JPS6327705B2 - - Google Patents
Info
- Publication number
- JPS6327705B2 JPS6327705B2 JP8516881A JP8516881A JPS6327705B2 JP S6327705 B2 JPS6327705 B2 JP S6327705B2 JP 8516881 A JP8516881 A JP 8516881A JP 8516881 A JP8516881 A JP 8516881A JP S6327705 B2 JPS6327705 B2 JP S6327705B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- washing
- complex
- fixing
- bath
- 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
- -1 silver halide Chemical class 0.000 claims description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- 229910052709 silver Inorganic materials 0.000 claims description 27
- 239000004332 silver Substances 0.000 claims description 27
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000002736 metal compounds Chemical class 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000004697 chelate complex Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- 238000005406 washing Methods 0.000 description 40
- 239000000243 solution Substances 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 238000004061 bleaching Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 239000012488 sample solution Substances 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 7
- 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 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 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 5
- 229960000583 acetic acid Drugs 0.000 description 5
- XNSQZBOCSSMHSZ-UHFFFAOYSA-K azane;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [NH4+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XNSQZBOCSSMHSZ-UHFFFAOYSA-K 0.000 description 5
- 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 5
- 239000003755 preservative agent Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 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 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 229940005740 hexametaphosphate Drugs 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 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 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940050410 gluconate Drugs 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- JKRNNIGZNCVVHA-UHFFFAOYSA-N 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;trimethylazanium Chemical compound C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JKRNNIGZNCVVHA-UHFFFAOYSA-N 0.000 description 2
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 2
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- AUJUKHGWOKKPAN-UHFFFAOYSA-J [Na+].[Na+].[Na+].[Na+].CC(CN(CC([O-])=O)CC([O-])=O)N(CC([O-])=O)CC([O-])=O Chemical compound [Na+].[Na+].[Na+].[Na+].CC(CN(CC([O-])=O)CC([O-])=O)N(CC([O-])=O)CC([O-])=O AUJUKHGWOKKPAN-UHFFFAOYSA-J 0.000 description 2
- LRSAWRZHGQQHBJ-UHFFFAOYSA-N acetic acid;benzene-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NC1=CC=CC=C1N LRSAWRZHGQQHBJ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- WJWWVWZMUNBTIJ-ZVGUSBNCSA-N (2r,3r)-2,3-dihydroxybutanedioic acid;lead Chemical compound [Pb].OC(=O)[C@H](O)[C@@H](O)C(O)=O WJWWVWZMUNBTIJ-ZVGUSBNCSA-N 0.000 description 1
- MBULCFMSBDQQQT-UHFFFAOYSA-N (3-carboxy-2-hydroxypropyl)-trimethylazanium;2,4-dioxo-1h-pyrimidine-6-carboxylate Chemical compound C[N+](C)(C)CC(O)CC(O)=O.[O-]C(=O)C1=CC(=O)NC(=O)N1 MBULCFMSBDQQQT-UHFFFAOYSA-N 0.000 description 1
- GVEYRUKUJCHJSR-UHFFFAOYSA-N (4-azaniumyl-3-methylphenyl)-ethyl-(2-hydroxyethyl)azanium;sulfate Chemical compound OS(O)(=O)=O.OCCN(CC)C1=CC=C(N)C(C)=C1 GVEYRUKUJCHJSR-UHFFFAOYSA-N 0.000 description 1
- WQXKGOOORHDGFP-UHFFFAOYSA-N 1,2,4,5-tetrafluoro-3,6-dimethoxybenzene Chemical compound COC1=C(F)C(F)=C(OC)C(F)=C1F WQXKGOOORHDGFP-UHFFFAOYSA-N 0.000 description 1
- MAYVZUQEFSJDHA-UHFFFAOYSA-N 1,5-bis(methylsulfanyl)naphthalene Chemical compound C1=CC=C2C(SC)=CC=CC2=C1SC MAYVZUQEFSJDHA-UHFFFAOYSA-N 0.000 description 1
- BOXPXLFVWVZCIU-UHFFFAOYSA-N 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(O)(C(O)=O)P(O)(O)=O BOXPXLFVWVZCIU-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- SWSQUVMRFRJPIB-UHFFFAOYSA-H 2,3-dihydroxybutanedioate;lanthanum(3+) Chemical compound [La+3].[La+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O SWSQUVMRFRJPIB-UHFFFAOYSA-H 0.000 description 1
- DCZIEFPBLCHYII-UHFFFAOYSA-N 2-hydroxy-2-phosphonopropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(O)=O DCZIEFPBLCHYII-UHFFFAOYSA-N 0.000 description 1
- VSEUCCPAJZHJSX-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;indium(3+) Chemical compound [In+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O VSEUCCPAJZHJSX-UHFFFAOYSA-K 0.000 description 1
- NCOYDQIWSSMOEW-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;lanthanum(3+) Chemical compound [La+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NCOYDQIWSSMOEW-UHFFFAOYSA-K 0.000 description 1
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
- ZLPZMGRIYAWMNV-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;samarium(3+) Chemical compound [Sm+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZLPZMGRIYAWMNV-UHFFFAOYSA-K 0.000 description 1
- AEAUQHHTSFLVAV-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;terbium(3+) Chemical compound [Tb+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O AEAUQHHTSFLVAV-UHFFFAOYSA-K 0.000 description 1
- FIJBDRURCNULES-UHFFFAOYSA-N 2-methyl-2-phosphonohexanedioic acid Chemical compound OC(=O)C(P(O)(O)=O)(C)CCCC(O)=O FIJBDRURCNULES-UHFFFAOYSA-N 0.000 description 1
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 description 1
- HMRDIZPIGAPVHB-UHFFFAOYSA-N 4-hydroxy-4,4-diphosphonobutanoic acid Chemical compound OC(=O)CCC(O)(P(O)(O)=O)P(O)(O)=O HMRDIZPIGAPVHB-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PYZGGPQPRHNJMZ-UHFFFAOYSA-N C(C)(=O)CC(C)=O.[Dy] Chemical compound C(C)(=O)CC(C)=O.[Dy] PYZGGPQPRHNJMZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
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- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- FLESAADTDNKLFJ-UHFFFAOYSA-N nickel;pentane-2,4-dione Chemical compound [Ni].CC(=O)CC(C)=O FLESAADTDNKLFJ-UHFFFAOYSA-N 0.000 description 1
- GBIHADTXLFMYDT-UHFFFAOYSA-N nickel;propanedioic acid Chemical compound [Ni].OC(=O)CC(O)=O GBIHADTXLFMYDT-UHFFFAOYSA-N 0.000 description 1
- NUMGUHMPKNCRJA-UHFFFAOYSA-N nitric acid;samarium Chemical compound [Sm].O[N+]([O-])=O NUMGUHMPKNCRJA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JZNKXIAEFQDQDF-UHFFFAOYSA-H oxalate;terbium(3+) Chemical compound [Tb+3].[Tb+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O JZNKXIAEFQDQDF-UHFFFAOYSA-H 0.000 description 1
- FLJKBWKLGAYSFH-UHFFFAOYSA-H oxalate;ytterbium(3+) Chemical compound [Yb+3].[Yb+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O FLJKBWKLGAYSFH-UHFFFAOYSA-H 0.000 description 1
- IBSDADOZMZEYKD-UHFFFAOYSA-H oxalate;yttrium(3+) Chemical compound [Y+3].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O IBSDADOZMZEYKD-UHFFFAOYSA-H 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- XPKABZOAVLLOPG-UHFFFAOYSA-N pentane-2,4-dione ytterbium Chemical compound [Yb].CC(=O)CC(C)=O XPKABZOAVLLOPG-UHFFFAOYSA-N 0.000 description 1
- WATYAKBWIQTPDE-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O WATYAKBWIQTPDE-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- TVOIPJPTFTYKQM-UHFFFAOYSA-N propanedioic acid;zinc Chemical compound [Zn].OC(=O)CC(O)=O TVOIPJPTFTYKQM-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 150000003317 samarium compounds Chemical class 0.000 description 1
- JPDBEEUPLFWHAJ-UHFFFAOYSA-K samarium(3+);triacetate Chemical compound [Sm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JPDBEEUPLFWHAJ-UHFFFAOYSA-K 0.000 description 1
- ICKYUJFKBKOPJT-UHFFFAOYSA-K samarium(3+);tribromide Chemical compound Br[Sm](Br)Br ICKYUJFKBKOPJT-UHFFFAOYSA-K 0.000 description 1
- QCZFMLDHLOYOQJ-UHFFFAOYSA-H samarium(3+);tricarbonate Chemical compound [Sm+3].[Sm+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QCZFMLDHLOYOQJ-UHFFFAOYSA-H 0.000 description 1
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 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
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 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
- 238000010186 staining Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003502 terbium compounds Chemical class 0.000 description 1
- UFPWIQQSPQSOKM-UHFFFAOYSA-H terbium(3+);trisulfate Chemical compound [Tb+3].[Tb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O UFPWIQQSPQSOKM-UHFFFAOYSA-H 0.000 description 1
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- JKNHZOAONLKYQL-UHFFFAOYSA-K tribromoindigane Chemical compound Br[In](Br)Br JKNHZOAONLKYQL-UHFFFAOYSA-K 0.000 description 1
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-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
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 150000003747 ytterbium compounds Chemical class 0.000 description 1
- OSCVBYCJUSOYPN-UHFFFAOYSA-K ytterbium(3+);triacetate Chemical compound [Yb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OSCVBYCJUSOYPN-UHFFFAOYSA-K 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
- KVCOOBXEBNBTGL-UHFFFAOYSA-H ytterbium(3+);trisulfate Chemical compound [Yb+3].[Yb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KVCOOBXEBNBTGL-UHFFFAOYSA-H 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 1
- QNLXXQBCQYDKHD-UHFFFAOYSA-K ytterbium(iii) bromide Chemical compound Br[Yb](Br)Br QNLXXQBCQYDKHD-UHFFFAOYSA-K 0.000 description 1
- 150000003748 yttrium compounds Chemical class 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 1
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 1
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- VRGNUPCISFMPEM-ZVGUSBNCSA-L zinc;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Zn+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VRGNUPCISFMPEM-ZVGUSBNCSA-L 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 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
本発明は、ハロゲン化銀カラー写真感光材料の
処理方法に関し、さらに詳しくは有機酸鉄キレー
ト錯体を含有する定着液の処理安定性が改良され
たハロゲン化銀カラー写真感光材料の処理方法に
関するものである。
一般にハロゲン化銀カラー写真感光材料は、画
像露光の後、発色現像工程と脱銀工程とを基本工
程とする一連の写真処理により色素画像を形成す
る。
上記の発色現像工程では、発色現像主薬の酸化
体が、共存するカラーカプラーとカツプリング反
応することによつて画像模様の色素画像を形成
し、同時に還元銀が生成される。ここに生成され
た銀は、引続く脱銀工程において漂白剤により酸
化され、定着剤の作用を受けて可溶性の銀錯体に
変化し、水洗によつて溶解し除去する。
実際の現像処理工程では、上記の発色現像およ
び脱銀を目的とする基本的な工程のほかに、画像
の写真的または物理的特性の向上に対する必要性
から、停止浴、硬膜浴、安定浴、バツキング除去
処理浴などの補助的な処理浴を設けている。
一方、脱銀工程としての定着浴においては、ハ
ロゲン化銀と反応して水溶性の銀錯体を形成する
化合物、たとえばチオ硫酸カリウム、チオ硫酸ナ
トリウム、チオ硫酸アンモニウムの如きチオ硫酸
塩、チオシアン酸カリウム、チオシアン酸ナトリ
ウム、チオシアン酸アンモニウムの如きチオシア
ン酸塩、あるいはチオ尿素、チオエーテル、高濃
度の臭化物、沃化物等が、さらに保恒剤として亜
硫酸塩、メタ重亜硫酸塩、アルデヒドの重亜硫酸
付加物等が用いられている。これらの中で、社会
環境的理由、ならびに経済的理由から定着剤とし
てはチオ硫酸塩が、保恒剤としては亜硫酸塩が通
常よく用いられている。前記亜硫酸塩は単独で定
着液に添加しても、ある程度の保恒性を得ること
ができるが、さらにメタ重亜硫酸塩を添加するこ
とにより、さらに効果的な保恒性が得られること
は既に知られている。
しかしながら、これらの保恒剤は共存する微量
の金属イオン、とりわけ感光材料に付着して混入
する漂白液成分である有機酸鉄キレート錯体によ
り触媒作用を受けて酸化分解して保恒効果が減少
し、定着液中の可溶性銀塩は硫化銀となりカラー
写真感光材料に汚染を生じたり自動現像機のフイ
ルターに目づまりを生じることが知られている。
そこでこの様な欠点を生じなくするために漂白浴
と定着浴の間に多量の水を流す水洗浴を設け、感
光材料に付着している漂白液中の有機酸鉄キレー
ト錯体を洗い落とすことにより定着液への混入を
防いでいる。
近年水資源の不足及び経済性のために水洗水量
の減少化が望まれているが、有機酸鉄キレート錯
体の定着液への混入による保存性の悪化のため多
量の水を流す水洗浴を設けざるを得ないのが実情
である。さらに漂白浴と定着浴の間に多量の水を
流す水洗浴を設けない際には、定着液中で有機酸
鉄（）キレート錯体は還元され有機酸鉄（）
キレート錯体となり発色現像で形成された色素、
とりわけシアン色素をリユーコ・ダイ（leuco
dye）に還元し、不完全発色色素にしてしまう致
命的な欠点を有している。以上の理由から漂白浴
と定着浴の間の水洗浴を除去したり、あるいは水
洗水量を著しく減少させることは極めて困難なこ
とである。
従つて本発明の目的は第１に、有機酸鉄キレー
ト錯体を含有した漂白浴と定着浴との間の水洗浴
を除去した際や、あるいは水洗水量を著しく減少
した水洗浴（以下本発明においては、予備水洗浴
と称する。）を使用する際にも、優れた保存安定
性を有したハロゲン化銀カラー写真感光材料の処
理方法を提供することであり、第２に、自動現像
機により処理を行なう際にも長期にわたり安定な
処理ができ、付属のフイルターの目づまりを起こ
さないハロゲン化銀カラー写真感光材料の処理方
法を提供することであり、第３に、有機酸鉄キレ
ート錯体が定着液に混入した際にもリユーコ・ダ
イを生じないハロゲン化銀カラー写真感光材料の
処理方法を提供するにある。
さらに本発明の第４の目的は、漂白浴と定着浴
の間に水洗水を全く流さなくてもよいか、あるい
は少量の水洗水を流すだけで良い様な水資源の節
減と、水洗水を加温するエネルギーの半減が図ら
れたハロゲン化銀カラー写真感光材料の処理方法
の提供にある。
本発明者は種々探索研究の結果、有機酸鉄キレ
ート錯体を含有する定着液で処理するハロゲン化
銀カラー写真感光材料の処理方法において、上記
有機酸鉄キレート錯体と金属核交換反応を行なう
ことにより安定な有機酸金属キレート錯体を形成
せしめ得る金属化合物を前記定着液中に存在せし
める際に上記の目的を達成し得ることを見出した
ものである。
本発明に係る有機酸鉄キレート錯体と金属核交
換反応を行なうことにより安定な有機酸金属キレ
ート錯体を形成しうる金属化合物としては、ニツ
ケル化合物、亜鉛化合物、鉛化合物、バナジウム
化合物、ランタン化合物、カドミウム化合物、ガ
ドリニウム化合物、イツトリウム化合物、ユーロ
ピウム化合物、サマリウム化合物、ジスプロシウ
ム化合物、イツテルビウム化合物、ホルミウム化
合物、エルビウム化合物、インジウム化合物、ネ
オジウム化合物、テルビウム化合物等が挙げられ
る。これら金属化合物は、ハロゲン化物、水酸化
物、硫酸塩、炭酸塩、硝酸塩、リン酸塩、酢酸塩
等の無機塩の形か、アセチルアセトン、ホスホノ
カルボン酸、ポリリン酸、オキシカルボン酸等の
有機のキレート剤錯塩又は有機酸塩の形で使用さ
れる。
次に、その好ましい具体的例示化合物を挙げる
が、本発明はこれらに限定されるものではない。
（例示化合物）
Ａ−１ 塩化亜鉛
Ａ−２ 臭化亜鉛
Ａ−３ 硫酸亜鉛
Ａ−４ 硝酸亜鉛
Ａ−５ 酢酸亜鉛
Ａ−６ 塩化鉛
Ａ−７ 硫酸鉛
Ａ−８ 硝酸鉛
Ａ−９ 塩化ニツケル
Ａ−10 硝酸ニツケル
Ａ−11 硫酸ニツケル
Ａ−12 酢酸ニツケル
Ａ−13 臭化ニツケル
Ａ−14 沃化ニツケル
Ａ−15 リン酸ニツケル
Ａ−16 メタバナジン酸ナトリウム
Ａ−17 オルトバナジン酸ナトリウム
Ａ−18 メタバナジン酸アンモニウム
Ａ−19 硫酸バナジル
Ａ−20 塩化ランタン
Ａ−21 硫酸ランタン
Ａ−22 硝酸ランタン
Ａ−23 酢酸ランタン
Ａ−24 炭酸ランタン
Ａ−25 塩化カドミウム
Ａ−26 硫酸カドミウム
Ａ−27 硝酸カドミウム
Ａ−28 酢酸カドミウム
Ａ−29 炭酸カドミウム
Ａ−30 水酸化カドミウム
Ａ−31 臭化カドミウム
Ａ−32 リン酸カドミウム
Ａ−33 硫酸ガドリニウム
Ａ−34 塩化ガドリニウム
Ａ−35 硝酸ガドリニウム
Ａ−36 酢酸ガドリニウム
Ａ−37 硝酸イツトリウム
Ａ−38 硫酸イツトリウム
Ａ−39 塩化イツトリウム
Ａ−40 フツ化イツトリウム
Ａ−41 硫酸ユーロピウム
Ａ−42 炭酸ユーロピウム
Ａ−43 酢酸ユーロピウム
Ａ−44 塩化ユーロピウム
Ａ−45 硫酸サマリウム
Ａ−46 炭酸サマリウム
Ａ−47 硝酸サマリウム
Ａ−48 酢酸サマリウム
Ａ−49 塩化サマリウム
Ａ−50 臭化サマリウム
Ａ−51 硫酸ジスプロシウム
Ａ−52 硝酸ジスプロシウム
Ａ−53 酢酸ジスプロシウム
Ａ−54 塩化ジスプロシウム
Ａ−55 硫酸イツテルビウム
Ａ−56 硝酸イツテルビウム
Ａ−57 酢酸イツテルビウム
Ａ−58 塩化イツテルビウム
Ａ−59 臭化イツテルビウム
Ａ−60 炭酸イツテルビウム
Ａ−61 硫酸ホルミウム
Ａ−62 酢酸ホルミウム
Ａ−63 塩化ホルミウム
Ａ−64 硫酸エルビウム
Ａ−65 硝酸エルビウム
Ａ−66 酢酸エルビウム
Ａ−67 塩化エルビウム
Ａ−68 塩化インジウム
Ａ−69 硫酸インジウム
Ａ−70 硝酸インジウム
Ａ−71 臭化インジウム
Ａ−72 塩化ネオジム
Ａ−73 硫酸ネオジム
Ａ−74 硝酸ネオジム
Ａ−75 酢酸ネオジム
Ａ−76 アセチルアセトン亜鉛錯塩
Ａ−77 ２−ホスホノブタン−１，２，４−トリ
カルボン酸亜鉛錯塩
Ａ−78 ヘキサメタリン酸亜鉛錯塩
Ａ−79 トリポリリン酸亜鉛錯塩
Ａ−80 クエン酸亜鉛
Ａ−81 シユウ酸亜鉛
Ａ−82 マロン酸亜鉛
Ａ−83 ジメチルグリオキシム亜鉛錯塩
Ａ−84 酒石酸亜鉛
Ａ−85 グルコン酸亜鉛
Ａ−86 アセチルアセトン鉛錯塩
Ａ−87 ２−ホスホノブタン−１，２，４−トリ
カルボン酸鉛錯塩
Ａ−88 ヘキサメタリン酸鉛錯塩
Ａ−89 クエン酸鉛
Ａ−90 シユウ酸鉛
Ａ−91 マロン酸鉛
Ａ−92 酒石酸鉛
Ａ−93 アセチルアセトンニツケル錯塩
Ａ−94 トリポリリン酸ニツケル錯塩
Ａ−95 クエン酸ニツケル
Ａ−96 シユウ酸ニツケル
Ａ−97 ヘキサメタリン酸ニツケル錯塩
Ａ−98 マロン酸ニツケル
Ａ−99 ジメチルグリオキシムニツケル錯塩
Ａ−100 クエン酸ランタン
Ａ−101 シユウ酸ランタン
Ａ−102 マロン酸ランタン
Ａ−103 酒石酸ランタン
Ａ−104 グルコン酸ランタン
Ａ−105 アセチルアセトンランタン錯塩
Ａ−106 シユウ酸カドミウム
Ａ−107 クエン酸カドミウム
Ａ−108 マロン酸カドミウム
Ａ−109 酒石酸カドミウム
Ａ−110 アセチルアセトンカドミウム錯塩
Ａ−111 ２−ホスホノブタン−１，２，４−ト
リカルボン酸カドミウム錯塩
Ａ−112 シユウ酸ガドリニウム
Ａ−113 クエン酸ガドリニウム
Ａ−114 シユウ酸イツトリウム
Ａ−115 マロン酸イツトリウム
Ａ−116 クエン酸ユーロピウム
Ａ−117 グルコン酸ユーロピウム
Ａ−118 アセチルアセトンユーロピウム錯塩
Ａ−119 シユウ酸サマリウム
Ａ−120 酒石酸サマリウム
Ａ−121 クエン酸サマリウム
Ａ−122 シユウ酸ジスプロシウム
Ａ−123 グルコン酸ジスプロシウム
Ａ−124 アセチルアセトンジスプロシウム錯塩
Ａ−125 マロン酸ジスプロシウム
Ａ−126 マロン酸イツテルビウム
Ａ−127 クエン酸イツテルビウム
Ａ−128 シユウ酸イツテルビウム
Ａ−129 アセチルアセトンイツテルビウム錯塩
Ａ−130 シユウ酸ホルミウム
Ａ−131 酒石酸ホルミウム
Ａ−132 クエン酸エルビウム
Ａ−133 アセチルアセトンエルビウム錯塩
Ａ−134 シユウ酸エルビウム
Ａ−135 シユウ酸インジウム
Ａ−136 クエン酸インジウム
Ａ−137 アセチルアセトンインジウム錯塩
Ａ−138 マロン酸インジウム
Ａ−139 グルコン酸インジウム
Ａ−140 シユウ酸ネオジム
Ａ−141 クエン酸ネオジム
Ａ−142 ヘキサメタリン酸ネオジム錯塩
Ａ−143 酒石酸ネオジム
Ａ−144 塩化テルビウム
Ａ−145 硫酸テルビウム
Ａ−146 シユウ酸テルビウム
本発明に係る上記の金属化合物は単独で用いて
も、また組合せて用いてもよく、その使用量とし
ては、有機酸鉄キレート錯体の1/2モル以上であ
ることが好ましく、とりわけ等モル以上の使用が
好ましい。
本発明に係る金属核交換反応とは、一つの金属
錯体（本発明では有機酸鉄キレート錯体を示す。）
の中心金属イオン（本発明では鉄イオン）を他の
金属イオンで置換する反応のことで、「錯形成反
応」（日本分析化学会編、丸善(株)発行、昭和49年
10月25日発行）353ページに記載されている“金
属置換反応”と同義である。
本発明に係る有機酸鉄キレート錯体は、現像に
よつて生成した金属銀を酸化してハロゲン化銀に
かえると同時に発色剤の未発色部を発色させる作
用を有するもので、その構造はアミノポリカルボ
ン酸または蓚酸、クエン酸等のポリカルボン酸の
有機酸で鉄、金属イオンを配位したものである。
このような有機酸鉄キレート錯体を形成するため
に用いられる最も好ましい有機酸としては、たと
えば下記一般式〔〕または〔〕で示されるポ
リカルボン酸或いはアミノポリカルボン酸があ
る。
一般式〔〕
HOCO−A1−Ｚ−A2−COOH
一般式〔〕
〔各一般式中、A1、A2、A3、A4、A5およびA6
はそれぞれ置換もしくは非置換の炭化水素基、Ｚ
は炭化水素基もしくはＮ−A7（A7は炭化水素基
もしくは低級脂肪族カルボン酸）を表わす。〕
これらのポリカルボン酸或いはアミノポリカル
ボン酸はアルカリ金属塩、アンモニウム塩もしく
は水溶性アミン塩であつてもよい。前記一般式
〔〕または〔〕で示されるアミノポリカルボ
ン酸或いはポリカルボン酸の代表的な例としては
次の如きものを挙げることができる。
(1) エチレンジアミンテトラ酢酸
(2) ジエチレントリアミンペンタ酢酸
(3) エチレンジアミン−Ｎ−（β−オキシエチル）
−Ｎ，N′，N′−トリ酢酸プロピレンジアミン
テトラ酢酸
(4) ニトリロトリ酢酸
(5) シクロヘキサンジアミンテトラ酢酸
(6) イミノジ酢酸
(7) ジヒドロキシエチルグリシン
(8) エチルエーテルジアミンテトラ酢酸
(9) グリコールエーテルジアミンテトラ酢酸
(10) エチレンジアミンテトラプロピオン酸
(11) フエニレンジアミンテトラ酢酸
(12) エチレンジアミンテトラ酢酸ジナトリウム塩
(13) エチレンジアミンテトラ酢酸テトラ（トリ
メチルアンモニウム）塩
(14) エチレンジアミンテトラ酢酸テトラナトリ
ウム塩
(15) ジエチレントリアミンペンタ酢酸ペンタナ
トリウム塩
(16) エチレンジアミン−Ｎ−（β−オキシエチ
ル）−Ｎ，N′，N′−トリ酢酸ナトリウム塩
(17) プロピレンジアミンテトラ酢酸ナトリウム
塩
(18) ニトリロトリ酢酸ナトリウム塩
(19) シクロヘキサンジアミンテトラ酢酸ナトリ
ウム塩
(20) クエン酸
(21) 蓚酸
(22) マレイン酸
(23) 酒石酸
(24) コハク酸
(25) スルフアミン酸
(26) フタル酸
(27) グルコン酸
本発明の効果は、上記の有機酸鉄キレート錯体
が前記の金属化合物と金属核交換反応を起して鉄
と他の金属とが交換し、不活性な有機酸金属キレ
ート錯体を形成し得ることに着目したもので、こ
の不活性な錯体によつてリユーコ・ダイの発生や
亜硫酸イオンの分解を未然に回避せしめて有機酸
鉄キレート錯体を含有する定着液の処理安定性を
高めたところに特徴を有するものである。そして
上記により放出された鉄イオンの受容体としてキ
レート剤を存在せしめて置くと、放出された上記
鉄イオンが水酸化鉄として沈澱することもなく、
されには金属核交換反応がより円滑に進行し得る
ので本発明においては、キレート剤を併用するこ
とが好ましい。
本発明に好ましく用いられる上記キレート剤の
具体例としては、以下の化合物が挙げられるが、
これらに限定されるものではない。
（例示化合物）
Ｂ−１ １−ヒドロキシエチリデン−１，１−ジ
ホスホン酸
Ｂ−２ ２−ホスホノブタン−１，２，４−トリ
カルボン酸
Ｂ−３ ヘキサメタリン酸ナトリウム
Ｂ−４ ピロリン酸ナトリウム
Ｂ−５ トリポリリン酸ナトリウム
Ｂ−６ １−ヒドロキシ−１，１−ジホスホノプ
ロパン−３−カルボン酸
Ｂ−７ １−ヒドロキシ−１−ホスホノエタン−
１−カルボン酸
Ｂ−８ １−ヒドロキシ−１−ホスホノ−プロパ
ン−１，２，３−トリカルボン酸
Ｂ−９ １，１−ジホスホノエタン−２−カルボ
ン酸カリウム
Ｂ−10 グルコン酸ナトリウム
Ｂ−11 ジ（ヒドロキシエチル）グリシン
Ｂ−12 トリエタノールアミン
Ｂ−13 ２−ホスホノペンタン−２，５−ジカル
ボン酸
Ｂ−14 ヒドロキシエチルイミノジ酢酸
Ｂ−15 ジエチレントリアミン五酢酸ナトリウム
上記キレート剤が、全く添加されない場合にも
本発明の効果を得ることはできるが、金属核交換
反応で放出された鉄イオンが沈澱しない程度で添
加することにより、より好ましい効果を得ること
ができる。
本発明のハロゲン化銀カラー写真感光材料の処
理方法における処理工程としては、公知の処理工
程を組合せて使用でき、次に挙げる如き工程があ
るが、これらに限定されるものではない。
発色現像−漂白−定着−水洗−安定
発色現像−漂白−少量水洗−定着−水洗−安
定
発色現像−漂白−定着−予備水洗−水洗−安
定
発色現像−漂白−少量水洗−定着−予備水洗
−水洗−安定
発色現像−停止−漂白−少量水洗−定着−予
備水洗−水洗−安定
発色現像−補力−漂白−少量水洗−定着−予
備水洗−水洗−安定
発色現像−停止−漂白−定着−予備水洗−水
洗−安定
上記工程の中で、定着工程の次に予備水洗工程
を配したものが本発明においては好ましく用いら
れる。その理由は、ハロゲン化銀写真感光材料に
付着して入る水洗工程中の公害成分が極めて少な
くなること及び定着液中に溶解している可溶性銀
塩の水洗工程への流失が減少し、銀の回収効率が
上昇することなど、社会環境的に、また経済的に
好ましい結果を得るからである。また処理工程数
は少ない方が迅速処理的に好ましく、この故に前
記工程の中で工程およびが、本発明において
はとりわけ好ましく用いられる。
さらに本発明で用いる少量水洗浴とは、ハロゲ
ン化銀カラー写真感光材料100cm2あたり200ml以下
の少量の水洗浴のことであり、本発明の効果はハ
ロゲン化銀カラー写真感光材料100cm2あたり40ml
以下の際に良好な結果を秦し、とりわけハロゲン
化銀カラー写真感光材料100cm2あたり15ml以下の
際に特に効果を発揮する。
本発明に用いられる定着液には、前記の定着
剤、保恒剤の他に公知の定着液成分を含有させる
ことができる。例えばPH調整剤として、水酸化カ
リウム、水酸化ナトリウム、水酸化アンモニウ
ム、リン酸ナトリウム、炭酸ナトリウムを、また
各種の消泡剤あるいは界面活性剤を含有させるこ
とができる。さらに、ヒドロキシルアミンやヒド
ラジンの如き保恒剤や、ニトロアルコール、硝酸
塩等の一種の安定剤、メタノール、ジメチルフオ
ルムアミド、ジメチルスルフオキシド等の有機溶
媒等を適宜含有させることができる。
また、本発明のハロゲン化銀カラー写真感光材
料としては、カラーペーパー、カラーネガフイル
ム、カラーポジフイルム、スライド用カラー反転
フイルム、映画用カラー反転フイルム、TV用カ
ラー反転フイルム、反転カラーペーパーなどのハ
ロゲン化銀カラー写真感光材料を使用できる。
以下、実施例によつて本発明の詳細を説明する
が、これにより本発明の実施の態様が限定される
ものではない。
実施例 １
サクラカラーフイルム（小西六写真工業(株)
製）をコニカFS−１カメラ（小西六写真工業(株)
製）を用いて撮影した後、次の工程に従つて自動
現像機にて連続的に処理を行なつた。自動現像機
は、ノーリツ鋼機(株)製吊下式フイルム自動現像機
タイプH4−220W−２を改造して使用した。
処理工程（38℃） 槽数 処理時間
発色現像 １槽 ３分15秒
漂 白 ２槽 ６分30秒
少量水洗 １槽 ３分15秒
定 着 １槽 ６分30秒
水 洗 ２槽 ４分20秒
安 定 １槽 ２分10秒
使用した発色現像液の組成は次のとおりであ
る。
炭酸カリウム 30ｇ
炭酸水素ナトリウム 2.5ｇ
亜硫酸カリウム ５ｇ
臭化ナトリウム 1.3ｇ
沃化カリウム ２mg
ヒドロキシルアミン硫酸塩 2.5ｇ
塩化ナトリウム 0.6ｇ
ジエチレントリアミン五酢酸ナトリウム 2.5ｇ
４−アミノ−３−メチル−Ｎ−エチル−Ｎ−
（β−ヒドロキシエチル）アニリン硫酸塩 4.8ｇ
水酸化カリウム 1.2ｇ
水を加えて１とし、水酸化カリウムまたは20
％硫酸を用いて、PH10.06に調整する。
使用した発色現像補充用液の組成は次のとおり
である。
炭酸カリウム 35ｇ
炭酸水素ナトリウム ３ｇ
亜硫酸カリウム ７ｇ
臭化ナトリウム 0.9ｇ
ヒドロキシルアミン硫酸塩 3.1ｇ
ジエチレントリアミン五酢酸ナトリウム 3.2ｇ
４−アミノ−３−メチル−４−エチル−Ｎ−
（β−ヒドロキシエチル）−アニリン硫酸塩
5.4ｇ
水酸化カリウム ２ｇ
水を加えて１とし、水酸化カリウムまたは20
％硫酸を用いて、PH10.12に調整する。
使用した漂白液の組成は、次のとおりである。
エチレンジアミンテトラ酢酸鉄アンモニウム
100ｇ
エチレンジアミンテトラ酢酸２ナトリウム 10ｇ
臭化アンモニウム 150ｇ
氷酢酸 10ml
水を加えて１とし、アンモニア水または氷酢
酸を用いて、PH5.8に調整する。
使用した漂白補充用液の組成は、次のとおりで
ある。
エチレンジアミンテトラ酢酸鉄アンモニウム
120ｇ
エチレンジアミンテトラ酢酸２ナトリウム 12ｇ
臭化アンモニウム 178ｇ
氷酢酸 21ml
水を加えて１とし、アンモニア水または氷酢
酸を用いて、PH5.6に調整する。
使用した定着液の組成は、次のとおりである。
チオ硫酸アンモニウム 150ｇ
無水亜硫酸ナトリウム 12ｇ
メタ重亜硫酸ナトリウム 2.5ｇ
エチレンジアミンテトラ酢酸２ナトリウム
0.5ｇ
炭酸ナトリウム 10ｇ
水を加えて１とする。
使用した定着補充用液の組成は、次のとおりで
ある。
チオ硫酸アンモニウム 200ｇ
無水亜硫酸ナトリウム 15ｇ
メタ重亜硫酸ナトリウム ３ｇ
エチレンジアミンテトラ酢酸２ナトリウム
0.8ｇ
炭酸ナトリウム 14ｇ
水を加えて１とする。
使用した安定液の組成は、次のとおりである。
ホルマリン（37％水溶液） ２ml
コニダツクス（小西六写真工業(株)製） ５ml
水を加えて１とする。
使用した安定補充用液の組成は、次のとおりで
ある。
ホルマリン（37％水溶液） ３ml
コニダツクス（小西六写真工業(株)製） ７ml
水を加えて１とする。
発色現像補充用液は、カラーネガフイルム100
cm2当り15ml発色現像浴に補充され、漂白補充用液
は、カラーネガフイルム100cm2当り18ml漂白浴に
補充され、定着補充用液は、カラーネガフイルム
100cm2当り７ml定着浴に補充され、さらに安定補
充用液は、カラーネガフイルム100cm2当り11ml安
定浴に補充された。また、少量水洗浴には、水が
カラーネガフイルム100cm2当り３ml補充され、水
洗浴には、水がカラーネガフイルム100cm2当り150
ml流された。
前記定着補充用液に水酸化アンモニウムまたは
酢酸を適宜添加して、カラーネガフイルムを連続
的に処理する間の定着浴のPHを6.5に常になるよ
うにして、1000m2を連続的に処理を行なつた後の
定着浴液を比較用試料液Ａとした。
さらに前記定着液に例示化合物Ａ−９を定着浴
中に存在するエチレンジアミンテトラ酢酸鉄アン
モニウムの1.5倍モルに常になるように添加し、
前記と同様にPHを6.5に保ちながら連続的にカラ
ーフイルムを1000m2処理を行なつた後の定着浴液
を本発明の試料Ｂとした。同様に、定着液に例示
化合物Ａ−９および例示化合物Ｂ−２（Ａ−９と
等モル濃度）加えて連続処理した定着浴液を本発
明の試料液Ｃとした。
試料液Ｃの例示化合物Ａ−９及びＢ−２をＡ−
４及びＢ−４に、Ａ−16及びＢ−６に、Ａ−20及
びＢ−１に、Ａ−28及びＢ−10に、Ａ−34及びＢ
−３に、Ａ−37及びＢ−５に、Ａ−44及びＢ−15
に、Ａ−45及びＢ−14に、Ａ−52及びＢ−２に、
Ａ−55及びＢ−12に、Ａ−63及びＢ−９に、Ａ−
65及びＢ−７に、Ａ−70及びＢ−８に、Ａ−72及
びＢ−11に、Ａ−81及びＢ−５に、Ａ−95及びＢ
−11に、Ａ−144及びＢ−13にそれぞれ替えて定
着浴のPHを6.5に保ちながらカラーフイルムを連
続的に1000cm2処理を行なつた後の定着浴液を本発
明の試料液ＣないしＴとした。
このようにして作成した試料液ＡないしＴを６
日間室温に放置してから、KS−７型感光計（小
西六写真工業(株)製）を用いて白色段階露光を与え
た前記カラーネガフイルムを前記工程に従つて発
色現像処理を行なつた。この発色現像処理を終つ
たものについて、PDA−60型光電濃度計（小西
六写真工業(株)製）を用いて赤感光層の最大濃度を
測定した。
さらに、前記６日間放置された定着液の沈澱発
生状態を観察した後、放置前後の亜硫酸イオンの
量を測定し、その減少率を求めた。
以上の結果をまとめて表１に示す。
The present invention relates to a method for processing silver halide color photographic materials, and more particularly to a method for processing silver halide color photographic materials in which the processing stability of a fixer containing an organic acid iron chelate complex is improved. be. Generally, in a silver halide color photographic material, a dye image is formed by a series of photographic processes whose basic steps are a color development step and a desilvering step after image exposure. In the above color development step, the oxidized color developing agent undergoes a coupling reaction with the coexisting color coupler to form a dye image with an image pattern, and at the same time, reduced silver is produced. The silver produced here is oxidized by a bleaching agent in the subsequent desilvering step, transformed into a soluble silver complex by the action of a fixing agent, and dissolved and removed by washing with water. In the actual processing process, in addition to the basic steps for color development and desilvering mentioned above, stopping baths, hardening baths, and stabilizing baths are required due to the need to improve the photographic or physical properties of images. , auxiliary treatment baths such as a bagging removal treatment bath are provided. On the other hand, in the fixing bath as a desilvering step, compounds that react with silver halide to form water-soluble silver complexes, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, potassium thiocyanate, Thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thioureas, thioethers, high concentrations of bromides, iodides, etc., and preservatives such as sulfites, metabisulfites, bisulfite adducts of aldehydes, etc. It is used. Among these, thiosulfate is commonly used as a fixing agent and sulfite is commonly used as a preservative for social and environmental reasons as well as economic reasons. Even if the sulfite salt is added alone to the fixing solution, it is possible to obtain a certain degree of preservability, but it has already been shown that even more effective preservability can be obtained by adding metabisulfite. Are known. However, these preservatives are catalyzed by trace amounts of coexisting metal ions, especially organic acid iron chelate complexes that are components of bleaching solutions that adhere to and mix with photosensitive materials, resulting in oxidation and decomposition, reducing the preservative effect. It is known that soluble silver salts in fixing solutions turn into silver sulfide and cause staining of color photographic materials and clogging of filters in automatic processors.
Therefore, in order to prevent such defects from occurring, a washing bath is provided between the bleaching bath and the fixing bath, in which a large amount of water flows, and the organic acid iron chelate complex in the bleaching solution adhering to the photosensitive material is washed away. Prevents contamination with liquid. In recent years, due to the lack of water resources and economic efficiency, it has been desired to reduce the amount of water used for rinsing.However, due to the deterioration of storage stability due to the contamination of organic acid iron chelate complexes into the fixing solution, rinsing baths that run a large amount of water have been installed. The reality is that this is unavoidable. Furthermore, when a washing bath that flows a large amount of water is not provided between the bleaching bath and the fixing bath, the organic acid iron () chelate complex is reduced in the fixing solution.
A dye formed by color development as a chelate complex,
In particular, the cyan dye is leuco dye.
It has the fatal disadvantage of reducing to dye), resulting in incomplete color development. For the above reasons, it is extremely difficult to eliminate the washing bath between the bleaching bath and the fixing bath or to significantly reduce the amount of washing water. Therefore, the first object of the present invention is to remove the water washing bath between the bleaching bath and the fixing bath containing the organic acid iron chelate complex, or to remove the water washing bath in which the amount of washing water is significantly reduced (hereinafter referred to in the present invention). The object of the present invention is to provide a method for processing silver halide color photographic materials that has excellent storage stability even when using a pre-washing bath (referred to as a pre-washing bath). The purpose of the present invention is to provide a method for processing silver halide color photographic materials that allows stable processing over a long period of time and does not cause clogging of attached filters. An object of the present invention is to provide a method for processing a silver halide color photographic material that does not cause Lyuko dye even when mixed with silver halide. Furthermore, a fourth object of the present invention is to save water resources by not having to run any washing water or only a small amount of washing water between the bleaching bath and the fixing bath, and to reduce the washing water. An object of the present invention is to provide a method for processing a silver halide color photographic material in which heating energy is reduced by half. As a result of various exploratory studies, the present inventor discovered that, in a method for processing silver halide color photographic light-sensitive materials in which a fixing solution containing an organic acid iron chelate complex is used, a method for processing a silver halide color photographic light-sensitive material is realized by carrying out a metal nuclear exchange reaction with the organic acid iron chelate complex. It has been discovered that the above object can be achieved when a metal compound capable of forming a stable organic acid metal chelate complex is present in the fixer. Examples of metal compounds that can form a stable organic acid metal chelate complex by performing a metal nuclear exchange reaction with the organic acid iron chelate complex according to the present invention include nickel compounds, zinc compounds, lead compounds, vanadium compounds, lanthanum compounds, and cadmium. compounds, gadolinium compounds, yttrium compounds, europium compounds, samarium compounds, dysprosium compounds, ytterbium compounds, holmium compounds, erbium compounds, indium compounds, neodymium compounds, terbium compounds, and the like. These metal compounds may be in the form of inorganic salts such as halides, hydroxides, sulfates, carbonates, nitrates, phosphates, acetates, etc., or organic salts such as acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, oxycarboxylic acids, etc. It is used in the form of chelating complex salts or organic acid salts. Next, specific preferable exemplary compounds will be listed, but the present invention is not limited thereto. (Exemplary compounds) A-1 Zinc chloride A-2 Zinc bromide A-3 Zinc sulfate A-4 Zinc nitrate A-5 Zinc acetate A-6 Lead chloride A-7 Lead sulfate A-8 Lead nitrate A-9 Nickel chloride A-10 Nickel nitrate A-11 Nickel sulfate A-12 Nickel acetate A-13 Nickel bromide A-14 Nickel iodide A-15 Nickel phosphate A-16 Sodium metavanadate A-17 Sodium orthovanadate A-18 Metavanazine Ammonium acid A-19 Vanadyl sulfate A-20 Lanthanum chloride A-21 Lanthanum sulfate A-22 Lanthanum nitrate A-23 Lanthanum acetate A-24 Lanthanum carbonate A-25 Cadmium chloride A-26 Cadmium sulfate A-27 Cadmium nitrate A-28 Cadmium acetate A-29 Cadmium carbonate A-30 Cadmium hydroxide A-31 Cadmium bromide A-32 Cadmium phosphate A-33 Gadolinium sulfate A-34 Gadolinium chloride A-35 Gadolinium nitrate A-36 Gadolinium acetate A-37 Yttrium nitrate A-38 Yttrium sulfate A-39 Yttrium chloride A-40 Yttrium fluoride A-41 Europium sulfate A-42 Europium carbonate A-43 Europium acetate A-44 Europium chloride A-45 Samarium sulfate A-46 Samarium carbonate A-47 Nitric acid Samarium A-48 Samarium acetate A-49 Samarium chloride A-50 Samarium bromide A-51 Dysprosium sulfate A-52 Dysprosium nitrate A-53 Dysprosium acetate A-54 Dysprosium chloride A-55 Ytterbium sulfate A-56 Ytterbium nitrate A -57 Ytterbium acetate A-58 Ytterbium chloride A-59 Ytterbium bromide A-60 Yterbium carbonate A-61 Holmium sulfate A-62 Holmium acetate A-63 Holmium chloride A-64 Erbium sulfate A-65 Erbium nitrate A -66 Erbium acetate A-67 Erbium chloride A-68 Indium chloride A-69 Indium sulfate A-70 Indium nitrate A-71 Indium bromide A-72 Neodymium chloride A-73 Neodymium sulfate A-74 Neodymium nitrate A-75 Neodymium acetate A-76 Acetylacetone zinc complex A-77 2-phosphonobutane-1,2,4-tricarboxylic acid zinc complex A-78 Hexametaphosphate zinc complex A-79 Tripolyphosphate zinc complex A-80 Zinc citrate A-81 Zinc oxalate A -82 Zinc malonate A-83 Dimethylglyoxime zinc complex A-84 Zinc tartrate A-85 Zinc gluconate A-86 Acetylacetone lead complex A-87 2-phosphonobutane-1,2,4-tricarboxylic acid lead complex A-88 Lead hexametaphosphate complex A-89 Lead citrate A-90 Lead oxalate A-91 Lead malonate A-92 Lead tartrate A-93 Acetyl acetone nickel complex A-94 Nickel tripolyphosphate complex A-95 Nickel citrate A-96 Nickel acid A-97 Nickel hexametaphosphate complex A-98 Nickel malonate A-99 Dimethylglyoxime nickel complex A-100 Lanthanum citrate A-101 Lanthanum oxalate A-102 Lanthanum malonate A-103 Lanthanum tartrate A-104 Glucon Lanthanum acid A-105 Acetylacetone lanthanum complex A-106 Cadmium oxalate A-107 Cadmium citrate A-108 Cadmium malonate A-109 Cadmium tartrate A-110 Acetylacetone cadmium complex A-111 2-phosphonobutane-1,2,4- Tricarboxylic acid cadmium complex A-112 Gadolinium oxalate A-113 Gadolinium citrate A-114 Yttrium oxalate A-115 Yttrium malonate A-116 Europium citrate A-117 Europium gluconate A-118 Acetylacetone europium complex A-119 Samarium acid A-120 Samarium tartrate A-121 Samarium citrate A-122 Dysprosium oxalate A-123 Dysprosium gluconate A-124 Acetylacetone dysprosium complex A-125 Dysprosium malonate A-126 Itterbium malonate A-127 Izuterium citrate Terbium A-128 Ytterbium oxalate A-129 Acetylacetone Ytterbium complex A-130 Holmium oxalate A-131 Holmium tartrate A-132 Erbium citrate A-133 Acetylacetone Erbium complex A-134 Erbium oxalate A-135 Indium oxalate A-136 Indium citrate A-137 Acetylacetone indium complex A-138 Indium malonate A-139 Indium gluconate A-140 Neodymium oxalate A-141 Neodymium citrate A-142 Neodymium hexametaphosphate complex A-143 Neodymium tartrate A- 144 Terbium chloride A-145 Terbium sulfate A-146 Terbium oxalate The above metal compounds according to the present invention may be used alone or in combination, and the amount used is 1% of the organic acid iron chelate complex. /2 mol or more is preferable, and it is especially preferable to use equimolar or more. The metal nuclear exchange reaction according to the present invention refers to one metal complex (in the present invention, it refers to an organic acid iron chelate complex).
A reaction in which the central metal ion (iron ion in the present invention) is replaced by another metal ion, and is referred to as a "complex formation reaction" (edited by the Japan Society for Analytical Chemistry, published by Maruzen Co., Ltd., 1972).
It has the same meaning as “metal substitution reaction” described on page 353 (published on October 25th). The organic acid iron chelate complex according to the present invention has the function of oxidizing metallic silver generated by development and converting it into silver halide, and at the same time coloring the uncolored areas of the color former, and its structure is made of aminopolymer. Iron or metal ions are coordinated with carboxylic acid or an organic acid such as polycarboxylic acid such as oxalic acid or citric acid.
The most preferred organic acid used to form such an organic acid iron chelate complex is, for example, a polycarboxylic acid or an aminopolycarboxylic acid represented by the following general formula [] or []. General formula [] HOCO−A 1 −Z−A 2 −COOH General formula [] [In each general formula, A 1 , A 2 , A 3 , A 4 , A 5 and A 6
are substituted or unsubstituted hydrocarbon groups, Z
represents a hydrocarbon group or N-A 7 (A 7 is a hydrocarbon group or a lower aliphatic carboxylic acid). ] These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts, or water-soluble amine salts. Representative examples of the aminopolycarboxylic acid or polycarboxylic acid represented by the general formula [] or [] include the following. (1) Ethylenediaminetetraacetic acid (2) Diethylenetriaminepentaacetic acid (3) Ethylenediamine-N-(β-oxyethyl)
-N,N',N'-triacetate Propylenediaminetetraacetic acid (4) Nitrilotriacetic acid (5) Cyclohexanediaminetetraacetic acid (6) Iminodiacetic acid (7) Dihydroxyethylglycine (8) Ethyl etherdiaminetetraacetic acid (9) Glycol Etherdiaminetetraacetic acid (10) Ethylenediaminetetrapropionic acid (11) Phenylenediaminetetraacetic acid (12) Ethylenediaminetetraacetic acid disodium salt (13) Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt (14) Ethylenediaminetetraacetic acid tetrasodium salt ( 15) Diethylenetriaminepentaacetic acid pentasodium salt (16) Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid sodium salt (17) Propylenediaminetetraacetic acid sodium salt (18) Nitrilotriacetic acid sodium salt ( 19) Cyclohexanediaminetetraacetic acid sodium salt (20) Citric acid (21) Oxalic acid (22) Maleic acid (23) Tartaric acid (24) Succinic acid (25) Sulfamic acid (26) Phthalic acid (27) Gluconic acid Effects of the present invention This method focuses on the fact that the above organic acid iron chelate complex can undergo a metal nuclear exchange reaction with the above metal compound, whereby iron and other metals are exchanged to form an inactive organic acid metal chelate complex. This inert complex prevents the generation of Lyuko-dye and the decomposition of sulfite ions, thereby increasing the processing stability of fixing solutions containing organic acid iron chelate complexes. be. If a chelating agent is present as a receptor for the iron ions released as described above, the released iron ions will not precipitate as iron hydroxide.
In addition, in the present invention, it is preferable to use a chelating agent in combination, since the metal nucleus exchange reaction can proceed more smoothly. Specific examples of the above-mentioned chelating agent preferably used in the present invention include the following compounds,
It is not limited to these. (Exemplary compounds) B-1 1-hydroxyethylidene-1,1-diphosphonic acid B-2 2-phosphonobutane-1,2,4-tricarboxylic acid B-3 Sodium hexametaphosphate B-4 Sodium pyrophosphate B-5 Tripolyphosphoric acid Sodium B-6 1-hydroxy-1,1-diphosphonopropane-3-carboxylic acid B-7 1-hydroxy-1-phosphonoethane-
1-Carboxylic acid B-8 1-hydroxy-1-phosphono-propane-1,2,3-tricarboxylic acid B-9 Potassium 1,1-diphosphonoethane-2-carboxylate B-10 Sodium gluconate B-11 Di( hydroxyethyl)glycine B-12 Triethanolamine B-13 2-phosphonopentane-2,5-dicarboxylic acid B-14 Hydroxyethyliminodiacetic acid B-15 Sodium diethylenetriaminepentaacetate When the above chelating agent is not added at all Although it is possible to obtain the effects of the present invention, a more preferable effect can be obtained by adding the iron ions to an extent that does not precipitate the iron ions released in the metal core exchange reaction. As the processing steps in the method for processing a silver halide color photographic material of the present invention, known processing steps can be used in combination, and include, but are not limited to, the following steps. Color development - bleaching - fixing - washing with water - stable Color development - bleaching - washing with a small amount of water - washing with water - fixing - washing with water - stable Color development - bleaching - fixing - pre-washing - washing with water - stable Color development - bleaching - washing with a small amount of water - fixing - pre-washing - washing with water - Stable Color development - Stop - Bleach - Small amount of water wash - Fixing - Pre-wash - Water wash - Stable Color development - Intensification - Bleach - Small amount of water wash - Fixing - Pre-wash - Water wash - Stable Color development - Stop - Bleach - Fixing - Pre-wash - Washing - Stability Among the above steps, a pre-washing step is preferably used in the present invention after the fixing step. The reason for this is that polluting components that adhere to silver halide photographic light-sensitive materials during the washing process are extremely reduced, and soluble silver salts dissolved in the fixing solution are less likely to be lost to the washing process. This is because favorable results can be obtained socially and environmentally as well as economically, such as increased collection efficiency. Further, it is preferable that the number of processing steps is small in terms of rapid processing, and therefore, among the above steps, steps and are particularly preferably used in the present invention. Further, the small amount washing bath used in the present invention refers to a small amount washing bath of 200 ml or less per 100 cm 2 of silver halide color photographic material, and the effect of the present invention is 40 ml per 100 cm 2 of silver halide color photographic material.
Good results are obtained in the following cases, especially when the amount of silver halide color photographic light-sensitive material is 15 ml or less per 100 cm 2 . The fixer used in the present invention may contain known fixer components in addition to the fixer and preservative described above. For example, potassium hydroxide, sodium hydroxide, ammonium hydroxide, sodium phosphate, and sodium carbonate may be contained as pH adjusters, and various antifoaming agents or surfactants may be contained. Furthermore, preservatives such as hydroxylamine and hydrazine, stabilizers such as nitro alcohol and nitrates, organic solvents such as methanol, dimethylformamide, and dimethyl sulfoxide, and the like can be appropriately contained. Further, the silver halide color photographic light-sensitive materials of the present invention include color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, color reversal paper, etc. Color photographic materials can be used. Hereinafter, the details of the present invention will be explained with reference to Examples, but the embodiments of the present invention are not limited thereby. Example 1 Sakura color film (Konishi Roku Photo Industry Co., Ltd.)
Konica FS-1 camera (manufactured by Konishiroku Photo Industry Co., Ltd.)
After photographing the images using an automatic processor (manufactured by Manufacturer Co., Ltd.), the images were continuously processed using an automatic processor according to the following steps. The automatic developing machine used was a modified hanging type automatic film developing machine type H4-220W-2 manufactured by Noritsu Koki Co., Ltd. Processing process (38℃) Number of tanks Processing time Color development 1 tank 3 minutes 15 seconds Bleaching 2 tanks 6 minutes 30 seconds Washing with a small amount of water 1 tank 3 minutes 15 seconds Fixing 1 tank 6 minutes 30 seconds Water washing 2 tanks 4 minutes 20 seconds Stability 1 tank 2 minutes 10 seconds The composition of the color developer used is as follows. Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 5g Sodium bromide 1.3g Potassium iodide 2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g Sodium diethylenetriaminepentaacetate 2.5g 4-Amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to make 1, potassium hydroxide or 20g
Adjust the pH to 10.06 using % sulfuric acid. The composition of the color development replenishment solution used is as follows. Potassium carbonate 35g Sodium hydrogen carbonate 3g Potassium sulfite 7g Sodium bromide 0.9g Hydroxylamine sulfate 3.1g Sodium diethylenetriaminepentaacetate 3.2g 4-Amino-3-methyl-4-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
5.4g potassium hydroxide 2g Add water to make 1, potassium hydroxide or 20g
Adjust the pH to 10.12 using % sulfuric acid. The composition of the bleaching solution used is as follows. Iron ammonium ethylenediaminetetraacetate
100g Disodium ethylenediaminetetraacetate 10g Ammonium bromide 150g Glacial acetic acid 10ml Add water to make 1, and adjust to PH5.8 using aqueous ammonia or glacial acetic acid. The composition of the bleach replenishment solution used is as follows. Iron ammonium ethylenediaminetetraacetate
120g Disodium ethylenediaminetetraacetate 12g Ammonium bromide 178g Glacial acetic acid 21ml Add water to make 1, and adjust the pH to 5.6 using aqueous ammonia or glacial acetic acid. The composition of the fixer used is as follows. Ammonium thiosulfate 150g Anhydrous sodium sulfite 12g Sodium metabisulfite 2.5g Disodium ethylenediaminetetraacetate
0.5g Sodium carbonate 10g Add water to make 1. The composition of the fixing replenisher used was as follows. Ammonium thiosulfate 200g Anhydrous sodium sulfite 15g Sodium metabisulfite 3g Disodium ethylenediaminetetraacetate
0.8g Sodium carbonate 14g Add water to make 1. The composition of the stabilizing solution used is as follows. Formalin (37% aqueous solution) 2ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 5ml Add water to make 1. The composition of the stable replenishment solution used is as follows. Formalin (37% aqueous solution) 3 ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7 ml Add water to make 1. Color development replenishment solution is color negative film 100
The color developing bath is replenished with 15ml per cm2 , the bleach replenisher is replenished with 18ml per 100cm2 of color negative film, and the fixing replenisher is replenished with the color negative film.
The fixing bath was replenished with 7 ml per 100 cm 2 of color negative film, and 11 ml of the stabilization bath was replenished with each 100 cm 2 of color negative film. In addition, 3ml of water is replenished per 100cm2 of color negative film in the small amount washing bath, and 150ml of water is replenished per 100cm2 of color negative film in the washing bath.
ml was washed away. Add ammonium hydroxide or acetic acid to the fixing replenishment solution as appropriate to keep the pH of the fixing bath at 6.5 during continuous processing of the color negative film, and continuously process 1000 m2 . The fixing bath solution after the fixing bath was designated as Comparative Sample Solution A. Further, exemplified compound A-9 is added to the fixing solution in a constant amount of 1.5 times the mole of iron ammonium ethylenediaminetetraacetate present in the fixing bath,
Sample B of the present invention was a fixing bath solution obtained by continuously processing 1000 m 2 of color film while maintaining the pH at 6.5 in the same manner as described above. Similarly, a fixing bath solution obtained by continuously adding Exemplified Compound A-9 and Exemplified Compound B-2 (equimolar concentrations as A-9) to the fixing solution was designated as Sample Solution C of the present invention. Exemplary compounds A-9 and B-2 of sample solution C were A-
4 and B-4, A-16 and B-6, A-20 and B-1, A-28 and B-10, A-34 and B
-3, A-37 and B-5, A-44 and B-15
, A-45 and B-14, A-52 and B-2,
A-55 and B-12, A-63 and B-9, A-
65 and B-7, A-70 and B-8, A-72 and B-11, A-81 and B-5, A-95 and B
-11, A-144 and B-13 respectively, and the color film was continuously processed for 1000 cm2 while maintaining the pH of the fixing bath at 6.5. It was set as T. Sample solutions A to T prepared in this way were
After being allowed to stand at room temperature for several days, the color negative film subjected to white stage exposure using a KS-7 sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.) was subjected to color development according to the above-mentioned process. After this color development process was completed, the maximum density of the red photosensitive layer was measured using a PDA-60 photodensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.). Furthermore, after observing the state of precipitation in the fixer that had been left for 6 days, the amount of sulfite ions before and after being left was measured, and the rate of decrease was determined. The above results are summarized in Table 1.
【表】
これより、本発明に係わる金属化合物が添加さ
れない試料液Ａは亜硫酸イオンの減少が大きく、
また最大濃度部に発色不良を生じ実用に供し得な
い。ところが、本発明に係わる金属化合物を添加
した試料液ＢないしＴは亜硫酸イオンの減少も少
なく、最大濃度部に発色不良は生じていなく良好
である。とりわけ、キレート剤を併用した試料液
ＣないしＴは水酸化鉄の沈澱発生もなく、さらに
亜硫酸イオンの減少も最大濃度部の発色不良もな
く、とりわけ良好である。
実施例 ２
実施例１の試料液Ｃ中の例示化合物Ａ−９の添
加量を試料液Ｃ中に存在するエチレンジアミンテ
トラ酢酸鉄アンモニウムのモル濃度に対して０
倍、0.5倍、1.0倍、1.5倍、2.0倍になるようにし
て実施例１と同様な実験を行なつた。
その結果を第２表に示す。[Table] From this, sample solution A to which the metal compound according to the present invention is not added has a large decrease in sulfite ions,
In addition, poor color development occurs in the maximum density area, making it impossible to put it to practical use. However, the sample solutions B to T to which the metal compound according to the present invention was added had a small decrease in sulfite ions and were good, with no defective color development occurring in the maximum concentration area. In particular, sample solutions C to T in which a chelating agent was used in combination were particularly good, with no precipitation of iron hydroxide, no decrease in sulfite ions, and no poor color development in the maximum concentration area. Example 2 The amount of exemplified compound A-9 added in sample solution C of Example 1 was set to 0 with respect to the molar concentration of iron ammonium ethylenediaminetetraacetate present in sample solution C.
The same experiment as in Example 1 was conducted with the magnifications increased by 0.5 times, 0.5 times, 1.0 times, 1.5 times, and 2.0 times. The results are shown in Table 2.
【表】
これより、本発明に係わる金属化合物Ａ−９の
添加量が、有機酸鉄キレート錯体（本実験ではエ
チレンジアミンテトラ酢酸鉄アンモニウム）の1/
２モル以上であれば最大濃度の発色不良及び亜硫
酸イオンの減少率に対して良好な効果を有する
が、とりわけ等モル以上の際に特に良好な効果を
示すことがわかる。
実施例 ３
実施例１の少量水洗を除去して試料液Ａないし
Ｆと同様の実験を行ない比較用試料液Ｕおよび本
発明試料液ＶないしＺとした。
結果を表３に示す。[Table] From this, the amount of addition of metal compound A-9 related to the present invention is 1/ of the organic acid iron chelate complex (in this experiment, iron ammonium ethylenediaminetetraacetate).
It can be seen that when the amount is 2 moles or more, it has a good effect on poor color development at the maximum concentration and on the reduction rate of sulfite ions, but particularly when the amount is equal mole or more, a particularly good effect is shown. Example 3 The same experiment as with sample solutions A to F was conducted by removing the small amount of water washing in Example 1 to obtain comparative sample solutions U and inventive sample solutions V to Z. The results are shown in Table 3.
【表】
これより、漂白浴が直接に定着浴に続く際にも
本発明の金属化合物を添加すれば、良好な結果を
得ることが判り、とりわけキレート剤を併用添加
したものは沈澱の発生もなく特に良好な結果を得
ることが判る。
実施例 ４
実施例１の処理工程の定着浴と水洗浴の間に、
さらに予備水洗浴を配し、この予備水洗に水をカ
ラーネガフイルム100cm2当り３ml補充しながら実
施例１と同様の実験を行なつたところ、同じ結果
を得た。
また、この定着浴の後に配した予備水洗浴のオ
ーバーフロー液をサクラリプロ製銀回収用スチー
ルウールカートリツヂ（サクラリプロユニツト１
型に通したところ620ｇの銀が回収された。さら
に水洗水中の化学的酸素要求量（以下、CODと
称す。）を測定したところ、実施例１のCODの1/
３に減少していた。このように定着浴の後に予備
水洗浴を設けると、水洗水中に流失していた銀も
回収され、またCODも著しく低下し、さらに良
好な結果を得た。[Table] From this, it is clear that good results can be obtained by adding the metal compound of the present invention even when the bleaching bath is directly followed by the fixing bath, and in particular, when a chelating agent is added together, precipitation does not occur. It can be seen that particularly good results can be obtained. Example 4 Between the fixing bath and washing bath in the treatment step of Example 1,
Furthermore, an experiment similar to that in Example 1 was conducted by providing a preliminary washing bath and supplementing the preliminary washing with 3 ml of water per 100 cm 2 of color negative film, and the same results were obtained. In addition, the overflow liquid from the preliminary washing bath placed after the fixing bath was transferred to a steel wool cartridge for silver recovery made by Sakura Repro (Sakura Repro unit 1).
When passed through a mold, 620g of silver was recovered. Furthermore, when we measured the chemical oxygen demand (hereinafter referred to as COD) in the washing water, we found that it was 1/1/2 of the COD in Example 1.
It had decreased to 3. By providing a pre-washing bath after the fixing bath in this manner, the silver that had been washed away in the washing water was recovered, and the COD was also significantly reduced, resulting in even better results.
Claims (1)
理するハロゲン化銀カラー写真感光材料の処理方
法において、上記有機酸鉄キレート錯体と金属核
交換反応を行なうことにより、安定な有機酸金属
キレート錯体を形成せしめ得る金属化合物を前記
定着液中に存在せしめることを特徴とするハロゲ
ン化銀カラー写真感光材料の処理方法。1. In a method for processing a silver halide color photographic light-sensitive material in which a fixing solution containing an organic acid iron chelate complex is used, a stable organic acid metal chelate complex is obtained by carrying out a metal core exchange reaction with the organic acid iron chelate complex. 1. A method for processing a silver halide color photographic material, characterized in that a metal compound that can be formed is present in the fixing solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8516881A JPS57200040A (en) | 1981-06-02 | 1981-06-02 | Treatment for silver halide color photographic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8516881A JPS57200040A (en) | 1981-06-02 | 1981-06-02 | Treatment for silver halide color photographic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57200040A JPS57200040A (en) | 1982-12-08 |
| JPS6327705B2 true JPS6327705B2 (en) | 1988-06-03 |
Family
ID=13851126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8516881A Granted JPS57200040A (en) | 1981-06-02 | 1981-06-02 | Treatment for silver halide color photographic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57200040A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6175353A (en) * | 1984-09-21 | 1986-04-17 | Fuji Photo Film Co Ltd | Method for processing color photosensitive material |
| US5434035A (en) * | 1993-12-29 | 1995-07-18 | Eastman Kodak Company | Fixer additives used in combination with iron complex based bleaches to improve desilvering |
| US5508150A (en) * | 1993-12-29 | 1996-04-16 | Eastman Kodak Company | Fixer additives used in combination with iron complex based bleaches to prevent iron retention |
-
1981
- 1981-06-02 JP JP8516881A patent/JPS57200040A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57200040A (en) | 1982-12-08 |
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