in which a ferrocyanide is used as the oxidizing agent.
- the former case is advantageous in that bleach-fixing can be done easily with a single solution which combines the bleaching and fixing since the oxidizing agent is stable with a thiosulfate but the employment of the former type bleaching solution is accompanied by disadvantages due to the weak oxidizing power of the oxidizing agent such that when a type of coupler is used, the leuco compound formed by the color forming development can not be oxidized into the dye.
- the bleaching power is sufiiciently strong and the reduction in image quality by weak bleaching does not occur but since the oxidizing power is strong, it decomposes a thiosulfate when a thiosulfate is used as a fixing agent together with ferricyanide, which requires the separate use of the bleaching process and the fixing process.
- the thiocyanate, dithiosuberic acid, and known mercapto compound as described in the specification of U.S. Pat. Nos. 3,335,004 and 3,342,598, are stable when present together with a ferricyanide, a single solution type of bleach-fixing solution can be used.
- Bleaching, fixing and hardening can be done with a single solution. That is to say, since it can be processed without an additional hardening bath, one processing bath can be omitted. This, as a matter of course, gives the advantages that the processing steps can be simplified and the processing period of time can be shortened.
- the single bleach-fixing solution according to the present invention has the same bleaching power and bleaching speed as those of a conventional ferricyanidetype bleaching bath and in addition, the solution has the same hardening power and hardening speed as those of a conventional hardening bath. Also, the stability of the processing solution per se is better than the conventional bleaching bath, fixing bath and hardening bath.
- the bleaching agent used in this invention is a ferricyanide or a combination of a ferricyanide and a ferrocyanide, e.g., an alkali metal salt such as the sodium, potassium or lithium salt and an ammonium salt.
- the fixing agent used in this invention is a thiocyanate (in which the associated counter ion is a positive ion other than an ion of Ag, Hg, Cu, and Au, for example, a positive ion such as the salt of NH K, Na, Ba, and the like).
- water-soluble compound having an aldehyde group or a methylol group used in this invention a compound represented by the following general Formula I R-CHO (I) wherein R represent a hydrogen atom, an alkyl group, an allyl group, an aryl group or-a heterocyclic residual group, in which each of the groups may be substituted, is preferably used.
- Examples of compounds shown by the general Formula I which can be used in this invention are formaldehyde, paraformaldehyde, acetaldehyde, aldol, propiolaldehyde, acrolein, crotonaldehyde, salicylaldehyde, glyoxylic acid, mucochloric acid, mucobromic acid, furfural, diglycolaldehyde, and the like.
- the compound to be used in this invention can also include precursors of the above-described compounds.
- water-soluble compound a compound represented by the following general Formula II OHC-R-CHO 11 wherein R represents a single bond, a divalent aliphatic group or a divalent aromatic group can be used.
- Examples of compounds represented by the general Formula II are glyoxal, succinaldehyde, glutaraldehyde,
- the compound to be used in this invention can include the precursors of the above-described compounds as shown, for example, in Japanese patent publication No. 27,570/ 64, for example 2,5-dialkoxy-tetrahydrofuran.
- water-soluble compound to be used in this invention compounds represented by the following general Formula III I R"CH OH (III) wherein R" represents an aliphatic group, an aromatic group or a heterocyclic group is preferably used.
- Examples of compounds represented by the general Formula III are N-methylol urea, N,N-dimethylol urea, N-methylolmethylenebismonoethyl urea, N'-methylol- N,N-dimethylol urea, methylohydantoin, hydroxydimethylbiuret, trihydroxymethylbiuret, 2,2,6,6-tetramethylolcyclohexanol, methyloldicyandiamide, the compounds described in the specification of British Pat. No. 1,116,944, such as 3 hydroxy-2,2-dihydroxymethylpropionic acid, and 2 nitroethanol derivatives described in Japanese patent application No. 67,799/ 69, such as 2-nitro-2-methyl-1,3-propandiol.
- the single bleach-fixing solution of this invention can contain a buffering agent to establish the pH range desired or other subsidiary chemicals. Further, the stabilizing bath subsequent to the processing by the single bleach-fixing solution of this invention can be omitted or the stabilizing processing as described in the specification of British Pat. No. 1,092,258 can be applied after the processing by the single bleach-fixing solution of this invention.
- Examples of light sensitive materials to be processed by the single bleach-fixing solution of this invention are color photographic light sensitive materials containing the acetanilide-type yellow couplers as described in the specification of British Pat. No. 1,113,038 and U.S. Pat. No. 3,409,439; the pyrazolone-type magenta couplers as described in the specification of British Pat. No. 1,142,553 and US. Pat. No. 3,337,344; and the phenolic couplers as described in the specification of US. Pats. Nos. 2,423,730, 2,474,293 and 2,801,171 but the light sensitive materials to which the invention is applicable are not limited to these examples.
- Solution-1 Solution-2 Sodium thiocyanate, g 32. 0 32. 0 Potassium nitrate, g 25. 0 25. 0 Ferricyanide, g-" 20. 0 20. 0 Boric acid, g 5. 0 5. 0 Borax, g 2. 5 2. 5 Formalin (35-40%), ml- 40. 0
- a color photographic paper prepared by coating a baryta-coated paper with a blue-sensitive silver iodobromide emulsion layer containing benzoylaceto-Z-chloro-S- dodecyloxycarbonyl anilide as a yellow coupler, a gelatin intermediate layer, a green-sensitive silver chlorobromide emulsion layer containing l-phenyl-3-[3-(N-butylcaprylamidopropionamido)j-5-pyrazolone as a magenta coupler, a gelatin intermediate layer, a red-sensitive silver chlorobromide emulsion layer containing 1-hydroxy-2-[3-(2,4- t-amylphenoxy)propyl]-naphthamide as a cyan coupler, and a protective gelatin layer successively was exposed and then subjected to the following processings at 30 C.
- PROCESS A The exposed color photographic paper was subjected to color development for 7 minutes, top-fixing for 2 minutes, washing for 2 minutes, bleaching for 2 minutes, washing for 2 minutes, hardening-fixing for 2 minutes, washing for 4 minutes, and buffering for 2 minutes.
- PROCESS B The exposed color photographic paper was subjected to color development for 7 minutes, stop-fixing for 2 minutes, washing for 2 minutes, bleaching-fixing using the bleach-fixing solution-1 for 2 minutes, washing for 2 minutes, hardening for 2 minutes, washing for 4 minutes, and buffering for 2 minutes.
- PROCESS C The exposed color photographic paper was subjected to color development for 7 minutes, stop-fixing for 2 minutes, washing for 2 minutes, bleach-fixing using bleach-fixing solution-l for 2 minutes, washing for 4 minutes, and butfering for 2 minutes.
- PROCESS D The exposed color photographic paper was subjected to color development for 7 minutes, stop-fixing for 2 minutes, washing for 2 minutes, bleach-fixing using bleachfixing solution-2 for 2 minutes, washing for 4 minutes, and buffering for 2 minutes.
- Process A B C D Process A B C D Time required for finishing bleching seconds 60 62 63 60
- Process A-D Process A-D Time required for finishing bleching seconds 60 62 63 60
- the fading ratio is the ratio of the color density reduced during the test to the initial color density.
- the additive is shown in the following table, in which the melting conditions of the emulsion layer by ferrotype drying, the time required for finishing the ferrotype drying and also the time required for finishing the bleaching are also shown.
- EXAMPLE 3 The color photographic paper subjected to color development, stop-fixing and washing as shown in Example 1 was processed for 2 minutes using the bleach-fixing solution as shown in Example 2 except that the additive was replaced with the additives shown in the following table and then subjected to washing and buifering.
- EXAMPLE 4 A color photographic film prepared by coating on a film support a blue-sensitive silver iodobromide emulsion layer containing the yellow coupler shown in Example 1, an intermediate gelatin layer, a red-sensitive silver chlorobromide emulsion layer containing the cyan coupler shown in Example 1, an intermediate gelatin layer, a green-sensitive silver chlorobromide emulsion layer containing the magenta coupler shown in Example 1 and, then a protective gelatin layer, successively, was subjected to color development and stop-fixing as in Example 1 and then processed using the bleach-fixing solution shown in the following table. In addition, the pH of the solution was adjusted to 7.0 using an aqueous NaOH solution.
- a single bleach-fixing solution for color photographic light sensitive materials comprising an alkali metal or ammonium ferricyanide and an alkali metal, ammonium or barium thiocyanate, characterized in that said bleach-fixing solution contains at least one compound having an aldehyde group or a methylol group.
- said compound having an aldehyde group or a methylol group is a compound represented by the following general formula R-CHO wherein R is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an allyl group and a heterocyclic residual group, and wherein said group may be substituted.
- a single bleaeh-fixing solution for color photographic light sensitive materials comprising an alkali metal or ammonium ferricyanide, an alkali metal or ammonium ferrocyanide and an alkali metal, ammonium or barium thiocyanate, characterized in that said bleach-fixing solution contains at least one compound having an aldehyde group or a. methylol group.
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Abstract
A SINGLE BLEACH-FIXING SOLUTION FOR COLOR PHOTGRAPHIC LIGHT-SENSITIVE MATERIALS COMPRISING A FERRICYANIDE AND A THIOCYANATE AND CONTAINING AT LEAST ONE COMPOUND HAVING AN ALDEHYDE GROUP OR A METHYLOL GROUP IS DISCLOSED.
Description
U measures Patent 01 ace 3,667,950 Patented June 6, 1972 3,667,950 BLEACH-FIXING SOLUTION FOR COLOR PHOTOGRAPHY Hiroyuki Amano, Haruhiko Iwano, and Kazuo Shrrasu, Kanagawa, Japan, assignors to Fuji Photo Film Co., Ltd., Kanagawa, Japan No Drawing. Filed Dec. 16, 1970, Ser. No. 98,881 Claims priority, application Japan, Dec. 16, 1969, 44/101,115 Int. Cl. G03c 5/32 U.S. Cl. 96-60 12 Claims ABSTRACT OF THE DISCLOSURE A single bleach-fixing solution for color photographic light-sensitive materials comprising a ferricyanide and a thiocyanate and containing at least one compound having an aldehyde group or a methylol group is disclosed.
BACKGROUND OF THE INVENTION (1) Field of the invention The present invention relates to an improved bleachfixing (blixing, solution in color photographic processings.
(2) Description of the prior art In general, the processings for color photographic materials include the steps of color development, stopping, first fixing, bleaching, second fixing, hardening, stabilizing, and the like, but such processings as they are usually practiced are simplified and the period of time for processing is shortened by conducting the stopping step and the first fixing step, the bleaching step and the second fixing step, or the second fixing step and the hardening step, in one bath. Further, such a technique is closely connected with the elements used for each light sensitive material.
The present invention provides an improved bleachfixing solution for the color photographic processings as described above.
Typical bleaching solutions for color photographic materials are a bleaching solution in which a water-soluble iron complex salt of ethylene diamine tetraacetic acid is used as the oxidizing agent and a bleaching solution in which a ferrocyanide is used as the oxidizing agent. The former case is advantageous in that bleach-fixing can be done easily with a single solution which combines the bleaching and fixing since the oxidizing agent is stable with a thiosulfate but the employment of the former type bleaching solution is accompanied by disadvantages due to the weak oxidizing power of the oxidizing agent such that when a type of coupler is used, the leuco compound formed by the color forming development can not be oxidized into the dye. It is known to use an additional oxidizing bath after applying such a bleach-fixing procedure for improving such disadvantages (see, for example, the specification of British Pat. No. 1,026,496), but such an approach necessitates the use of a number of processing baths complicating the processing. Also, various attempts are known in which various types of accelerators are added in the case of using the water-soluble iron complex salt of ethylene-diamine tetraacetic acid (see, for example, the specification of British Pat. Nos. 1,150,466 and 926,569), but such approaches are inferior in bleaching speed to the process in which a ferricyanide is used.
On the other hand, when a ferricyanide is used, the bleaching power is sufiiciently strong and the reduction in image quality by weak bleaching does not occur but since the oxidizing power is strong, it decomposes a thiosulfate when a thiosulfate is used as a fixing agent together with ferricyanide, which requires the separate use of the bleaching process and the fixing process. However, since the thiocyanate, dithiosuberic acid, and known mercapto compound, as described in the specification of U.S. Pat. Nos. 3,335,004 and 3,342,598, are stable when present together with a ferricyanide, a single solution type of bleach-fixing solution can be used.
SUMMARY OF THE INVENTION As the result of various investigations on single types of bleach-fixing solutions containing the ferricyanide (or the ferricyanide and ferrocyanide) and the thiocyanate as described above, it has been discovered that by adding a compound having an aldehyde group or a methylol group to the above solution, the advantageous characteristics shown below can be obtained.
(1) Bleaching, fixing and hardening can be done with a single solution. That is to say, since it can be processed without an additional hardening bath, one processing bath can be omitted. This, as a matter of course, gives the advantages that the processing steps can be simplified and the processing period of time can be shortened.
(2) The occurrence of physical damages, such as scratching of emulsion layer which can occur at the bleach-fixing procedure, can be prevented.
(3) The stability, and in particular the light fastness and the heat resistance of images, is improved.
(4) The reduction in color density or fading which can occur on ferro-type finishing of a light sensitive material containing a type of magenta coupler is prevented.
Moreover, the single bleach-fixing solution according to the present invention has the same bleaching power and bleaching speed as those of a conventional ferricyanidetype bleaching bath and in addition, the solution has the same hardening power and hardening speed as those of a conventional hardening bath. Also, the stability of the processing solution per se is better than the conventional bleaching bath, fixing bath and hardening bath.
DETAILED DESCRIPTION OF THE INVENTION The bleaching agent used in this invention is a ferricyanide or a combination of a ferricyanide and a ferrocyanide, e.g., an alkali metal salt such as the sodium, potassium or lithium salt and an ammonium salt. The fixing agent used in this invention is a thiocyanate (in which the associated counter ion is a positive ion other than an ion of Ag, Hg, Cu, and Au, for example, a positive ion such as the salt of NH K, Na, Ba, and the like). Also, as the water-soluble compound having an aldehyde group or a methylol group used in this invention, a compound represented by the following general Formula I R-CHO (I) wherein R represent a hydrogen atom, an alkyl group, an allyl group, an aryl group or-a heterocyclic residual group, in which each of the groups may be substituted, is preferably used.
Examples of compounds shown by the general Formula I which can be used in this invention are formaldehyde, paraformaldehyde, acetaldehyde, aldol, propiolaldehyde, acrolein, crotonaldehyde, salicylaldehyde, glyoxylic acid, mucochloric acid, mucobromic acid, furfural, diglycolaldehyde, and the like. The compound to be used in this invention can also include precursors of the above-described compounds.
Also, as the water-soluble compound, a compound represented by the following general Formula II OHC-R-CHO 11 wherein R represents a single bond, a divalent aliphatic group or a divalent aromatic group can be used.
Examples of compounds represented by the general Formula II are glyoxal, succinaldehyde, glutaraldehyde,
ot-methylglutaraldehyde, cyclopentane-dicarboxyaldehyde, and the dialdehydes described in the specification of British Pat. No. 1,102,001, for example, OHCCH OCH CHO and OHCCH NHCH CHO, and French Pat. No. 1,543,- 694, for example, 2,4-di-aldehyde phenol. Also, the compound to be used in this invention can include the precursors of the above-described compounds as shown, for example, in Japanese patent publication No. 27,570/ 64, for example 2,5-dialkoxy-tetrahydrofuran.
Furthermore, as the water-soluble compound to be used in this invention, compounds represented by the following general Formula III I R"CH OH (III) wherein R" represents an aliphatic group, an aromatic group or a heterocyclic group is preferably used.
Examples of compounds represented by the general Formula III are N-methylol urea, N,N-dimethylol urea, N-methylolmethylenebismonoethyl urea, N'-methylol- N,N-dimethylol urea, methylohydantoin, hydroxydimethylbiuret, trihydroxymethylbiuret, 2,2,6,6-tetramethylolcyclohexanol, methyloldicyandiamide, the compounds described in the specification of British Pat. No. 1,116,944, such as 3 hydroxy-2,2-dihydroxymethylpropionic acid, and 2 nitroethanol derivatives described in Japanese patent application No. 67,799/ 69, such as 2-nitro-2-methyl-1,3-propandiol.
It is astonishing that the reducing compounds shown by the above described compounds (I), (II), and (III) are stable in a bleach-fixing bath containing, a strongly oxidizing ferricyanide.
The amounts of the compounds to be used in the present invention are as shown in the following table.
From 2 glitter to tht maximum solubility.
From 1 g./liter to the maximum solubility.
Compound having an aldehyde group or a methylol group.
If necessary the single bleach-fixing solution of this invention can contain a buffering agent to establish the pH range desired or other subsidiary chemicals. Further, the stabilizing bath subsequent to the processing by the single bleach-fixing solution of this invention can be omitted or the stabilizing processing as described in the specification of British Pat. No. 1,092,258 can be applied after the processing by the single bleach-fixing solution of this invention.
The advantages of the single bleach-fixing solution of this invention are stated above but, in particular, formaldehyde and paraformaldehyde of the compounds shown by the general Formula I, the compounds shown by the general Formula II, and the Z-nitroethanol derivatives shown by the general Formula III are effective to obtain the advantages 1 to 4 mentioned above, While the other compounds are particularly effective to obtain the advantages 3 and 4 described above.
Examples of light sensitive materials to be processed by the single bleach-fixing solution of this invention are color photographic light sensitive materials containing the acetanilide-type yellow couplers as described in the specification of British Pat. No. 1,113,038 and U.S. Pat. No. 3,409,439; the pyrazolone-type magenta couplers as described in the specification of British Pat. No. 1,142,553 and US. Pat. No. 3,337,344; and the phenolic couplers as described in the specification of US. Pats. Nos. 2,423,730, 2,474,293 and 2,801,171 but the light sensitive materials to which the invention is applicable are not limited to these examples.
Now the experimental results typically obtained with the various improvements obtained by using the singlebath bleach-fixing and hardening solution of this invention are shown by the following examples although the invention is not to be interpreted as being limited thereby.
EXAMPLE 1 5 Color forming developing solution (pH 10.6)
Sodium metaborate g 25.0 Sodium sulfite g 2.0 Hydroxylamine (sulfate) g- 2.0 Potassium bromide g 0.5
6-nitrobenzimidazole (nitrate) g 0.02 Sodium hydroxide g 4.0 Benzyl alcohol ml.... 15.8 Diethylene glycol ml 20.0 N ethyl N B (methane sulfoneamideethyU- p-phenylene diamine (sulfate) g 8.0
Water added to make 1 liter.
Stop-fixing solution (pH 4.5)
Ammonium thiosulfate g 120.0
Sodium pyrosulfite g 20.0 Glacial acetic acid g 10.0 Water added to make 1 liter.
Bleaching solution (pH 7.2)
Potassium nitrate g 25.0 Ferricyanide g 20.0 Potassium bromide g 8.0 Boric acid g 5.0
Borax g 2.5
Water added to make 1 liter.
Bleach-fixing solution (pH 7.2)
Solution-1 Solution-2 Sodium thiocyanate, g 32. 0 32. 0 Potassium nitrate, g 25. 0 25. 0 Ferricyanide, g-" 20. 0 20. 0 Boric acid, g 5. 0 5. 0 Borax, g 2. 5 2. 5 Formalin (35-40%), ml- 40. 0
Water Added to make 1 liter.
Hardening-fixing solution (pH 9.5
Ammonium thiosulfate g 120.0
Sodium sulfite g 5.0 Boric acid g 2.5 Formalin (35-40%) ml 40.0 Water added to make 1 liter.
Hardening solution (pH 9.5)
00 Sodium metaborate g 0.5 Formalin (35-40%) ml 40.0 Water added to make 1 liter.
Buffering bath (pl-I 5.0)
Zinc sulfate g 10,0 Tartaric acid g 10.0 Sodium metaborate g 20.0 Water added to make 1 liter.
A color photographic paper prepared by coating a baryta-coated paper with a blue-sensitive silver iodobromide emulsion layer containing benzoylaceto-Z-chloro-S- dodecyloxycarbonyl anilide as a yellow coupler, a gelatin intermediate layer, a green-sensitive silver chlorobromide emulsion layer containing l-phenyl-3-[3-(N-butylcaprylamidopropionamido)j-5-pyrazolone as a magenta coupler, a gelatin intermediate layer, a red-sensitive silver chlorobromide emulsion layer containing 1-hydroxy-2-[3-(2,4- t-amylphenoxy)propyl]-naphthamide as a cyan coupler, and a protective gelatin layer successively was exposed and then subjected to the following processings at 30 C.
PROCESS A The exposed color photographic paper was subjected to color development for 7 minutes, top-fixing for 2 minutes, washing for 2 minutes, bleaching for 2 minutes, washing for 2 minutes, hardening-fixing for 2 minutes, washing for 4 minutes, and buffering for 2 minutes.
PROCESS B The exposed color photographic paper was subjected to color development for 7 minutes, stop-fixing for 2 minutes, washing for 2 minutes, bleaching-fixing using the bleach-fixing solution-1 for 2 minutes, washing for 2 minutes, hardening for 2 minutes, washing for 4 minutes, and buffering for 2 minutes.
PROCESS C The exposed color photographic paper was subjected to color development for 7 minutes, stop-fixing for 2 minutes, washing for 2 minutes, bleach-fixing using bleach-fixing solution-l for 2 minutes, washing for 4 minutes, and butfering for 2 minutes.
PROCESS D The exposed color photographic paper was subjected to color development for 7 minutes, stop-fixing for 2 minutes, washing for 2 minutes, bleach-fixing using bleachfixing solution-2 for 2 minutes, washing for 4 minutes, and buffering for 2 minutes.
After the processings were finished, the color paper was subjected to ferrotype drying at 80 C. and the following Key.O=No layer melted, A=S1ightly melted, X =Entirely melted.
As is clear from the experimental results set forth above, in Process C in which the conventional bleach-fixing solution-1 was used and the hardening bath was omitted, the time required for ferrotype drying was longer and the melting of emulsion layer was very severe. On the other hand, in the case of processing using the bleach-fixing solution-2 of this invention (Process D), the time required for ferrotype drying was the same as that in the Process A in which the conventional bleaching bath and the conventional hardening-fixing bath were employed and, also, almost no melting of the emulsion layer was observed. Accordingly, the hardening bath and the washing accompanied by the hardening processing is unnecessary. Therefore, it is possible to omit two processing baths, which results in a simplification of the photographic processings and a shortening in the processing period of time.
The period of time required for finishing the bleaching was almost the same in Processes A-D, as is shown in the following table.
Process A B C D Process A B C D Time required for finishing bleching seconds 60 62 63 60 With respect to the color papers processed by Process A-D, respectively (bleach-fixing for 2 minutes), the stability of the images obtained was tested under the conditions shown in the following table.
The fading ratio is the ratio of the color density reduced during the test to the initial color density.
As is clear from the experimental results, in Process C in which the bleach-fixing solution having conventional composition was used and the hardening bath was omitted, the stability of the image to heat and light was reduced greatly, while in Process D in which the improved bleachfixing solution of this invention was employed, the stability of the image to light and heat was excellent.
After processing 4 m. /liter of the color photographic paper by the bleaching solution or the bleach-fixing solution used in this experiment, the solution was allowed to stand for 3 months but each solution was similarly stable. On the other hand, a bleach-fixing solution in which a thiosulfate was used as a fixing agent formed a considerable amount of precipitate within 15 minutes, which made it impossible to use the solution further.
As anticipated as a matter of course, when a film base was employed instead of the baryta-coated paper, similarly excellent results were obtained with respect to the bleaching speed and the stability of image.
EXAMPLE 2 After exposing and processing the color developing solution and the stop-fixing solution as shown in Example I, the color photographic paper as shown in Example 1 was processed with a bleach-fixing solution having the following composition:
Water added to make 1 liter.
The additive is shown in the following table, in which the melting conditions of the emulsion layer by ferrotype drying, the time required for finishing the ferrotype drying and also the time required for finishing the bleaching are also shown.
Melting Bleachin Additive condition Drying time time g Paraiormaldehyde 4 min 60 sec. Succmaldehyde 3 min. and 55 see- 62 sec. Glutaraldehyde. -A 4 sec.
mm 2-nitro- 2-methyl-1,3-pro- 3 min. and 55 sec 60 sec.
pandiol.
On comparing the experimental results and the results shown in the table of Example 1, it is clear that in using each of the bleach-fixing solutions of this invention, the ferrotype drying time, the state of emulsion layer, and the bleaching speed were almost the same as those in Process A in which the known bleaching bath and the known hardening-fixing bath were employed and further in using the bleach-fixing solution of this invention, one processing bath and one washing bath could be omitted.
The results of testing the stability of the image and the stability of the solution per se were almost the same as those in Example 1.
EXAMPLE 3 The color photographic paper subjected to color development, stop-fixing and washing as shown in Example 1 was processed for 2 minutes using the bleach-fixing solution as shown in Example 2 except that the additive was replaced with the additives shown in the following table and then subjected to washing and buifering.
In the following table are shown the results of testing the ferrotype fading of the magenta color image (ratio to natural drying) formed by subjecting the color photographic paper processed above to ferrotype drying at C. and also the results of conducting the same experiment for testing the stability of the magenta color image to heat and light as in Example 1. The numerical values in the table are fading ratios at a density of 0.5.
Exposure Ferrotype for 5 days to Stored for drying at fluorescent 7 days at Additive (3 g.,lliter oi bleach- 80 C. lamp (10 76.7 C fixing solution) (percent) lux) (percent) Aoetaldehyde 8 2 Acrolein O 10 3 Crotonaldehyde 0 10 3 Salicylaldehyde. 0 1O 4 Cinnamaldehyde. 2 12 Glyoxylie acid 2 11 4 Mucochloric acid-. 1 12 5 0 3 Methylolhydantoin l) *J 2 Hydroxymethylbiurct. 1 12 -'l Methylol dicyandiamid l) 10 2 None (process 0) 8t] 5t) From these experimental results, it is clear that the improved bleach-fixing solution of this invention was greatly eifective for the prevention of fading to ferrotype drying and fading to heat and light.
EXAMPLE 4 A color photographic film prepared by coating on a film support a blue-sensitive silver iodobromide emulsion layer containing the yellow coupler shown in Example 1, an intermediate gelatin layer, a red-sensitive silver chlorobromide emulsion layer containing the cyan coupler shown in Example 1, an intermediate gelatin layer, a green-sensitive silver chlorobromide emulsion layer containing the magenta coupler shown in Example 1 and, then a protective gelatin layer, successively, was subjected to color development and stop-fixing as in Example 1 and then processed using the bleach-fixing solution shown in the following table. In addition, the pH of the solution was adjusted to 7.0 using an aqueous NaOH solution.
Water No'rE.- (3)-(8) designates bleach-fixing solutions 3 to 8.
In this case, the time required for the bleach fixing and the stability of the magenta color image are as shown in the following table.
Bleaching time, see 47 49 47 50 55 50 Exposure for 5 days to a fluorescent lamp (10* lux), percent 12 12 10 8 25 Stored for 7 days at 76.7 C. under low humidity, percent 3 4 3 3 2 45 From the experimental results shown above, it is clear that the bleach-fixing solution of this invention gives an image having an excellent stability with the same bleaching speed as that in the known bleach-fixing solution (bleaching fixing solution 8).
The fading prevention eifect of the magenta image to ferrotype fading in processing the color photographic paper as shown in Example 1 by each of the bleach-fixing solutions 3-7 was same as in Example 3. Also, the emulsion layer condition and period of time for ferrotype drying were almost the same as the case of Process D in Example 1.
What is claimed is:
1. A single bleach-fixing solution for color photographic light sensitive materials comprising an alkali metal or ammonium ferricyanide and an alkali metal, ammonium or barium thiocyanate, characterized in that said bleach-fixing solution contains at least one compound having an aldehyde group or a methylol group.
2. The bleach-fixing solution as claimed in claim 1, wherein said compound having an aldehyde group or a methylol group is a compound represented by the following general formula R-CHO wherein R is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an allyl group and a heterocyclic residual group, and wherein said group may be substituted.
3. The single bleach-fixing solution as claimed in claim 1, wherein said compound having an aldehyde group or a methylol group is a compound represented by the following general formula wherein R is selected from the group consisting of a direct bond, a divalent aliphatic group and a divalent aromatic group.
4. The single bleach-fixing solution as claimed in claim 1, wherein said compound having an aldehyde group or a methylol group is a compound represented by the following general formula wherein R" is selected from the group consisting of an aliphatic group, an aromatic group and a heterocyclic residual group.
5. A single bleaeh-fixing solution for color photographic light sensitive materials comprising an alkali metal or ammonium ferricyanide, an alkali metal or ammonium ferrocyanide and an alkali metal, ammonium or barium thiocyanate, characterized in that said bleach-fixing solution contains at least one compound having an aldehyde group or a. methylol group.
6. The single bleach-fixing solution as claimed in claim 5, wherein said compound having an aldehyde group or a methylol group is a compound represented by the following general formula R-CHO wherein R is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an allyl group, and a heterocyclic group, and wherein said group may be substituted.
7. The single bleach-fixing solution as claimed in claim 5, wherein said compound having an aldehyde group or a methylol group is a compound represented by the following general formula wherein R is selected from the group consisting of a direct bond, a divalent aliphatic group and a divalent aromatic group.
8. The single bleach-fixing solution as claimed in claim 5, wherein said compound having an aldehyde group or a methylol group is a compound represented by the following general formula wherein R" is selected from the group consisting of an aliphatic group, an aromatic group and a heterocyclic residual group.
9. The single bleach-fixing solution as claimed in claimv 1, wherein said compound having an aldehyde group or methylol group is formaldehyde.
10. The single bleach-fixing solution as claimed in claim 1, wherein said ferricyanide is potassium ferricyanide, wherein said thiocyanate is sodium thiocyanate and wherein said compound having an aldehyde or methylol group is formaldehyde.
11. The single bleach-fixing solution as claimed in claim 1, wherein said ferricyanide is potassium ferricyanide, wherein said thiocyanate is potassium thiocyanate and wherein said compound having an aldehyde or methylol group is formaldehyde.
12. The single bleach-mixing solution as claimed in claim 1, wherein said ferricyanide is potassium ferricyanide, wherein said thiocyanate is ammonium thiocyanate, and wherein said compound having an aldehyde or methylol group is formaldehyde.
References Cited UNITED STATES PATENTS 3/ 1967 Wrisley et al 96 22 5/1967 Bard 96-60 US. Cl. X.R.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP44101115A JPS4834175B1 (en) | 1969-12-16 | 1969-12-16 |
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| Publication Number | Publication Date |
|---|---|
| US3667950A true US3667950A (en) | 1972-06-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US98881A Expired - Lifetime US3667950A (en) | 1969-12-16 | 1970-12-16 | Bleach-fixing solution for color photography |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3667950A (en) |
| JP (1) | JPS4834175B1 (en) |
| DE (1) | DE2062032A1 (en) |
| GB (1) | GB1328825A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3833376A (en) * | 1972-11-24 | 1974-09-03 | Minnesota Mining & Mfg | Color development process and compositions |
| US3879202A (en) * | 1971-09-30 | 1975-04-22 | Fuji Photo Film Co Ltd | Color photographic process |
| US3931004A (en) * | 1972-04-21 | 1976-01-06 | Fuji Photo Film Co., Ltd. | Method of treating waste liquids from photographic processings |
| US4033771A (en) * | 1973-08-16 | 1977-07-05 | Eastman Kodak Company | Stabilized bleach-fixing baths |
| US4036715A (en) * | 1971-12-20 | 1977-07-19 | Eastman Kodak Company | Method of recovering silver from photographic bleach-fix and concurrently regenerating the bleach-fix |
| US4921779A (en) * | 1988-12-19 | 1990-05-01 | Eastman Kodak Company | Bleach-accelerating compositions containing a dye-stabilizing agent and use thereof in photographic color processing |
| US4960682A (en) * | 1988-12-19 | 1990-10-02 | Eastman Kodak Company | Bleaching compositions containing a dye-stabilizing agent and use thereof in photographic color processing |
| US4975356A (en) * | 1988-12-19 | 1990-12-04 | Eastman Kodak Company | Bleach-accelerating compositions containing a dye-stabilizing agent and use thereof in photographic color processing |
| EP0432499A1 (en) * | 1989-11-16 | 1991-06-19 | Fuji Photo Film Co., Ltd. | Method for processing silver halide photographic material and composition having fixing ability |
| US5424177A (en) * | 1991-07-05 | 1995-06-13 | Konica Corporation | Stabilizer for silver halide color photographic light-sensitive materials and its concentrated composition, and processing method using said stabilizer |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50147280U (en) * | 1974-05-21 | 1975-12-06 | ||
| JP6124234B1 (en) * | 2016-11-30 | 2017-05-10 | 株式会社Ｍｏｇｕ | Trunk supporter and innerwear equipped with it |
-
1969
- 1969-12-16 JP JP44101115A patent/JPS4834175B1/ja active Pending
-
1970
- 1970-12-15 GB GB5958870A patent/GB1328825A/en not_active Expired
- 1970-12-16 DE DE19702062032 patent/DE2062032A1/en active Pending
- 1970-12-16 US US98881A patent/US3667950A/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3879202A (en) * | 1971-09-30 | 1975-04-22 | Fuji Photo Film Co Ltd | Color photographic process |
| US4036715A (en) * | 1971-12-20 | 1977-07-19 | Eastman Kodak Company | Method of recovering silver from photographic bleach-fix and concurrently regenerating the bleach-fix |
| US3931004A (en) * | 1972-04-21 | 1976-01-06 | Fuji Photo Film Co., Ltd. | Method of treating waste liquids from photographic processings |
| US3833376A (en) * | 1972-11-24 | 1974-09-03 | Minnesota Mining & Mfg | Color development process and compositions |
| US4033771A (en) * | 1973-08-16 | 1977-07-05 | Eastman Kodak Company | Stabilized bleach-fixing baths |
| US4921779A (en) * | 1988-12-19 | 1990-05-01 | Eastman Kodak Company | Bleach-accelerating compositions containing a dye-stabilizing agent and use thereof in photographic color processing |
| US4960682A (en) * | 1988-12-19 | 1990-10-02 | Eastman Kodak Company | Bleaching compositions containing a dye-stabilizing agent and use thereof in photographic color processing |
| US4975356A (en) * | 1988-12-19 | 1990-12-04 | Eastman Kodak Company | Bleach-accelerating compositions containing a dye-stabilizing agent and use thereof in photographic color processing |
| EP0432499A1 (en) * | 1989-11-16 | 1991-06-19 | Fuji Photo Film Co., Ltd. | Method for processing silver halide photographic material and composition having fixing ability |
| US5120635A (en) * | 1989-11-16 | 1992-06-09 | Fuji Photo Film Co., Ltd. | Method for processing silver halide photographic material and composition having fixing ability |
| US5424177A (en) * | 1991-07-05 | 1995-06-13 | Konica Corporation | Stabilizer for silver halide color photographic light-sensitive materials and its concentrated composition, and processing method using said stabilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2062032A1 (en) | 1971-07-15 |
| JPS4834175B1 (en) | 1973-10-19 |
| GB1328825A (en) | 1973-09-05 |
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