JPS6122295B2 - - Google Patents
Info
- Publication number
- JPS6122295B2 JPS6122295B2 JP25034483A JP25034483A JPS6122295B2 JP S6122295 B2 JPS6122295 B2 JP S6122295B2 JP 25034483 A JP25034483 A JP 25034483A JP 25034483 A JP25034483 A JP 25034483A JP S6122295 B2 JPS6122295 B2 JP S6122295B2
- Authority
- JP
- Japan
- Prior art keywords
- bleach
- color
- bath
- salt
- acid
- 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
Links
- 150000003839 salts Chemical class 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 24
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- -1 silver halide Chemical class 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 17
- 229910001447 ferric ion Inorganic materials 0.000 claims description 17
- 238000011161 development Methods 0.000 claims description 16
- 238000003672 processing method Methods 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 32
- 239000002253 acid Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000010410 layer Substances 0.000 description 18
- 239000007844 bleaching agent Substances 0.000 description 16
- 238000004061 bleaching Methods 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 14
- 238000012545 processing Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 7
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000008280 blood Substances 0.000 description 5
- 210000004369 blood Anatomy 0.000 description 5
- 239000002738 chelating agent Substances 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 4
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- 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 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000012089 stop solution Substances 0.000 description 3
- JYHRLWMNMMXIHF-UHFFFAOYSA-N (tert-butylamino)boron Chemical compound [B]NC(C)(C)C JYHRLWMNMMXIHF-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- GPMCZKILFBRNNY-UHFFFAOYSA-N 2,3-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=C(O)C=CC(O)=C1C(C)(C)CC GPMCZKILFBRNNY-UHFFFAOYSA-N 0.000 description 1
- SUVZGLSQFGNBQI-UHFFFAOYSA-N 2,5-bis(sulfanyl)hexanedioic acid Chemical compound OC(=O)C(S)CCC(S)C(O)=O SUVZGLSQFGNBQI-UHFFFAOYSA-N 0.000 description 1
- PDHFSBXFZGYBIP-UHFFFAOYSA-N 2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethanol Chemical compound OCCSCCSCCO PDHFSBXFZGYBIP-UHFFFAOYSA-N 0.000 description 1
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical compound [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 description 1
- GLBRRZZDOLYTCD-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]-n-(carboxymethyl)anilino]acetic acid Chemical class OC(=O)CN(CC(O)=O)C1=CC=CC=C1N(CC(O)=O)CC(O)=O GLBRRZZDOLYTCD-UHFFFAOYSA-N 0.000 description 1
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 1
- LQLJZSJKRYTKTP-UHFFFAOYSA-N 2-dimethylaminoethyl chloride hydrochloride Chemical compound Cl.CN(C)CCCl LQLJZSJKRYTKTP-UHFFFAOYSA-N 0.000 description 1
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 1
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical class OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 description 1
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- KZYPRKQUJIYCPE-UHFFFAOYSA-N O.S(=O)(=O)(O)O.NC1=C(C=C(N(CC)CCO)C=C1)C.S(=O)(=O)(O)O.S(=O)(=O)(O)O.NC1=C(C=C(N(CC)CCO)C=C1)C.O Chemical compound O.S(=O)(=O)(O)O.NC1=C(C=C(N(CC)CCO)C=C1)C.S(=O)(=O)(O)O.S(=O)(=O)(O)O.NC1=C(C=C(N(CC)CCO)C=C1)C.O KZYPRKQUJIYCPE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 150000004982 aromatic amines Chemical class 0.000 description 1
- VTYVIFFJJXAHTG-UHFFFAOYSA-M azanium;sodium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [NH4+].[Na+].[O-]S([O-])(=O)=S VTYVIFFJJXAHTG-UHFFFAOYSA-M 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical class OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
（産業上の利用分野）
本発明は写真処理法に関している。詳しくは改
良された漂白定着法に関している。とくに漂白定
着力を強力にする漂白促進剤を用いることを特徴
とした改良された上記の方法又は組成物に関して
いる。
（従来の技術）
一般に、ハロゲン化銀カラー写真感光材料の処
理の基本工程は、発色現像工程と脱銀工程であ
る。すなわち、露光されたハロゲン化銀カラー写
真材料を、発色現像工程に入れる。ここでは発色
現像主薬によりハロゲン化銀が還元されて銀を生
ずるとともに、酸化された発色現像主薬は発色剤
と反応して色素の画像を与える。しかるのちに、
カラー写真材料を脱銀工程に入れる。ここでは、
酸化剤（漂白剤と通称する）の作用により前の工
程で生じた銀が酸化されたのち、定着剤と通称さ
れる銀イオンの錯化剤によつて溶解され、除かれ
る。したがつて、これらの工程を経た写真材料に
は色素画像のみが出来上がる、実際の現像処理
は、上記の発色現像および脱銀と云う二つの基本
工程のほかに、画像の写真的、物理的品質を保つ
ため、あるいは画像の保存性を良くするため等の
補助的な工程を含んでいる。たとえば、処理中の
感光層の過度の軟化を防ぐための硬膜剤、現像反
応を効果的に停止させる停止浴、画像を安定化さ
れる画像安定浴あるいは支持体のバツキング層を
除くための脱膜浴などが挙げられる。
また、上記した脱銀工程も、漂白剤と定着剤を
共存させた漂白定着浴により一工程で行なう場合
と、それぞれ別浴とし、漂白浴と定着浴の二工程
で行なう場合とがある。
一般に、漂白液には酸化剤として赤血塩が使用
されている。しかし、赤血塩を使用した漂白液の
欠点は、疲労した漂白液を交換しなければならな
いこと、処理中のオーバーフロー及び漂白後水洗
水への持ち込みなどで排出されるフエリシアンイ
オン及びその還元形のフエロシアンイオンが光化
学酸化を受けてシアン化合物を生成することであ
る。これらのシアン化合物は毒性が強く、大きな
害を与える。
他方、従来から赤血塩以外の漂白剤としては重
クロム酸カリウム、第２鉄イオン錯塩、過硫酸
塩、キノン、銅塩などが使用されているが、酸化
力が弱いこと及び取り扱いにくいという欠点を有
している。
近年カラー写真感光材料において、処理の迅速
簡略化と環境汚染防止が要請されている観点から
第２鉄イオン錯塩（例えば、アミノポリカルボン
酸第二鉄イオン錯塩等とくにEDTA−鉄（）錯
塩）を主体とした漂白処理方法が主に利用されて
いる。
第２鉄イオン錯塩はカラー印画紙の漂白定着液
の漂白剤として使用されることがある（ドイツ特
許第866605号、同第966410号、英国特許第746567
号、同第933088号、同第1014396号等の明細書）。
しかしながら、第２鉄イオン錯塩を含む漂白定着
剤は酸化力が弱いために、高濃度のハロゲン化銀
を有し、沃臭化銀を用いている撮影用カラー感光
材料にはほとんど使用されていない。
それ故、第２鉄イオン錯塩を使用した漂白定着
液の漂白力（又は酸化力）を増加させることが望
まれる。
（発明の目的）
本発明の目的は第一に写真特性に悪影響を及ぼ
さない新規な漂白促進剤、およびこれを用いた漂
白定着処理を施すカラー写真処理方法を得ること
にある。第二にこのような漂白促進剤を用いた迅
速カラー写真処理法を得ることにある。第三に撮
影感度を有するカラー写真材料を迅速に漂白定着
する方法を得ることにある。
（発明の構成）
本発明者らは種々検討した結果、露光済みハロ
ゲン化銀カラー写真感光材料に少くとも発色現像
処理と脱銀処理を施すカラー写真処理法におい
て、第２鉄イオン錯塩含有の漂白定着浴又はその
前浴中に、下記一般式の化合物を含有させること
を特徴とするカラー写真処理法によつて、上記目
的を達成できた。
ｎは１または２である。R1とR2は水素原子、
炭素数１〜２の低級アルキル基又は炭素数１〜３
のアシル基を表わす（但し、R1とR2の両方とも
が水素原子であることはない。）。好ましい化合物
は、R1、R2のいずれかが−COCH3か−COC2H5
で他の一方は水素原子である化合物またはR1、
R2ともCH3又はC2H5である化合物である。
本発明で使用する前記一般式の化合物の具体例
として次のようなものを挙げることができるが、
本発明はこれらの例示化合物に限定されない。
本発明の化合物は、第２鉄イオン錯塩を含む漂
白定着液において、優れた漂白促進剤である。
本発明の化合物は公知の合成法により容易に合
成されうるが、以下に代表的合成例を示す。
化合物(1)の合成法
チオ尿素76grをエタノール250mlに溶かし、こ
れにＮ−（２−クロロエチル）−ジメチルアミン塩
酸塩143ｇのエタノール溶液500mlを加え、６時間
加熱還流する。反応後冷却し、酢酸エチル1000ml
とリグロイン250mlの混合液を加えた後、結晶を
取し、無水エタノールより再結晶して、チウロ
ニウム塩を得る。
収量 88gr（48％） mp174〜５℃。
次に得られたチウロニウム塩33grを冷水300ml
に溶かし、これに水酸化ナトリウム6grを含む水
溶液100mlを加えて加水分解する。反応液を塩析
してエーテル500mlにて抽出し、乾燥後、減圧蒸
留して目的物を得る。
bp3 108℃ 収量5.6gr（15％）。
化合物(4)の合成法
２−アミノエタンチオール77grを酢酸300mlに
溶かし、これに無水酢酸200mlを撹拌下徐々に滴
下する。滴下終了後湯浴上にて1.5時間加熱し、
冷却する。酢酸、無水酢酸を留去した後減圧蒸留
にてアセチル体を得る。
bp2.5 114〜118℃ 収量74.4gr（60％）。
アセチル体12grをエタノール20mlに溶かし、冷
却しながら33％過酸化水素水10.3grを滴下する。
減圧濃縮後反応物はアメ状となり、放置すると結
晶化する。
mp87℃ 収量8gr（33％）。
他の化合物もこれらの合成法に準じて合成でき
る。
本発明で用いる漂白促進剤は漂白定着浴又は前
浴（発色現像後で、且つ漂白定着処理前の浴）中
に化合物の種類や目的に応じて任意の濃度で添加
できるが、溶液１当り約２×10-6〜約２×10-1
モルを目安に使用することがよく、好ましくは１
×10-4〜５×10-2モルの範囲で使用する。
本発明の漂白剤として用いる第２鉄イオンの錯
塩は配位子として有機化合物、中でもアミノポリ
カルボン酸、アミノポリホスホン酸やこれらの塩
などの有機キレート化剤を用いるものが好まし
く、特に配位子としてアミノポリカルボン酸また
はその塩を用いるものが安価であることや比較的
公害を生じさせる危険が少ないなどの点で好まし
い。
これらの漂白定着液は以下の如き、赤血塩漂白
液の欠点がない点ですぐれている。すなわち、赤
血塩を使用した漂白液は第１に疲労した漂白液を
交換しなければならないこと、第２に処理中のオ
ーバーフローや漂白後の水洗水への持ち込みなど
で排出されるフエリシアン錯イオン及び、フエロ
シアン錯イオンが光化学酸化を受けて毒性の強い
シアン化合物を生成し、大きな害を与えることな
どの欠点がある。
これらのアミノポリカルボン酸及びアミノポリ
ホスホン酸あるいはそれらの塩などの例は以下に
挙げることができる。すなわちエチレンジアミン
テトラ酢酸類（エチレンジアミンテトラ酢酸やそ
のジナトリウム塩、ジアンモニウム塩、テトラ
（トリメチルアンモニウム）塩、テトラカリウム
塩、テトラナトリウム塩、トリナトリウム塩な
ど）、ジエチレントリアミンペンタ酢酸類、（ジエ
チレントリアミンペンタ酢酸やそのペンタナトリ
ウム塩など）、エチレンジアミン−Ｎ−（β−オキ
シエチル）−Ｎ・N′・N′−トリ酢酸類（この酸や
そのトリナトリウム塩、トリアンモニウム塩な
ど）、プロピレンジアミンテトラ酢酸類（この酸
やそのジナトリウム塩など）、ニトリロトリ酢酸
類（この酸やそのトリナトリウム塩など）、シク
ロヘキサンジアミンテトラ酢酸類（この酸やその
ジナトリウム塩など）、やその他イミノジ酢酸
類、ジヒドロキシエチルグリシン類、エチルエー
テルジアミンテトラ酢酸類、グリコールエーテル
ジアミンテトラ酢酸類、エチレンジアミンテトラ
プロピオン酸類、フエニレンジアミンテトラ酢酸
類、１・３−ジアミノプロパノール−Ｎ・Ｎ・
N′・N′−テトラメチレンホスホン酸類、エチレ
ンジアミンＮ・Ｎ・N′・N′−テトラメチレンス
ルホン酸類、１・３−プロピレンジアミン−Ｎ・
Ｎ・N′・N′−テトラメチレンホスホン酸類な
ど。
アミノポリカルボン酸やアミノポリホスホン酸
と塩を形成する塩基としては例えば苛性アルカリ
（アルカリ金属の水酸化物）、アンモニア、アミン
類などである。アルカリ金属としてはナトリウ
ム、カリウム、リチウムなどであり、アミン類と
してはメチルアミン、ジエチルアミン、トリエチ
ルアミン、ブチルアミンの如きアルキルアミン、
シクロヘキシルアミンの如き指環式アミン、アニ
リン、ｍ−トルイジンの如きアリールアミン、及
びピリジン、モルホリン、ピペリジンの如き複素
環アミンである。
第２鉄イオン錯塩は錯体の形で漂白定着浴に添
加しても良い。また第２鉄塩（例えば硫酸第２
鉄、塩化第２鉄、硝酸第２鉄、硫酸第２鉄アンモ
ニウム、リン酸第２鉄など）とアミノポリカルボ
ン酸又はアミノポリホスホン酸などのキレート化
剤とを用いて漂白定着浴中に添加して溶液中で第
２鉄イオン錯塩を形成させてもよい。錯体の形で
添加する場合は、１種類の錯塩を用いてもよい
し、又２種類以上の錯塩を用いてもよい。一方、
第２鉄塩とキレート化剤を用いて溶液中で錯体を
形成する場合は第２鉄塩を１種類又は２種類以上
使用してもよい。更にキレート化剤を１種類又は
２種類以上使用してもよい。また、いずれの場合
にも、キレート化剤を第２鉄イオンの錯体を形成
する以上に過剰に用いてもよい。
本発明の漂白定着液に用いられる定着剤は、通
常の定着剤（例えば、チオ硫酸ナトリウム、チオ
硫酸アンモニウム、チオ硫酸アンモニウムナトリ
ウム、チオ硫酸カリウムの如きチオ硫酸塩；チオ
シアン酸ナトリウム、チオシアン酸アンモニウ
ム、チオシアン酸カリウムの如きチオシアン酸
塩；エチレンビスチオグリコール酸、３・６−ジ
チア−１・８−オクタンジオールの如きチオエー
テル化合物などの水溶性のハロゲン化銀溶解剤）
を、１種あるいは２種以上混合して併用すること
ができる。
漂白定着浴における各成分の量は、漂白定着液
１当り、第２鉄イオン錯塩は約0.1〜２モル、
定着剤は約0.2〜４モル、である。
漂白定着浴には、前述した添加剤の他亜硫酸塩
（例えば亜硫酸ナトリウム、亜硫酸カリウム、亜
硫酸アンモニウム）などを含有させることができ
る。更に、既に公知の漂白定着促進性を有する化
合物（例えば特公昭45−8836号公報記載のポリア
ミン化合物、特公昭45−8506号公報記載のチオ尿
素誘導体、ドイツ特許第1127715号明細書記載の
沃化物、ドイツ特許第966410号明細書記載のポリ
エチレンオキサイド類、ドイツ特許第1290812号
明細書記載の含窒素ヘテロ環化合物、その他チオ
尿素類）などを１種類以上有することもできる。
また、漂白定着液のPHは、使用に際して、通常約
4.0〜8.0、特に好ましくは5.0〜7.0になればよ
い。
本発明に用いる漂白定着浴には、第２鉄イオン
の錯塩及び前記の新規漂白促進剤の他に、ハロゲ
ン化物〔たとえば、アンモニウムやアルカリ金属
（たとえば、ナトリウムやカリウム）の臭化物、
塩化物、沃化物である。〕を含んでもよい。
本発明の漂白定着液には、更に、硼酸、硼砂、
メタ硼酸ナトリウム、酢酸、酢酸ナトリウム、炭
酸ナトリウム、炭酸カリウム、亜燐酸、燐酸、燐
酸ナトリウム、クエン酸、クエン酸ナトリウム、
酒石酸などのPH緩衝能を有する１種以上の無機
酸、有機酸及びこれらの塩を添加することができ
る。
上記の漂白定着浴に用いる薬剤は、本発明の漂
白促進剤を併用すると、優れた漂白定着剤の組成
物を調製することができる。
上記の漂白定着液又はこれらの組成物は、漂白
定着工程に使用する液、又は使用中の漂白定着液
の補充液として使用することができる。
本発明はカラーペーパー、カルーネガフイル
ム、カラー反転フイルム、カラーポジフイルムな
どのハロゲン化銀を用いた全てのカラー感光材料
のいずれの処理にも適用できて、脱銀促進効果を
上げることができる。本発明は、カラーネガフイ
ルムやカラー反転感材に対してより効果をあげる
ことができ、特にカラー反転感材に対して顕著な
効果をあげることができる。
本発明の漂白促進剤を、漂白定着液又は前浴
（例えば第２停止浴）の中に添加して用いると短
時間に銀を充分に漂白定着することができる。
本発明に用いるハロゲン化銀カラー写真感光材
料中の沃臭化銀中の沃素含有量は、特に制限はな
いが約１〜８モル％程度が好ましく、特に３〜７
モル％が好ましい。
カラー反転感材の処理工程は、通常例えば黒白
現像（浴）→停止（浴）→水洗→かぶらせ（浴）
→水洗→発色現像（浴）→停止（浴）→（硬膜
（浴））→水洗→漂白定着（浴）→水洗→安定
（浴）→乾燥の順である。またこれらの工程中に
前浴、前硬膜浴、中和浴などを設けることができ
る。一方、上記工程より安定浴や、漂白定着前後
の水洗等は省略することができる。
かぶらせ浴はｔ−ブチルアミンボラン、ナトリ
ウムボロハイドライド、又はSn（）錯体を含
む処理浴にして、発色現像前にかぶらせてから発
色現像することもできる。又かぶらせ剤（例えば
ｔ−ブチルアミンボラン、ナトリウムボロハイド
ライドなど）を発色現像液に添加することによ
り、かぶらせ浴を省略することができる。また、
かぶらせ浴は再露光に換えることができる。
各処理工程の処理温度は約20℃〜70℃程度で行
うことができ、好ましくは30℃〜60℃である。
処理するカラー感材が、反転カラー感光材料で
ある場合には、カプラーを写真乳剤中に含む「内
型」感材でもよいし、またカプラーを発色現像液
中に含む「外型」感材でもよい（要するに特に本
発明は実用しうる任意の設計の反転カラー感材に
適用できる）
発色現像液、黒色現像液（カラー反転処理用）
停止液、などは通常用いられているものを適用す
ることができる。
例えば、カラー反転処理用発色現像液として
は、実施例に挙げたものが代表的であるが、その
他、この現像液に更に例えばエチレンジアミンも
添加することができる。
カラーネガ感材の処理工程は、通常例えば発色
現像（浴）→漂白定着（浴）→水洗→乾燥の順で
ある。また、これらの工程中、発色現像と漂白定
着との間に停止（浴）、硬膜（浴）、水洗などを設
けてもよく、漂白定着と水洗との間に安定（浴）
などを設けてもよい。
各処理工程の処理温度は約20〜70℃程度で行う
ことができる。
発色現像液、停止液、硬膜液、安定液などは通
常用いられているものを適用することができる。
その他、本発明のカラー処理法で処理されるカ
ラー感材に用いることのできる写真ハロゲン化銀
乳剤やその他の親水性コロイド液およびその調製
法ならびに写真用添加剤（または写真用要素材）
などについては、「リサーチ（Research） デイ
スクロージヤー（Disclosure）」誌No.92（1971年
12月）107〜110頁に記載のものを適宜用いること
ができる。
実施例 １
カラー反転写真感光材料は、トリアセテートフ
イルムベース上に、以下の順序に各層を塗布して
作つた。
第１層（赤感性乳剤層）
塗布液：赤感性ヨウ臭化銀乳剤（ヨウ化銀：７モ
ル％）とシアンカプラー乳化物（シアンカプラ
ーとして１−ビドロキシ−４−クロロ−２−ｎ
−ドデシルナフトアミド、カプラー溶剤として
ジブチルフタレート）とを銀／カプラーのモル
比が8.0になるように混合する。
塗布銀量；1.5ｇ Aｇ/m2とする。
第２層（中間層）
ジ−ｔ−アミル・ハイドロキノンを分散、含有
させたゼラチン中間層。
第３層（緑感性乳剤層）
塗布液：緑感性ヨウ臭化銀乳剤（ヨウ化銀：６モ
ル％）とマゼンタカプラー乳化物（マゼンタカ
プラーとして１−（２・４・６−トリクロロフ
エニル）−３−〔３−（２・４−ジ−ｔ−アミル
フエノキシアセタミド）ベンズアミド〕−５−
ピラゾロン、カプラー溶媒としてトリクレシル
フオスフエート）とを銀／カプラーのモル比が
9.5になるように混合する。
塗布銀量；1.5ｇAｇ/m2とする。
第４層（黄色フイルター層）
黄色コロイド銀とゼラチンとからなるフイルタ
ー層。
第５層（青感性乳剤層）
塗布液：青感性ヨウ臭化銀乳剤（ヨウ化銀：６モ
ル％）イエローカプラー乳化物（イエローカプ
ラーとしてα−ピバロイル−２−クロロ−５−
〔γ−（２・４−ジ−ｔ−アミルフエノキシ）ブ
タンアミド〕アセトアニリド、カプラー溶媒と
してジブチルフタレート）とを銀／カプラーの
モル比が8.01になるように混合する。
塗布銀量；0.98ｇAｇ/m2とする。
第６層（保護層）
ゼラチンを主体とする保護層。
このカラー反転フイルムに露光（タングステン
灯を光源として光楔を通つて1/100秒露光）を行
なつたのち、以下の反転処理を行なつた。
処理工程 温度 時間
第一現像（黒白） 37℃ ３分
停 止 37℃ ２分
水 洗 37℃ ２分
発色現像 37℃ ６分
（カブラシ剤を含む）
停 止 37℃ ２分
水 洗 37℃ ２分
漂白定着 37℃ ４分又は６分
水 洗 37℃ ２分
安 定 ― 30秒
乾 燥 37℃
第一現像液の組成
亜硫酸ナトリウム 60.0ｇ
１−フエニル−３−ピラゾリドン 0.3ｇ
ハイドロキノン 5.0ｇ
炭酸ナトリウム（一水塩） 41.0ｇ
臭化カリウム 2.0ｇ
ヨウ化カリウム（１％水溶液） 1.0ml
ロダンカリウム（1N水溶液） 10.0ml
水酸化ナトリウム（10％水溶液） 2.0ml
水を加えて 1.0
停止液の組成
酢酸ナトリウム 30ｇ
氷酢酸 ８ml
水を加えて 全量 １
発色現像液の組成
ベンジルアルコール 5.0ml
水酸化ナトリウム 0.5ｇ
ジエチレングリコール 3.0ml
ヘキサメタリン酸ナトリウム 2.0ｇ
亜硫酸ナトリウム 2.0ｇ
臭化カリウム 2.0ｇ
４−アミノ−３−メチル−Ｎ−エチ
ル−Ｎ−（β−ヒドロキシエチル）
アニリンセスキサルフエートモノ
ハイドレート 10.0ｇ
シトラジン酸 0.4ｇ
メタ硼酸 0.5ｇ
メタホー酸ナトリウム四水塩 77.0ｇ
ナトリウムボロハイドライド 0.1ｇ
水を加えて 全量 1.0
漂白定着液の組成
鉄（）−EDTA・2Na 120 ｇ
EDTA−2Na ５ ｇ
NH4Br 110 ｇ
（NH4）2S2O3（70重量％水溶液） 100 c.c.
Na2SO3 4.5ｇ
NH4OH 15 c.c.
水を加えて １
安定液の組成
ホルマリン（37％） 10c.c.
富士ドライウエル ５c.c.
水を加えて 全量 １
前述した漂白定着液、及びそれに前記の本発明
の化合物（前記の化合物番号のもの）を各1.5ｇ/
添加した液で、それぞれ漂白定着を４分または
６分行つた。処理後フイルム中に残留する銀量
（最高濃度部と最低濃度部の２ケ所）は螢光Ｘ線
分析により求め、その結果を表に示した。
(Industrial Field of Application) The present invention relates to photographic processing methods. The details relate to an improved bleach-fixing method. In particular, it relates to the above-mentioned improved method or composition characterized in that it uses a bleach accelerator that enhances the bleach-fixing power. (Prior Art) Generally, the basic steps in processing silver halide color photographic materials are a color development step and a desilvering step. That is, the exposed silver halide color photographic material is subjected to a color development process. Here, silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former to provide a dye image. However, later on,
Color photographic materials are subjected to a desilvering process. here,
After the silver produced in the previous step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), it is dissolved and removed by a silver ion complexing agent, commonly called a fixing agent. Therefore, only a dye image is produced in the photographic material that has gone through these steps.In addition to the two basic steps of color development and desilvering mentioned above, the actual development process also takes into account the photographic and physical quality of the image. It includes auxiliary steps to maintain the quality of images or to improve the storage stability of images. For example, hardeners to prevent excessive softening of the photosensitive layer during processing, stop baths to effectively stop the development reaction, image stabilizing baths to stabilize images, or de-layering agents to remove backing layers from supports. Examples include membrane baths. Further, the above-mentioned desilvering step may be carried out in one step using a bleach-fixing bath in which a bleaching agent and a fixing agent coexist, or may be carried out in two steps, a bleaching bath and a fixing bath, using separate baths. Generally, red blood salt is used as an oxidizing agent in bleaching solutions. However, the disadvantages of bleaching solutions using red blood salts are that the bleaching solution must be replaced when it is exhausted, and that felician ions and their reduced forms are emitted due to overflow during processing and carried into the washing water after bleaching. ferrocyanide ions undergo photochemical oxidation to produce cyanide compounds. These cyanide compounds are highly toxic and cause great harm. On the other hand, potassium dichromate, ferric ion complex salts, persulfates, quinones, copper salts, etc. have traditionally been used as bleaching agents other than red blood salt, but these have the drawbacks of weak oxidizing power and difficulty in handling. have. In recent years, ferric ion complex salts (e.g., aminopolycarboxylic acid ferric ion complex salts, etc., especially EDTA-iron() complex salts) have been used in color photographic materials, from the viewpoint of rapid and simple processing and prevention of environmental pollution. Bleaching treatment methods are mainly used. Ferric ion complex salts are sometimes used as bleaching agents in bleach-fix solutions for color photographic paper (German Patent No. 866605, German Patent No. 966410, British Patent No. 746567).
No. 933088, No. 1014396, etc.).
However, bleach-fixers containing ferric ion complex salts have weak oxidizing power and therefore contain a high concentration of silver halide, so they are rarely used in color photographic materials that use silver iodobromide. . Therefore, it is desirable to increase the bleaching power (or oxidizing power) of bleach-fix solutions using ferric ion complex salts. (Objectives of the Invention) The first object of the present invention is to obtain a novel bleaching accelerator that does not adversely affect photographic properties, and a color photographic processing method for carrying out a bleach-fixing process using the same. The second object is to obtain a rapid color photographic processing method using such a bleach accelerator. The third object is to obtain a method for rapidly bleaching and fixing color photographic materials having photographic sensitivity. (Structure of the Invention) As a result of various studies, the present inventors found that in a color photographic processing method in which an exposed silver halide color photographic light-sensitive material is subjected to at least a color development treatment and a desilvering treatment, bleaching containing a ferric ion complex salt is necessary. The above object was achieved by a color photographic processing method characterized by containing a compound of the following general formula in the fixing bath or its pre-bath. n is 1 or 2. R 1 and R 2 are hydrogen atoms,
Lower alkyl group having 1 to 2 carbon atoms or 1 to 3 carbon atoms
(However, R 1 and R 2 are not both hydrogen atoms.) A preferred compound is one in which either R 1 or R 2 is -COCH 3 or -COC 2 H 5
and the other one is a hydrogen atom or R 1 ,
R 2 is also a compound that is CH 3 or C 2 H 5 . Specific examples of the compound of the above general formula used in the present invention include the following:
The present invention is not limited to these exemplified compounds. The compounds of the present invention are excellent bleach accelerators in bleach-fix solutions containing ferric ion complex salts. The compounds of the present invention can be easily synthesized by known synthesis methods, and typical synthesis examples are shown below. Synthesis method of compound (1) 76g of thiourea is dissolved in 250ml of ethanol, 500ml of an ethanol solution of 143g of N-(2-chloroethyl)-dimethylamine hydrochloride is added thereto, and the mixture is heated under reflux for 6 hours. After the reaction, cool and add 1000ml of ethyl acetate.
After adding a mixture of ligroin and ligroin (250 ml), the crystals are collected and recrystallized from absolute ethanol to obtain thiuronium salt. Yield 88gr (48%) mp174~5℃. Next, add 33g of the obtained thiuronium salt to 300ml of cold water.
Dissolve it in water and add 100ml of an aqueous solution containing 6gr of sodium hydroxide to hydrolyze it. The reaction solution is salted out, extracted with 500 ml of ether, dried, and distilled under reduced pressure to obtain the desired product. bp3 108℃ Yield 5.6gr (15%). Synthesis method of compound (4) 77 gr of 2-aminoethanethiol is dissolved in 300 ml of acetic acid, and 200 ml of acetic anhydride is gradually added dropwise thereto under stirring. After dropping, heat on a hot water bath for 1.5 hours,
Cooling. After acetic acid and acetic anhydride are distilled off, an acetyl compound is obtained by distillation under reduced pressure. bp2.5 114-118℃ Yield 74.4gr (60%). Dissolve 12g of acetyl body in 20ml of ethanol, and add 10.3g of 33% hydrogen peroxide solution dropwise while cooling.
After concentration under reduced pressure, the reaction product becomes candy-like and crystallizes when left standing. mp87℃ Yield 8gr (33%). Other compounds can also be synthesized according to these synthesis methods. The bleach accelerator used in the present invention can be added to the bleach-fix bath or pre-bath (bath after color development and before bleach-fix treatment) at any concentration depending on the type of compound and purpose, but approximately 2×10 -6 ~ approx. 2×10 -1
Moles are often used as a guide, preferably 1
It is used in the range of ×10 −4 to 5×10 −2 mol. The complex salt of ferric ion used as the bleaching agent of the present invention preferably uses an organic compound as a ligand, especially an organic chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or a salt thereof, and is particularly suitable for coordination. It is preferable to use aminopolycarboxylic acid or a salt thereof as a carrier because it is inexpensive and has relatively little risk of causing pollution. These bleach-fix solutions are superior in that they do not have the following drawbacks of red blood salt bleach solutions. In other words, bleaching solutions that use red blood salt are: firstly, the bleaching solution must be replaced when it is worn out, and secondly, ferrician complex ions are discharged due to overflow during processing or carried into the washing water after bleaching. Another disadvantage is that the ferrocyanide complex ions undergo photochemical oxidation to produce highly toxic cyanide compounds, which can cause great harm. Examples of these aminopolycarboxylic acids and aminopolyphosphonic acids or salts thereof are listed below. Namely, ethylenediaminetetraacetic acids (ethylenediaminetetraacetic acid and its disodium salt, diammonium salt, tetra(trimethylammonium) salt, tetrapotassium salt, tetrasodium salt, trisodium salt, etc.), diethylenetriaminepentaacetic acid, (diethylenetriaminepentaacetic acid, pentasodium salt, etc.), ethylenediamine-N-(β-oxyethyl)-N・N′・N′-triacetic acid (this acid, its trisodium salt, triammonium salt, etc.), propylenediaminetetraacetic acid (this acid, its trisodium salt, triammonium salt, etc.), acid and its disodium salt, etc.), nitrilotriacetic acids (this acid and its trisodium salt, etc.), cyclohexanediaminetetraacetic acids (this acid and its disodium salt, etc.), other iminodiacetic acids, dihydroxyethylglycine, Ethyl ether diamine tetraacetic acids, glycol ether diamine tetraacetic acids, ethylenediaminetetrapropionic acids, phenylenediaminetetraacetic acids, 1,3-diaminopropanol-N・N・
N', N'-tetramethylenephosphonic acids, ethylenediamine N, N, N', N'-tetramethylene sulfonic acids, 1,3-propylenediamine-N,
N・N′・N′-tetramethylenephosphonic acids, etc. Examples of bases that form salts with aminopolycarboxylic acids and aminopolyphosphonic acids include caustic alkali (alkali metal hydroxide), ammonia, and amines. Alkali metals include sodium, potassium, lithium, etc.; amines include alkylamines such as methylamine, diethylamine, triethylamine, and butylamine;
Ring amines such as cyclohexylamine, arylamines such as aniline, m-toluidine, and heterocyclic amines such as pyridine, morpholine, piperidine. The ferric ion complex salt may be added to the bleach-fixing bath in the form of a complex. Also, ferric salts (e.g. ferric sulfate)
iron, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc.) and a chelating agent such as aminopolycarboxylic acid or aminopolyphosphonic acid into the bleach-fix bath. A ferric ion complex salt may be formed in solution. When added in the form of a complex, one type of complex salt or two or more types of complex salts may be used. on the other hand,
When forming a complex in a solution using a ferric salt and a chelating agent, one or more types of ferric salts may be used. Furthermore, one type or two or more types of chelating agents may be used. Further, in either case, the chelating agent may be used in excess of the amount required to form a complex of ferric ions. The fixing agent used in the bleach-fixing solution of the present invention is a conventional fixing agent (for example, thiosulfate such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate; sodium thiocyanate, ammonium thiocyanate, thiocyanic acid). thiocyanates such as potassium; water-soluble silver halide solubilizers such as thioether compounds such as ethylene bisthioglycolic acid and 3,6-dithia-1,8-octanediol)
These can be used alone or in combination of two or more. The amounts of each component in the bleach-fix bath are approximately 0.1 to 2 moles of ferric ion complex salt per bleach-fix solution;
The fixing agent is about 0.2 to 4 moles. The bleach-fix bath may contain the above-mentioned additives as well as sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite), and the like. Furthermore, compounds already known to have bleach-fix accelerating properties (for example, polyamine compounds described in Japanese Patent Publication No. 45-8836, thiourea derivatives described in Japanese Patent Publication No. 45-8506, iodides described in German Patent No. 1127715) , polyethylene oxides described in German Patent No. 966410, nitrogen-containing heterocyclic compounds described in German Patent No. 1290812, and other thioureas).
In addition, the pH of the bleach-fix solution is usually approximately
It should be 4.0 to 8.0, particularly preferably 5.0 to 7.0. In addition to the ferric ion complex salt and the novel bleach accelerator, the bleach-fix bath used in the present invention contains halides [for example, ammonium and bromides of alkali metals (such as sodium and potassium),
They are chlorides and iodides. ] may also be included. The bleach-fix solution of the present invention further includes boric acid, borax,
Sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate,
One or more inorganic acids, organic acids, and salts thereof having PH buffering capacity, such as tartaric acid, can be added. When the above chemicals used in the bleach-fix bath are used in combination with the bleach accelerator of the present invention, an excellent bleach-fix composition can be prepared. The above bleach-fix solution or composition thereof can be used as a solution used in the bleach-fix step or as a replenisher for the bleach-fix solution in use. The present invention can be applied to the processing of all color light-sensitive materials using silver halide, such as color paper, color negative film, color reversal film, color positive film, etc., and can enhance the effect of promoting desilvering. The present invention is more effective for color negative films and color reversal photosensitive materials, and is particularly effective for color reversal photosensitive materials. When the bleach accelerator of the present invention is added to a bleach-fix solution or a pre-bath (for example, a second stop bath), silver can be sufficiently bleach-fixed in a short period of time. The iodine content in silver iodobromide in the silver halide color photographic light-sensitive material used in the present invention is not particularly limited, but is preferably about 1 to 8 mol%, particularly 3 to 7 mol%.
Mol% is preferred. The processing steps for color reversal sensitive materials are usually, for example, black and white development (bath) → stop (bath) → washing with water → fogging (bath).
The order is → washing with water → color development (bath) → stopping (bath) → (hardening film (bath)) → washing with water → bleach-fixing (bath) → washing with water → stabilization (bath) → drying. Further, a pre-bath, a pre-hardening bath, a neutralization bath, etc. can be provided during these steps. On the other hand, a stabilizing bath, washing with water before and after bleaching and fixing, etc. can be omitted from the above steps. The fogging bath may be a treatment bath containing t-butylamine borane, sodium borohydride, or Sn() complex, and the color development may be carried out after being fogged before color development. Also, by adding a fogging agent (eg, t-butylamine borane, sodium borohydride, etc.) to the color developer, the fogging bath can be omitted. Also,
Fog bath can be replaced with re-exposure. The treatment temperature in each treatment step can be about 20°C to 70°C, preferably 30°C to 60°C. When the color photosensitive material to be processed is a reversal color photosensitive material, it may be an "inner type" photosensitive material containing a coupler in a photographic emulsion, or an "outer type" photosensitive material containing a coupler in a color developing solution. Good (in short, the present invention is particularly applicable to reversal color sensitive materials of any practical design) Color developer, black developer (for color reversal processing)
A commonly used stop solution can be used. For example, as a color developer for color reversal processing, those mentioned in the examples are typical, but in addition to this, for example, ethylenediamine may also be added to this developer. The processing steps for color negative photosensitive materials are usually in the order of, for example, color development (bath) → bleach-fixing (bath) → washing → drying. In addition, during these steps, a stop (bath), hardening (bath), water washing, etc. may be provided between color development and bleach-fixing, and a stabilizing film (bath) may be provided between bleach-fixing and water washing.
etc. may be provided. The treatment temperature in each treatment step can be about 20 to 70°C. As the color developing solution, stop solution, hardening solution, stabilizer, etc., commonly used ones can be used. In addition, photographic silver halide emulsions and other hydrophilic colloid liquids that can be used in color sensitive materials processed by the color processing method of the present invention, their preparation methods, and photographic additives (or photographic element materials)
For more information, please refer to "Research Disclosure" magazine No. 92 (1971).
Those described on pages 107 to 110 (December) can be used as appropriate. Example 1 A color reversal photographic material was prepared by coating each layer on a triacetate film base in the following order. 1st layer (red-sensitive emulsion layer) Coating solution: red-sensitive silver iodobromide emulsion (silver iodide: 7 mol %) and cyan coupler emulsion (1-hydroxy-4-chloro-2-n as cyan coupler)
-dodecylnaphthamide, dibutyl phthalate as the coupler solvent) are mixed at a silver/coupler molar ratio of 8.0. Coated silver amount: 1.5g Ag/m 2 . 2nd layer (intermediate layer) A gelatin intermediate layer containing di-t-amyl hydroquinone dispersed therein. 3rd layer (green-sensitive emulsion layer) Coating solution: green-sensitive silver iodobromide emulsion (silver iodide: 6 mol%) and magenta coupler emulsion (1-(2,4,6-trichlorophenyl) as magenta coupler) -3-[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-
pyrazolone, tricresyl phosphate as the coupler solvent) and the silver/coupler molar ratio
Mix to make 9.5. Coated silver amount: 1.5gAg/ m2 . 4th layer (yellow filter layer) A filter layer consisting of yellow colloidal silver and gelatin. 5th layer (blue-sensitive emulsion layer) Coating solution: Blue-sensitive silver iodobromide emulsion (silver iodide: 6 mol%) Yellow coupler emulsion (as a yellow coupler α-pivaloyl-2-chloro-5-
[γ-(2,4-di-t-amylphenoxy)butanamide] acetanilide and dibutyl phthalate as a coupler solvent are mixed so that the silver/coupler molar ratio is 8.01. Coated silver amount: 0.98gAg/ m2 . 6th layer (protective layer) A protective layer mainly composed of gelatin. After this color reversal film was exposed to light (1/100 second exposure through a light wedge using a tungsten lamp as a light source), the following reversal process was performed. Processing process Temperature Time First development (black and white) 37℃ 3 minutes Stop 37℃ 2 minutes Washing with water 37℃ 2 minutes Color development 37℃ 6 minutes (including brushing agent) Stopping 37℃ 2 minutes Washing with water 37℃ 2 minutes Bleach fixing 4 or 6 minutes at 37°C Washing with water 2 minutes at 37°C Stability - 30 seconds Drying at 37°C Composition of the first developer Sodium sulfite 60.0g 1-phenyl-3-pyrazolidone 0.3g Hydroquinone 5.0g Sodium carbonate Water salt) 41.0g Potassium bromide 2.0g Potassium iodide (1% aqueous solution) 1.0ml Rodan potassium (1N aqueous solution) 10.0ml Sodium hydroxide (10% aqueous solution) 2.0ml Add water 1.0 Composition of stop solution Sodium acetate 30g Glacial acetic acid 8ml Add water Total volume 1 Color developer composition Benzyl alcohol 5.0ml Sodium hydroxide 0.5g Diethylene glycol 3.0ml Sodium hexametaphosphate 2.0g Sodium sulfite 2.0g Potassium bromide 2.0g 4-Amino-3-methyl-N- Ethyl-N-(β-hydroxyethyl) Aniline sesquisulfate monohydrate 10.0g Citrazic acid 0.4g Metaboric acid 0.5g Sodium metaphorate tetrahydrate 77.0g Sodium borohydride 0.1g Add water Total volume 1.0 of bleach-fix solution Composition Iron ()-EDTA・2Na 120 g EDTA-2Na 5 g NH 4 Br 110 g (NH 4 ) 2 S 2 O 3 (70% by weight aqueous solution) 100 cc Na 2 SO 3 4.5 g NH 4 OH 15 cc Water In addition: 1 Composition of stabilizing solution Formalin (37%) 10 c.c. Fuji Drywell 5 c.c. Add water Total volume 1 The above-mentioned bleach-fix solution, and the above-mentioned compound of the present invention (with the above-mentioned compound number) ) each 1.5g/
Bleach-fixing was carried out for 4 minutes or 6 minutes, respectively, using the added solution. The amount of silver remaining in the film after processing (at two locations, the highest density area and the lowest density area) was determined by fluorescent X-ray analysis, and the results are shown in the table.
【表】
本発明の実施態様を以下に記す。
(1) 第２鉄イオンの錯体がアミノポリカルボン酸
第２鉄錯塩である特許請求の範囲記載のカラー
写真処理法。
(2) ハロゲン化銀カラー写真感材が支持体上に少
くとも一層のハロゲン化銀写真乳剤層を有して
おり、且つそのハロゲン化銀乳剤層は沃素含有
量が約１〜８モル％の沃臭化銀乳剤からなる特
許請求の範囲記載のカラー写真処理法。
(3) 漂白促進剤の漂白定着浴又は前浴中に於る含
有量が２×10-6ないし２×10-1モル／である
特許請求の範囲第１項記載のカラー写真処理
法。
(4) 漂白促進剤の漂白定着浴、又は前浴中に於る
含有量が１×10-4ないし５×10-2モル／であ
る特許請求の範囲記載のカラー写真処理法。
(5) 一般式で表わされる化合物が(1)、(2)、(3)、(4)
又は(5)の化合物である特許請求の範囲記載のカ
ラー写真処理法。
(6) 第２鉄イオン錯塩の漂白定着浴中の含有量が
約0.1〜2.0mol/である特許請求の範囲に記載
のカラー写真処理法。[Table] Embodiments of the present invention are described below. (1) A color photographic processing method according to the claims, wherein the ferric ion complex is an aminopolycarboxylic acid ferric complex salt. (2) The silver halide color photographic material has at least one silver halide photographic emulsion layer on the support, and the silver halide emulsion layer has an iodine content of about 1 to 8 mol%. A color photographic processing method according to the claims, comprising a silver iodobromide emulsion. (3) The color photographic processing method according to claim 1, wherein the content of the bleach accelerator in the bleach-fixing bath or pre-bath is 2×10 -6 to 2×10 -1 mol/. (4) The color photographic processing method according to the claims, wherein the content of the bleach accelerator in the bleach-fixing bath or pre-bath is 1×10 -4 to 5×10 -2 mol/. (5) The compound represented by the general formula is (1), (2), (3), (4)
or (5), the color photographic processing method according to the claims. (6) The color photographic processing method according to the claims, wherein the content of the ferric ion complex salt in the bleach-fixing bath is about 0.1 to 2.0 mol/.
Claims (1)
少くとも発色現像処理と脱銀処理を施すカラー写
真処理法において、第２鉄イオン錯塩含有の漂白
定着浴又はその前浴中に、下記一般式の化合物を
含有させることを特徴とするカラー写真処理法。 〔ｎは１または２である。R1とR2は水素原子、炭
素数１〜２の低級アルキル基、又は炭素数１〜３
のアシル基を表わす、但し、R1とR2の両方とも
が水素原子であることはない。〕 ２ 一般式の化合物が、 【式】または である特許請求の範囲第１項記載のカラー写真処
理法。[Scope of Claims] 1. In a color photographic processing method in which an exposed silver halide color photographic light-sensitive material is subjected to at least a color development treatment and a desilvering treatment, in a bleach-fix bath containing a ferric ion complex salt or a prebath thereof, , a color photographic processing method characterized by containing a compound of the following general formula. [n is 1 or 2. R 1 and R 2 are hydrogen atoms, lower alkyl groups having 1 to 2 carbon atoms, or 1 to 3 carbon atoms
represents an acyl group, provided that both R 1 and R 2 are not hydrogen atoms. ] 2 The compound of the general formula is [Formula] or A color photographic processing method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25034483A JPS59151155A (en) | 1983-12-27 | 1983-12-27 | Method for processing color photograph |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25034483A JPS59151155A (en) | 1983-12-27 | 1983-12-27 | Method for processing color photograph |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP998177A Division JPS5395630A (en) | 1977-02-01 | 1977-02-01 | Color photograph processing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59151155A JPS59151155A (en) | 1984-08-29 |
| JPS6122295B2 true JPS6122295B2 (en) | 1986-05-31 |
Family
ID=17206515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25034483A Granted JPS59151155A (en) | 1983-12-27 | 1983-12-27 | Method for processing color photograph |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59151155A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62115158A (en) * | 1985-11-13 | 1987-05-26 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide color photographic sensitive material |
| JPS62168159A (en) * | 1986-01-20 | 1987-07-24 | Konishiroku Photo Ind Co Ltd | Color image forming method |
-
1983
- 1983-12-27 JP JP25034483A patent/JPS59151155A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59151155A (en) | 1984-08-29 |
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